Патент USA US2409881код для вставки
SR 11.5673 XR search Roorp‘ Fbb iiill“ illilZWUi‘l ZQQO‘FQQ'YS Patented Oct. 22, 1946v 2,409,878 UNITED STATES PATENT Eric's 2,409,878 LUBRICATING OIL Robert L. May, Chicago, 111., assignor to Sinclair Re?ning Company, New York, N. Y., a corpora tion of Maine No Drawing. Application July 15, 1944, Serial No. 545,195 5 Claims. (Cl. 252—32.7) 1 2 This invention relates to a lubricating oil com What depending upon the characteristics of the position having improved characteristics espe cially with respect to oxidation and corrosion. In my Patent No. 2,379,313 I have described and claimed a new class of organic-metal com pounds comprising the zinc salts of organic com pounds resulting from the reaction of an alkyl turpentine-P285 condensation product, the nature and proportions of the alkylated phenols reacted therewith to form the intermediate material, the conditions under which the reactions are effected and to some extent upon the proportions of zinc oxide and the intermediate material used in its ated phenol with a condensation product of a production. Also the character of the inhibitor terpene, such as is present in turpentine, and is in?uenced by the conditions under which the phosphorus pentasul?de. The turpentine-phos 10 zinc oxide is reacted with the intermediate ma phorus pentasul?de condensation products are terial. the subject of my co-pending application, Serial The reaction temperature employed in the last No. 494,688, ?led July 14, 1943, and the materials mentioned reaction, in the preparation of my in resulting ‘from the reaction thereof with alkylated phenols are the subject of my Patent No. 2,379,312. 15 hibitor, is with advantage maintained within the range of about 275° F. to about 300° F., although I have now discovered that the zinc salts of my reaction temperatures somewhat outside of this ?rst said patent are especially effective in re range are permissible. Particularly desirable re pressing or inhibiting the deterioration of lubri sults have been obtained where the temperature eating oil compositions and the corrosion of metal parts in contact therewith. . 20 has been raised to about 280° F. during this reac tion. Also I have found it desirable to use an I am at present unable de?nitely to identify by amount of zinc oxide somewhat in excess of that chemical formula either the zinc salts or the con equivalent to the acid number of the intermediate densation products of turpentine and phosphorus material and to ‘filter 01? unreacted excess zinc pentasul?de or the products resulting from (“the oxide as previously indicated. reaction of said condensation product with the The lubricating composition of my present in alkylated phenol. For convenience and brevity, vention may consist solely of the lubricating oil I shall herein refer to the former as my inhibitor, constituent and my inhibitor. However, the in to the condensation product as the turpentine hibitor of my present invention has been found P2S5 condensation product and to the composi tion resulting from the reaction of the alkylated 30 to be compatible with other desirable lubricating oil addends and the inclusion of such other ad~ phenol with the turpentine-P285 condensation dends, especially addends of the type known as product as the intermediate material, each of detergents, is within the contemplation of my which is hereinafter more fully described. present invention and constitutes an important Although the intermediate material itself has aspect thereof. been found to be a desirable component of lubri eating oil compositions, the use of such inter The inclusion of certain so-called detergents, mediate materials for this purpose is subject to for instance, in internal combustion engine lubri certain disadvantages. For instance, it is subject cants, has been found highly advantageous. An to the objection that they have somewhat acidic especially effective lubricating oil composition for characteristics, due to phosphorus acidity which 40 the lubrication of internal combustion engines and the like, contemplated by my present inven has been found to have a tendency to promote sludging of mineral oil compositions. The lubri cating oil compositions of my present invention are free from this objection. tion, is one comprising, in addition to the lubri cating oil constituent and my inhibitor, a minor proportion of a calcium-containing detergent, for In general, my inhibitor may be prepared by 45 instance, the calcium salt of various alkyl esters reacting zinc oxide with the intermediate ma of aromatic acids, particularly the calcium salt terial by intimately admixing the zinc oxide with of iso-octyl salicylate and the calcium salt of the intermediate material with, moderate heating. capryl salicylate. These and various other or The product of this reaction is then with advan tage diluted and ?ltered to remove any excess or 50 garlic-calcium salts have been found particularly effective as detergents in lubricating oil composi unreacted zinc oxide present. In the preparation tions used in internal combustion'engines, the two of such compounds for use as a constituent of my improved lubricating oil compositions, the diluent particularly named calcium salts being more fully is with advantage a light neutral lubricating oil described in Letters Patents 2,347,547 and 27,339, fraction which may be permitted to remain in 55 692, issued on applications of Willard L. Finley. the product. A further highly effective lubricating oil com‘ The characteristics of my inhibitors vary some po'sition ‘contemplated by my present invention" 2,409,878 is one comprising, in addition to the lubricating oil constituent and my inhibitor, a calcium petro leum sulfonate, as a detergent. Other detergents which may be used with advantage include the barium phenolate of sulfurized diamyl phenol, such as currently marketed under the trade name of “Aerolube B,” metallic phenolates of sulfurized 4 should be a saturated aliphatic group. Each molecule of the alkylated phenol may contain one or more such groups. The number of carbon atoms in each aliphatic group is not critical. De sirable products may be obtained where each such group contains from 1 up to 12 to 16, or even up to 25 to 35 carbon atoms. Alkylated phenols con tertiary amyl phenol, such as currently marketed - , taining 5 or more carbon atoms in .each alkyl group have been found especially desirable, be under the trade names “Calcium Paranox” and “Barium Paranox” and various metallic soaps, 10 cause of the greater oil solubility of the resultant product. The alkyl group or groups may be either either basic or neutral, metallic sulfonates, alco normal or branched chain. holates and alkoxides and metallic derivatives of alkylated salicylic acid. When used in conjunction with these deter- ' gents, particularly the calcium salts, including Alkylated phenols, herein designated codimer alkylated phenols, such as prepared by the reac tion, in the presence of sulfuric acid, of phenols with the ole?nes in commercial codimer, resulting ‘from the phosphoric acid polymerization of mixed calcium petroleum sulfonates previously men tioned, these detergents and my inhibitors have olefines of 4 carbon atoms or less per molecule and been found to complement each other so that the comprising propylene, butene-l, butene-Z and effectiveness of each is promoted. The tendency of the detergent to promote oxidation of the oil 20 iso-butylene, the codimer consisting of a major portion of Ca ole?nes, together with some 06- C71 at the termination of its oxidation induction pe C9, C10, C11, C12 and higher ole?nes, have been riod is minimized by the presence of my inhibitor used with advantage. These codimer alkylated without destroying the effectiveness of either the phenols are comprised primarily of mono- and detergent or the inhibitor. The proportions of the inhibitor used in the 25 poly-alkylated phenols having alkyl groups, as noted above, but with Ca alkyl groups predomi compounding of my improved lubricating oil com position may be varied somewhat but in any case nating. I have further used with advantage in the prep-, only a minor proportion is used. The optimum aration of my improved lubricating oil composi proportion to be used will depend upon whether or tion, alkylated phenols, prepared by the method not a detergent, such as previously mentioned, is just described for the preparation of codimer al present and the particular use to which the lu kylated phenols except that the phenol was re bricating oil composition is to be put. The opti mum proportion will also vary, depending upon acted with codimer bottoms, the codimer bottoms used being the bottoms obtained by a redistilla the particular member of my new class of in tion of the previously described codimer to a 350 hibitors used. In the preparation of my improved lubricating to 360° F. end point overhead. Thisbottom was oil composition, I have found itadvantageous to comprised primarily of C12 ole?nes, but contains prepare the inhibitor in solution in about an equal some somewhat lower and some somewhat higher weight of a petroleum lubricating oil fraction, as molecular weight ole?nes. As previously noted, I'am at- present unable hereinafter more fully described. As a motor oil 40 which does not contain detergents, 0.2 to 05% of de?nitely to identify by chemical formula either the 50% concentrate of my inhibitor may, with the inhibitor used in the preparation of my im advantage, be admixed with the lubricating oil proved lubricating oil compositions or the inter constituent. When used as an anti-oxidant in mediate material or the turpentine-P285 conden turbine oils or hydraulic oils, the 50% concentrate 4,5 sation product from which they are prepared. maybe added to the lubricating constituent in However, I have found it desirable that the tur proportions‘ advantageously ranging from about pentinewPzss condensation product used in ac 0.1 to about 0.3% by weight. In heavy duty oils cordance with my present invention contain no containing detergents, such as previously men ' , 60 unreacted Pass. tioned, for use in gasoline or Diesel engines, the Since the characteristics of my improved lubri 50% concentrate of my inhibitor may, with ad cating oil composition are somewhat in?uenced vantage, be added in proportions ranging from about 1% to about 10% by weight, depending upon the nature and concentration of the deter gent, the severity of the service for which the lubricating oil composition is to be used and the particular inhibitor employed. The molar proportions of PzSs, turpentine and alkylated phenol used in the preparation of the intermediate material, which I react with zinc ox ide in the preparation of my new class of in hibitors, may be varied over aconsiderable range. Molar proportions of 2:6:3 have been used with by the characteristics of the particular‘ inhibitor used, which in turn are influenced by the charac teristics of the intermediate materials from which my inhibitors are prepared, a detailed description of the preparation and the character of the par ticular inhibitor'used will be included in the spe ci?ic illustrations 'of my invention hereinafter set forth. However, it will be understood that my in vention is not limited to the use of these particu lar inhibitors illustrated nor‘with respect to the method by which the inhibitor is prepared, but in cludes lubricating oil compositions ‘comprising particular advantage, assuming the molecular the inhibitors herein described by whatever proc 65 weight of the turpentine to be L36. However, for ess the inhibitor may be made. each two moles of P255 there may be used 5 to 7 moles of turpentine and 1 to 5 moles of alkylated phenol, but it is desirable that the sum total of the number of moles of turpentine and the moles of alkylated phenol for each two moles of P285 fall within the range of about 8:10. In the preparation of my novel class of inhib Generally, in the preparation of the turpentine PzSs condensation product used in the prepara tion of my inhibitors, the molar ratio of turpene tine-P2555 is with advantage approximately 3:1. However, this ratio may vary somewhat in either I direction. For instance, highly desirable prod ucts may be produced from intermediate material itors considerable latitude is permissible in the which in turn have been produced from turpen selection of the alkylated phenol used. In gen eral, the alkyl radical of the alkylated phenol 75 tine-P255 condensation products in which the liviti’il‘dl l “lllbllii Search Room ice 2,409,878 5 6 ratio of turpentine to P285 is within the range of about 5:2 to about 7.: 2, as previously noted. The reaction of turpentine with P2555 is highly added and the mixture stirred for one hour, at the endof which time 225 grams of zinc oxide was added, the mixture stirred for an additional hour exothermic and proceeds spontaneously after be ing initiated by slight heating. A desirable meth and thereafter the temperature increased slowly to 280° F. In ‘order to facilitate ?ltration, the resulting od of effecting this reaction is to heat the turpen tine in a vessel to about 200° F. and then, without product Was thinned by intimately admixing further heating, slowly stirring in the phosphorus therewith 4380 grams of a light petroleum lubri pentasul'?de in the powdered form. The heat of cating oil fraction. The mixture was then ?l reaction is great and, consequently, the sul?de 10 tered and the ?ltrate was found by analysis to should be added slowly so as toavoid the possi have an acid number of 30.0 and an A. P. I. grav bility of the reaction’s becoming uncontrollable. ity of 11.1 and to contain 3.19% phosphorus, 3.04% sulfur and 0.48% zinc. sirable that the temperature during this addition Example II not be permitted to exceed about 250° F., although 15 higher temperatures are permissible. To a turpentine-P285 condensation product pre ‘After the addition of phosphorus pentasul?de pared, as in Example I, from 2040 grams of steam is completed and the exothermic heating is 1ess~ distilled wood turpentine, 1110 grams of powdered phosphorus pentasul?de, at a temperature of 230° ened, it is usually necessary to apply heat exter nally‘ to complete the reaction. The temperature 20 F., there was added 1755 grams of diamylphenol during this last stage is preferably maintained at and the mixture heated and stirred at a tempera about ‘300° F., though temperatures of about 200 ture of 200° F. for one hour. Thereafter, 225 to about 400° F. may be employed. The second grams of Zinc oxide was added and the mixture stage of the reaction should be continued until stirred for one hour. The temperature was then all of the Past is dissolved. The material thus 25 gradually raised to 280° F‘. to complete the reac prepared is a viscous liquid at elevated tempera tion. The product of the reaction was then thinned, tures, but, in the absence of excess turpentine, For the purpose of my present invention, it is de to facilitate ?ltration, by intimately admixing solidi?es on cooling to room temperature. In general, the intermediate material used in therewith 4905 grams of a light petroleum lubri the preparation of my inhibitors may be prepared 30 cating oil fraction and the mixture ?ltered. The by adding the alkylated phenol gradually to the ?ltrate was found by analysis to have an acid number of 28.3, an A. P. I. gravity of 13.1 and to turpentine-BS5 condensation product, advan tageously at a temperature of about 230° F. The contain 3.0’? % phosphorus, 7 .82% sulfur and optimum temperature of the condensation prod 0.24% zinc. uct for the introduction of the alkylated phenol 35 Example III will vary, depending upon the particular alkyl ated phenol used. During the ?nal step of the production of the turpentine-Pass condensation product, the temperature will usually be substan The product was prepared using the procedure, ingredients and proportions thereof identical with those of Example II, with the exception that the tially in excess of 230° F., usually about 300° F., 40 diamylphencl constituent was added to the tur pentine-PzSs condensation product while the lat and in commercial operations two to three hours ter was at a temperature of 300° F. The prod would normally be required for lowering the tem uct was thinned and filtered, as previously de perature to 230° F. by natural cooling.‘ Such scribed, and the ?ltrate was found by analysis to cooling is usually unnecessary and may be avoided since these alkylated phenols are relatively sta 4-3 havean acid number of 26.2. an A. P. I. gravity of 13.3 and to contain 3.11% phosphorus, 8.28% sul ble toward heat and may be safely admixed with fur and 21% zinc. the turpentine-Pass condensation products at temperatures as high as 300° F. Ermnple I V In reacting the alkylated phenols with the tur A product was prepared by the procedure of pentine-Pzss condensation products, very little 50 Example II from 1‘200 grams of turpentine, 1110 heat is evolved. After the alkylated phenol has grams of P285, 1755 grams of diamylphenol and been added. the mixture is maintained at an ele 56 grams of zinc oxide. The product was thinned vated temperature, advantageously at about 200° by intimately admixing therewith 4565 grams of F. or higher, for about one hour with stirring. a light petroleum lubricating oil fraction and was The following speci?c examples of various then ?ltered. The ?ltrate was found by analysis members of my new class of inhibitors and the to have an acid number of 33.3, an A. P. I. gravity procedure by which they have been successfully prepared, are given as illustrative of the class. Example I 2040 grams of turpentine was placed in a ?ask of 13.1 and to contain 3.67% phosphorus, 10.28% sulfur and 0.182% Zinc. 60 Example V equipped with a stirrer, a thermometer and a funnel, and heated therein to 240° F. There was then added to the turpentine 1110 grams of phos phorus pentasul?de at such a rate that the tem perature of the reaction mixture did not rise above 275° F. The mixture was stirred during this addi tion. When all of the P255 had been added, the temperature of the mixture was raised to 300° F. and the mixture held at this temperature for two hours with stirring. At the end of this period, all of the phosphorus pentasul?de had dissolved and the product was ‘a viscous, amber—celored liq uid. Thereafter, the mixture was cooled to 230° F. and 1230 grams. of p-tert-amyl phenol was ” r I A product was prepared by the procedure of Example II from 2040 grams of turpentine, 1110 grams of P265, 1172 grams of diamylphenol and » 56 grams of Zinc oxide. The product was thinned by intimately admixing herewith 4.322 grams of a light petroleumlubricating oil fraction and there after ?ltered. The ?ltrate was found by analysis to have an acid number of an A. P. I. gravity of 11.9 and to contain 3.20% phosphorus, 9.36% sulfur and 0.090% zinc. Example VI A product was prepared by the procedure of Example II using the constituents and propor . 1e ‘ 2,409,878 8 7 ample VIII except for using as the alkylated phenol constitutent 2570 grams of ‘a codimer bottoms alkylated phenol consisting of a mix tureof a codimer bottoms alkylated phenol'hav ing a phenol number of 134.9, an apparent mo lecular weight of 415 and a codimer bottoms alkylated phenol having a phenol number of tions therein described except that, in place of the diamylphenol, 1425 grams of a butene alkyl ated phenol having a phenol number of 294.3 and an apparent molecular weight of 190 was used and the resulting product was thinned by admixing therewith 4575 grams of the light petro leum lubricating oil fraction.~ After ?ltration the ?ltrate was found to have an acid number of 31.3, an A. P. I. gravity of 12.8 and to contain 3.13% phosphorus, 7.19% sulfur and 0.46% zinc. Example VII 127.5 and an apparent molecular weight of 441. Prior to ?ltration, the product was diluted by 10 the addition of 5090 grams of the lubricating oil fraction. The ?ltration was found by analysis to have an acid number of 20.5, an A. P. I. gravity of 16.5 and to contain 2.84% phosphorus, 6.43% A product was prepared by the procedure of Ex sulfur 0.07% zinc. ample II, using the constituents and proportions therein described except that, in place of the di 15 Example XII amylphenol, 2050 grams of a codimer alkylated phenol having a phenol number of 203.7 and an apparent molecular weight of 275 was used and This product was prepared by the method and from the ingredients and proportions used ‘in Example VIH except for using as the alkylated the product was thinned by intimately admixing therewith 5,200 grams of the light petroleum lu 20 phenol constituent, 1920 grams of a codimer‘loot toms alkylated phenol having a phenol num bricating oil fraction. The product was then ber of 116.2 and an apparent molecular weight of ?ltered and the ?ltrate was found by analysis to 483. Prior to ?ltration the product was diluted have an acid number of 23.7, an A. P. I. gravity of by the addition of 4440 grams of the lubricating 14.4 and to contain 2.70% phosphorus, 7.83% sul 25 oil fraction. The product was found by analysis fur and 0.13% zinc. to have an acid number of 22.5, an A. P. I. gravity Example VIII of 15.2 and to contain 2.62% phosphorus, 7.68% sulfur and 0.115% zinc. A product was prepared by the procedure de The light petroleum oil fraction used‘ in each scribed in Example II from 1632 grams of turpen of- the foregoing examples to facilitate ?ltration tine, 888 grams of Past, 2,149 grams of a codimer was a Mid-Continent neutral having the follow-v bottoms alkylated'phenol, and 180 grams of zinc oxide. ‘ The codimer bottoms alkylated phenol used had a phenol number of 151.2 and an appar . ent molecular weight of 371. The resulting prod uct was diluted by intimately admixing therewith 4669 grams of the light petroleum lubricating oil fraction and was ?ltered. The ?ltrate was found by analysis to have an acid number of 21.3, an A. P. I. gravity of 15.2, and to contain 2.86% phos 40 phorus, 6.70% sulfur and 0.12% zinc. Example IX This product was prepared by the method and from the ingredients and proportions used in Example VIII except for using as the alkylated phenol constituent 1765 grams of codimer alky lated phenol having a phenol number of 190.9 and an apparent molecular weight of 294. The product was diluted prior to ?ltration by inti mately admixing therevidth 4285 grams of the light lubricating oil fraction. The ?ltrate was found by analysis to have an acid number of 25.0, an A. P. I. gravity of 14.5 and to contain ing characteristics: Gravity, °A. P. 1: __________ _; __________ __ 27.9 Flash, °F _____________________________ __ Fire, "F _______________________________ __ 365 405 Viscosity at 100°,F., SUS-__.._v ___________ __ 107.8 Viscosity at 210° F., SUS _______________ __ Pour, °F __ Color _____________________________ _'____ 39.5 20 2— rI‘he codimer alkylated phenol and the codimer bottoms alkylated phenol were prepared as pre viously described herein. From the foregoing speci?c illustrations, it appears that the com 'bining ratios of zinc oxide and the intermediate materials vary somewhat with the excess of zinc oxide present. The duration of the reaction period also appears to in?uence the zinc content of‘ ‘the ?nished product. The presence of a considerable excess of zinc oxide during the reaction is usually desirable. The turpentine -P2S5 condensation product from which the members of my new class of in 2.68% phosphorus, 7.51% sulfur and 0.23% zinc. 55 hibitors are prepared is, in the absence of excess Example X turpentine, normally a brittle, resinous solid. It‘ is with advantage prepared from‘turpentine, This product was prepared by the method and from the ingredients and proportions used in Example VIII except for using as the alkylated phenol constituent 2670 grams of a codimer bot toms alkylated phenol, consisting of a mixture of a codimer bottoms alkylated phenol having a phenol number of 125.9 and an apparent molecu either steam-distilled wood turpentine or gum 5.88% sulfur and 0.11% zinc. Example XI This product was prepared by the method and from the ingredients and proportion used in Ex 75 Mid-Continent _ or South Texas neutrals or a spirits, consisting mainly of alpha pinene, a bicyclic terpene having the empirical formula ClOHlS. Pure alpha pinene and other more costly terpenes will react similarly with P285 but, for reasons including economic considerations, I pre fer to use the more readily available turpentine. lar weight of 445 and a codimer bottoms alkylated phenol having a phenol number of 124.7 and an 65 The turpentine used in the speci?c examples herein was a technical grade steam-distilled wood apparent molecular weight of 448. Prior to .?l turpentine comprising about 90% alpha pinene. tration 5,190 grams of the lubricating oil diluent As the lubricating oil constituents, various was added. The ?ltrate was found by analysis petroleum lubricating oil fractions may be used. to have an acid number of 19.8, and A. P. I. gravityof 16.6 and to contain 3.12% phosphorus, 70 For instance, solvent treated or acid treated blend of such neutrals with‘ bright stock or a solvent re?ned lubricating oil fraction from a Pennsylvania crude or various blends of such lubricating oil fractions may be employed. Char-1 i: billresinous. that‘ 0 Search Room ' UKUBD mil‘ LKENUE I) C. 2,499,878 9'. 10 acteristics of several such’ oils which have been identi?ed, was 255.6,- milliliters and the bearing metal corrosion, loss. was» 5.8 milligrams. By- in corporating in, this. base oil 0.1% of my inhibitor prepared as described in Example II, the mean used with advantage and. which were used in the compounding of my ‘lubricating oil: compositions hereinafter set forth, as illustrative of my in veniiion, appear in the following Table I in which 5 oxygen absorption rate‘ was reduced .to 12.7 milli ibase .oilA. is. a. solventetreated Mid:Continent, liters and the bearing metal corrosion loss was S. A. E.. 10011 and base. oil. B. is. a. sn?onated MidContinent S.. A. E. 30- 035k prepared: by treating a raw Midecontinent stock with 40 pounds of 99.3%. suliuric acid per. barrel, separating the in reduced to $3. milligrams. ‘.By compounding with this same base oil 0.25% of said inhibitor, the mean oxygen absorption rate was reduced to 4.6 milliliters and the- bearing~ metal corrosion loss sludge formed, neutralizing the acid oil with reducedto 2.6.- ~ lime, heating the mixture to drive off all water 5 ’ Further illustrations of my improved lubri present and ?ltering the dehydrated oil. eating oil compositions and the characteristics Base oil C is an- S'. A. E. 30 sol-vent treated thereof with respect‘to oxygen, absorption rates neutral’. Base oil D is a solvent treated aircraft 1'5 and bearing metal corrosion losses are set forth oi-l. Base Oil E‘ is a Mid-Continent base oil con~ in the following Table II. In each instance the ventionally re?ned by» acid treatment. Base oil F is also an acid treated Mid-Continent base oil. Base oil G is an acid treated aircraft lubricating ' oil fraction. inhibitor was compounded with the previously identi?ed base oil B, the characteristics of the base oil B without the inhibitor being included 2Q for comparison. Table I Base oil A Gravity, at. P.I __________ .. Flas 13 29.5 " 25.5 ’ 27.0 °F 405 ‘: ' , 435 500 512.1 0.20 Calcium, percent _________________ _. D E 25.3 F I G 25.0 24.7 540 305 450 510 515 010 432.3 1934.6 455 200.5 510 402.9 505 2,011.0 120.5 450 24.0 00.2 50.9 124.1 44.5 53.7 77.0 5, 80.3 5 88.7 10 51.4 15 54.0 1 10 0.03 0.58 0.02 0.05 1.15 0.127 0. 20 0. 39 0 49 0.25 __ ____________ __ Sulfur, percent ____________ _. o 0.35 0.061 Neutralization No _______________________ __ 81.3 -5 __________________________________ __ 0.00 0.04 0.00 0 03 0.00 For the purpose of further illustrating my in- Table II vention and the advantage derived therefrom, I 40 have herein set forth the results of oxygen ab. . . . sorpt1on and bearing corrosion tests of vanous . , . Inhibitor 7' of my improved lubricating oil compositions. ‘Identity The advantages of my present invention with re- ' " _ . Mean me Of ‘ Beam Ozabsorpg_ tipnmiper rglseigllcgs Pg’eg‘getffini mm'ggesf 10° mgs. ’ ' spect to oxidation and corrosion characteristics 2L6 M illustrated of my improved by their lubricating mean oxygen oil compositions absorption rates, are ‘é:.5- 0 0- 2 . . as compared with the oxygen absorption rates of> 3.00 4.15 +0.1 metal the base in oil, contact and the withcorrosion the respective losses lubricants. of bearing 2: These tests were carried out in a closed sys tem in which pure oxygen was circulated through +0.1 Fromthe results oi these tests, it appears that though the base oils had high corrosion rates 156 grams of the lubricant being tested. The and high oxygen absorption rates, the lubricating pressure of the system'was maintained constant 55 oil compositions prepared therefrom, in accord by introducing oxygen from a burette, and the time With my invention. showed in each instance sample was maintained at 360° F. and in con tact with two pieces of copper-lead bearings hav substantially reduced oxygen absorption rates ‘bearing metal corrosion losses. The .e?ectiveness of. my improved lubricating ing an approximate combined area of one square inch of copper-lead alloy surface and one square 60 01.1‘ compositions inhibiting-oil deterioration and bearing. metal corrosion further appears- from re inch of steel surface. The rateof oxygen absorp tion is calculated as milliliters of oxygen ab sorbed per minute per 100 grams of oil, measuring 5141118 of tests made in accordance with the pro cedure recommended by the American Society of Testing Materials, published October 1942, and the oxygen under standard conditions of temper 65 entitled‘ “Proposed method of test for oxidation ature and pressure. The bearing corrosion loss is reported as milligrams, the plus sign indicating characteristics of heavy duty crankcase'oils” and conventionally known as the “Chevrolet engine gain in weight. test.” The improved characteristics of my lubri , The proportions of inhibitor indicated as used in each of the tests herein are based on the weight of the undiluted inhibitor, as distinguished from cating oil compositions are further shown by the results of tests carried onin accordance with the method conventionally known as “Heavy duty oil oxidation test,” a modification of the test usually the 50% concentrate previously described, designated “Best,” herein‘designated HDOOT; for iwhensubjected to the foregoing test, the mean brevity. ' ’ oxygen absorption rate of base oil A, previously 75. Various lubricating oil compositions, such as - . _ i1 This lubricating oil composition was composed just identi?ed, will further illustrate my inven tion. 1-2 Composition D contemplated by my present invention and the characteristics thereof, as indicated by the tests of the following: - Per cent 77.7 ' Composition A Base oil C___‘ Base oil D ' 6.0 Calcium sulfonate detergent ____________ __ 14.0 Inhibitor of Example II _________________ _.. 2.2 This lubricating oil composition was composed of the following: Per cent Base oil C _____________________________ __ 83.9 10 Pour depressant ________________________ __' 0.1 Sodium sulfonate detergent _____________ .._ 14.8 Inhibitor of Example II ____________ __‘_____ When tested by the previously identi?ed HDOOT, the roof deposit was’ 1.2 grams and the CuPb bearing metal corrosion loss 8 milligrams. 1.3 The composition contained 0.09% sodium and the equivalent of 0.15% of P285. When tested by the previously identi?ed I-IDOOT, there re After the test the used oil was found to contain 0.23% naphtha insoluble, to have increased in viscosity at 210° F. by 2.7 seconds and to have'a neutralization number of 1.6. Composition E This lubricating oil composition was composed sulted a roof deposit of only 3.2 grams, and a CuPb bearing metal loss of 30 milligrams. At the end of the 135 hours test, the oil was found to contain 0.34% of 86° naphtha insoluble material. Its increase in viscosity at 210° F. was 2.0 seconds and its neutralization number was 0.6. of the following: Composition B This lubricating oil composition was come 25 posed of the following: Per cent Base oil C ____________________________ __ 83.34 Sodium sulfonate detergent ____________ __ 14.71 Inhibitor of Example II ________________ __ _ 1.95 ' 7 Per cent Base oil F _____________________________ __ 62.3 Base ‘oil G _____________________________ __ 15.0 Calcium sulfonate detergent ____________ __ 20.0 Inhibitor of Example II.v ________________ __ 2.5 Pour depressant ________________________ __ 0.2 The composition contained 0.10% calcium and the equivalent of 0.31% P2S5. The depressant 30 used was that previously identi?ed. When tested by the previously described HDOOT, the roof deposit was 1.9 grams and the CuPb bearing metal loss was 1 milligram. Fol scribed HDOOT, the roof deposit was found to ' be 0.14 gram and the CuPb bearing metal loss 27 35 lowing the test, the oil was found, tocOntain It contained 0.09% sodium and the equivalent of . When tested by the above de-, 0.22% of P285. 0.42% naphtha insolubles, to have increased in milligrams. The naphtha insoluble in the used viscosity at 210° F. by 3.2 seconds and to have a oil was 0.44%, the viscosity rise at 210° F. was 2.9 neutralization number of 1.7. and the neutralization number was 0.3. When subjected to the previously identi?ed Base oil C alone when subjected to said tests resulted in a roof deposit of 37.5 grams anda 40 “Chevrolet engine test,” the combined sludge and varnish rating was Bland the CuBb bear CuPb bearing metal loss of 204 milligrams. The ing corrosion loss for the complete bearing was oil after the test of 135 hours was found to con 0.095 gram. At the end of the 36 hour test, the tain 1.2% of naphtha insoluble material, to have increased in viscosity at 210° F. by 4.2 seconds and used oil was found to have a neutralization num to have a neutralization number of 1.5. ber of 1.65 and to have increased in viscosity at 100° F. by 149 seconds. In compositions of this type, proportions of ' A blend of this same base oil, containing 15% of sodium sulfonate and 85% base oil, when sub jected ‘to the foregoing test resulted in a roof deposit of 29.1 grams and a CuPb bearing metal loss of 665 milligrams. After the test, the oil was found to contain 1.5% of naphtha insoluble ma terial, to have increased in viscosity at 210° F. by 4.3 seconds and to have a neutralization number of 2.2. the addencl as high as 4% have been used with advantage. Composition F This lubricating oil composition was composed of the following: Per cent ' Composition C This lubricating oil composition was composed of the following: Base oil C ____________________________ __ 96.05 Detergent (“Aerolube B”) ______________ __ Inhibitor of Example II ________________ __ The composition contained 0.20% barium and the equivalent of 0.22% P285. When tested by the previously described Per cent Base oil C _____________________________ __ 79.3 Base oil D- __ _ 2.0 1.95 5.0 I-IDOOT, the roof deposit was 1.8 grams, the sump was clean and the CuPb bearing metal loss was 3 milligrams. Following the test, the used oil Pour depressant______________________ __‘__ 0.2 was found to contain. 0.3% naphtha insoluble, to The composition contained 0.07% calcium and 65 have increased in viscosity at 210° F. by 1.5 sec onds and to have a neutralization number of the equivalent of 0.19% P285. The depressant contained in the oil was a commercial product 0.10. Calcium sulfonate detergent ____________ __ 14.0 Inhibitor of Example II _________________ __ 1.5 Composition G marketed under the trade-name “Santopour.” When tested by the previously described This lubricating oil composition was composed HDOOT, the roof deposit was 2.4 grams and. the 70 of the following: CuPb bearing metal loss 28 milligrams. Follow Per cent ing the test, the oil was found to contain 0.26% Base oil C ____________________________ __ 84.86 naphtha insoluble. to have increased in viscosity at 210° F. by 4.3 seconds and to have a neutrali zation number of .1.7. y - 75 Calcium sulfonate detergent ___________ __ 13.81 Inhibitor of Example‘IV___n_ ___________ __ 1.33 1 nine. QRUSS Rtl’ tlitNUt 4c 1 . 2,409,878 13 14 When tested by the previously identi?ed When tested by the HDOOT, the roof deposit HDOOT, the roof deposit was 5.3 grams, the con dition of the sump was clean and the CuPb bear ing loss was 15 milligrams. Following the test the used oil was found to contain 0.31% of was 1.8 grams. the sump was clean and the bear ing corrosion loss was 4 milligrams. The used oil contained 0.47% of naphtha insoluble, showed a rise in viscosity at 210° F. of 1.0 and had a neutralization number of 0.4. naphtha insoluble, to have increased in viscosity at 210° F. by 3.6 seconds and to have a neutral In each of these and numerous other tests, it ization number of 1.7. has been found that lubricating oil compositions prepared in accordance with my present inven Composition H 10 tion are superior with respect to the oxidation This lubricating oil composition was composed and corrosion characteristics of the composition. of the following: These results are obtained whether the composi Per cent tions consist solely of the lubricating oil con Base oil C____-_ _______________________ __ 84.92 Calcium sulfonate detergent ___________ __ 13.82 Inhibitor of Example V ______ __- ________ __ 1.26 stituent and my inhibitor or also contain a deter 15 gent such as previously noted, for instance cal cium petroleum sulfonates. However, the latter When tested by the previously described HDOOT, the roof deposit was 3.2 grams, the con dition of the sump was clean, and the CuPb bear ing loss was 8 milligrams. The used oil con compositions are particularly advantageous, as previously noted herein. I claim: 1. A lubricating oil composition comprising a major proportion of a petroleum lubricating oil in viscosity at 210° F. by 2.6 seconds and had a and a minor proportion, e?ective to retard oxida neutralization number of 1.3. tion of the oil, of the reaction product of zinc Composition I oxide and an organic compound resulting from 25 the reaction of an alkylated phenol with the con The lubricating oil composition was composed densation product of turpentine and phosphorus of the following: pentasul?de, the alkyl group of the alkylated Per cent phenol being a saturated aliphatic radical. Base oil E _____________________________ __ 37.4 2. A_lubricating oil composition comprising a tained 0.37% of naphtha insoluble, had increased Base oil G _____________________________ __ 25.0 Calcium sulfonate detergent ____________ __ 34.9 Inhibitor of Example VII _______________ __ 2.5 Pour depressant ________________________ __ 0.2 20 30 major proportion of a petroleum lubricating oil and a minor proportion, effective to retard oxida ‘ tion of the oil, of the reaction product of zinc oxide and an organic compound resulting from the reaction of an alkylated phenol with the con HDOOT, the roof deposit was 1.0 gram, the sump 35 densation product of turpentine and phosphorus was clean and the bearing metal loss was 4 milli pentasul?de, the alkyl group of the alkylated grams. The used oil contained 0.55% naphtha phenol being a saturated aliphatic radical con insoluble, showed a decrease in viscosity at 210° taining at least 5 carbon atoms. F. of 2.7 seconds and had a neutralization num 3. A lubricating oil composition comprising a 40 major proportion of a petroleum lubricating oil "oer of 1.4. When subjected to the “Chevrolet engine test,” and a minor proportion, effective to retard oxida the sludge and Varnish ratings were each 49, tion of the oil, of the reaction product of zinc the bearing corrosion loss for the entire bearing oxide and an organic compound resulting from was 0.132 gram, the viscosity rise at 100° F. was the reaction of a polyalkylated phenol with the 62.2’ and the neutralization number of the used 45 condensation product of turpentine and phos oil was 2.2. phorus pentasul?de, the alkyl groups of the Composition J alkylated phenol being saturated aliphatic radi cals. This lubricating oil composition was composed 4. A lubricating oil composition comprising a of the following: major proportion of a petroleum lubricating oil Per cent and a minor proportion, e?ective to retard oxida Base oil C ____________________________ __ 82.86 tion of the oil, of the reaction product of zinc Sodium sulfonate detergent ____________ __ 14.62 oxide and an organic compound resulting from Inhibitor of Example XI ________________ __ 2.52 When tested by the previously identi?ed the reaction of diamyl phenol with the condensa When tested by the HDOOT, the roof deposit 5. tion product of turpentine and phosphorus penta was 2.5 grams, the sump was clean, the bearing corrosion loss was 5 milligrams, the naphtha insoluble material in the used oil was 0.40%, the viscosity rise at 210° F. was 1.3 and the neutral ization number of the used oil was 0.5. 60 Composition K This lubricating oil composition was composed of the following: Per cent Base oil C--- ____ 83.14 Sodium sulfonate detergent______________ 14.67 Inhibitor of Example XII ______________ .._ 2.19 sul?de. 5. A lubricating oil composition comprising a major proportion of a petroleum lubricating oil and about 0.1 to about 5%, based on the weight of the oil constituent, of the reaction product of zinc oxide and an organic compound resulting from‘ the reaction of an alkylated phenol with the condensation product of turpentine and phos phorus pentasul?de, the alkyl group of the alky1~ ated phenol being a saturated aliphatic radical. ROBERT L. MAY.