Патент USA US2354536код для вставки
Patented July 25, ‘1944 2,354,536 ‘ UNITED STATES ' PATENT ONE‘ ' 2,354,536 LUBRICATIN G OIL COMPOSITION - . a } Joseph F. Nelson, Elizabeth, N. J., assignor to Standard Oil Development Company, a corpo ration of ‘Delaware , No Drawing.~ ApplicationJanuar-y 2, 1941, a . ‘ Serial No. 372,893 4 '9 Claims. ; (01. 252-48) This invention relates to the preparation of im the number- of such alkyl carbons should be in- ‘ creased correspondingly. In general there is no proved lubricating compositions and is particu larly concerned with certain new types of addi tion agents which, whenincorporated in lubri cating compositions, impart thereto able stability characteristics. . advantage in having a larger portionof the mole cules in the form of alkyl chains thanis re highly desir- ‘ 1 . quired to obtain adequate oil solubility, though in certain instances the alkylportion may be The maintenance of satisfactory automobile performance requires that a ?lm of. lubricating increased to obtain'special properties such as the ability to depress the pour .point of the oil composition be present‘ on moving engine sur or to increase the viscosity index. faces, and that the composition be of good lubri 10 cating quality, and satisfactory chemical stability. ' ‘ _ Among the various suitable compounds em‘ played in the invention, those having the phos This film must be maintainableon exposed sur phorus acid esteri?ed with'at least one alkylated faces over periods of prolonged stoppage of ‘the aromatic alcohol or a phenol aresuitable and, engine, even when the surfaces are vertical, and also sustainable or rapidly replaceable under se 15 of these compounds, the oxyphosphites and 'thlo phosphites are particularly desirable. In the case vere operating conditions so as to prevent con tact of unprotected metallic surfaces with each other. Desirable properties, therefore, of auto mobile engine lubricants include rapid formation of tenacious ?lms, high penetrating and lubri cating capacity, and homogeneity and stability of mixed phosphitesjthat-is, those which con tain dissimilar groups attached to‘the phosphorus atom, the compounds which contain at least one alkylated aromatic radical attached through the 20 oxygen or sulfur to the phosphorus atom or at ' least in the presence of acidic and oxygen-containing an‘ alkylated aromatic radical in the ~ xanthogen group or groups of the compounds gases at elevatedtemperatures. are particularly suitable. The various alkyl and The present invention is concerned with the a ' .alkylated aromatic groups in these various com preparation of highly stable lubricating compo sitions by the addition of small quantities of oil 25 pounds may contain‘halogenconstituents, espe cially chlorine. When Z1 and/or Z: are xantho soluble or oii-dispersible compounds of anew type to mineral lubricating oils. gen groups the class of compounds may be rep A group of resented by the formulae '30 7 _ i (RXC s s), \PY s , RX-iL-S and (RXCSSMPY. Z1—X>PY z,—x/ > ' . in which R is an organic radical, usually pre dominantly hydroc'arbon in character, X is oxy~ gen or sulfur, Y is oxygen or sulfur when'phos phorus is pentavalent or it is omitted when phos- - 40 phorus is trivalent. and Z1 and Z: may be simi lar or dissimilar metals, onium bases, unsubsti ., ' . Instead of phosphorus in the above general 35 class of compounds; arsenic, antimony or bis muth may be substituted and the compounds are advantageous lubricating‘ oil ‘addition agents within the scope of the invention. The com pounds of the invention therefore include certain ‘phospho-xanthogen compounds, that is, certain xanthogen-containing phosphates, vthiophosphates, thiophosphites, the phosphites, ' correspond tuted or substituted, organic radicals, especially. ing arsenic, antimony and bismuth compounds; hydrocarbon or heterocyclic radicals, or xantho and substituted derivatives thereof. The man gen groups. By the term xanthogen group is 45 thogen-containing compounds of this invention ' designated the monovalentgrouping (RXCS)-'+ in which R is an organic radical and X may be either oxygen or sulfur. The organic radical R are those which have physical properties which insure adequate blending quality in the particu- ' lar type of vehicle used in the lubricant. Such, properties are largely determined by the molecu 50 lar weight of the particular compound and ‘in; tuted or substituted alkyl radical or a benzyl in thexanthogen group is usually an unsubsti group or homolog, thereof. The total alkyl radi~ cals in the compound should containrat least 6 carbon-atoms to provide the desired oil solubility, clude adequate oil ‘solubility or oil dispersibility, suitable boiling point and satisfactory chemical stability. Anotherclass of compounds falling . and when many non-organic groups are present 65 within the scope of the invention are those in which the element represented by X in the xan~ 2,354,586 2 These radicals can replace hydrogen in acids such as phosphorous acid, thiophosphorous acid, thogen group in the general formula may be ni trogen. In this latter case, the R in the general formula must be replaced by two monovalent phosphoric acid, thionphosphoric acid, (S=P(0H)a), groups such as two hydrogen atoms or two mon ' ovalent hydrocarbon groupings, or it must be re monothiolphosphoric acid placed by a divalentrradical such as the penta methylene group. All the compounds of the invention may be classified in terms of the following more general - thiontrithiolphosphoric acid, S=P(SH)3, etc. formula: Thus, classes of compounds within the scope of this invention include: carboalkoxy phos phites, thiolphosphates and thionphosphates; thiocarboalkoxy phosphites, thiolphosphates and 16 thionphosphates; carbodialkylamino phosphites, thiolphosphates and thionphosphates, thiocar in which B. may be a hydrogen atom or a hydro- ' bodialkylamino phosphates, thiolphosphates and thionphosphates; carboalkylmercapto phos phites, thiolphosphates and thionphosphates; thiocarboalkylmercapto phosphites, thiolphos phates and thionphosphates; carboallwlamino carbon or substituted hydrocarbon radical; X may be oxygen, sulfur, or'nitrogen; ,Y maybe oxygen or sulfur; D may be phosphorus, or a metalloid like arsenic, antimony, or bismuth; Z may be an organic radical which may contain phosphites, _ thiolphosphates andv thionphos phates; ‘and thiocarboalkylamino phosphites, halogen, nitro, amino, hydroxy, keto, mercapto, carboxy, nitroso, ,amido, alkoxy, aroxy, or other thiolphosphates and thionphosphates; and cor responding derivatives bearing substituents in the alkyl groups and containing ordinary phos phite, thiophosphite, phosphate, or thiophos ,phate linkages; or compounds of the latter type substituent groups; may be a metal or a group containing a metal or an onium base like am monium, sulfonium, phosphonium, or it maybe a xanthogen group; a may be either 1 or 2,; b may be 1, 2 or 3;lc is 0 or 1, d is 0, 1 or 2; the‘ 80 containing no hydrocarbon groups in the “thio carboxy” portions of their molecules. In addi choice of the value of ,these' subscripts vfor these tion to these phosphorus compounds, the corre groups depends on the valency requirements of spondingarsenic, antimony and bismuth are also the various atoms and radicals in the compounds. included within the scope of the invention. The following radicals are examples of the Examples of individual compounds within the scope of this invention are diamylphenylthiocar groups 7 . boethoxy Y. '(RIXC) , C5Hn0!3— I Carbopentoxy (CzHsOCSS) :As: lauryl dicarbomethylmercapto dithiophosphite, S ' ‘ 053110 g— ' > I 0 o , v (CHr-s JQL shP-O CnHu ' Thiocarbopentoxy H (Cal-111C050): phate, ,(CzHsOCSSMPO; trithiocarboethoxy tri thiophosphite, (CzHsOCSS) 3P; trithiocarboethyl mercapto trithiophosphite (CzHsSCSShP; tri thiocarboethoxy trithioarsenite, in the above formula: V monothiophosphite, (C2H5OCSS)P; trithiocarboethoxy trithiol phos phosphoryl octyl xanthate, ' (CsH1i):N-gv" Csrbodiamylamino > 50 ' S (clunoili-snko di-isobutoxy thiophosphoryl dilauryl monothiol carbamate, I Thiomrbocyclohexylamino Ca-KDg-i , , - s (C1|Hu)rN("]>—S-—Ig—(O 01H’)! - and the calcium salt of lauryl carbothiopentoxy monothiol phosphoric acid, 0 , so, Thiocarboethoxyphenylsmino ' 65 O causti Carboamylmercapto S V 0 ‘Hi1 S H-‘— Thiocarboamylmercapto When compounds of this invention are incor porated in lubricating compositions in small 70 amounts, that is in concentrations ranging be tween 0.05% and 2% and preferably between 0.1% and 1.0%, the resulting lubricating oil com positions a_re highly stable, especially as regards resistance to breakdown in an oxidizing atmos 15 phere and to the development of corrosiveness 9,354,536 . towardlalloy bearings of the cadmium-silver or copper-lead type. The lubricating oil base stock ‘of the composi tions of the invention maybe any lubricating oil, wax or grease, of natural or synthetic origin. It a mineraloil, it may be wholly a distillate or may contain residual products and may be any such material that has been refined by a re?ning ‘process, such as acid treating, solvent extraction, tion. tion agents of this invention may be used as the junction with other materials capable of en hancing, as for example,» the viscosity index, the pour point, extreme pressure, oiliness, rust pre venting, spreading, detergent, dispersing and solvent characteristicsof the oils. . . , Lasn TOLERANCE Tas'r hydrogenation, clay contacting, etc.‘ The -addi-‘ 10 , sole addition agents or they may be used in con 3 under oxidizing conditions. The procedure oi‘ the test is described in Proc. A. S. T. M., v. 24, II, page 964 (1924): the only exception to this pro cedure wasthat theoxidation was conducted for 24 hours in testing the compounds of this inven ‘ (Underwood test) This testis used to determine the tendency of an oil to corrode bearings. In this test, 1500 cc. of the oilis maintained at 325° F. and sprayed for5 hours upon four alloyed half-bearings, two being of copper-lead and two being cadmium silver. The oil droppingfroin the bearings is recirculated. The bearings are weighed before and after the test to determine any_ loss in' The lubricating compositions thus prepared . 7 weight. The test is then repeated with various are investigated for quality by certain recognized additions of soluble lead compoundj"usually lead standard tests of the vpetroleum industry. The 1 oleate, to the oil ‘in increments .of 0.005% by tests by which the lubricants of 1the present in weight of lead. When the lossin weight of a vention were rated were the Oxygen absorption, half bearing amounts to 50 mg., the “lead toler Cone, Bligh and Lead tolerance tests. These ance” of the oil has been exceeded and the tests are brie?y described below: amount of lead added in the previous test is re OxYeaN Ansonrriou Tasr corded asthe "lead tolerance". A lead toler-' ance of above 0.02% is generally considered This test is used for'the most part in judging the oxidation susceptibility of a lubricating oil at engine operation temperatures. In this-test satisfactory. ‘ I’ ' , The preparation of the compounds employed as addition agents in this invention, may be 11 a known amount of oxygen is bubbled at atmos pheric pressure through 10 cc. of the lubricating 30 lustrated by the preparation of di-amylphenyl- oil maintained at 200° C. The oxygen is ‘con tinuously recycled. At the end of succeeding 15 minute periodsthe amount of oxygen absorbed thiocarboethoxy mono thio phosphite; 9.2 grams tendency of an oil to deposit solid matter upon heated metallic surfaces ‘such as are present'in of another phase of 'the preparation, 32 grams (0.2 mole) of potassium ethylxanthate were add ~ (0.4 mole) of sodium were added to 200 cc, of absolute ethyl alcohol and to the resulting solu tion were added_65.6 grams (0.4 mole) jot ter by the oil is measured. The oxidation rate of the oil is given as the number'of cubic ‘centi 35 tiaryamylphenol dissolved in 100 cc. of absolute ethyl alcohol. The resulting sodium amylphe meters of oxygen absorbed by 10 cc. of the oil nate was obtained in'a dry state by distilling oil’ per 15 minute interval at 200° C. the alcohol, the last traces of which were removed CONE TEST under vacuum. The sodium amylphenate was This ,test is the meansv for determining the dissolved in 350 ‘cc. of dry ethyl ether. As part the ‘combustion chamber of spark-ignition type ed to 27.5 grams (0.2'mole) of phosphorus tri engines. It consists in slowly dropping the oil V chloride dissolved in 100 cc. of dry carbon tetra— to' be tested upon a heated metal (generally (5 chloride. The mixture was gently heated until all of the solid materials had dissolved. A gela steel) cone having a circumferential ‘groove milled out in screw fashion uponjthe periphery, ' tinous mass formed,V and this was carefully add-' the time or contact between the heated steel sur ed to the ether solution‘ of sodium amylphenate. faceand the oil being about one minute. A During vthis addition, heat was evolved. After total of 60 cc.‘ of oil is dropped onto a cone from 50 re?uxing the resultant mixture for 1 hourand a' dropping funnel during a period of Zhours. washing it with water, the solution was washed The cone may be maintained at any desired temperature but, in testing automobile crankcase with potassium xanthatesolution to remove all traces of acid. After being washed further with lubricating oils, a temperatureofl250° C. is pref . water and dried, the product was obtained as a erable. The cone is weighed before the test. 55 residue by distilling oil.’ the solvents.~ Analysis of After 60 cc. of oil havebeen passed over the the product established the sulfur content as be cone, the latter is washed with naphtha to .re move the adhering oil and the amount of solid deposits formed is determined by the weight diil'erential. , ' ' The test does not appear to vhave any relation to the oxygen absorption test since lubricating oil blends of two separate compounds may give the same cone deposits but have widely different oxygen absorption rates, and vice versa.~ The test is, however, an important indication of the ing 5.51% formula: and the following approximate (CsHuCeHsO) 2.5 (C2H5QCSS) o,sP Thus, the product was presumably'a mixture of two or more compounds. The sulfur contained therein was su?ficiently stable that the product was not corrosive to copper when a 0.5% solution or the compound in a hydrocarbon vlubricating oilwas heated to 210° F. for 3 hours in the pres ence of a copper strip. ' _ ' ' ability» of an oil to resist deterioration at high temperatures. It has been found that the Cone Another example or the preparation of a com test gives data which closely. approximate the ' pound suitable for use as an ‘addition agent for results obtained in the C. F. 1%. (Cooperative 10 lubricating oils, accordingv to this invention,,is Fuel Research) test engine. the preparation of trithiocarboethoxytrithiol phosphate. 240 grams (1.5 mole) of potassium SLIGH Tnsr ethylxanthate were suspended in 1500 cc. of ben This test is used as an indication of the tend ency of a lubricating composition to form sludge 1| zene. While the suspension ‘was being agitated, a benzene solution of 80 grams (about 0.5- mole) . 4 . 9,854,586 ducing the oxidation rate of the oil and also it . of freshly distilled phosphorus oxychloride was added through a dropping funnel. The resulting improved the corrosion resistance or the oil. mixture was heated to insure completion of the A lubricating oil blend of, di-amylphenylthio carboethoxy monothio phosphite was tested by theCone test; the following data were obtained: reaction. Small quantities of potassium ethyl xanthate were added to the reaction mixture un til a sample of the latter gave a basic reaction 7 , of hydrolysis. The reaction products were iso lated by adding ice to the reaction mixture and then washing the benzene layer free of base.‘ Calcium chloride was employed to dry the ben Blended S. A. E. 40 mineral oil composition.. 0.39 These data indicate that di-amylphenylthio . carboethoxy monothio phosphite reduced residue zene solution. They benzene was‘then distilled 0115 and the residue heated under vacuum to remove formation from the oil‘ under conditions similar traces of low-boiling impurities. The product, trithiocarboethoxy trithiol phosphate was a clear liquid, containedv'l.39% of phosphorus and cor 15 responded in composition to'the formula Cone test-Gain in weight of cone, g. Unblended S. A. E. 40 mineral oil ________ __ 0.50 ' (czrnocss'nro ' to thoseexisting during automobile engine opera tion. - i - ' ' EXAMPLE 2 The following oxidation rate data were ob tained on an 0.25% blend of trithiocarboethoxv trithio phosphite (CzH5OCSS)aP in an S. A. E. 20 mineral oil: A further example according to the present in ' ‘ Oxidation rate vention is the preparationof trithiocarboethoxy 20 Unblended S. A. E. 20 mineral oil___ 20, 38, 37, 31 Blended S. A.-E. 20 mineral oil com trithio phosphite. 160 grams (1 mole) of potas . position _____ __‘_______________ -_ sium ethylxanthate were suspended in 500 cc. of 3, 4, 5, 9 benzene and 46 grams (1/5 mole) of phosphorus ExAMru: 3 . trichloride dissolved in benzene was added to the The e?ect of the thiocarboxy group is shown mixture from a dropping funnel while the mix 26 by the following comparative Cone test data on ture was agitated vigorously. Agitation was con 0.25% blends of paratolyl phosphite and di-amyl tinued until all of the potassium ethylxanthate phenylthiocarboethoxy monothio phosphite in an vhad reacted and then the benzene layer was ‘ ' ' water~washed. The benzene solutionwas then 30 S. A. E. 40 oil: Cone test-Gain, in dried and the benzene was removed by distilla _ _ ' ' . weight of cone, g. tion. \iTheji product trithiocarboethoxy trithio S. A. E. 40 Oil ______ "7-; __________ _‘_ _____ .._ .50 phosphite ‘was a‘ yellow-liquid, contained 8.79% +0.25% p-tolyl phosphite ____ _'_ __________ __ .43 of phosphorus and corresponding in .composition to the formula (C2H5OCSS)3P. v Trithiocarboethoxy , r' ; trithioarsenite, another as +0.25 %' di-amylphenylthiocarboethoxy monothio phosphite ___________________ __ .39 The following results were obtained in the Sligh compound suitable as an addition agent,,accord test on blends of these compounds in an S. A. E. ing to the present invention, was preparedas fol 20 lows: . i - _ oil: ' ' " ' , A suspension of '240 grams (1.5 mole) of potas sium 'ethylxanthate in 1200' cc. of benzene .was 40 rapidly stirred while 90.5 grams (0.5_mole) of Sligh test S. A. E. 20 mineral oil + 0.25% para-tolyl 32.5 ' phosphite __________ __;_ _______________ _. S. A. E. 20.mineral oil + 0.25% di-amyl- V arsenic trichloride wasv added from a dropping ' 'phenylthiocarboethoxy‘ monothio 'phos- _ funnel over a period of 30minutes. The benzene phite ______________ __' _______________ __ 19.7 in the mixture was re?uxed for, 1.5 hours. A 45 benzene solution of the product was washed with Thesedata demonstrate that the thiocarbo ethoxyphosphite compound has a greatere?ect in reducing the formation of hard deposits from an dried over'anhydroussodium sulphate, the hem ' oil upon heated-metallic surfaces of spark-igni zene was distilled from the dried mixture. The product, trithiocarboethoxy trithioarsenite, was 50 tion type engines and also inhibits the formation of sludge in an oil to a greeted extent than d a yellow solid. A yield of 95% was obtained; An- , ‘ ' .water to remove salts. After the; mixture was alysis of the product established the presence of 18.2% of arsenic, whereas. the theoretical value for the compound is 17.1%. - V 7' EXAMPLE 1 the simple organic phosphites. sented merely to illustrate and convey an ap preciation of the invention. It is possible to formulate other embodiments of ‘the invention In order to. demonstratethe "advantages in-: herent' in the use of the compounds of this inf vention as blending agents for lubricating oils, and employ compounds other than those speci? cally mentioned as additives in lubricating oils the oxidation rateand lead tolerance of a lubri , cating oil composition prepared by blending 0.25% ' without departing from the scope of the inven tion described herein. It is therefore desired to claim all the novelty inherent in the disclosure of di-amylphenylthiocarboethoxy monothio phos phite, the preparation of which was previously described, in an S. A. E. 20 oil were determined. The following results were obtained :7. Oxidation Lead tol- > ‘rate cranoe‘ Unblended S. A. E. 20 mineral oil _______ __ 74,40, 35, 38 Blended S. A..»E. 20 mineral oil com osition _________________ _. ............. .;_ _ ' 724,26,22,l8 . 0.010 ‘ ‘ ' ‘The present invention is not limited to the speci?ccompounds previously mentioned since 56 these, embodiments of the invention’ are pre 0,5 which has been made;v What is claimed is:v " . ~ ' 1. An improved lubricating composition which ‘comprises a mineraloil lubricant and between 0.05% and 2% of a‘compound of formula (R.X(")Y)| 70 ' 0.035 ' - V /DY. -(ZY)I These datashow that di-mnylphenylthiocarbo ethoxy monothio phosphite was effective .in re 75 » in which R is a radical of the class consisting of hydrogen and organic radicals. X is an element 2,364,538 of the class consisting of oxygen, sulfur and nitro gen, Y is an element of the class consisting of oxygen and sulfur, D is an element of the class 5 0.05% and 2% of a phospho-xanthogen com pound of formula consisting of phosphorus, arsenic, antimony and bismuth, Z is a grouping selected from the vclass if metals, monovalent organic radicals and onium bases; and the subscripts, a, b, c and d have numerical values in accordance with valency re in which R is an alkyl group. .X is an element selected from the class of oxygen and sulfur and quirements. Z1 and Z2 are alkylated aromatic groupings. 2. An improved lubricating composition which 10 5. An improvedlubricating composition which comprises a mineral oil lubricant and between comprises a mineral oil lubricant in between 0.05%. and 2% of a phospho-xanthogen compound 0.05% and 2% oi’ diamylphenylthiocarboethoxy of fonnula V monothio phosphite. (Rx-o s s ) 6. An improved lubricating composition which 15 comprises ‘a mineral oil lubricant and between 0.05% and 2% of a phospho-xanthogencompound Z1—X7PY z,-x ' of formula - in which R. is an organic radical, X is an element (RXCSS) 3P selected from the class of oxygen and sulfur, 20 in which R is a grouping selected from the class Y when phosphorus is pentavalent is an element of alkyl and alkylated phenyl groups and X is an selected from the class of oxygen and sulfur and element selected from the class of oxygen and Z1 and Z2 are groups selected from the class of sulfur. xanthogen groups and organic radicals. ! 7. An improved lubricating composition which Y 3. An improved lubricating composition which 25 comprises a mineral oil lubricant andbetween comprises a mineral oil lubricant and between 0.05% and 2% of phospho-xanthog’en compound - 0.05% and 2% of of formula - phospho-xanthogen compound ' of formula ' (RXCSS) 3P (RX-C s s) Zr-X-P 30 in‘ which R is an alkyl group and X is an element , _, selected from the class of oxygen and sulfur. 8. An improved lubricating composition con Zr taining a mineral oil lubricant and a small quan in which R is an organic radical, X is an element tity of trithiocarboethoxy trithio phosphite. selected from the class of oxygen and sulfur and 35 9. An improved lubricating composition which Z1 and Z: are groupings selected from the class comprises a mineral oil lubricant and a small of xanthogen groups and organic radicals.’ 4. An improved lubricating composition which comprises a mineral oil lubricant and between / quantity of trithiocarboethoxy' trithioarsenite. JOBEPH F. NELSON.