US2764550A - Gear oil lubricants - Google Patents

Gear oil lubricants Download PDF

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US2764550A
US2764550A US212694A US21269451A US2764550A US 2764550 A US2764550 A US 2764550A US 212694 A US212694 A US 212694A US 21269451 A US21269451 A US 21269451A US 2764550 A US2764550 A US 2764550A
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oil
solvent
gear
neutral
bright
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US212694A
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Joseph B Stucker
Norman D Williams
Wolfram George
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Pure Oil Co
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Pure Oil Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102Aliphatic fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/104Aromatic fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106Naphthenic fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108Residual fractions, e.g. bright stocks
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/083Dibenzyl sulfide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/12Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/02Bearings

Definitions

  • the present invention re1atesgt0..lubricating i,compos-itions having extreme pressure characteristics and more particularly to lubricants for gears such as hypoid gears, transmissions and differentials.
  • aration of the extreme pressure additive was anesterof a dihydroxy alcohol and a.rnonoethenoid acid 'of the general formula CnHza-zO vcontending from l( to4 -24 carbon atoms in themoleculeinstead of, the triglyceride type of material such as lard oil, this diihculty was eliminated.
  • suitable starting esters are monoor di-esters of propylene glycol or; butylene glycol. The use of these esters as starting materials for the sulfurization-phosphorization reaction mot fonly.A solved ithelproblem of compatibility with these lubricating oil stocks but also improved the pour characteristics of the nished product.
  • The'present invention i's based: upon discovery thatya lubricating ⁇ oil compositiomcontaining 1 the solventi refined lubricating oil base stocks or the Pennsylvania bright stocksmav bey made compatibleiwith the; less expensive 6 sulfurized-phosphorized fatty. oil extremepres'sule.l addif tives by-incorporating asapart offthe composition afprodf uct from the solvent extraction or reningfofflubiicating oils.
  • Thisproduct as will-.behseen notfonlvenhancs the compatibility characteristics. of.y the nished gear-"oilg but also replaces: a pa-rtof.S the more expensiveubricatingvoil portionof thecomposition.
  • A- thirdobj'ect Yof'this invention is to provide a new univer's'algear oillcontainihgsulfurizedaphosphorized fatty body extreme pressure agent, ,blends of neutrals with solvent renedbright stock and/or, aPennsylvania bright stock in a compatible, homogeneouscomposition.
  • Thefojurth object of',4 this invention -istoprovide aV gear;A oil lubncatingrcompositjion which meets the. requirements.;
  • V. l'. 'cutinay'beobtainedbv usifnga Water solution off' phenol during 'the extrr'rctlion ⁇ and al high, V. l. cut may be obtained by using anhydrousphe ,A
  • Table I sets;forth thecharacteristicsofisix solvent extraction products which may. berllSGd in accordance' with this invention. These are phenol-extracts and were obtained during ordinary extraction 'practices 'as just described.
  • the Gulf Coast 160 Bright is not a solvent repend on the type of solvent used and the type of lubrifined oil and is completely compatible with the S-P lard eating oil fraction treated. It may be that the aromatic oil. Even lowering the Weight percent composition to. content of the extract is the solubilizing agent, for ex- 9% and using a less viscous extreme pressure base failed treme pressure agents. However, the invention is not to to give perfect compatibility as shown by composition 9. be limited to any theory of solubilization. l Composition 10 shows that 5% by weight of phenol TABLE I Characteristics of phenol extracts No. Source API Vis. 100 Vis. 130 Vis. 210 V. I. ⁇ Pour F. Percent Percent Gravity F. F. F. C. R.
  • 80 grade gear oil compositions which meet MIL-L- 2105 requirements must have a viscosity at 210 F. of from to 65 SUS, a minimum viscosity index of S5 and a channel point of 30 F. maximum.
  • 90 grade gear oils under MlL-L-2l05 approval must have a viscosity at 210 F. of 80 to 90 and a minimum viscosity index of 85 and show a 0 F. maximum channel.
  • a compatible gear oil composition will shown no change in viscosity or separation of insolubles during storage at room temperature and 32 F. for 60 days. A drop in viscosity is yan indication of a tendency to separation. A composition should pass both the room temperature test and the 32 F. test to be acceptable. Percentages shown are weight percent. Table Il reveals that Mid+Continent solvent refined 200 neutral is cornpatible with sulfurized-phosphorized lard oil extreme pressure base (composition 6). However, the same extreme pressure base as in composition 6 proved to be nnhave a viscosity of between 800 to 1500 SUS at 100 F., an extrapolated viscosity at 0 F. of 100,000 maxi-L mum and a channel below 20 F. Military requirements for storage stability are described in test pro-l cedure CRC-L-22-445 and require no precipitation of sludge or separation during storage for 60 days at room temperature and 32 F.
  • Table III shows certain combinations of and grade gear oil compositions using various solvent extracts described in Table I.
  • Compositions 1l throughy 18 are 90 grade and compositions 19 and 20 are so-callecl 5.15 80/90 f grade combination.
  • zTable LIII f demonstratesthat both SAE -and militaryrequirements y'for-cold weather operation and storage stability may be met by the. present compositions. Bythe laddition of from ⁇ .5 vvto v2,'5
  • Table III shows that ythe proper combination of ⁇ ingredients to form a compatible compositionis Adependent on at least four factors: the viscosity of'the extreme'pressure additive, the characteristics of the solvent extract, the type of mineral lubricating oil, and the desired physical properties of the nished blend.
  • AExtreme-pressure additives prepared in accordance with lUnited .L'States Patent 2,211,306 have relatively low viscosities,as, S300 to 700 SUS/210 F.
  • liI-he high speed axle test is designated CRC-L-19-645 and the high torque axle test as sired 'physical properties -of ⁇ the n-linished -blend aise 45 -incorperating compounds like Ortholeum 20,2 and Vdi- 7 benzyl disulfide in the composition.
  • Ortholeum 202 is asulfurized terpenic compound the preparation of which is described in United States Patent 2,443,823. Cornpositions prepared in accordance with this invention From the above table it is apparent that gear oil comi position 14, containing 9% by weight of phenol extract 3, is comparable to the reference oil A, which is an accepted product.
  • the gear oil oxidation stability test is conmelhetglergn ofrugeslsl'bcam is the 5 ducted in a device designed to simulate conditions in a CRC L 20 545 for determining 10ad carrying, Wear, power transmission unit.
  • the gear oil is subjected to stability and corrosion characteristics under conditions of agitation by a rotating gear impeller in the presence of high torque and low speed. For the purpose of demoiiair while heated to a temperature of from about 275 to str ating that gear oils compounded in accordance with l 325 F. for a Period of about 17 hours.
  • a thermal regulator is used oil A having the following composition (percent Weight): 15 t0 regulate the gea-f Oil temperature
  • the gear Oil OXda- 12% s P lard oil tion tests in-Table IV were conducted for 17 hours at 1% dibenzyl disumde 300 F.
  • the invention H0111 applies broadly to the use of solvent extracts from any lubricating oil fraction to impart solubility to extreme pressure agents especially those containing sulfur and COHStlUeDI Weight per Cent phosphorus which are or tend to be insoluble in solvent Sulfurized-phosphorized lard oil (vis/210 F. refined lubricating oil fractions.
  • solvent Sulfurized-phosphorized lard oil vis/210 F. refined lubricating oil fractions.
  • the 525 SUS) 12.0 amount of solvent extract used will be that amount which Dibenzyl disulfide 1.0 brings about the desired compatibility of thel composition High V. I. 150 SUS, vis/210 F. bright stock 17.0 Wlthout deletewusly aectmspther propertls- 170 SUS vis. at 100 F. 100 v. 1. neutral 0il 48.5
  • lt is to be underlubricating oils (API gravity 15.4, Vis/2105 stood that the invention is not to be limited to composi- F. 372 SUS) 21.0 tions using the lubricants listed in Table VI, these being Meth 1 methacr late 01 mer 0 5 merely illustrative of the type of oils that may be used.
  • y y p y It is also emphasized that the invention is not limited to lubrcatllg Compsltlons as those Wherem a major 4.
  • a gear oil lubricant having the following composiportlon is a lubricating oil.
  • the solvent tion extracts may be used to dissolve the additive itself for use in subsequent compounding in a mineral lubricating oil.
  • the solvent extracts may be added to lubricating Constituent: Weight per cent oil fractions to make them compatible with extreme pressuIfmizedphosphorzed lard Oil (Vis/210 F. sure additives. 908 SUS) 12 0
  • neutral stocks having vis- D.b 1 di 1'0 cosities of around 500 SUS at 100 F. are incompatible P en? s t f ⁇ f"""f*""l with S-P fatty bodies.
  • One such oil is a Mid-Continent eno exfrac rom manu-ac uore o0 mmerao solvent retined 500 neutral.
  • the invention applies with lubricating 011s (API gravlty 1*6 VIS/210 equal force to attaining compatibility on blends containing .F' 310'1) -j 9'0 these high viscosity neutral stocks, as to the problem pre- 40 Hlgh V- L 150 SUS, VIS/210 F- bfli1-1t Stock 18-5 sented by solvent rened lubricating oils, especially the Raw neutral (edwaxed) (API gravity 22.4, bright stocks and Pennsylvania bright stocks. vis/210 F. 51.4 SUS) 59.5

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Description

United `States C GEAR-.10]L LUBRICANTS Joseph B'. Stucker, Des Plaines, Norman` D. Williams,
Chicago, andfGeorge z Wolfram,- Unioin, Ill.,` assigno'rsc tch'llrlfureil Company, (lhicago,v 111.-, afcorporation; or o` y No Drawing. Application February 24, 1951, Serial No. 212,694*
4 Claims. (Cl. 252-46.@
The present invention re1atesgt0..lubricating i,compos-itions having extreme pressure characteristics and more particularly to lubricants for gears such as hypoid gears, transmissions and differentials. y
In United States Patents J:2,211g36 and,2,;483,571-;there are disclosed and claimedprocesses for making extreme pressure additives for use:;in lubricating oil;compos`i`tions. These extreme pressure additives afamado-by sulfurizing a fatty body or fatty oil and then phosphorizing the sulfurizedproduct so produced. Extremepressure additives made intaccordance with these patents have been successfully used formally years 'and have proven highly. satisfactory. The'se extreme pressure additives. whcnmade fromordinary fatty. oils, as for example lard oil', have one disadvantageand that is their lack of solubility and. compatibility with solvent r'eiined'hydrocarbon oils andI with Pennsylvania bright-stocks. This lack of compatibile ity withgthese lubricating oilfractions leads to instability of the,iinifshedlubricating composition during storage.
Since the majority o'f lubricating oil fractions presently available andbeing used for compounding iare the solvent reiined varietyand since Pennsylvania bright stocks are highly desirableconstituents the probl'emwas presented to ascertain why the sulfrizedphosphorized fatty oils were insoluble therein. The lack of solubility ofext'rer'ne pressure additives was found to be due to the presence of high molecular weight polymers in the finished, ploduct. It was found that if the starting material used in 'the prepf. aration of the extreme pressure additive was anesterof a dihydroxy alcohol and a.rnonoethenoid acid 'of the general formula CnHza-zO vcontending from l( to4 -24 carbon atoms in themoleculeinstead of, the triglyceride type of material such as lard oil, this diihculty was eliminated. Examples of suitable starting esters are monoor di-esters of propylene glycol or; butylene glycol. The use of these esters as starting materials for the sulfurization-phosphorization reaction mot fonly.A solved ithelproblem of compatibility with these lubricating oil stocks but also improved the pour characteristics of the nished product. 'Ihis development is thesubjctmatterof twocopending applications bearing Serial Number 653,438, led March 9, 1946, now Patent No. 2,542,161, and Serial Number 740,723, iled April l0, 1947, now Patent- No. 2,541,789, 5
by one of the coeiventors herein.
The special extreme pressure additives prepared from these special esters arequite expensive and for this 'reason it is highly desirable that a wayxbe foundltorinorease the solubility and compatibility of extreme pressure additives in solvent rened and Pennsylvania bright lubricating oil stocks by less expensivemeans.
The'present invention i's based: upon discovery thatya lubricating` oil compositiomcontaining 1 the solventi refined lubricating oil base stocks or the Pennsylvania bright stocksmav bey made compatibleiwith the; less expensive 6 sulfurized-phosphorized fatty. oil extremepres'sule.l addif tives by-incorporating asapart offthe composition afprodf uct from the solvent extraction or reningfofflubiicating oils. Thisproduct, as will-.behseen notfonlvenhancs the compatibility characteristics. of.y the nished gear-"oilg but also replaces: a pa-rtof.S the more expensiveubricatingvoil portionof thecomposition. @ther advantages-` ofi the V2,764,550 Patented Sept. 25, 19456 invention `will :be seen Aas the description thereof proceeds.
Accordingly the mainy object-of 'this inventioni'sktoA provide a means-for solubilizing-sulfurized=phosphorized fattybody-re'xtreine pressure agentsfim the presence of.1 solventA refined 'lubricating oil bright stocks and bright-4 stockffro'inPennsylvaniay oils.
A second object` of lthis-'inve'nt'i`ni 'isI to "prc'ivicle-'aSbas'eJ oil Whichexhibits satisfactory solubility and compatibility for extreme pressure additives, especially sulfurized-phosphoriie'dfatty vlzo'ly extreme pressure agents.
A- thirdobj'ect Yof'this invention is to provide a new univer's'algear oillcontainihgsulfurizedaphosphorized fatty body extreme pressure agent, ,blends of neutrals with solvent renedbright stock and/or, aPennsylvania bright stock in a compatible, homogeneouscomposition.
Thefojurth object of',4 this invention -istoprovide aV gear;A oil lubncatingrcompositjion which meets the. requirements.;
of United Stagtjsr'Army Speciication Y MIL-B42101- Ar' further `object of lthis invention is;.to .prov`ide a new superior blended gear. oilv composition containing solvent, extract from lubricating oil stocks; y
Other-.objects and advantages of.this,inven tion will bef. como apparent .y asv .the-description thereof, proceeds.
Theiextraction products.abovefreferred v.to Jwhich are-to.
befincorporated aspart of geen oil,v compositions in 21.6-, cordancewi-th this-invention,- a-re obtained from .the solventl extraction -of lubricating; oils. After. the'fxemg-ases, gas?. oline, naphtha. kerosene; and. light lubricating; fractions, havebeen removed. by.-fractionationfrom a .crudeoL-.thef reduced, crude so' produced( is deasplralted; The deas.. phalted: oilf isv neXt' extractedy withv a solvent toproduce, highlylfvrefinedI aviation;y lubricating oils, and, resultant.jsol vent` extract I used i -accorelancewithn this. invention: For,y example: av Van Zandt., crude oil i with7 an ABI gravi-ty] of. 33-1 was topped t0 remove suchrllghtifyra. lonstasfaasoline naphthmkerosene and a light lubricating distillate. The vacuum residue was a reduced crude having a viscosity of 1'25'1 SUSat21-'0-"F.', 222% sulfur and API gravity of 12.6. This reduced.crudewas deasphalted -by treatment with propano yielding a, deasphalted oil` having. a. viscosity-- at 2lf0 F. of; 174 SUS and API gravity of 21.7. The deas- 'phalte'doil was'jreated with phenol-to producega raiiinate from which an aviation lubricating oil may be; produced.
Theextract4 Vfrom` this phenol-treatment isrea-dv foruse 5 low V. l'. 'cutinay'beobtainedbv usifnga Water solution off' phenol during 'the extrr'rctlion` and al high, V. l. cut may be obtained by using anhydrousphe ,A A The following Table I sets;forth thecharacteristicsofisix solvent extraction products which may. berllSGd in accordance' with this invention. These are phenol-extracts and were obtained during ordinary extraction 'practices 'as just described. Thekphenolextracts numbered 1 4. and 4a were prepared bvpt'rleatine'iit filiielltstokfrom `aflfar'l Crude., oil. These tivez extracts have, llSllpOilsof fromA about 5 51m-"550 lnana fir/points ef, 59,01" oralsex/e. Pirenei extract 5 is from aso-called neutral lubricatingv oil fraction; rlhis. extractis characterized-by.itslower viscosity, The-hash poi'ntisv 395 E. and the lirepoint upto 485 F. Throughout -thef balance of` the speciicationthese. six extracts will: be referred-mbv. their` corresponding numbers. in theI leftrlrandf column of Table- I-i These extracts are listed, as merely4 illustrativeand the invention is` notto be limited thereby. lt is to be understood that any solvent extract from the refining of a lubricating oil fraction for the purpose of separating paratlnic from non-parafinic hydrocarbons will apply and be useful in the present stable in a Mid-Continent solvent refined bright stock in the saine proportions by weight as shown by composition 7. Composition 8 shows that a high concentration of solvent refined 500 neutral has an adverse effect on the invention. The characteristics of the extracts will de- 5 stability. The Gulf Coast 160 Bright is not a solvent repend on the type of solvent used and the type of lubrifined oil and is completely compatible with the S-P lard eating oil fraction treated. It may be that the aromatic oil. Even lowering the Weight percent composition to. content of the extract is the solubilizing agent, for ex- 9% and using a less viscous extreme pressure base failed treme pressure agents. However, the invention is not to to give perfect compatibility as shown by composition 9. be limited to any theory of solubilization. l Composition 10 shows that 5% by weight of phenol TABLE I Characteristics of phenol extracts No. Source API Vis. 100 Vis. 130 Vis. 210 V. I. `Pour F. Percent Percent Gravity F. F. F. C. R. Sulphur 1 Bright Stock fr. van 11 1 25, 319 4,750 282 -40 +55 7.2 2.65 Zandt Crude. e 2..- do 13.7 25,000 5,400 355 +27 +80 2.18 3 12.0 36, 410 4,310 310.1 -1 +80 4. 70 2.27 14.0 19, 500 4, 305 313 +27 +90 4.7 2. 27 do 15.4 32, 500 372 +5 +60 4.13 2.33 16o/180 Neutral fr. van 12.5 986 322 61. 5 -38 +50 0. 29 2. 49
Zandt Crude.
The solubilizing effect of solvent extracts of lubricat- 5 extract 1 is insuiiicient to obtain storage stability and ing oils on extreme pressure agents in lubricating oils of the solvent `reined and Pennsylvania bright stock variety is best demonstrated by `actual storage stability tests of diterent lubricating oil compositions. For this purpose various gear oil compositions have been used to demonstrate rst the storage stability and insolubility problem and secondly its solution. Gear oil compositions are used as merely illustrative and the invention is not to be limited thereby. Table II following shows that with solvent refined bright stock the S-P lard oil is unstable. This phenomenon is not ordinarily experienced with solvent refined neutral stocks except highly viscous neutrals or stocks which are not solvent refined except the Pennsylvania bright stocks.
TABLE Il again demonstrates that for all practical purposes S-P lard oil is incompatible with a Mid-Continent solvent refined 150 bright stock. K
80 grade gear oil compositions which meet MIL-L- 2105 requirements must have a viscosity at 210 F. of from to 65 SUS, a minimum viscosity index of S5 and a channel point of 30 F. maximum. 90 grade gear oils under MlL-L-2l05 approval must have a viscosity at 210 F. of 80 to 90 and a minimum viscosity index of 85 and show a 0 F. maximum channel.
SAE requirements for 80 and 90 grade oils are not as' severel as the military and conform to compositions intended for ordinary commercial use. Under SAE re`-' quirements a combination 80/90 grade gear oi1 should' Stability of S-P fatty oil E. P. agents in various hydrocarbon oil compositions Composition V1s./
Storage Stability Pour, 0 F.
R. T. 32 F. Days 18% S-P Lard Oil 82% Mid-Continent Solvent Refined 200 Neutral.
18% S-P Lard Oil 82% Mid-Continent Solvent Refined Bright Stock.
12% S-P Lard O11 2 5% 89. 5 62.5% Mld-Continent Solven Refined 500 Neutral. 9%3 1S-P Dioleate of Propylene ycol. 1% Ortholeum 202 90% Mid-Continent Solvent Rened Bright Stock. 9% S-P Lard Oil 1% Ortholeum 202 5% Pehnol Extract #l 43% Mid-Continent Solvent Refined 150 Bright Stock. 42% Mid-Continent Solvent Refined 200 Neutral.
OK O`K Separation (noted cosity) drop in vis- 60 OK Separation 0K OK |2O Heavy Separation OK in 48 hrs.
A compatible gear oil composition will shown no change in viscosity or separation of insolubles during storage at room temperature and 32 F. for 60 days. A drop in viscosity is yan indication of a tendency to separation. A composition should pass both the room temperature test and the 32 F. test to be acceptable. Percentages shown are weight percent. Table Il reveals that Mid+Continent solvent refined 200 neutral is cornpatible with sulfurized-phosphorized lard oil extreme pressure base (composition 6). However, the same extreme pressure base as in composition 6 proved to be nnhave a viscosity of between 800 to 1500 SUS at 100 F., an extrapolated viscosity at 0 F. of 100,000 maxi-L mum and a channel below 20 F. Military requirements for storage stability are described in test pro-l cedure CRC-L-22-445 and require no precipitation of sludge or separation during storage for 60 days at room temperature and 32 F.
Table III following shows certain combinations of and grade gear oil compositions using various solvent extracts described in Table I. Compositions 1l throughy 18 are 90 grade and compositions 19 and 20 are so-callecl 5.15 80/90 f grade combination. zTable LIII fdemonstratesthat both SAE -and militaryrequirements y'for-cold weather operation and storage stability may be met by the. present compositions. Bythe laddition of from ``.5 vvto v2,'5
arretrato iiuence :thelquantty andtypewfef solvent extract` useable toattain 'afbalanced composition. -flhevupperilfirnit v:of the `amount: 'foffSOIVenteX-FraetiA usedbinagiven iformulation is .=;`governed iprimarilyfby fthe -V. fIf., tpourfand=v channel weight per cent of a pourdepressant like Acryloid 150, characteristics ldesired-wint-hefnishedwblend. Solventtexa resinous or polymer-like esterL of Iacrylic'a'cidj-such :as tracts often ha'vedljighipour --pointsubecause oftheir-wax methyl methacrylate polymers, inlfgeneralf Athos'e"-1ul'nicat centena-consequently toofhighfa concentration'cf extract ing oilrcompositions 'containing :up -to f 12% by@ weightznf may: raisevthex-pour andichannel? pointsvaboutfacceptable extreme pressure Vbase mayvbevmadento meet they-pour limits. DewaxingI-rhe extract lowers-the pourrandalloivs and `channel requirements. largeri-'a'mountl-tofbemsedfinf'blending. Weihaveffound 'TABLE III lsolvent extract vnf/zwar.
. 105.14100" 'Composition' (wt. percent) i y @tRCLL-Zmt'storage Stability V. I. Channel 9% sa# Lard 011,' Vie-amleto. v 1% Ortholenm 202...
% High V. I. Bright. Raw Neutral (dewaxe 9% S-P Lard Oil, Vis./210/908 1% Dibenzyl Disulfide 11% Phenol Extract #3 22.5% High V. I. 160 Bright.-.. 56.5% Raw Neutral (dewaxed).... 9% lS-P Destearinized LPU Lard 1l. 1% Ortholeum 202 15% Phenol Extract #2.. 22% High V. I. 150 Brigh 53% Raw Neutral (dewaxe Vis. 210/908- fide 59.5%` Raw Neutral (dewaxed *12% S-P Lard Oil, Vis. 210/384- 1% Dibenzyl Disulde 14% Phenol Extract #4- 14% High V. I. 150 Bright.-.. 59% Raw Neutral (dewaxed) *Addition of 0.1% Acryloid 150 to above blend.
12% S-P Lard O 1% Dibenzyl Disulfide...
85.0 (Vis/0 F,
10"F 0K 0K 1o 20F or; 10K
0K at -15 F., Channel at +5 `0K at 5 channel at 45 Y errar.
Table III shows that ythe proper combination of `ingredients to form a compatible compositionis Adependent on at least four factors: the viscosity of'the extreme'pressure additive, the characteristics of the solvent extract, the type of mineral lubricating oil, and the desired physical properties of the nished blend. AExtreme-pressure additives prepared in accordance with lUnited .L'States Patent 2,211,306 have relatively low viscosities,as, S300 to 700 SUS/210 F. and are generally more compatible on blending than additives prepared in accordance"with United States Patentl 2,483,571, wherein the reaction is conducted with air bubbling therethrough faind f-th'e product has a viscosity of 900 to 1200 SUSYZIOMF. "The physical characteristics of thef'eXtract:itselfintluence its ability lto overcome storage instabilityrand these characteristics may vary with the extractionprocess. The -de- .9% .to by weight of solventfextriact-,Jlioweverthese proportions Iaresubject to thefactors "above mentioned.
ftemperature ishabove'OiF. VUnder these conditions and c'onsideringthatload pressures up to 400,000 p. s. i. and --sliding `rvelocitieszoffO to 18,000 feet per minute are experienced on 'the..gear surfaces ofthe modern transmission land diie'rential, it is the ipractiee ftofseverely test n:gearlubricants 'afs to their high speed and high torque characteristics. liI-he high speed axle test is designated CRC-L-19-645 and the high torque axle test as sired 'physical properties -of `the n-linished -blend aise 45 -incorperating compounds like Ortholeum 20,2 and Vdi- 7 benzyl disulfide in the composition. Ortholeum 202 is asulfurized terpenic compound the preparation of which is described in United States Patent 2,443,823. Cornpositions prepared in accordance with this invention From the above table it is apparent that gear oil comi position 14, containing 9% by weight of phenol extract 3, is comparable to the reference oil A, which is an accepted product. The gear oil oxidation stability test is conmelhetglergn ofrugeslsl'bcam is the 5 ducted in a device designed to simulate conditions in a CRC L 20 545 for determining 10ad carrying, Wear, power transmission unit. The gear oil is subjected to stability and corrosion characteristics under conditions of agitation by a rotating gear impeller in the presence of high torque and low speed. For the purpose of demoiiair while heated to a temperature of from about 275 to str ating that gear oils compounded in accordance with l 325 F. for a Period of about 17 hours. A bronze thrust glgslil? gli Cllgle Twgeprlmsgpgtl washer maintained adjacent the gear impeller to cat- CRC-L-20-545 and oxidation stability tests on composialyz oxfdatlon and Sumlate the bronze beam-1g sflrfas tion Number 14 from Tame 111 and a commercial gear present in a transmission. A thermal regulator is used oil A having the following composition (percent Weight): 15 t0 regulate the gea-f Oil temperature The gear Oil OXda- 12% s P lard oil tion tests in-Table IV were conducted for 17 hours at 1% dibenzyl disumde 300 F. The test gives a direct indication of the ability 03% acryloid 150 of the gear oil to withstand actual operating conditions 41% Gulf Coast 160 Bright 20 in a power transmission unit. 4511915; Mid-Continent conventionally rened 200 Neu- A Combination 80/90 gear lubricant preparad in acra cordance with this invention and having the following TABLE Iv composition: High torque-low speed and oxidation performance tests 0n 90 grade gear Oils 25 BLEND N0 21 Composition N0 A 14 12% S-P lard oil (vis./210=525) CRC L 545 1.0% dibenzyl disulfide Gear Conditionl7% high V. I. 150 Bright StOClC Pm Ltpgagggs glghtgi 48.5% 17o/10o neutral Ring light wear uigvsei 21% Phenol extract #4a Rating pass pagg 0.5% acryloid 150 Gear Oil Oxidation Stabilty test- Thrust washer thin black deposit Hggwn has been qualified and accepted by the Review Board of Sump deposit tfgcsehll deposit one Army Ordnance. The following Table V gives the results Vis. Change/210 F 4% 6% of physical and performance tests conducted using the Rating very good excellent 40 above blended gear lubricant.
TABLE V Physical and performance characteristics of blend No. 21
Requirements Test Results MIL-Ir2105 SAE SAE 90 n Be1oW0 F.
Percent Lead Percent Sulfur (Total) Percent Sulfur (in Mineral oil) Rust (Steel Strip, 4 hrs/150 F.) Copper Strip Activity (1 hr./250 F.) SAE/1,000 R. P. M SAE/500 R. P. M. (after heating) Pressure (p. s. Foam Test Sequence (1), Room Temp..
cc CRCL20545 Gear Condition Pinion Gear; Dull burnish, Medium wear. Ring Gear: Dull burnish, Light wear.
average back lash: 0.0001 meh increase, trace and light staining of ditereutial gears, no deposits, discoloration or corrosion of fatigue on either,
axle shafts.)
Rating Pass Pass GRC-L-19-645 Gear Condition (Duplicate runs): Ring and Pinion Gears Drive side, no scoring, Ring and Pinion Gears Coast side, no scoring.
Rating Pass Pass 1n duplicate.. CRC-L-12-445:
Sequence (l), Room Temp 0 cc 650 ccJMax Sequence (2) 200 F 50 ce 650 tze/Max (No surface In Table V the CRC-L-20-545 Dynamometer Test, a high torquelow speed test, was conducted, using a Dodge S 9% inch Hypoid axle, viith the oil temperature at 200250 F. for 30 hours with 32,311 pound-inch amount of a sulfurized-phosphorized fatty body to impart extreme pressure characteristics thereto, and a sufficient amount of phenol extract obtained from the extraction of mineral lubricating oils for the purpose of separating gique at 62trevr191llt10115 Pefllm@ The CRCJlw/S 5 parailiiiic from non-paraffinic hydrocarbons therein to ynainom el est was con uct Elsmg a new .evotet prevent separation of said sulfuriZed-phosphorized fatty Hypoid third member assembly with a 9-37 ratio in a bod from Said com Osition dynaniometer installation to simulate a Chevrolet pasy .p Senger Vehicle .2: The composition in accordance with claim l cori- Although the invention has been demonstrated by 10 tammg about 9 to 30 Welght per cent of Bald Phenol specific examples it is not to be limited thereby and extractl numerous ramifications may be practiced without depart- 3- A gear 011 lubllcant having the OHOWlIlg Composiing from the sphere of the invention. The invention H0111 applies broadly to the use of solvent extracts from any lubricating oil fraction to impart solubility to extreme pressure agents especially those containing sulfur and COHStlUeDI Weight per Cent phosphorus which are or tend to be insoluble in solvent Sulfurized-phosphorized lard oil (vis/210 F. refined lubricating oil fractions. For this result the 525 SUS) 12.0 amount of solvent extract used will be that amount which Dibenzyl disulfide 1.0 brings about the desired compatibility of thel composition High V. I. 150 SUS, vis/210 F. bright stock 17.0 Wlthout deletewusly aectmspther propertls- 170 SUS vis. at 100 F. 100 v. 1. neutral 0il 48.5
The ollwm Tabl-e-v glves the Characteristics 0f Phenol extract from manufacture of mineral the lubricating oil fractions used herein: lt is to be underlubricating oils (API gravity 15.4, Vis/2105 stood that the invention is not to be limited to composi- F. 372 SUS) 21.0 tions using the lubricants listed in Table VI, these being Meth 1 methacr late 01 mer 0 5 merely illustrative of the type of oils that may be used. y y p y It is also emphasized that the invention is not limited to lubrcatllg Compsltlons as those Wherem a major 4. A gear oil lubricant having the following composiportlon is a lubricating oil. For example the solvent tion: extracts may be used to dissolve the additive itself for use in subsequent compounding in a mineral lubricating oil. Also the solvent extracts may be added to lubricating Constituent: Weight per cent oil fractions to make them compatible with extreme pressuIfmizedphosphorzed lard Oil (Vis/210 F. sure additives. 908 SUS) 12 0 We have also found that neutral stocks having vis- D.b 1 di 1'0 cosities of around 500 SUS at 100 F. are incompatible P en? s t f `f"""f*""l with S-P fatty bodies. One such oil is a Mid-Continent eno exfrac rom manu-ac uore o0 mmerao solvent retined 500 neutral. The invention applies with lubricating 011s (API gravlty 1*6 VIS/210 equal force to attaining compatibility on blends containing .F' 310'1) -j 9'0 these high viscosity neutral stocks, as to the problem pre- 40 Hlgh V- L 150 SUS, VIS/210 F- bfli1-1t Stock 18-5 sented by solvent rened lubricating oils, especially the Raw neutral (edwaxed) (API gravity 22.4, bright stocks and Pennsylvania bright stocks. vis/210 F. 51.4 SUS) 59.5
TABLE VI Characteristics of mineral lubricating oils used in compositions A. SOLVENT REFINED Name API Flash Fire Vis. Vis. 130 Vis. 210 NPA Pour, Percent Percent V.I
Gravity F. F. F. Color F. Sulfur O. R.
High V. I. Bright stuck 26.9 590 650 2,450 93s 155. 5 +6 0 0. 7i 100 High v. I. 150 Bright stock 26.5 570 630 2, iso 83s 141. 4 +5 +5 0.47 0. 6s 9s High V. I. 200 Neutral 30. 6 425 485 193. 6 102 46.1 i 0 0.20 0.02 99 Mid-Continent i60/180 Neutral 29. s 425 480 185. 5 9s. 9 45. 5 0 0. 29 98 Mid-Continent 17o/100 Neutral 31.0 425 174. 2 44.8 +5 0. 29 0.0 100 Sinclair Bright 25. 2 540 600 993 749 125. 7 7+ +15 0. 3i 0. 62 90 Sinclair 200 Neutral 29. 7 410 470 201 105 46 +135 +10 0.17 0. 0i 91 Mitioontiuent 500 Neutral.. 2s. 3 475 535 527 232 63.1 2% +10 0. 06 89 Mid-Continent 120 Bright Stoch 27.0 525 595 i, 731 668 121. 6 +6 +15 0.17 0. 5s 96 Mid-Contiuent Bright Stock 27.5 2 420 148.9 +6 86 B. NON-SOLVENT REFIN'ED Pennsylvania 150 Neutral. 155 43. 0 87 Gulf Coast Bright 15. 9 505 560 601.0 1,537 147. 5 +355 dil +20 0.395 0. 83 i0 Raw Neutral (dewaxed) 22. 4 435 500 355 159 51. 4 7 o 1.23 0.1 60 Mid-Continent 200 Neutral 26. 3 400 455 206.6 104 45. 5 +2% +15 0.46 0.05 76 It is claimed: References Cited in the file of this patent t 1. A lubricating1 cgipostion citlimpriing a major por; UNITED STATES PATENTS ion o a minera u rica ing o con aining as a par thereof lubricating oils selected from the group consisting 2211306 lvgvhlttler etlal ug' of solvent rened lubricating oil and Pennsylvania bright Dlgigte 15;' 21 1349 stock in an amount sucient to cause incom atibili of 1 p ty 2,483,600 stucker et al oct. 4, 1949 sulfurized-phosphorized fatty bodies therewith, sutcient

Claims (1)

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR PORTION OF A MINERAL LUBRICATING OIL CONTAINING AS A PART THEREOF LUBRICATING OIL, SELECTED FROM THE GROUP CONSISTING OF SOLVENT REFINED LUBRICATING OIL AND PENNSYLVANIA BRIGHT STOCK IN AN AMOUNT SUFFICIENT TO CAUSE INCOMPATIBILITY OF SULFURIZED-PHOSPHORIZED FATTY BODIES THEREWITH. SUFFICIENT AMOUNT OF A SULFURIZED-PHOSPHORIZED FATTY BODY TO IMPART EXTREME PRESSURE CHARACTERISTICS THERETO, AND A SUFFICIENT AMOUNT OF PHENOL EXTRACT OBTAINED FROM THE EXTRACTION OF MINERAL LUBRICATING OILS FOR THE PURPOSES OF SEPARATING PARAFFINIC FROM NON-PARAFFINIC HYDROCARBONS THEREIN TO PREVENT SEPARATION OF SAID SULFURIZED-PHOSPHORIZED FATTY BODY FROM SAID COMPOSITION.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2211306A (en) * 1935-12-19 1940-08-13 Pure Oil Co Lubricant and method of preparing same
US2373094A (en) * 1943-03-18 1945-04-10 Socony Vacuum Oil Co Inc Mineral oil composition
US2473511A (en) * 1945-05-07 1949-06-21 California Research Corp Mineral oil compositions and the like
US2483600A (en) * 1946-05-16 1949-10-04 Pure Oil Co Preparation of high-viscosity extreme pressure base by airblowing

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2211306A (en) * 1935-12-19 1940-08-13 Pure Oil Co Lubricant and method of preparing same
US2373094A (en) * 1943-03-18 1945-04-10 Socony Vacuum Oil Co Inc Mineral oil composition
US2473511A (en) * 1945-05-07 1949-06-21 California Research Corp Mineral oil compositions and the like
US2483600A (en) * 1946-05-16 1949-10-04 Pure Oil Co Preparation of high-viscosity extreme pressure base by airblowing

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