US2849398A - Mineral-base lubricating oils and methods for using same - Google Patents

Mineral-base lubricating oils and methods for using same Download PDF

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US2849398A
US2849398A US375137A US37513753A US2849398A US 2849398 A US2849398 A US 2849398A US 375137 A US375137 A US 375137A US 37513753 A US37513753 A US 37513753A US 2849398 A US2849398 A US 2849398A
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oil
additive
octane
fuel
contributing
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US375137A
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Leonard E Molldy
Alexander H Popkin
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority to US375137A priority Critical patent/US2849398A/en
Priority to GB20433/54A priority patent/GB773999A/en
Priority to DEST8597A priority patent/DE1035299B/de
Priority to FR1124444D priority patent/FR1124444A/fr
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    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
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    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
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    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/108—Phenothiazine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
    • C10M2225/041—Hydrocarbon polymers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/08—Groups 4 or 14
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/16—Groups 8, 9, or 10

Definitions

  • the present invention relates to improved lubricating oils for use in internal gasoline combustion engines of the reciprocating type. More particularly, the invention is concerned with improved automotive motor oils which are mineral-base lubricating oil compositions having, in comparison with prior art formulations, reduced tendency to contribute to an increase in the requirement of octane number of gasoline for knock-free operation of high compression ratio internal combustion engines. The invention is also concerned with methods for operating automotive engines having compression ratios above about 7.0:1 with these improved lubricating oils in combination with essentially hydrocarbon gasoline fuels, which are essentially hydrocarbon mixtures, under conditions that result in a decrease of the formation of combustion chamber deposits of the type which contributes to octane requirement increase. This invention is particularly concerned with motor oils containing mineral oil base stocks and addition agents improving the characteristics of the composition, in which neither the base stock nor at least one of the addition agents contributes substantially to octane requirement increase during the operation of high compression ratio engines.
  • combustion chamber deposits of this type are responsible for such substantial effects seems anomalous. They are not strictly speaking of the carbon type. Furthermore, careful measurements of the deposit volumes showed thatl the decrease in combustion chamber volume due to them (and thus the increase in compression ratio) could account for only about l to 15% of the octane requirement increase observed. It was then found that temperature effects (heat capacity and heat transfer) account for the remainder of the deposit harm. The insulating nature of these resin-like deposits was found to retain heat in the combustion chamber. Thus, the deposits decrease cooling through the combustion chamber walls. This results in heating up the ineoming'charge and raises the overall combustion temperature, whichV in turn makes the engine -more prone to knock. These effects are due to -thev poor heat conductivity of the deposits.
  • a further object of this invention is directed to improved mineral oil-base lubricating oils containing one or more characteristic improving addition agents in which the base stock and at least one of the addition agents do not substantially contribute to octane requirement increase when used to lubricate high .compression ratio engines.
  • resinication index refers to the relative freedom of a fuel or lubricant from tendency to form tenaciously adhering resin-like deposits when subjected to combustionV in a container under a hot, smokeless, flame, e. g., a hydrogen flame, as will be explained in more detail bel'ow.
  • a superior motor oil composition suitable for use in' present ⁇ day high compression ratio engines consists Iof a'v mineral oil base stock'that has a low resinification'indexin combination with'at least one addition agent that, when ydissolved in the base stock, has also a low resinication index.
  • An oil formulated by this procedure not only rcaps the advantages of having improved characteristics imparted by the addition agent, but also has unexpectedly improved properties with regard to decreased contribution to octane requirement increase in engine use.
  • a more specific aspect of this invention contemplates a composition in which a substantially non-contributing mineral oil base stock has dissolved therein a-multiadditive system in which at least two of the addition improving agents do not themselves contribute to octane requirement increase. Under these conditions it is possible to tolerate the presence of octane requirement increase contributing agents in small amounts and yet obtain the advantages of this composition.
  • a preferred composition in accordance with this in- Vention contains a substantially non-contributing mineral oil base stock and at least three different non-mineral oil addition agents, ,each of which improves a different characteristic of the composition without at the same time contributing substantially to octane requirement increase. More preferably, all of the components of the finished composition are non-contributing to octane requirement increase.
  • mineral oil base stocks are relined mineral oil distillates that -are free of mineral oil bright stock residuums. It has been found that bright stocks, even of the highly refined variety, have high resinication indexes. They contribute substantially to the formation o-f harmful deposits even when present in small concentrations. Although it is known that bright stocks can deposit carbon, as mentioned above, they have been used heretofore in concentrations ranging from as low as about 5% up to as high as 98% in premium grade mineral oil compositions. It is therefore surprising to find that they are harmful even at low concentrations. More particularly, refined mineral oil distillates or so-called neutrals that are substantially free of constituents that boil above about 600 F. at a pressure of 10 mm. (Hg) absolute, are preferred.
  • the higher boiling mineral oil constituents contribute to the formation of harmful deposits.
  • base stocks boiling within the range of about 275 to 600 F. at this pressure are quite useful.
  • Those boiling below about 575 F. at this pressure have excellent low resinification indexes, substantially independent of the origin and chemical constitution of the crude oil.
  • the initial boiling point is not critical as regards deposit-forming characteristics, but it should be high enough to avoid excessive oil consumption by vaporization when used in the motor.
  • the present base stocks when formulated with suitable synthetic or non-petroleum additives, are not only not contributing to the formation of poor heat conductivity deposits, but also give superior all-weather motor lubricants having excellent viscosity and viscosity index characteristics, low pour-point, good stability, and low oil consumption when used in high compression ratio phospho-sulfurized polyolefns, metal dithiophosphates, phosphosulfurized terpenes, and the like. At least one of these non-contributing additives will be used in the present invention. It is preferred that no more than two, and preferably no more than one, of a different type of additive that contributes substantially to octane requirement increase, be used in combination with the non-contributing additive. Specifically preferred compositions include a combination of at least two of the above different types of addition agents that are non-contributing with no more than one contributing agent.
  • octane requirement increase can be reduced by about two or three units in contrast to performance with the same fuel and a relatively high resiniiication index lubricating oil.
  • this improvement is substantial, unexpectedly better engine performance is obtained by using fuels having low resinication index characteristics in combination with the improved oils.
  • a leaded fuel containing low and critical amounts of sulfur when used in combination with the lubricating oil of this invention will give improved engine operation.
  • Leaded fuels containing certain high boiling scavenging agents also give superior results.
  • Certain high octane fuels containing no tetraethyl lead are also superior to conventional fuels in this respect.
  • Figure 1 is a plot of the viscosity-temperature characteristics of typical commercial oils and of the SAE 5W-20-type oils of the present invention.
  • Figure 2 is a plot of the effect of sulfur content of leaded gasolines on equilibrium octane requirement.
  • the cars used were new 1951 Oldsmobile 88 sedans (compression ratio-7.5 :1).
  • the initial octane requirements of the engines were determined, both before and after spark settings were adjusted to the manufacturers recommendation, usiug the Co- ⁇ ordinatingResear-ch" Coun-
  • the cars werev charged with the gasolines and'lubricatingoils'tobe' tested cils Standard Uniontown procedure;
  • Octane requirement was determined-by the Standard Uniontown procedure, CRC'Designation E'-l-943, as described in the C. R. CQ Handbookp, 90 et seq., 19 ⁇ 46 edition.
  • Octanerequirement increase (ORI) ⁇ is the difference in the nal and initial octane requirement of the engine.
  • Equilibriumoctane requirement (EOR) is the octanerequirement of the engine after several-thousand miles (usually 5000 miles) of use at Which'octane requirement reaches a substantially constant level.
  • ORI and EOR are based on road octane numbers usingA primary'reference fuels.
  • Test 2 Combuszn test forr'esinifcatowndex This test isv described in detail in copending application Serial No. 352,373, tiled in the name of Alexander H. Popkin on May 1, 1953, now U. S. 2,761,766.
  • a sample of material to be tested such as a lubricatingoil
  • a gasoline or other material is placedin an open' vessel having smooth non-absorptive inner surfaces, such asa glass beaker, porcelain Crucible, etc.
  • gen llame although other clean flames such as methane, etc. may be used, is directed into the opening of the vessel.
  • the burner tip forintroducing the gas and air or oxygen (if needed), is directed toward the interior of the vessel.
  • Oils and Gasoline additives Sample charge, g 5.000 200.0 Pyrex beaker size, ec; 250 400 HzzAirratio, in cubic feet/m 0. 1610.12 0. 59:0 Burning time, minutes -10 25-35 Test 3.-Laus0n engine test A hot, smokeless, clean llame, preferably a hydro-V CTL secondary reference fuels using an oscilloscope which gave visual ratings of knock intensity via a sensitive pickup attached tov one of the studs of the engine. This procedure was found to be more accurate than the audiotype ratings usually used'in the Standard Uniontown procedure, because knocking in the Lauson engine is difficult to hear. Operations at the low power level ofv 0.5 b'. kw. gave good' ORI and EOR correlations' with full scale road testsI of the typel described' in Test 1.
  • Base stockBr-Tliisiproduct was obtained by dewaxing theV above solvent'ratlinate ⁇ to about a 74% yield of dewaxed product having a'pourpoint of about 15 F. This dewaxed product wasy then distilled to obtain an overhead fraction designated-as base stock B.
  • Base stockv C This base stock was a light solvent neutral overhead fraction obtained by the distillation of the same charge'stock used in making base stock A.
  • Base stock D.-Tl1 ⁇ is base stock was a light solvent neutral'overhead'fraction-obtained by distilling the same charge stockiusedin making base stock A to obtain a fraction intermediate base stocksv B and C.
  • Base stock G.-Thisba'se stock was a blend containing 92% by volume of base stock B and 8% by volume of basestock F.
  • Base stock l.-This base stock was also obtained by the sulfuric acid'treatmcnt of a lube oil distillate obtained from a Texas Coastal crude. v
  • Base stock K.-A cycle stock was made by catalytic cracking a Mid-Continent type 4gas oil using a silicaaluminacatalyst.y This' cycle'oil boiled in approximately the same range as the original gas oil feed stock. The cycle stock was then selectively extracted with phenol solvent to a 50% railinate yield. The rainate was solvent dewaxed to a +25 F. pour point, the dewaxed oil yield being based on the solvent ralinate. The dewaxed oil was then distilled to obtain a 0-27% light neutral overhead fraction designated as base stock K.
  • Base slack L'.-This base stock was a ypolybutene having a Staudinger average molecular weight of about 400.
  • the polybutene was prepared by the conventional polymerization of isobutylenei using a Friedel-Crafts catalyst.
  • Additive 2 This was another polybutylene concentrate consisting of 22% by weight of polyisobutylene having a Staudinger average molecular weight of about 15,000 and 78% by Weight of base stock A.
  • Additive 3 This was a commercially available detergent additive containing a high proportion of alkaline earth metals (approximately 1.5 Wt. percent barium and 2.0 Wt. percent calcium).
  • Additive 4. This was a commercially available polymethacrylate ester-type viscosity index improver consisting 1of about 37% by weight of a polymerized C-Cm alcohol ester of methacrylic acid (of about 12,000 molecular weight) and 63% by Weight of mineral lubricating oil.
  • Additive 5-1 ⁇ his was a commercially available antioxidant vconsisting of about 55 weight percent of zinc dialkyl dithiophosphate in mineral lubricating oil.
  • Additive 6. This was ya commercially available antioxidant consisting ⁇ of about 50% of a P2S5-treated alphapinene in a mineral lubricating oil. The oil concentrate analyzed about 13% sulfur and 4.6% phosphorus.
  • Additive 7.-'1 ⁇ his was an ashless detergent additive prepared by treating a polyisobutene having an Aaverage Staudinger molecular weight of about 1100 With about 10 vweight percent P285 at a temperature of about 330- 420 F. for 11 hours.
  • the iinished additive was ⁇ a 50% concentration yof the active ingredient in mineral lubricating oil.
  • the sulfur content of the active ingredient was about 1.7 ⁇ Weight percent.
  • Additive 9A This was a commercial detergent addi- .tive containing the potassium salt of P2S5-treated polybutene and having a potassium content of 2.6% Iand a phosphorus content of 1.8%
  • Additive 9B This was a commercial detergent additive containing the barium salt of P2S5-treated polybutene, having a .barium content of 4.1% and a phosphorus content of 1.6%.
  • Additive 10 This was an experimental polyrnethacrylate-type ester useful as an ashless detergent additive. It consisted of about 40% by Weight of a polymerized long chain aliphatic ester of methacrylic acid in mineral lubricating oil. The active ingredient appeared to have an empirical formula of about C127H248O13-2N.
  • F del 3.-'i'his was a motor gasoline comprising a blend of isopentane, catalytic, and virgin naphthas.
  • Base stock L (polybutene) 79 2 Base stock C (l) 4 Base stock C+10% additive 1 78 1 15,000 M. W. polybutene per se 2.
  • Base stock B 86 i8 Base stock .T 83 13 Base stock C+% additive Erl-0.2% additive 6+ 10.5% additive 2 .T 83 17 Base stock H+5% additive 3-1-0 2% additive 6+ l 10.5% additive 2 83 17 Base stock G 90 38 l Not determined.
  • the deposits in the combustion chambers of the cars andLauson engines were resinous-base deposits (as shown by their insolubility in solvents) containing carbon or other dark substances imbedded therein. In some cases flaky, dark deposits covered the resin-base.
  • the two types of ⁇ deposits did not, have exactly the same appearance, an excellent correlation was obtained between the amount of resinous deposits as determined by the hydrogen combustion test and the EOR in actual engine tests.
  • Lube oil base stocks and additives having low resinilication indexes do not contribute to ORI.
  • a useful method for testing the contribution of a particular ⁇ additive is to carry out a combustion test on a blend of the additive at a desired concentration in a non ORI-contributing oil base stock. This will give information on the tendency of the additive to contribute to ORI, regardless of the type of base stock eventually empolyed for the additive.
  • Finished additive-containing lubricating oil compositions preferably have a resinication index below about mg./5 g., although those having an index level below 10, more especially below 5 nig/5 g., will give superior engine performance.
  • I3 increase, regardless of whether they were Mid-Continent or Coastal types. Those boiling above about 600 F. at 10 mm. (about 500 F. at 1 mm. Hg pressure) contributed substantially to octane requirement increase.
  • the polybutene-type viscosity index improver as shown previously,4 was non-contributing to ORI in both the Lauson and full-scale tests.
  • the polymethacrylate ester additive contributed slightly over one unit octane requirement increase for each percent present. It is interesting to note that the use of the ORI contributing additive in base stock C is about equivalent to the performance of ORI-contributing base stock B.
  • the combination of a low ORI contributing oil base stock with at least one low ORI contributing additive gives greatly superior results.
  • compositions contained about 5% additive 3.
  • At least one, and preferably more than one ofthe additives should be substantially non-ORI contributing. This applies particularly to the additives, such as viscosity index improvers and detergency improvers, that are present in substantial amounts.
  • Formula 1 Component Amount, weight percent Base stock D (74 S. U. S. at 100 F.) 85.3 Additive 3 5.0 Additive 6 0.2 Additive 1 7.0 Additive 4 2.5
  • Component Amount, weight percent Base stock D (74 S. U. S. at 100 F.) 84.8 Additive 1 10.0 Additive 8 5.0 Additive 6 0.2
  • the amount of aromatics boiling above 300 F. should be maintained at low levels in the preferred fuel mixtures.
  • Lower boiling aromatics, particularly those boiling between about 250 to 300 F. should not be present in amounts above about 20%, based on the total fuel.
  • Table XlI presents the levels of equilibrium octane requirement obtainable with various cornbinations of mineral base lubricants and fuels of varying degrees of contribution. EOR data are reported at eld test levels regardless of Whether the tests were run in Lauson engines or full scale engines.
  • fIso-octane contained 2 cc. TEL/gallon and 0.014 wt. percent added
  • Sui ibid-octane contained 2 cc. TEL/gallon and about 0.0008% sulfur.
  • tielliriroula 4 containing 5 Wt. percent additive SlB instead of 5% addi- A deiinite improvement was obtained using an oil having a medium tendency to contribute to Gill when using a high ORI fuel. Better results were obtained with either low or medium ORI oils of this invention when used in combination with medium ORl fuels.
  • Oils (l) and (4) not only gave superior performance as low-ORI contributing oils but also had excellent engine cil consumption characteristics for such low viscosity oils. Oil consumptions much less than one quart per 500 miles were consistently obtained in the field tests.
  • EXAMPLE X A bright-stock free, SAE SVV-20 oil was formulated consisting essentially of 87.5 volume percent oil base stock C, 10.5 vol. percent additive l, 0.2 vol. percent additive 6, 1.3 vol. percent of a mixed calcium-barium salt of tert.octyl phenol sulfide and 0.5 vol. percent alka line calcium petroleum sulfonate (about 950 average molecular weight).
  • This oil composition had a resinitication index of below 20 nig/5 grams oil and a viscosity index above 150. Two cars were tested with this oil by the procedure of test l using fuel 3 containing 2 cc. TEL/ gallon.
  • the non-contributing mineral lubricating oil base stocks used in the practice of the present invention may be obtained from Mid-Continent, Coastal, Middle East, Pennsylvania, and the like crudes, but Mid-Continent distillates having good viscosity characteristics are preferred. These are preferably distillates that have been refined by conventional procedures to remove the bulk of the relatively more aromatic, carbon-forming constituents (such as measured by the Conradson test), and that have also been treated to remove those constituents that form resins when subjected to combustion undera smokeless flame as heretofore described, to give a final product having a resiniication index below about l0 mg./5 g.
  • the conventional refining procedures useful for removing the more aromatic portions, sulfur and other harmful con stituents include treatment with mineral acids, such as sulfuric acid; treatment with alkalis; solvent refining with various solvents such as phenol, furfural, sulfur dioxide, and the like; treatment with aluminum halides; extraction With silica gel; clay treatment; hydrogenation; desulfurization such as hydrotining; propane precipitation; solvent dewaxing; catalytic cracking; etc.
  • a lubricating oil distillate obtained from a suitable crude may be distilled to obtain a fraction of approximately the desired boiling range, acid-treated or solvent extracted (and dewaxed if neces'- sary to remove high pour point constituents) and then redistilled to remove resinifying heavy ends.
  • Another suitable source of mineral oil base stocks is in refined catalytically cracked cycle stocks.
  • Such cycle stocks are the more refractory hydrocarbons that resist cracking to lower boiling constituents when residual hydrocarbons, gas oils or other relatively high boiling hydrocarbons are cracked in the presence of metal oxide cat alysts or the like.
  • the cycle oil that has been recycled through the cracking zone several tnnes is withdrawn, refined for the removal of the relatively more aromatic constituents, dewaxed if desired, and distilled to recover a fraction of the proper boiling range and viscosity.
  • Such refined fractions are stable, low sulfur content materials that make excellent base stocks per se or may be blended with other mineral oil distillates to form suitable base stocks.
  • White oils i. e., mineral oils refined with fuming sulfuric acid for the complete removal of aromatic-type constituents, may also be used as blending agents for the base stocks.
  • the preferred mineral oil base stocks of the present invention are those from which mineral oil components boiling much above about 600 F. (in a simple distillation at a pressure of l mm. Hg, which corresponds to about 890 F. at a pressure of 760 mm. Hg) have been removed.
  • a suitable boiling range is within the range of about 275 to 575 F., or preferably within about 300 to 575 F., at 10 mm. Hg pressure absolute, with less than about to 10% of components boiling about 550 F. The lower end of the boiling range will depend to a large extent on oil consumption characteristics of the lubricant, and generally components boiling much below about 275 to 300 F. at 10 mm. Hg absolute are too high in volatility for use in most high compression ratio internal combustion engines.
  • the distillation test is ASTM Method D1160-52-T.
  • the above lower boiling oils are particularly useful in formulating SAE 5W-20 oils.
  • blends of the low-boiling stocks and higher 'boiling stocks may be made that meet both resiniiication index and viscosity requirements.
  • a blend of 60% light solvent neutral having a resinification index of about 3 and of 40% of a solvent refined distillate having an S. U. S. viscosity at 100 F. of about 150 and a resinification index of about 20 will have a resinilication index below about 10 mg./5 g. and meet certain high viscosity requirements.
  • this invention contemplates base stock blends made from various components providing the base stock is low in ORI contribution. It is also preferred that the base stocks have viscosity indexes above 100 in order to make premium grade lubricants. For this reason oils that have only been refined Iby acid treatment are less preferred than the extracted Mid-Continent Middle East and other such high V. I. oils. Base stocks having pour points below about F. are also preferred.
  • An example of a suitable SAE 10W-30 oil is one in which the base stock is a 50-50 mixture of oil base stocks B and D (described above) containing of 5 different additives for V. I., detergency, corrosion inhibition, antioxidant and pour point improvement, and in which one of the additives, constituting a major portion of the additive system, has a resiniication index below 5 mg./5 grams.
  • the total lubricating oil will have a resinifcation index below 2O mg./5 grams, S. U. S. viscositiles at 0 F., 100 F., 210 F., and 300 F., rsepectively, of 10,000; 356; 69.3; and 44.5 and a V. I. of 140.
  • suitable oil base stocks In order to meet viscosity specifications required of suitable oil base stocks, it is preferred that these stocks have a viscosity in the range of 50 to 160 S. U. S. at 100 F. and of about 33 to 50 S. U. S. at 210 F. If the base stock is to have a viscosity of much above 40 S. U. S. at 210 F., relatively narrow cut distillates, such as those boiling in the range of about 400 to 550 F., 450 to 600 F., 500 to 575 F., and the like (at 10 mm. Hg absolute) may also be used to reduce the concentration of higher boiling, ORI-contributing components. Mineral oil base stocks having less than about 5 to 10% of components boiling below 390 F. at 10 mm. Hg are preferred from the standpoint of oil consumption.
  • Suitable base stock constituents and blending agents which may be used in combination with mineral oils of the type described include low resinification index hydrogenated oils, synthetic oils resembling petroleum oils (polymerized olefins, synthesis products from the Cir reaction of oxides ⁇ of carbon with hydrogen or from hydrogenated coals, shale oil derivatives, etc.), synthetic polyester and polyether-type lubricants and the like.
  • Synthetic oils include esters made from a monohydric alcohol and a monobasic organic acid or diesters made from alcohols dibasic acids. Specific examples include di-Z- ethyl hexyl sebacate and di-Ca Oxo alcohol sebacate.
  • Alcohols include the C7, C9, C10, C11, C12 and C13 alcohols made by the Oxo process from olelins.
  • Suitable dibasic acids include adipic, azeleic and sebacic acid.
  • Complex esters made fro-m a monohydric alcohol, a dihydric alcohol (glycol) and a dibasic acid may also be used.
  • Polyalkylene oxide-type synthetic oils with suitable terminal alcohol groups, complex formals, mercaptals and their esters, and the like are also useful.
  • Oil base stocks containing synthetic lubricating oils preferably consist of a major portion of a suitable mineral oil base stock of the type described with only minor amounts of low resinication-index synthetic-types of blending agents having lubricating oil characteristics. Generally less than 10 to20% 'by weight of synthetic or non-petroleum oil blending agents of the type described, based on the total base stock, will be used.
  • the additive components useful in the practice of the present invention to formulate finished lubricants must be selected with great care not only from the standpoint of the specific characteristic of the oil to be improved but also with regard to the extent to which the additive itself will contribute to octane requirement increase at the concentration level needed to improve a specific characteristic.
  • the multi-additive system have a resinification index below 20 mg./5 grams, preferably below 10 mg./5 grams.
  • Useful systems include those in which at least two different additives constituting a major portion of the additive system have a combined resinification index below 5 mg./5 grams.
  • Especially useful mixtures of additives, preferably three or more different types, will have resinilication indexes below about 5 rng./5 grams. The following paragraphs will give due consideration to suitable additives with particular emphasis being placed on the types that have low resinilication indexes when blended with various oils.
  • a viscosity index improver is a high molecular weight hydrocarbon such as an olefin, including the polymerized C3 to C5 olefins.
  • oils having S. U. S. viscosities below about 40 at 210 F. may be increased to higher viscosity oils such as those having viscosities above about 45 S. U. S. at 210 F., by the use of these V. l. thickening agents.
  • viscosity index improvers include the polymethacrylate esters, fumarate-vinyl acetate copolymers, polyalkylstyrenes, and the like. Since the polymerized esters generally contribute to octane requirement increase, they are less preferred than the polymerized olefins as viscosity index improvers. As a general rule, ORI-contributing types may be used in amounts below about 3%,
  • Finished .lubricants containing a mixture of polyolelins and polyesters may be formulated to avoid substantial increases in octane requirement. Thus from 3 to 10% of polybutene and 0.5 to 3% of a polyester may be used. However, it is much preferred to employ only the oleiins as viscosity index improvers.
  • Another important additive to be employed in the tinished lubricating oil of the present invention consists of at least one detergency improving additive. These agents will help maintain oil insoluble oxidation products and the like suspended in the oil and will in general improve engine cleanliness.
  • a wide variety of detergency improvers may be employed.
  • One class of additives for this use consists of the phosphorus and sulfur-containing hydrocarbons prepared ⁇ by treatment of an essentially hydrocarbon material with a sulfide of phosphorus or a combination of the elements phosphorus and sulfur. These reaction products are Well known to the art.
  • the desired hydrocarbon such as a paran, an olen, a naphthene, an aromatic, a terpene, hydrocarbon resins, high molecular weight polymerized oleiins, mineral oils such as lubricating oil distillates, and the like are treated with a sulfide of phosphorus using a ratio of about one mole of phosphorus sulfide for 1 to 10, preferably 2 to 5, mols of hydrocarbon at a temperature in the range of about 275 to 550 F.
  • the resulting reaction product may be used as such, but it is preferred to refine it further by treatment with a suitable agent such as by reaction with a basic reacting material or by reaction With an esterication agent.
  • Suitable basic reacting materials include the alkaline metal and alkaline earth metal oxides, carbonates, hydroxides, hydrides and the like, specifically, po-tassium, sodium, barium, and calcium compounds.
  • Basic inorganic compounds of heavier metals may be used, such as those of molybdenum, tin, zinc, chromium, manganese, nickel and the like.
  • Suitable ashless treating agents include nitrogen bases such as ammonia, and organic nitrogen bases such as amines and amine derivatives, guanidines and their derivatives, morpholine, pyridine, quinoline and like substances. Guanidine and its derivatives are particularly useful, the symmetrical tri-substituted compounds such as trialkyl, triphenyl and trinaphthenyl guanidines and the like being useful.
  • Other useful compounds include the biguanides, dicyandiamides, dicyandiamidines, hydrazines, ureas, thioureas, semicarbazides, thiosemicarbazides maleate and fumarate esters, aminoalcohols, acrylonitrile, alcohols, vinyl esters, phenols, oletins such as diisobutylene, dipentene and the like.
  • Such treating agents are disclosed in the art such as U. S. Patents U. S. 2,613,205; 2,640,030; and 2,640,053.
  • Treatment of the product with these and other agents may be carried out at any suitable temperature, such as from about room temperature up to 400 F. o-r so using suiiicient treating agent at least to partially neutralize, esterify, or combine with the titratable acidity of the phosphosulfurized material. Completely neutralized materials are usually preferred.
  • the essentially hydrocarbon material to be treated with the combination of phosphorus and sulfur is preferably one that itself has a low resinirication index.
  • paraliins, ⁇ oleins, naphthenes, neutral oils and the like give better results than aromatics, bright stocks, etc.
  • the hydrocarbon to be treated preferably has a resinitication index below about mg./ 5 grams.
  • the phosphorus and sulfur containing product is obtained by treating a high molecular Weight olefin such as a polyisobutene having a molecular weight in the range of about 300 to 30,000 with the sulfur and phosphorus containing agent, followed by treatment of the acidic product with one of the agents outlined above.
  • a high molecular Weight olefin such as a polyisobutene having a molecular weight in the range of about 300 to 30,000
  • the sulfur and phosphorus containing agent is obtained by treating a high molecular Weight olefin such as a polyisobutene having a molecular weight in the range of about 300 to 30,000 with the sulfur and phosphorus containing agent, followed by treatment of the acidic product with one of the agents outlined above.
  • alkali and alkaline earth hydroxides or guanidine or one "2@ of its substituted derivatives and the basic reacting salts thereof, such as guanidine carbonate are specifically useful.
  • the treating procedure may be varied in several different Ways.
  • the acidic phosphosulfurized hydrocarbon may be hydrolyzed by treatment with steam followed by treatment with the treating agent.
  • the partially or completely neutralized products may be hydrolyzed by steam treatment, or the neutralization and hydrolysis may be carried out simultaneously.
  • Hydrolysis in general reduces sulfur content, particularly helping to remove unstable sulfur, and improves the resinification index characteristics of the additive.
  • metal soaps such as hydrocarbon sulfonates including metal salts of petroleum sulfonic acids, metal phenates, metal alkylates, metal alkyl phenol sullides such as barium tert.-octyl phenol sultide, phosphates,
  • detergent additives are usually employed in rather large amounts, from as low as about 0.5 up to 10.0 or 15.0% by weight, based on the total oil, specific attention must be given to the extent to which the particular detergent additive will contribute to resin-type combustion chamber deposits. Many commercial detergent additives are harmful in this respect, and oils containing only noncontributing types are greatly preferred. Mixtures of both contributing and non-contributing types are also useful, in which case a blend consisting of a major portion of a non-contributing additive with only minor amounts of a contributing additive may 'be used.
  • a mixture of non-contributing types is a combination of the alkali or alkaline earth metal salt of a phosphorus sulfide-treated polybutene, such as a barium or potassium salt, and a guanidine neutralized phosphorus sulfide-treated polybutene.
  • a suitable anti-oxidant or bearing corrosion inhibitor additive In order to minimize oxidation characteristics of the oils of the present invention, it is generally desired to add a small amount of a suitable anti-oxidant or bearing corrosion inhibitor additive.
  • a suitable anti-oxidant or bearing corrosion inhibitor additive Some of the detergent additives listed above have anti-oxidant characteristics, but in other cases they may adversely affect this property of the lubricant.
  • the type of additive employed is preferably one that does not substantially contribute to octane requirement increase.
  • Particularly useful additives in this respect are lower olelinic hydrocarbons, particularly terpene hydrocarbons, that have been treated with a sulfide of phosphorus or with a combination of sulfur and phosphorus by the procedure described above.
  • a specifically preferred additive is prepared by treating alpha pinene w-ith phosphorus pentasuliide. This product may be used in amounts in the range of about 0.05 to 2.0% by weight in the finished composition without harmful effects.
  • ⁇ Other anti-oxidants include metal and non-metal salts of dihydrocarbon dithiophosphates, such las zinc dialkyl dithiophosphate, and lamine dialkyl dithiophosphates, phenols, such as alkyl phenols, bis-alkyl phenols and the like, phenol sultides -such a tert-alkyl phenol suliides, metal dithiocarbamates, phenothiaz-ine and its alkylated derivatives, sulfohalogenated olefins that have been dehalogenated by known means, such as diisobutylene treated with a sulfur chloride followed by dehalogenation, sulfur-ized dipentenes, etc.
  • antioxidants and corrosion inhibitors may be used.
  • the yamount of anti-oxidant employed in the finished lubricant will depend to a large extent on the type of base stock and the types of other improving agents added 23 thereto. As a general rule, in the range of about 0.01 to 5.0% by weight, based on the total composition, will suflice to minimize the deleterious effects of oxidation. In the event the particular anti-oxidant contributes substantially to octanerequirement increase, it is preferred that it be used in small amounts in combination with a noncontributing anti-oxidant.
  • a pour depressant additive is preferably employed in small 'amounts in order to meet pour point specifications.
  • This additive should be one that not only reduces the pour point substantially when used in small concentrations but ⁇ should also be relatively stable in this regard when the oil is subjected to alternate cycles of heating and cooling; i. e., have a good pour point stability.
  • Such pour point depressants include the chlorinated wax naphtha-iene condensation products, various polymers and copolymers of unsaturated esters and the like. These additives are generally used in rather small amounts, in the range of about 0.01 to 2.0 weight percent based on the total composition. Such small amounts will not generally contribute to the octane requirement increase dilliculty discussed above,
  • ⁇ Other agents may also be present in the composition, such as dyes, oilness agents, anti-rust agents, plasticizers and defoamers, extreme pressure agents ⁇ and the like.
  • Suitable anti-rust agents include the partial esters of polyhydroxy compounds such as the oleate of sorbitan, polyglycerols, etc.; Lorol mercapto-acetic acid; ditriricinoleates; alkyl phosphoric acids; acid phosphates, etc.
  • the finished oils of the present invention will be compounded to include at least one substantially non-ORI contributing additive, yalthough two, and preferably three or more different types of additives are generally desirable to formulate compositions meeting all ot the requirements of modern high compression ratio engines. Based on the total composition, the additives will usually constitute a minor amount, yand generally will be present in amounts below about 25% by weight, preferably about 3 to 20% by weight.
  • the base stock of the present invention will make up the remaining portion of the lubricating oil.
  • the finished oil will preferably have a resiniication index below about 20 mg./5 grams, especially below l5 :ng/5 grams.
  • the gafsolines to be used in the high compression ratio automotive engines 'and the like lubricated by the oils of the present invention may be any suitable high octane, essentially hydrocarbon gasoline such as one having an ASTM Research octane number in the range of about 75 to 100. -In a preferred aspect of the present invention, however, the gasoline will have ⁇ a reduced resinicaton index in comparison with conventional commercial fuels. It is particularly preferred that the gasoline be one that will contribute no more than about octane requirement units, preferably below one unit, increase when used in combination with the preferred lubricating oils of the present invention.
  • gasolines Conventional components may be used in formulating such gasolines. These components include straight run distillates from various types of crudes, alkylates prepared by the alkylation of olens with isoparans; high octane polymers prepared by the catalytic polymerization of lower molecular weight olens; hydroformates prepared by hydroforming naphthenic-type hydrocarbon distillates to form high octane aromatic components; reformed gasoline fractions prepared from straight run gasolines using conventional platinum catalysts, metal oxide catalysts and the like; catalytic cracked naphthas prepared by cracking 24 gas oils, residuals, etc., in the presence of metal oxide catalysts such as silica-alumina, silica-magnesia, and the like; and various other types of components that are conventionally employed in gasolines.
  • Such gasolines are usually formulated by mixing two or more of the above general types of components in order to form gasolines meeting octanee requirement, vapor pressure, stability, and other specifications.
  • Aromatic components particularly those having a boiling point higher than toluene contribute substantially to octane requirement increase. Those boiling above about 300 F. are especially undesirable for this purpose. Therefore it is preferred that the gasoline contain no more than 20% by weight, of aromatic hydrocarbons boiling above about 300 F., and more especially less than 20% by weight of aromatics boiling above about 250 F.
  • Lead tetraethyl is used in most commercial gasolines in concentrations ranging from about 0.1 to 3.0 cc./ gallon in order to increase octane number.
  • Lead scavenging agents such yas ethylene dibromide 'and ethylene dichloride may be present in such compositions.
  • leaded fuels contain below about 0.20% by weight, preferably about 0.1% by weight, of sulfur.
  • leaded fuels contain below about 0.20% by weight, preferably about 0.1% by weight, of sulfur.
  • unexpected advantage in decreased ORI can be ⁇ achieved by lowering the sulfur content of gasoline critically below the level at which the sulfur has any effect on the actual octane number of the v gasoline containing TEL.
  • For minimizing ⁇ ORI it is important ⁇ to decrease the sulfur content of leaded gasoline below about 0.02%, ⁇ and preferably below about 0.005% by weight. This may be achieved by treating the various components that go into the gasoline, in order to reduce the sulfur content to relatively non-contributing amounts.
  • Treating procedures for sulfur reduction include prompt caustic washing of the sulfur-containing material in the absence of oxygen soon after a catalytic cracking operation; hydroning of cracked naphthas in which the naphtha is treated with a catalyst in the presence of hydrogen; treating naphtha with formaldehyde at elevated ternperatures, with or without sulfuric acid; and treatment of sulfur-containing naphthas with finely divided sodium in the presence of secondary or tertiary alcohols, ethers or kctones; and the like.
  • the extent to which any or all of the components treated will of necessity depend on the amount of sulfur contained in each of them and the amount of the particular component going into the gasoline blend. It is preferred to employ a fuel that contains relatively small amounts of sulfur as heretofore described, and non-contributing amounts of aromatics when the fuel is leaded with tetraethyl lead.
  • a lead scavenging agent that is relatively high boiling may be added to the fuel.
  • trichlorobenzene 2,4-dichlorotoluene, their mixtures and the like.
  • Higher boiling means those agents having substantially the volatility characteristics of tetraethyl lead; preferably they have vapor pressures at 120 F. of about 0.5 to 5.0 mm. Hg. In excess of about 0.5, preferably above about 1.0 stoichiometrical equivalents of these agents, based on the TEL, may be added to the fuel.
  • Such higher boiling scavenging agents are taught in U. S. patents including 2,496,983; 2,574,321; 2,479,900; etc.
  • the gasoline fuel may also contain other addition agents such as antioxidants, gum inhibitors, solvent oils, rust inhibitors, metal deactivators, etc.
  • This invention has particular application to the operation of automotive engines and the like that have compression ratios above about 7:1, and is particularly applicable to those having higher compression ratios, for example 7.5 to l and as high as 12 to l and higher.
  • Such engines are extremely susceptible to octane requirement increase as mentioned heretofore, especially when they are run under rather mild conditions such as stop and go city traic, suburban driving at relatively low speeds, and the like. Under these conditions the combustion chamber is particularly susceptible to deposit formation from resinous forming constituents in the lubricant and/or fuel.
  • the invention is not restricted to automotive engines but will apply generally to the operation of any relatively high compression engine of this type, such as those in small motor boats, aircraft and the like where automotive-type engines are subject to a substantial amount of mild operation.
  • viscosity index improver selected from the -group consisting of polyoleins having a molecular weight in the range of 5,000 to 50,000 and polymethacrylate esters; in the range of 1 to 15 Weight percent of a detergent consisting of a phosphosulfurized hydrocarbon having a molecular weight in the range of 300 to 30,000 neutralized with a metal containing reagent; and in the range of 0.01 to 5 Weight percent of a zinc dialkyl dithiophosphate as an antioxidant.
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GB20433/54A GB773999A (en) 1953-08-19 1954-07-13 Improvements in or relating to improved mineral-base lubricating oils and methods for using same
DEST8597A DE1035299B (de) 1953-08-19 1954-08-10 Schmieroel fuer Verbrennungskraftmaschinen mit hohem Verdichtungsverhaeltnis
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US2992987A (en) * 1958-06-26 1961-07-18 Monsanto Chemicals Lubricating oil additive concentrate
US3018247A (en) * 1960-03-15 1962-01-23 California Research Corp Lubricating oil compositions containing metal dithiophosphate-nu-dialkylaminoalkyl alkenyl succinimide blends
US3053766A (en) * 1958-07-25 1962-09-11 Exxon Research Engineering Co High detergency automotive engine lubricant
US3085978A (en) * 1960-02-25 1963-04-16 Phillips Petroleum Co Internal combustion engine lubricant
US3086940A (en) * 1960-01-07 1963-04-23 Standard Oil Co Lubricant addition agents and lubricants containing same
US3135692A (en) * 1956-05-21 1964-06-02 Sinclaire Res Inc Oxidation resistant lubricant
US3146201A (en) * 1960-07-22 1964-08-25 Lubrizol Corp Lubricant composition
US3256183A (en) * 1963-07-10 1966-06-14 Lubrizol Corp Lubricant having improved oxidation resistance
US3294684A (en) * 1963-07-11 1966-12-27 Standard Oil Co Lubricant compositions containing detergency additives
US3321400A (en) * 1964-07-04 1967-05-23 Exxon Research Engineering Co Lubricant containing phosphosulfurized hydrocarbon derivative
US3329612A (en) * 1963-03-11 1967-07-04 Chevron Res Lubricant compositions and detergent additives therefor
US3351647A (en) * 1963-05-14 1967-11-07 Lubrizol Corp Nitrogen, phosphorus and metal containing composition
US3405054A (en) * 1965-06-23 1968-10-08 Standard Oil Co Refinery process stream anti-foulant
EP0465118A1 (de) * 1990-06-29 1992-01-08 Exxon Chemical Patents Inc. Schmierölzusätze
US20040045344A1 (en) * 2001-06-29 2004-03-11 Berhard Jakoby Device for evaluating the signal from a viscosity sensor
CN112852531A (zh) * 2021-01-29 2021-05-28 浙江华凯科技有限公司 一种航空润滑油及其制备方法

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US3135692A (en) * 1956-05-21 1964-06-02 Sinclaire Res Inc Oxidation resistant lubricant
US2991245A (en) * 1957-04-04 1961-07-04 Exxon Research Engineering Co Lubricating oil containing silica gel treated bright stock
US2992987A (en) * 1958-06-26 1961-07-18 Monsanto Chemicals Lubricating oil additive concentrate
US3053766A (en) * 1958-07-25 1962-09-11 Exxon Research Engineering Co High detergency automotive engine lubricant
US3086940A (en) * 1960-01-07 1963-04-23 Standard Oil Co Lubricant addition agents and lubricants containing same
US3085978A (en) * 1960-02-25 1963-04-16 Phillips Petroleum Co Internal combustion engine lubricant
US3018247A (en) * 1960-03-15 1962-01-23 California Research Corp Lubricating oil compositions containing metal dithiophosphate-nu-dialkylaminoalkyl alkenyl succinimide blends
US3146201A (en) * 1960-07-22 1964-08-25 Lubrizol Corp Lubricant composition
US3329612A (en) * 1963-03-11 1967-07-04 Chevron Res Lubricant compositions and detergent additives therefor
US3351647A (en) * 1963-05-14 1967-11-07 Lubrizol Corp Nitrogen, phosphorus and metal containing composition
US3256183A (en) * 1963-07-10 1966-06-14 Lubrizol Corp Lubricant having improved oxidation resistance
US3294684A (en) * 1963-07-11 1966-12-27 Standard Oil Co Lubricant compositions containing detergency additives
US3321400A (en) * 1964-07-04 1967-05-23 Exxon Research Engineering Co Lubricant containing phosphosulfurized hydrocarbon derivative
US3405054A (en) * 1965-06-23 1968-10-08 Standard Oil Co Refinery process stream anti-foulant
EP0465118A1 (de) * 1990-06-29 1992-01-08 Exxon Chemical Patents Inc. Schmierölzusätze
US20040045344A1 (en) * 2001-06-29 2004-03-11 Berhard Jakoby Device for evaluating the signal from a viscosity sensor
US7089784B2 (en) * 2001-06-29 2006-08-15 Robert Bosch Gmbh Device for evaluating the signal from a viscosity sensor
CN112852531A (zh) * 2021-01-29 2021-05-28 浙江华凯科技有限公司 一种航空润滑油及其制备方法

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GB773999A (en) 1957-05-01
FR1124444A (fr) 1956-10-12

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