US3350348A - Lubricating oil additives - Google Patents

Lubricating oil additives Download PDF

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US3350348A
US3350348A US445697A US44569765A US3350348A US 3350348 A US3350348 A US 3350348A US 445697 A US445697 A US 445697A US 44569765 A US44569765 A US 44569765A US 3350348 A US3350348 A US 3350348A
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lubricating oil
grams
reaction
temperature
acid
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Braid Milton
Myers Herbert
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ExxonMobil Oil Corp
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Mobil Oil Corp
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Priority to US445697A priority Critical patent/US3350348A/en
Priority to NL6603247A priority patent/NL6603247A/xx
Priority to FR53262A priority patent/FR1482059A/fr
Priority to DE1966M0069025 priority patent/DE1593002B2/de
Priority to GB14825/66A priority patent/GB1094284A/en
Priority to BE679063D priority patent/BE679063A/xx
Priority to US666464A priority patent/US3646172A/en
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    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C10M137/105—Thio derivatives not containing metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1653—Esters of thiophosphoric acids with arylalkanols
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings

Definitions

  • This invention relates to a novel class of compositions useful in lubricating oils and to the method of preparing same. More specifically, it relates to novel oil-soluble compositions and lubricating oil compositions having improved antioxidant activity, bearing corrosion protection and extreme pressure properties, containing the same.
  • lubricating oils are generally formulated with antioxidants which are designed to inhibit the formation of oxidation products and thus lengthen the life of the lubricating oil.
  • antioxidants which are designed to inhibit the formation of oxidation products and thus lengthen the life of the lubricating oil.
  • organophosphorus sulfur compounds are a useful type of inhibitor.
  • novel compounds of this invention have the structure:
  • n is an integer of 1 to 2;
  • R is an alkyl, including both primary and secondary alkyl, or cycloalkyl or al- 3,35%,348 Patented Oct. 31, 1967 ice kenyl radical containing from 1 to 12 carbon atoms, or an aryl, alkylaryl or alkenylaryl radical having from 1 to 5 alkyl substituents attached to the aromatic nucleus, the alkyl substituents containing from 1 to 12 carbon atoms and having a total of up to 18 carbon atoms, or a hydroxy or halogen derivative of the above-defined alkyl or aryl radical;
  • R is hydrogen or an alkyl or cycloalkyl or alkenyl radical or (when n is 2) an alkylene, alkenylene or arylene radical having from 1 to 11 carbon atoms; or an aryl radical, such as phenyl or naphthyl, or aralkyl or alkaryl or an alkenylaryl radical, the
  • n 1 and R may be the bracketed group itself; or when n is 2 and R is alkylene, alkenylene or arylene, the carboxylates are dibasic as indicated by the formula Suitable dicarboxylates include oxalates, succinates, maleates, fumarates, phthalates, or cyclohexane dicarboxylates.
  • a phosphorodithioic acid reactant is mixed gradually and with agitation, with an alkyl carboxylate reactant reactive at the alpha carbon at a temperature in the range of about 40 to about C.
  • R, R and R have the aforementioned definitions (R"' being substantially the same as R" except that it is the alkylidene or aralkylidene thereof by virtue of the double bond as shown), M is an alkali metal, and X is either a halogen group such as chloro, iodo or bromo, or a tosyl group.
  • the ratio of the alkyl carboxylate to the phosphorodithioic reactant is at least stoichiometric and usually in the range of about 0.75 to 4.0, and preferably 1.0 to 1.5, moles of carboxylic ester per mole of phosphorodithioic acid compound.
  • the temperature is held at the temperature of the reaction until the reaction is deemed complete.
  • the total reaction time takes about 30 minutes to five hours, preferably 1 to 2 hours.
  • the reaction is preferably carried out in a liquid phase. If sufficient phosphorodithioic acid reactant is used no additional solvent is necessary. If desired, an organic solvent which is not reactive to the reaction mixture may be added. Such solvents include benzene, n-heptane, cyclohexane, or any of the known solvent-refined processing oils.
  • the temperature for the reaction is maintained at a moderate level, in the range of about 40 C. to about 150 C., and preferably from about 45 C. to 90 C. Once the product has been formed in the reaction mixture the temperature can be increased without danger of thermal decomposition of the product.
  • Suitable esters ⁇ or use as the carboxylate reactants in this invention include the vinyl and substituted vinyl esters of carboxylates described hereinabove and specifically vinyl acetate, vinyl propionate, vinyl butyrate, butenyl propionate and other aliphatic acid esters containing up to 12 carbon atoms, including branched aliphatic acid esters, such as vinyl isobutyrate.
  • Aromatic esters include vinyl benzoate and vinyl naphthoate.
  • esters which may also be used include dicarboxylic acid esters, such as divinyl succinate; aryl dicarboxylic acid esters, such as divinyl phthalate and divinyl terephthalate: and the unsaturated carboxylic esters, such as divinyl maleate and di- 'vinyl fumarate.
  • Halogenated esters include alpha-chloroethyl acetate, alpha-chloroethyl propionate, alpha-chloroethyl benzoate, alpha-chloropropyl acetate, di-alpha- :chloroethyl succinate.
  • the tosylated methyl esters and alpha-tosyl alkyl esters are readily obtained.
  • the phosphorodithioic acid ester reactants are normally prepared by the reaction of 4 moles of an alcohol or phenol with one mole of phosphorus pentasulfide as follows:
  • Suitable alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, amyl alcohol, isoamyl alcohol, hexyl alcohol, oleyl alcohol, isohexyl alcohol, isodecyl alcohol, trimethylpentyl alcohol, crotyl alcohol, benzyl alcohol, tetrahydrofurfuryl alcohol, dimethylbutyl alcohol, and cyclic alcohols, such as cyclohexanol.
  • Suitable aromatic alcohols include phenol and alkylphenols which have up to 5 alkyl groups on the ring, including cresol and nonylphenol.
  • Halogenated alcohols may also be used, such as chlorophenol and ethylene or propylene chlorohydrin.
  • the resulting product is hereafter referred to as 0,0-dialkylor 0,0-diarylphosphorodithioic acid.
  • Mixed esters may also be utilized, and hence any combinations of the above alkyl and aryl compounds are satisfactory in employing the present invention.
  • the alkali metal salts are prepared by simply reacting the esters with metal hydroxides or alkoxides in a conventional neutralization reaction.
  • the 1-(0,0-diorganophosphorodithiato)alkyl carboxylate products of this invention have excellent solubility in the typical lubricating oils in which they are intended to be used. Generally their solubility exceeds the amount required to obtain the desired antioxidant and anticorrosion characteristics furnished by these products.
  • Example 1 Preparati0n 0 0,0-diisobutylphosphorodithioic acid Into a four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer are added 296 grams (4.0 moles) of isobutyl alcohol and the contents are heated to 75 C. At that temperature 222 grams (1.0 mole) of phosphorus pentasulfide are added portionwise over an hour period with agitation. After all of the sulfide reactant is introduced, the temperature is raised to 90 C. and held for three hours. The evolution of hydrogen sulfide gas indicates a substantially complete reaction. The reaction product is cooled and filtered.
  • Example 2 Preparati0n of 1-(0,0-diisobutylphosphorodithiato) ethyl acetate
  • the temperature during this addition is maintained at 78 C.
  • the reaction mixture is heated for one hour at a temperature ranging from C. to C.
  • the reaction mixture is then passed into a rotary film evaporator heated by a boiling water bath and the unreacted vinyl acetate removed under reduced pressure.
  • the yield of product is 650.9 grams of an amber-colored oil indicating a yield of about 99%.
  • This product was also produced by the alternative procedure as follows:
  • Example 3 Preparation of 1-(0,O-di0leylph0sphor0dithiato) ethyl acetate 0,0-dioleylphosphorodithioic acid prepared through the reaction of 400 grams (1.6 moles) of oleyl alcohol and 100 grams (0.45 mole) of phosphorus pentasulfide is charged into a reaction flask equipped with a stirrer and thermometer and heated to 45 C. Vinyl acetate (103 grams, 1.2 moles) is then added over a half-hour period with agitation. During this addition, the temperature rises to 85 C. The reaction product is then maintained at 85- 90 C. with stirring for an additional hour and topped to a vapor temperature of 100 C. at 0.2 mm. to give 453 grams of a dark, amber colored adduct.
  • Example 4 Pre paration of 1- 0,0-di-2,2,4-trimethylpentylphosphorodithiato) ethyl acetate
  • the phosphorodithioic acid obtained in the example is prepared by a reaction between 122 grams (0.55 mole) of phosphorus pentasulfide and 260 grams (2.0 moles) of 2,2,4-trimethylpentan-l-ol, according to the procedure of Example 1.
  • To this acid are added 69 grams (0.8 mole) of vinyl acetate over a 10-minute period at a temperature of 60 C. When the addition is complete, the temperature of the reaction mixture is raised to the reflux temperature, in the range of about 90 to 95 C. Refluxing is continued for four and one-quarter hours.
  • the reaction product is washed with a aqueous sodium hydroxide solution to remove excess acid and dried over sodium sulfate.
  • the treated product is distilled under a nitrogen atmosphere at 3.5 mm. Hg pressure to a pot temperature of 120 C.
  • the liquid product obtained from this procedure is slightly hazy. Further treatment by sodium sulfate followed by filtration through Hi-Flo (diatomaceous earth filter aid) produces a clear yellow liquid substance.
  • the reaction yields 337 grams (96%) of product.
  • Example 5 Preparation of 1-(0,0-diphenylph0sphor0- dithiat0)ethyl acetate
  • the acid in this example is obtained by reacting phenol with phosphorus pentasulfide using the procedure of Example 1.
  • a solution of 43 grams (0.50 mole) of vinyl acetate in 250 ml. of benzene is added Into a reaction flask equipped with a stirrer and thermometer is added a solution of 43 grams (0.50 mole) of vinyl acetate in 250 ml. of benzene. This solution is heated as a second solution, consisting of 70.6 grams (0.25 mole) of 0,0-diphenylphosphorodithioic acid in 200 ml. of benzene, is added over a half-hour period with agitation. The temperature is raised to 70 C.
  • Example 6 Preparation of 1- [0,0-di(n0nylphenyl)phosph0rodithiat01ethyl acetate
  • the acid is prepared in this example by using nonylphenol in the reaction with phosphorus pentasnlfide.
  • a solution containing 116 grams (0.20 mole) of 0,0-di (nonylphenyl)phosphorodithioic acid in 150 ml. of henzene is added to a reaction flask equipped with a stirrer and thermometer.
  • To this solution are added 34.4 grams (0.40 mole) of vinyl acetate over an 18-minute period with agitation. The temperature during this addition is maintained at about C. and the agitation is continued at this temperature for an additional hour.
  • 131 grams (96% yield) of a clear yellow liquid adduct remains.
  • Example 7 Preparati0n of 1-(0,0-dimethylphosphor0- dithiat0)ethyl acetate Using similar procedures as in the previous examples to produce the acid, 215 grams (2.5 moles) of vinyl acetate are added to 2.0 moles of 0,0-dimethylphosphorodithioic acid prepared from the reaction between methanol and phosphorus pentasulfide, as described in Example 1. The reaction mixture requires frequent ice bath applications to keep the temperature at about 40 C. to C. After the vinyl acetate addition the reaction mixture is heated at C. for an additional hour. The product obtained from this reaction is 400.7 grams (82% yield) of a straw-colored clear liquid product.
  • Example 8 Preparation of 1-(0,0-cliis0pentylphosphorodithiato) ethyl acetate
  • the acid is obtained by a reaction between isopentyl alcohol and phosphorus pentasulfide using the procedure of Example 1.
  • Into a reaction flask equipped with a stirrer and thermometer are added 100 grams (0.37 mole) of 0,0-diisopentylphosphorodithioic acid.
  • 50 grams (0.58 mole) of vinyl acetate over a half-hour period with agitation. During this addition the temperature is raised to C., afterward the reaction mixture is maintained at 90 C. with agitation for an additional hour.
  • Unreacted vinyl acetate is removed under reduced pressure in a rotary film evaporator heated by a boiling water bath.
  • the adduct consists of 125 grams yield) of an amber-colored oil.
  • Example 9 Preparati0n of 1-(0,0-diisobutylphosphorodithiat0)ethyl benzoate Using similar procedures as in the previous examples, 50 grams (0.336 mole) of vinyl benzoate are added to 81.5 grams (0.336 mole) of 0,0-diisobutylphosphorodithioic acid in benzene. The addition takes half an hour during which time the temperature is held at about 85 C. The reaction mixture is held for an additional hour at 85 C. A yield of pale yellow liquid adduct is obtained.
  • Example 10 Preparation 0f 1-(0,0-a'i-(1,3-dimethylbatyl)ph0sph0rodithiato)ethyl acetate
  • the acid used in this example is obtained by a reaction between 4 moles of 1,3-dimethylbutan-1-ol with 1.1 moles of phosphorus pentasulfide as described in Example 1.
  • To the crude product of this reaction are added 170 grams (2 moles) of vinyl acetate over a 15 minute period. During the addition the temperature is in the range of 60 C. to 70 C. Benzene ml.) is added.
  • the reaction mixture is agitated and heated at a temperature of from 90 C. to 95 C. for a total of 6 hours.
  • the reaction product is washed with 10% aqueous sodium hydroxide solution, dried over sodium sulfate and distilled under nitrogen at 3.5 mm. Hg pressure to a pot temperature of 120 C.
  • the remaining liquid has the following analysis:
  • Example 11 Preparati0n of 1-(0,0-di-isobutylph0sphorodithiato) ethyl butyrate
  • the acid used for this example is the same as that prepared in Example 1.
  • 100 grams (0.88 mole) of vinyl butyrate is added to grams (0.70 mole) 0,0-di-isobutylphosphorodithioic acid with agitation.
  • the addition takes half an hour in which time the temperature is increased from 45 C. to 85 C.
  • the reaction mixture is held for an additional hour at 85 C.
  • the unreacted vinyl butyrate is removed leaving a liquid product having the following analysis:
  • Example ]4 Preparati0n of di[1-(0,0-diis0butylph0sph0r0dithiat0)]ethyl succinate
  • di-l-chloroethyl succinate prepared by the reaction of 26.7 grams (0.173 mole) of succinyl chloride with grams (0.46 mole) of acetaldehyde in 100 m1.
  • benzene containing 0.2 gram of dry zinc chloride there is added dropwise over a 15 minute period a solution of 97 grams (0.35 mole) of potassium 0,0-diisobutylphosphorodithioate in 150 ml. of N,N-dimethylformamide while stirring.
  • the temperature is maintained at 50 C. during the addition and is then raised to 80 and stirring is continued at this temperature for one additional hour.
  • di-l-(0,0-diisobutylphosphorodithiato)ethyl succinate for which the infrared spectrum is very similar to that of 1-(0,0-diisobutylphosphorodithiato)ethyl acetate.
  • Example 15 Preparati0n of 1 (0,0-diis0decylph0sphorodithiato) ethyl acetate
  • the acid is obtained by a reaction between isodecyl alcohol and phosphorus pentasulfide using the procedure of Example 1.
  • Into a reaction flask equipped with a stirrer and thermometer are added 790 grams (1.9 moles) of 0,0-diisodecylphosphorodithioic acid.
  • To the contents of the flask are added 250 grams (3.0 moles) of vinyl acetate.
  • the reaction mixture is held for 2 hours at a temperature of 80 to 90 C. Unreacted vinyl acetate is thereafter removed.
  • the yield of the liquid adduct is 100%; it has the following analysis:
  • compositions of this invention prevent the oxidation of lubricating oils, even in the presence of metal catalysts.
  • bearing corrosion test it will be noted by comparison that the same lubricating oil containing no additives at all permits an extremely high weight loss.
  • EXTREME PRESSURE PROPERTIES The extreme pressure properties of two products prepared in the above examples were tested using SAE solvent-refined mineral base oil.
  • the oil was blended with (1) 6.2% of the product of Example 4 and (2) 5.2% of the product of Example 10.
  • the two oil blends were tested on an SAE load machine. In this test, two cylinders, driven at different speeds, are rotated against one another, and these roll and slide in line contact under controlled loads. The faster cylinder was operated at 500 rpm. The load is increased until failure, i.e. scutfing or seizure occurs; the loading rate is about 78 lbs. per second. At this point the total load is reported. Each sample oil was tested twice.
  • Oil composition Seizure load, lbs. (1) Composition 4 270,275 (2) Composition 10 270,290
  • L-l CATERPILLAR ENGINE TEST The products of Examples 2 and 6 were tested in a lubricating oil in the L-l Caterpillar Engine Test using a non-metallic detergent.
  • the Caterpillar engine test determines the ability of the oil to prevent deposits around important parts of the engine including the piston and crankcase areas.
  • a l-cylinder, 4-cycle Caterpillar engine is run under the following operating conditions:
  • the duration of the test was 480 hours
  • the diesel fuel of the engine contained 1% sulfur.
  • a typical refined lubricating oil each containing 1% by weight of the products of Examples 2 and 6 and 3% of a commercial detergent.
  • the engine was examined for deposits at various times during the run. The test results are reported below.
  • the engine rating expresses the over-all conditions of the engine at the end of the test run; a scale of to 100 is used, a 100 rating indicating a perfectly clean engine.
  • the lacquer demerits indicate the amount of deposits coating the rings, the grooves and lands and the skirts of the piston; demerits are given for quantity of coating and degree of lacquering as evidence by color standards, and the sticking tendencies of the piston ring; the scale is from 0 to 100, a rating of 0 indicating completely clean surfaces and no demerits of any kind.
  • the top groove packing rating indicates in percent of volume the amount of the carbon deposited in the top groove of the piston; the scale is from 0 to 100%, a rating of 0 indicating a completely clean groove.
  • THERMAL GRAVIMETRIC TEST This test investigates the stability of the novel com-- pounds of this invention at high temperatures by subjecting the compounds to increasing heat while the rate of weight loss is observed.
  • the temperature at which weight loss rate is markedly increased is designated as the inflection temperature; hence, a high inflection temperature indicates satisfactory stability.
  • the products which were tested have been prepared according to the procedures used in the above examples, including products not specifically described hereinbefore.
  • a lubricating oil composition comprising a major amount of a lubricating oil selected from the group consisting of a mineral lubricating oil and a synthetic lubricating oil, said oil being of lubricating viscosity suitable for lubricating high frictional surfaces of engines, and a minor amount of a 1-(0,0-diorganophosphorodithiato) alkyl carboxylate the said alkyl group having at least two carbon atoms.
  • R is selected from the group consisting of alkyl, hydroxyalkyl, and haloalkyl having from 1 to 12 carbon atoms and aryl, hydroxyaryl, haloaryl, and alkaryl having up to 5 alkyl substituents on the aromatic nucleus with from 1 to 12 carbon atoms per alkyl substituent and a total of up to 18 carbon atoms.
  • R is selected from the group consisting of methyl, butyl, isobutyl, pentyl, dimethylbutyl, trimethylpentyl, and decyl.
  • R is selected from the group consisting of phenyl, methylphenyl, butylphenyl and nonylphenyl.
  • the lubricating oil composition of claim 3 wherein the carboxylate group is selected from the group consisting of acetate, propionate, butyrate, succinate and benzoate.
  • l-(0,0-diorganophosphorodithiato)alkyl carboxylate is l-(0,0-diisobutylphosphorodithiato)ethyl benzoate.
  • reaction sequence (a) should appear as shown below instead of as in the patent:

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US445697A 1965-04-05 1965-04-05 Lubricating oil additives Expired - Lifetime US3350348A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US445697A US3350348A (en) 1965-04-05 1965-04-05 Lubricating oil additives
NL6603247A NL6603247A (xx) 1965-04-05 1966-03-11
FR53262A FR1482059A (fr) 1965-04-05 1966-03-14 Nouveaux additifs pour huiles lubrifiantes
DE1966M0069025 DE1593002B2 (de) 1965-04-05 1966-04-02 Verwendung von 1-(o,o-diorganodithiophosphorsaeure)-alkylcarbonsaeureestern als zusatz zu schmieroelen
GB14825/66A GB1094284A (en) 1965-04-05 1966-04-04 New phosphorodithioate esters and lubricating oils containing them
BE679063D BE679063A (xx) 1965-04-05 1966-04-05
US666464A US3646172A (en) 1965-04-05 1967-09-08 1 - (o o - diorganophosphorodithiato) alkyl carboxylates and process for making same

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US445697A US3350348A (en) 1965-04-05 1965-04-05 Lubricating oil additives
US66646467A 1967-09-08 1967-09-08

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Cited By (14)

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US4322303A (en) * 1979-09-18 1982-03-30 Ciba-Geigy Corporation Dithiophosphate stabilizers
US5057235A (en) * 1988-06-23 1991-10-15 Mobil Oil Corporation Sulfur-phosphorus adducts of chromium catalyzed polyalphaolefins
US5071577A (en) * 1988-12-30 1991-12-10 Mobil Oil Corporation Phosphite derived propylene based multifunctional lubricants and multifunctional lubricant additives
US5116523A (en) * 1988-06-23 1992-05-26 Mobil Oil Corporation Sulfide adducts of high viscosity index polyalphaolefins
US5334319A (en) * 1990-06-18 1994-08-02 Tonen Corporation Composition for hydraulic lubrication and coupling
US5334320A (en) * 1990-06-29 1994-08-02 Tonen Corporation Compositions for hydraulic, lubricating and coupling
US5362419A (en) * 1992-06-02 1994-11-08 Ciba-Geigy Corporation Dithiophosphoric acid derivatives as lubricant additives
US5512189A (en) * 1993-03-02 1996-04-30 Mobil Oil Corporation Antiwear and antioxidant additives
US6380139B1 (en) * 1992-06-02 2002-04-30 Ciba Specialty Chemicals Corporation Bisdithiophosphoric acid derivatives as lubricant additives
US6468946B2 (en) 1998-07-06 2002-10-22 The Lubrizol Corporation Mixed phosphorus compounds and lubricants containing the same
US6486102B1 (en) * 1999-01-28 2002-11-26 Unisor Oil-in-water emulsion comprising at least one lubricating additive
US20090093384A1 (en) * 2007-10-03 2009-04-09 The Lubrizol Corporation Lubricants That Decrease Micropitting for Industrial Gears
CN101818094A (zh) * 2010-05-15 2010-09-01 兰州惠锋生物科技有限公司 清洁化节能型硫代烃酯无灰抗磨剂及其制备方法
US9481841B2 (en) 2004-12-09 2016-11-01 The Lubrizol Corporation Process of preparation of an additive and its use

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JPS5226506A (en) * 1975-08-27 1977-02-28 Nippon Oil Co Ltd Lubricating oil composition for compressor
US4175043A (en) * 1978-09-21 1979-11-20 Mobil Oil Corporation Metal salts of sulfurized olefin adducts of phosphorodithioic acids and organic compositions containing same
US4199460A (en) * 1978-09-26 1980-04-22 The United States Of America As Represented By The Secretary Of Agriculture Fatty acid-derived lubricants and additives
US4435338A (en) * 1980-09-29 1984-03-06 Ciba-Geigy Corporation Dithiophosphates

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US5057235A (en) * 1988-06-23 1991-10-15 Mobil Oil Corporation Sulfur-phosphorus adducts of chromium catalyzed polyalphaolefins
US5116523A (en) * 1988-06-23 1992-05-26 Mobil Oil Corporation Sulfide adducts of high viscosity index polyalphaolefins
US5071577A (en) * 1988-12-30 1991-12-10 Mobil Oil Corporation Phosphite derived propylene based multifunctional lubricants and multifunctional lubricant additives
US5334319A (en) * 1990-06-18 1994-08-02 Tonen Corporation Composition for hydraulic lubrication and coupling
US5334320A (en) * 1990-06-29 1994-08-02 Tonen Corporation Compositions for hydraulic, lubricating and coupling
US5362419A (en) * 1992-06-02 1994-11-08 Ciba-Geigy Corporation Dithiophosphoric acid derivatives as lubricant additives
US6380139B1 (en) * 1992-06-02 2002-04-30 Ciba Specialty Chemicals Corporation Bisdithiophosphoric acid derivatives as lubricant additives
US5512189A (en) * 1993-03-02 1996-04-30 Mobil Oil Corporation Antiwear and antioxidant additives
US6468946B2 (en) 1998-07-06 2002-10-22 The Lubrizol Corporation Mixed phosphorus compounds and lubricants containing the same
US6486102B1 (en) * 1999-01-28 2002-11-26 Unisor Oil-in-water emulsion comprising at least one lubricating additive
US9481841B2 (en) 2004-12-09 2016-11-01 The Lubrizol Corporation Process of preparation of an additive and its use
US20090093384A1 (en) * 2007-10-03 2009-04-09 The Lubrizol Corporation Lubricants That Decrease Micropitting for Industrial Gears
CN101818094A (zh) * 2010-05-15 2010-09-01 兰州惠锋生物科技有限公司 清洁化节能型硫代烃酯无灰抗磨剂及其制备方法

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BE679063A (xx) 1966-10-05
DE1593002A1 (de) 1970-05-14
DE1593002B2 (de) 1976-11-11
GB1094284A (en) 1967-12-06
NL6603247A (xx) 1966-10-06
US3646172A (en) 1972-02-29

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