US3843530A - Liquid oil-soluble non-crystallizing mixtures of zinc salts of dialkyl dithiophosphates - Google Patents

Liquid oil-soluble non-crystallizing mixtures of zinc salts of dialkyl dithiophosphates Download PDF

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Publication number
US3843530A
US3843530A US00123385A US12338571A US3843530A US 3843530 A US3843530 A US 3843530A US 00123385 A US00123385 A US 00123385A US 12338571 A US12338571 A US 12338571A US 3843530 A US3843530 A US 3843530A
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zinc
zinc salts
salts
neutral
mixed
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US00123385A
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E Niedzielski
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to US00123385A priority Critical patent/US3843530A/en
Priority to IT21202/72A priority patent/IT948010B/it
Priority to ES400361A priority patent/ES400361A1/es
Priority to CA136,726A priority patent/CA976538A/en
Priority to GB1100872A priority patent/GB1358478A/en
Priority to FR7208496A priority patent/FR2128847B1/fr
Priority to DE19722211782 priority patent/DE2211782A1/de
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Classifications

    • 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
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • 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
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

  • This invention relates to novel liquid zinc salts of dialkyl dithiophosphates. More specifically, this invention relates to liquid mixtures of basic zinc salts of dialkyl dithiophosphates and liquid mixtures of basic and neutral zinc salts of dialkyl dithiophosphates.
  • neutral metal dialkyl dithiophosphates as lubricating oil additives is well known in the art.
  • These neutral salts in the form of, for example, zinc dialkyl dithiophosphates are known to improve various properties of lubricating oils for internal combustion engines, diesel engines and spark ignition engines.
  • the zinc dialkyl dithiophosphates in order to be effectively utilized must be oil soluble.
  • a problem assoliated With the zinc salts of dialkyl dithiophosphates has been the difficulty of preparing oil concentrates of these salts. It is common practice to prepare and market lubricant additives in a mineral oil solution containing at least 35% active ingredient.
  • the lower molecular weight salts are low in cost but are insufficiently oil soluble to form concentrates in the oil.
  • the higher molecular weight zinc salts are sufiiciently soluble to form oil concentrates, they are relatively expensive. Thus there has been an effort in the past to combine the low molecular weight salts with the high molecular weight salts to strike a balance between oil solubility and cost.
  • these novel compositions of matter are oil soluble liquid compounds containing at least 12% by weight of zinc which comprise zinc salts selected from the group consisting of (a) mixed basic zinc salts of dialkyl dithiophosphates containing 4-l3 different alkyl radicals and having an average carbon content of 3.5-4.5 carbon atoms and (b) mixtures of said basic zinc salts with mixed neutral zinc salts of dialkyl dithiophosphates containing 4-13 different alkyl radicals and having an average carbon content of 3.5-4.5 carbon atoms and wherein the alkyl radicals of (a) and (b) are primary or secondary radicals of 1-13 carbon atoms and wherein the concentration of said alkyl radicals are (l) a maximum of 30 mole percent of each C -C alkyl radical (2) a maximum of 58 mol percent of the combined C -C alkyl radicals (3) a maximum of 70 mol percent of each C alkyl radical (4) a maximum of 82 mol percent of the combined C
  • the present invention is concerned with novel compositions of matter comprising zinc compound selected from the group consisting of (1) mixed basic zinc salts represented by the formula and (2) mixtures of said mixed basic zinc salts and compounds represented by the formula [(RO) PSS] Zn wherein R is a mixture of 4-13 primary or secondary alkyl radicals of l-13 carbon atoms having an average carbon content of 3.5-4.5 carbon atoms wherein the concentration of each of the C C C alkyls does not exceed 30 mole percent( the combined concentration of said C -C alkyls does not exceed 58 mole percent, the concentration of C alkyl does not exceed 70 mole percent and the combined concentration of C -C alkyl does not exceed 82 mole percent, the concentration of secondary alkyls does not exceed 25 mole percent and wherein compounds (l) or (2) contain at least 12% by weight zinc.
  • R is a mixture of 4-13 primary or secondary alkyl radicals of l-13 carbon atoms having an average carbon content of 3.5-4.5 carbon atoms wherein the
  • oil soluble liquid zinc dialkyl dithiophosphate compositions are provided many of which have pour points of 0 F. or below, and higher zinc content and better viscosity properties than commercially available oil concentrates.
  • liquid compositions of this invention are highly stable to crystallization on storage at ambient temperatures. Additionally, since they are prepared as liquids, they do not require the addition of a carrier solvent or oil to render them fluid.
  • the zinc dialkyl dithiophosphates of this invention are prepared by reacting mixtures of alcohols with P S to produce mixed dialkyl dithiophosphoric acids which are converted to basic or neutral salts according to known procedures. Th-e surprising fluidity of the mixed zinc dialkyl dithiophosphates of this invention depend on the combination and distribution of the alkyl groups present. When three different alcohols are used with P 5 to prepare the mixed basic zinc salt, as many as 126 different basic salts can be in the resultant mixture. In the preparation of neutral zinc salts, three alcohols can produce as many as 21 different neutral salts. As the number of ditferent alcohols increases, the number of different salts present in the mixture rises.
  • the redistribution mixtures formed are due to random intermolecular exchange of the alkyl radicals.
  • the mixtures formed constitute all possible compounds that may be formed considering the various alcohols in the reactant and the corresponding alkyl groups of these alcohols.
  • the composition of these mixtures depends on the initial amounts of the different alcohols.
  • the amount of neutral salts may vary up to 75% by weight of the entire mixture.
  • the range of weight ratios of mixtures of basic zinc salts to neutral zinc salts, as defined in this invention, are 100-25 weight percent of the basic to -75 weight percent of the neutral salts.
  • Preferred ranges are 65-35 weight percent basic salts to 35-65 weight percent neutral salts.
  • Most preferred is 58-62 weight percent basic to 42-38 weight percent of the neutral salts.
  • the mixed basic and neutral zinc dialkyl dithio-phosphates may be prepared by first preparing mixtures of dialkyl dithiophosphoric acids and then treating these acids with water and zinc oxide.
  • One mole of phosphorus pentasulfide is reacted with about 4 moles of a mixture of alcohols at a temperature sufficient to cause reaction, e.g., 40-l00 C., and held at this temperature until evolution of H S ceases.
  • the mixture is cooled and filtered to remove any unreacted P 5
  • the reaction proceeds according to the equation
  • the mixed dialkyl dithiophosphoric acids are dissolved in a suitable solvent, such as n-heptane, benzene, or toluene. Water and then zinc oxide are added and the reaction is held at a temperature sufficient for reaction, e.g., -100 C.
  • the slurry is filtered and the filtrate is vacuum distilled to remove water and solvent to yield an oily liquid product.
  • Mixture of basic and neutral salts in all proportions may be prepared by this procedure by varying the ratio of zinc oxide and water to the dialkyl dithiophosphoric acids.
  • the temperature of the reaction also plays a part in the composition of the end product.
  • mixtures of basic and neutral salts may also be obtained by combining mixtures of the basic salts with mixtures of the neutral salts to obtain any desired proportion.
  • Mixed neutral zinc dialkyl dithiophosphates may be prepared by a convenient method involving reacting the mixed dialkyl dithiophosphoric acids with zinc oxide in an organic solvent, such as toluene, xylene, n-heptane or neutral oil.
  • the reaction is illustrated as follows
  • Mixed basic zinc salts are prepared by a procedure wherein the mixed dialkyl dithiophosphoric acids are dissolved in an aqueous alkali metal solution and an aqueous solution of a zinc salt such as ZnCl is added. The layers are separated, the bottom oily layer is washed and the basic zinc salts of the mixed dialkyl dithiophosphates are recovered.
  • the reaction proceeds as follows:
  • the reaction may be carried out in various ways.
  • the alcohols may be added to the P S and optionally mixed with a hydrocarbon solvent.
  • the alcohols and the P S may be placed into reactor together or the P 5 may be added to the alcohol mixture in the reactor.
  • the alcohols useful in the preparation of the mixed basic zinc salts and the mixtures of the mixed basic and mixed neutral zinc salts of dialkyl dithiophosphates of the invention are primary and secondary aliphatic alcohols having 1 to 13 carbon atoms.
  • Representative examples of such alcohols include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, 2-butanol, l-pentanol, 2- methyl-l-butanol, 3-methyl-l-butanol, 2,2-dimethylpropanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, l-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 2-ethyll-butanol, 4-methyl-1-pentanol, 3-methyl-1-pentanol, nheptanol, 2-heptanol, 3-hept
  • the alcohol mixture may be composed entirely of primary alcohols or mixtures of primary and secondary alcohols. In the latter case, the concentration of the secondary alcohols in the total alcohol mixture should not exceed mole percent.
  • the alcohol mixture should not contain more than mole percent of each of C C and C alcohols, and also the combined concentration of these C C alcohols should not exceed 58 mol percent.
  • the concentration of the C alcohols should not exceed 70 mole percent, and the combined concentration of C -C alcohols should not exceed 82 mole percent.
  • the mixture of the basic zinc salts and mixtures of basic and neutral zinc salts of dialkyl dithiophosphates thus obtained have an average carbon content of 3.5 to 4.5.
  • a preferred carbon content is 3.9 to 4.2.
  • Zinc salts having an average carbon content of less than about 3.5 tend to have less solubility in lubricating oil and may crystallize on standing, while the salts having a carbon content of more than 4.5 have a lower proportion of zinc to carbon and thus present a higher treating cost to the refiner.
  • the preferred oil soluble mixed basic zinc dialkyl dithiophosphates of this invention include (a) those preprepared from 5 different alcohols consisting of methanol, iso-butanol and mixed primary hexanols (b) those prepared from 5 different alcohols consisting of methanol, iso-butanol and mixed oxo-tridecyl alcohols containing at least 3 isomers.
  • the preferred oil soluble mixed neutral-basic zinc dialkyldithiophosphates of this invention are mixed :50 weight percent basic and neutral zinc salts prepared from 12 dilferent alcohols consisting of C C C C C and C primary alcohols.
  • EXAMPLE 1 Preparation of a Mixture of Dialkyl Dithiophos phoric Acids Into a 2-liter round bottomed, 4-necked flask equipped with agitation and a reflux condenser connected to a caustic trap, were charged 307.3 grams of mixed alcohols [consisting of 15.8 grams methanol, 39.9 grams ethanol, 49.6 grams n-propanol and 202 grams mixed primary hexanols consisting of 2-methyl-1-pentanol (21.6 wt. percent), 4-methyl-1-pentanol (17.2 wt. percent), 3-methyll-pentanol (22 wt. percent) and l-hexanol (38.4 wt.
  • EXAMPLE 2 Preparation of a Mixture of Basic Zinc Dialkyl Dithiophosphates
  • a 2-liter, round bottomed, 4-necked flask, equipped w th agitation and a reflux condenser was dissolved 48 grams NaOH in 150 grams water.
  • 220 Grams of the dialkyl dithiophosphoric acid product obtained in Example 1 was added, keeping the temperature below 60 C.
  • An aqueous solution containing 81.7 grams of ZnCl in grams water was added dropwise with agitation at 60 C. over a period of 15 minutes, then cooled. An oily yellow product was obtained.
  • EXAMPLE 3 Preparation of a Mixture of Basic and Neutral Zinc Dialkyl Dithiophosphates 220 Grams of the dialkyl dithiophosphoric acid product obtained in Example 1 was dissolved in grams heptane and 16 grams water, and charged into a 2-liter, round bottomed, 4-necked flask equipped with agitationand a reflux condenser. To this was added slowly, with agitation, 73 grams ZnO in small portions, keeping the temperature below 60 C. The reaction mass was held at 60 C. for about one hour. The slurry was filtered hot with the aid of a filtering aid, and the filtrate containing heptane and water was distilled under vacuum.
  • the resulting product 245.8 grams (95% yield) was an oily liquid, Analysisz' 13.0% Zn, 11.3% P, 21.6% S.
  • the neutral'equivalent was 1420, determined with perchloric acid in acetonitrile. This indicated the product was a mixture of 60.6% by weight of the basic zinc salts and 39.4% by weight of the neutral zinc salts.
  • EXAMPLE 4 Preparation of a Mixture of Neutral Zinc Dialkyl Dithiophosphates A 295.9 grams mixture of alcohols (16.2 grams methanol, 24.7 grams ethanol, 30.6 grams n-propanol, 37.7 grams n-butanol, 37.7 grams i-butanol, 44.8 grams mixed C primary alcohols, 52.1 grams 2-methylpentanol-1 and 52.1 grams 2-ethylbutanol-1) was charged into a 2-liter, round bottomed, 4-necked flask equipped with agitator and reflux condenser. The mixture was heated to 6570 C. and 222 grams of P 5 was added over a 2-hour period. The reaction mass was refluxed at 85 C. for2 hours, cooled and filtered. The dialkyl dithiophosphoric acid mixture, 464.3 grams, obtained had an acid normality of 4.19.
  • isobutanol (183.2 grams, 2.4 mole) and mixed C C C C C and C alkyl alcohols (110.2 grams, 0.8 mole) 10% of which are branched or secondary, in a 2-liter, round bottomed, 4-necked flask equipped with stirrer and reflux condenser, over a period of 30 minutes as the tem- 1.041) of mixed dialkyl dithiophosphoric acids having a total acid number 3.75 (94.1% yield).
  • EXAMPLE 27 Mixture of Basic Zinc Salts-Physical mixture of 3 salts
  • a mixture of three basic zinc salts was prepared by mixing 7.42 grams basic zinc salt of dimethyldithiophosphate, 61.0 grams basic zinc salt of di-isobutyldithiophosphate and 18.7 grams basic zinc salt of di-n-hexyldithiophosphate with 300 ml. n-heptane at room temperature. The
  • Nos. 15 and 16 of Table IV also prepared from ethanol, iso-butanol and primary hexanols, but falling within the limits of the invention, do not crystallize.
  • No. 22 has a pour point higher than those of the other mixed salts, it does not influence the pour point of the oil in which it is dissolved. For instance, when 10 wt. percent of No. 22 is introduced into a formulation additive composition containing only 5% neutral oil, 120 SUS at F., the pour point of the concentrate drops to 5 F.
  • the same additive composition containing 12.9 wt. percent of a commercial concentrate containing mixed neutral salts having 10.4 Wt. percent zinc has a pour point of 20 F., as shown below:
  • Composition contains 10 wt. percent of mixed salts No. 22.
  • Composition contains 12.9 wt. percent of an oil concentrate of commercial additive B.
  • compositions of the invention were demonstrated with representative mixtures in the MS Sequence IIB and IIIB tests, as specified 1n ASTM Special Technlcal Publication No. 315-D,
  • Oil solubility Marginal solubility i.e. determined by solubility of 1 wt. percent of the zinc salt in a neuused for evaluating rusting, deposition, wear and rumble.
  • the test method was designed to relate particularly to short trip service under typical winter conditions in the upper midwestern United States. It is used for motor oil specification acceptance. The results are shown in Table VII above compared with commercial additives A and B.
  • Table VIII shows that the lubricating oils containing the additives of the invention undergo oxidative deterioration than those containing the neutral salt commercial additives A & B. Absorption of 5.8 indicates the presence of carbonyl radicals. Absorption at 6.3 indicates presence of carboxyl radicals.
  • the oil containing additive No. 21 shows about the same amount of carboxyl groups as the additives A and B, however, the concentration of zinc is lower and therefore demonstrates equal inhibition at a lower zinc level. With respect to the presence of carbonyl groups, the additives of the invention show greater inhibition to oxidation.
  • the liquid zinc salt compositions of the invention are soluble in neutral distillate oils in an amount sufiicient to give at least 0.l0 wt. percent zinc content in the oil.
  • the salt compositions are contemplated for use in neutral distillate base stock lubricating oils which may also contain some bright stock. They are also useful in automatic transmission oils, which are chiefly lighter neutral oils, and in lubricating base stock for greases which contains neutral distillate oils, bright stock and thickener.
  • the additives of the invention may be used in conjunction with a variety of other additives commonly used in lubricating oils, such as dispersants, anti-oxidants, pour point depressants, corrosion inhibitors and the like.
  • An oil soluble non-crystallizing liquid composition containing at least 12% by weight of zinc which comprises zinc salts selected from the group consisting of (a) mixed basic zinc salts of dialkyl dithiophosphates containing 4 to 13 different alkyl radicals and having an average carbon content of 3.5 to 4.5 carbon atoms of the formula ((R) PSS) Zn OI-I and (b) mixtures of said basic zinc salts with mixed neutral zinc salts of dialkyl dithiophosphates containing 4 to 13 different alkyl radicals and having an average carbon content of 3.5 to 4.5 carbon atoms of the formula ((RO) PSS) Zn and wherein the alkyl radicals of (a) and (b) are primary or secondary radicals of 1-13 carbon atoms and wherein the concentration of said alkyl radicals are (1) a maximum of 30 mol percent of each C C alkyl radical (2) a maximum of 58 mol percent of the combined C -C alkyl radicals (3) a maximum of 70 mol percent of
  • composition of Claim 4 wherein (b) is composed of 35-65% by weight of mixed neutral zinc salts and 6535% by weight of mixed basic zinc salts.
  • An oil composition comprising a major amount of lubricating oil and sulficient weight percent of the oil soluble liquid composition of Claim 1 to have a zinc content of from about 0.01 to 0.25% by weight.
  • An oil composition comprising a major amount of a lubricating oil and sufficient weight percent of the oil soluble liquid composition of Claim 3 to have a zinc content of from about 0.01 to 0.25% by weight.
  • An oil composition comprising a major amount of a lubricating oil and sufficient weight percent of the oil soluble liquid composition of Claim 5 to have a zinc content of from about 0.01 to 0.25% by weight.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
US00123385A 1971-03-11 1971-03-11 Liquid oil-soluble non-crystallizing mixtures of zinc salts of dialkyl dithiophosphates Expired - Lifetime US3843530A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US00123385A US3843530A (en) 1971-03-11 1971-03-11 Liquid oil-soluble non-crystallizing mixtures of zinc salts of dialkyl dithiophosphates
IT21202/72A IT948010B (it) 1971-03-11 1972-02-29 Miscele liquide di sali di zinco basici di dialchil ditiofosfati
ES400361A ES400361A1 (es) 1971-03-11 1972-03-02 Un procedimiento para la preparacion de una composicion de aceite lubricante inhibidora de la corrosion y estable a la oxidacion.
CA136,726A CA976538A (en) 1971-03-11 1972-03-08 Liquid mixtures of basic zinc salts of dialkyl dithiophosphates
GB1100872A GB1358478A (en) 1971-03-11 1972-03-09 Liquid mixtures of basic zinc salts of dialkyl dithiophosphates
FR7208496A FR2128847B1 (enExample) 1971-03-11 1972-03-10
DE19722211782 DE2211782A1 (de) 1971-03-11 1972-03-10 Flüssige Gemische von basischen Zinksalzen von Dialkyldithiophosphaten

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Application Number Priority Date Filing Date Title
US00123385A US3843530A (en) 1971-03-11 1971-03-11 Liquid oil-soluble non-crystallizing mixtures of zinc salts of dialkyl dithiophosphates

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CA (1) CA976538A (enExample)
DE (1) DE2211782A1 (enExample)
ES (1) ES400361A1 (enExample)
FR (1) FR2128847B1 (enExample)
GB (1) GB1358478A (enExample)
IT (1) IT948010B (enExample)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4042323A (en) * 1972-07-17 1977-08-16 Petrolite Corporation Process of inhibiting corrosion of metal in an aqueous environment with mixtures of thio-, oxygen and thio- oxygen phosphates and pyrophosphates
US4085053A (en) * 1977-05-23 1978-04-18 Standard Oil Company (Indiana) Metal dithiophosphate process and/composition
US4123370A (en) * 1977-05-19 1978-10-31 The Lubrizol Corporation Preparation and use of basic metal salt compositions of phosphorus-containing acids
US4179384A (en) * 1978-11-09 1979-12-18 Gulf Research And Development Company Stabilized hydraulic fluid
US4466895A (en) * 1983-06-27 1984-08-21 The Lubrizol Corporation Metal salts of lower dialkylphosphorodithioic acids
WO1989006237A1 (en) * 1988-01-04 1989-07-13 The Lubrizol Corporation Basic metal dihydrocarbylphosphorodithioates
US5015402A (en) * 1986-11-07 1991-05-14 The Lubrizol Corporation Basic metal dihydrocarbylphosphorodithioates
US5178782A (en) * 1985-03-12 1993-01-12 The Lubrizol Corporation Metal salts of mixed aromatic/aliphatic phosphorodithioic acids

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4042323A (en) * 1972-07-17 1977-08-16 Petrolite Corporation Process of inhibiting corrosion of metal in an aqueous environment with mixtures of thio-, oxygen and thio- oxygen phosphates and pyrophosphates
US4123370A (en) * 1977-05-19 1978-10-31 The Lubrizol Corporation Preparation and use of basic metal salt compositions of phosphorus-containing acids
US4085053A (en) * 1977-05-23 1978-04-18 Standard Oil Company (Indiana) Metal dithiophosphate process and/composition
US4179384A (en) * 1978-11-09 1979-12-18 Gulf Research And Development Company Stabilized hydraulic fluid
US4466895A (en) * 1983-06-27 1984-08-21 The Lubrizol Corporation Metal salts of lower dialkylphosphorodithioic acids
JPS6019793A (ja) * 1983-06-27 1985-01-31 ザ　ル−ブリゾル　コ−ポレ−シヨン ジアルキルホスホロジチオ酸の金属塩，この金属塩を含む濃厚添加剤と潤滑剤組成物
EP0131400A3 (en) * 1983-06-27 1985-08-07 The Lubrizol Corporation Metal salts of lower dialkylphosphorodithioic acids
US5178782A (en) * 1985-03-12 1993-01-12 The Lubrizol Corporation Metal salts of mixed aromatic/aliphatic phosphorodithioic acids
US5015402A (en) * 1986-11-07 1991-05-14 The Lubrizol Corporation Basic metal dihydrocarbylphosphorodithioates
WO1989006237A1 (en) * 1988-01-04 1989-07-13 The Lubrizol Corporation Basic metal dihydrocarbylphosphorodithioates

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DE2211782A1 (de) 1972-09-28
ES400361A1 (es) 1975-07-01
GB1358478A (en) 1974-07-03
CA976538A (en) 1975-10-21
FR2128847A1 (enExample) 1972-10-20
FR2128847B1 (enExample) 1976-10-29
IT948010B (it) 1973-05-30

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