US3337456A - Lubricating compositions - Google Patents

Lubricating compositions Download PDF

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Publication number
US3337456A
US3337456A US485912A US48591265A US3337456A US 3337456 A US3337456 A US 3337456A US 485912 A US485912 A US 485912A US 48591265 A US48591265 A US 48591265A US 3337456 A US3337456 A US 3337456A
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United States
Prior art keywords
oil
metal
alkaline earth
metal salt
extreme pressure
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Expired - Lifetime
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US485912A
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English (en)
Inventor
Andreas G Papayannopoulos
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ExxonMobil Oil Corp
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Mobil Oil Corp
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Publication date
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Priority to US485912A priority Critical patent/US3337456A/en
Priority to GB36373/66A priority patent/GB1088338A/en
Priority to NL6611532A priority patent/NL6611532A/xx
Priority to SE11969/66A priority patent/SE311713B/xx
Priority to FR75501A priority patent/FR1491859A/fr
Priority to AT847666A priority patent/AT274190B/de
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Publication of US3337456A publication Critical patent/US3337456A/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/042Metal salts thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/08Groups 4 or 14
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/08Hydraulic fluids, e.g. brake-fluids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015Dispersions of solid lubricants
    • C10N2050/02Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating

Definitions

  • This invention relates to lubricating compositions having extreme pressure properties and in particular it relates to lubricating oil compositions containing novel metal complexes of oil-insoluble phosphorus compounds.
  • Extreme pressure lubricants are extensively used in lubricating engines and transmissions of trucks, tractors or other automotive vehicles
  • One of the requirements of extreme pressure lubricants is that they possess the ability to form a film on the surfaces of the moving metal parts.
  • the high pressures present in the operation of such equipment often cause the lubricant film to become disrupted.
  • metal makes contact with metal occasioning seizure and welding to occur.
  • the formation of a tough film of lubricant on the metal surfaces prevents this seizure and welding from occurring.
  • This lubricant film on the metal is achieved by chemical reaction.
  • the additives, blended into the lubricating oil compositions, are able to react with the metal at the surface.
  • the resulting metal reaction product is.in the form of a thin film which coats the metal surfaces.
  • the most commonly used additives include oil-soluble compounds containing sulfur, chlorine and phosphorus atoms, bonded in a particular chemical state, with which the metal may react to form sulfides, phosphates and chlorides. Unfortunately, however, the resulting film is usually only momentary.
  • the film is either loosely held to the metal surface and is wiped away or squeezed away by the move ment of the metal parts, or else the presence of the particular anionic-reacting radical -is insuflicient to form strong bonds with the metal.
  • the metal reaction product is as soluble in the oil as the additive and hence it is dissolved away from the metal surface into the oil composition.
  • higher concentrations of additives must be employed so that the disrupted film may be continually replaced by a new film.
  • phosphorus and sulfur compounds such as organic phosphates, phosphosulfurized hydrocarbons, sulfur-treated fats and olefins, dithiophosphate and sulfides have been used as extreme pressure additives.
  • the hydrocarbon group must be of sufficient size to render the additive oil-soluble; thus the amount of sulfur and phosphorus atoms in the compound is diluted.
  • lower hydrocarbon compounds are too insoluble in oil to provide uniform extreme pressure properties.
  • Another object of this invention is to provide lubricants containing oil-soluble extreme pressure agents which will form strong protective coatings over metal.
  • a further object of this invention is to provide an oilsoluble additive for lubricating oils which are adapted to form oil insoluble coatings for metals.
  • Another object of this invention is to provide novel oil-soluble complexes containing chlorine and trivalent phosphorus atoms.
  • a further object of this invention is to provide extreme pressure lubricating compositions having improved storage stability.
  • Another object of this invention is to provide a method of preparing extreme pressure agents for lubricating oils having sufficient solubility in oil to provide extreme pressure properties.
  • lubricating oil compositions having excellent extreme pressure properties may now be prepared by adding to a major proportion of a lubricating oil a minor proportion sufiicient to provide extreme pressure properties thereto of a complex of (1) a chloroalkylphosphite, and (2) a basic alkaline earth metal petroleum or aromatic sulfonate or basic alkaline earth metal phenate.
  • a complex of (1) a chloroalkylphosphite, and (2) a basic alkaline earth metal petroleum or aromatic sulfonate or basic alkaline earth metal phenate a complex of (1) a chloroalkylphosphite, and (2) a basic alkaline earth metal petroleum or aromatic sulfonate or basic alkaline earth metal phenate.
  • the alkyl radical of the phosphite contains from 1 to 4 carbon atoms, although the maximum may be as high as 20 carbon atoms.
  • the lubricating compositions of this invention are particularly suitable in lubricating transmission, final drive, hydraulic systems and even the engines of vehicles equipped with high pressure motors, such as industrial or Iagricultural tractors, and as automatic transmission fluids or transaxle fluids.
  • high pressure motors such as industrial or Iagricultural tractors
  • automatic transmission fluids or transaxle fluids such as automatic transmission fluids or transaxle fluids.
  • the phosphite is itself insoluble in oil, it is discovered that the'complexing of the phosphite with the basic metal sulfonate or phenate renders the resulting complex product sufiiciently oilsoluble to enable the oil medium to carry the product homogenously throughout the machinery.
  • the mechanism of the formation of the protective film is brought about by an almost simultaneously breaking down of the oil-soluble complex and metal reaction with the chloroalkylphosphite.
  • the resulting metal phosphite film is not removed even after many hours of machinery operation.
  • the complexes of this invention are prepared by mixing the reactants together and heating at a temperature in the range of about to about 200 F.
  • the reactants may be combined in any convenient manner and the reaction mass is stirred until a homogenous solution is obtained.
  • the time for the reaction usually lasts from about 5 to about 30 minutes.
  • the chloroalkylphosphite reactant suitable for use in this invention includes the mono-, bisand tris-chloroalkylphosphites. These compounds may be prepared by known commercial methods, such as the reaction between phosphorus trichloride and alcohols or alkylene oxides. The total number of carbon atoms in the alkyl group may range from 1 to about 20. It is preferred to use the relatively insoluble phosphite in this invention, and phosphites having from 1 to 4 carbon atoms are employed with maximum benefit. The most preferred reactant is tris-betachloroethylphosphite.
  • phosphites include those having mixed alkyl groups such as methyl-ethyl, methyl-propyl, methyl-isopropyl and the like. Many commercial chloroalkylphosphites contain mixtures of alkyl groups. Although their oil solubility may be very low low they have been useful in forming the complexes of this invention. It is believed of special advantage that the chlorine atom be attached in the alpha or, more preferably, beta position of the alkyl radical in order that the concurrent breakdown of the complex and film forming reaction be achieved to the most desirable eifect. Thus the most preferred position for the chlorine atom on alkyl groups having 2 or more carbon atoms is the beta position.
  • the basic alkaline earth metal sulfonates and phenates which may be used in this invention include those in which excess metal has been combined with the normal metal salts thereof. These compounds are referred to as overbased metal sulfionates and phenates. The higher the degree of overbasing the less is necessary to form the oil soluble complex.
  • the metal used in these overbased salts are taken from Group II of the Periodic Table: barium, calcium, and magnesium are especially effective.
  • Those overbased sulfonate salts described in U.S. Patents Nos. 3,133,019 and 3,158,572 are representative of the suitable sulfonate reactants for use in this invention. They include the petroleum and aromatic sulfonates.
  • the alkaline earth metal phenates described in US. Patent No. 2,916,454 are examples of the phenate reactants suitable for use in this invention.
  • the amount of metal in the overbased salts may range from about 1% to about 20% of the total compound.
  • These basic compounds are also rated for alkalinity by a total base number (TBN) in terms of milligrams of potassium hydroxide per gram of sample, using the ASTM D-664 method.
  • TBN total base number
  • Suitable basic salts having TBNs ranging from about to 400 may be used.
  • the complex of this invention it is desirable to have a minimum Weight ratio of 1:1 of the overbased timum benefit that the complex contain at least of the metal salt.
  • the amount of complex added to the lubricating oil may range from 0.001% to about 20% by weight of the total lubricant; from about 0.1% to about 3 by Weight is normally sufficient.
  • Example 1a The product of Example 1a was tested in the Falex load test, the Almen load test and the SAE tests. These tests have been described thoroughly in literature. Three percent of the Example I complex was added to a highly refined white mineral base oil. A second complex, using the same calcium petroleum sulfonate as in Example I except that the rate of sulfonate to phosphite was 2:06, was also tested at a concentration of 2.6%. These complexes were compared with varying amounts of tricresylphos-phate, tributylphosphite and with tris-betachloroisopropylphosphite in the presence of the same calcium sulfonate. The concentrations and the results of the extreme pressure tests are tabulated in the following table. (The percent of phosphorus provided by each of the additives is also given.)
  • the complex product of Example I was tested for storage stability over an extended period at both room temperature and at 150 F.
  • the reactants used to prepare the product of Example I were added individually to another sample of the base oil using the same concentration for each as would be present in the complex.
  • the base oil in this test was a mixture of mineral oil stock. After one week at room temperature the complex product remained dissolved in oil in a clear solution. The sample containing the individual components showed a precipitate. Of the samples held for one week at 150 F., the product of Example I remained in solution in the oil; a considerably greater precipitate formed in the comparison blend than the corresponding room temperature sample. This test indicates that the complex cannot be produced in the oil medium.
  • complexes can not be prepared from neutral sulfonates or phenates.
  • the salt must contain some degree of overbasing.
  • complexes were prepared from both overbased and neutral salts. The complexes were tested in the storage stability test at a concentration of 3%. The same base stock was used as in the previous test.
  • the neutral sulfonate reactants were barium dinonyl naphthalene sulfonate, ethylenediamine dinonyl naphthalene sulfonate, lead dinonyl naphthalene sulfonate, sodium petroleum sulfonate and zinc petroleum sulfonate.
  • the overbased sulfonate reactants were also a calcium petroleum sulfonate containing 3% calcium with a TBN of 22; a synthesized barium sulfonate containing 15% barium with a TBN of 63; a synthesized magnesium sulfonate containing 7.2% magnesium with a TBN of 300; and a calcium phenate containing 9.3% calcium with a TBN of 255.
  • the results of the solubility in oil and the storage stability of the complex are tabulated below.
  • Lubricant mineral oils may be used for the base fluid in this invention, as well as synthetic ester lubricants and polymer lubricants.
  • the complexes of this invention are compatible with other known additives for lubricating oils and they may be combined with other detergents, viscosity index improvers, antioxidants, antifoamers, and the like.
  • Of incidental utility in this invention is the detergency nature of the sulfonates and phenates. The detergency and neutralizing power of the complexes remains at a high level even before the breakdown. After the breakdown of the phosphite complex, these overbased salts are available to continue to provide equivalent detergency and neutralizing properties to the oil composition.
  • a novel complex reaction product prepared by the reaction at up to about 200 F. of a chloroalkylphosphite wherein the alkyl group has from 1 to about 20 carbon atoms and an overbased metal salt selected from the group consisting of alkaline earth metal sulfonates and phenates.
  • a novel complex reaction product prepared by the reaction at up to about 200 F. of a betachloroalkylphosphite wherein the alkyl group has from 1 to about 20 carbon atoms and an overbased alkaline earth metal salt selected from the group consisting of sulfonates and phenates.
  • a novel complex reaction product prepared by the reaction at from about to about 200 F. of trisbetachloroalkylphosphite wherein the alkyl group has from 1 to 4 carbon atoms and an overbased alkaline earth metal salt selected from the group consisting of sulfonates and phenates wherein the weight ratio of metal salt to phosphite is at least about 1:1.
  • a novel complex reaction product prepared by the reaction at from about 100 to about 200 F. of trisbetachloroethylphosphite and an overbased alkaline earth metal salt selected from the group consisting of sulfonates and phenates wherein the percent of metal is in the range of about 1.0% to about 20% wherein the weight ratio of metal salt to phosphite is at least about 1:1.
  • reaction product of claim 4 wherein the weight ratio of metal salt to phosphite is in the range of about 1:1 to 5:1.
  • the method of producing novel oil-soluble reaction products comprising the steps of (1) admixing a chloroalkylphosphite wherein the alkyl groups contain from 1 to about 20 carbon atoms and an overbased alkaline earth metal salt selected from the group consisting of sulfonates and phenates wherein the weight ratio of metal salt to phosphite is at least about 1:1 and (.2) stirring the resulting reaction mixture while maintaining the temperature in the range of about 100 F. to about 200 F. until a homogenous solution is obtained.
  • a method of producing novel oil-soluble reaction products comprising the steps of (1) admixing a betachloroalkylphosphite wherein the alkyl groups contain from 1 to 4 carbon atoms and an overbased alkaline earth metal salt selected from the group consisting of sulfonate and phenates wherein the weight ratio of metal salt to phosphite is at least about 1:1 and (2) stirring the resulting reaction mixture in the temperature in the range of about 100 F. to about 200 F. until a homogeneous solution is obtained.
  • betachloroalkylphosphite is tris-betachloroethylphosphite.
  • overbased metal salt is an overbased calcium sulfonate.
  • a lubricating oil composition comprising a major proportion of a lubricating oil and a minor proportion sufficient to provide extreme pressure properties thereto of an oil-soluble reaction product prepared by the heating at up to about 200 F., a mixture of a chloroalkylphosphite wherein the alkyl group has from 1 to about 20 carbon atoms and a basic alkaline earth metal salt selected from the group consisting of an alkaline earth metal sulfonate and an alkaline earth metal phenate wherein the weight ratio of metal salt to phosphite is at least about 1:1.
  • a lubricating oil composition containing a major proportion of a lubricating oil and a minor proportion sufficient to provide extreme pressure properties thereto of an oil-soluble reaction product prepared by the reaction at from about 100 to about 200 F. of a betachloroalkylphosphite, wherein the alkyl group has from 1 to 4 carbon atoms, and an overbased alkaline earth metal salt selected from the group consisting of sulfonates and phenates wherein the weight ratio of metal salt to phosphite is at least about 1:1.
  • a lubricating oil composition comprising a major proportion of a lubricating oil and a minor proportion sufiicient to provide extreme pressure properties thereto of an oil-soluble reaction product prepared by the reaction at from about 100 to about 200 F. of trisbetachloroalkylphosphite wherein the alkyl group has from 1 to 4 carbon atoms and an overbased alkaline earth metal salt selected from the group consisting of sulfonates and phenates wherein the weight ratio of metal salt to phosphite is at least about 1:1.
  • a lubricating oil composition comprising a major proportion of a lubricating oil and a minor proportion sufiicient to provide extreme pressure properties thereto of an oil-soluble reaction product prepared by the reaction at from about 100 to about 200 F. of trisbetachloroethylphosphite and an overbased alkaline earth metal salt selected from the group consisting of sulfonates and phenates wherein the percent of metal is in the range 8 of about 1% to about 20% wherein the weight ratio of metal salt to phosphite is at least about 1:1.
  • a lubricating oil composition comprising a major proportion of a lubricating oil and a minor proportion suificient to provide extreme pressure properties thereto of an oilsoluble reaction product prepared by the reaction at from about 100 to about 200 F. of a trisbetachloroethylphosphite and an overbased alkaline earth metal salt selected from the group consisting of sulfonates and phenates wherein the Weight ratio of metal salt to phosphite is in the range of about 1:1 to about 5:1.
  • a lubricating oil composition comprising a major nate wherein the weight ratio of sulfonate to phosphite is in the range of about 1:1 to 5:1.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
US485912A 1965-09-08 1965-09-08 Lubricating compositions Expired - Lifetime US3337456A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US485912A US3337456A (en) 1965-09-08 1965-09-08 Lubricating compositions
GB36373/66A GB1088338A (en) 1965-09-08 1966-08-15 Oil-soluble metal-containing complexes of chloroalkyl-phosphites
NL6611532A NL6611532A (de) 1965-09-08 1966-08-16
SE11969/66A SE311713B (de) 1965-09-08 1966-09-06
FR75501A FR1491859A (fr) 1965-09-08 1966-09-07 Nouveaux additifs pour huiles lubrifiantes
AT847666A AT274190B (de) 1965-09-08 1966-09-08 Schmierölzusammensetzung

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US485912A US3337456A (en) 1965-09-08 1965-09-08 Lubricating compositions

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AT (1) AT274190B (de)
GB (1) GB1088338A (de)
NL (1) NL6611532A (de)
SE (1) SE311713B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4804489A (en) * 1987-10-29 1989-02-14 The Lubrizol Corporation Low molecular weight viscosity modifying compositions
US5256319A (en) * 1989-03-30 1993-10-26 Institut Francais Du Petrole New thiophosphoretted compounds, their preparation and their use as additives for lubricants

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2916454A (en) * 1957-02-18 1959-12-08 Socony Mobil Oil Co Inc Preparation of complex carbonated metal salts of alkyl phenol sulfides and mineral oil fractions containing the same
US3030304A (en) * 1958-02-11 1962-04-17 Castrol Ltd Lubricating compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2916454A (en) * 1957-02-18 1959-12-08 Socony Mobil Oil Co Inc Preparation of complex carbonated metal salts of alkyl phenol sulfides and mineral oil fractions containing the same
US3030304A (en) * 1958-02-11 1962-04-17 Castrol Ltd Lubricating compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4804489A (en) * 1987-10-29 1989-02-14 The Lubrizol Corporation Low molecular weight viscosity modifying compositions
US5256319A (en) * 1989-03-30 1993-10-26 Institut Francais Du Petrole New thiophosphoretted compounds, their preparation and their use as additives for lubricants

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Publication number Publication date
NL6611532A (de) 1967-03-09
AT274190B (de) 1969-09-10
GB1088338A (en) 1967-10-25
SE311713B (de) 1969-06-23

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