EP0113199B1 - Reibungsmodifizierender Zweikomponentenzusatz eine Kraftübertragungsflüssigkeit enthaltend - Google Patents

Reibungsmodifizierender Zweikomponentenzusatz eine Kraftübertragungsflüssigkeit enthaltend Download PDF

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Publication number
EP0113199B1
EP0113199B1 EP83307345A EP83307345A EP0113199B1 EP 0113199 B1 EP0113199 B1 EP 0113199B1 EP 83307345 A EP83307345 A EP 83307345A EP 83307345 A EP83307345 A EP 83307345A EP 0113199 B1 EP0113199 B1 EP 0113199B1
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Prior art keywords
component
thio
bis
alkanol
carbon atoms
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EP83307345A
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English (en)
French (fr)
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EP0113199A2 (de
EP0113199A3 (en
Inventor
William Kenneth Stephen Cleveland
Jack Ryer
Harold Eugene Deen
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M135/24—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives 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
    • 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
    • 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
    • C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives 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
    • 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
    • C10M2223/041—Triaryl phosphates
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to functional fluid compositions containing a two-component ester additive thereby providing to functional fluid or power transmitting oleaginous compositions, such as hydraulic fluids or automatic transmission fluids (ATF), useful friction modification properties.
  • functional fluid compositions containing a two-component ester additive thereby providing to functional fluid or power transmitting oleaginous compositions, such as hydraulic fluids or automatic transmission fluids (ATF), useful friction modification properties.
  • the invention relates to the use of mono- and di-esters of thio-bis alkanols and alkenyl succinic acid or anhydrides in combination with phosphite esters which are especially effective as friction modifier additives for tractor hydraulic fluids.
  • U.S. Patent 4,344,853 discloses that the esters of thio-bis-alkanols and alkenyl succinic acid or anhydride do have useful friction properties. These are the same materials which form one component of the two-component system of the present invention.
  • mineral oil compositions useful as power transmission shift fluids containing a two-component additive in an amount effective to improve the friction characteristics of said composition
  • the first component being (i) a succinate mono- or di- ester, or mixture thereof, formed by the reaction of (a) thio-bis-alkanols of the formula: wherein R and R' each independently may be hydrogen, methyl or ethyl, x may be 1-4, a, b, c, and d each independently may be 1-3; with (b) 1 to 2 moles, per mole of the thio-bis-alkanol, of an aliphatic hydrocarbon-substituted succinic acid or anhydride or mixtures thereof wherein the aliphatic hydrocarbon group contains from 12 to 50 carbon atoms and the second component being (ii) a phosphite diester of the formula (R"0)2P(:O)H where R" is an alkyl or alkenyl
  • the term "monoester” or “hemiester” refers to product made from equimolar proportions of said thio-bis-alkanol and a succinic acid or anhydride, that is, one free hydroxyl group remains; while the term “di-ester” refers to those products wherein each hydroxyl group of the thio - bis-alkanol is esterified with a hydrocarbyl-substituted or polyolefin-substituted succinic acid or anhydride. In either case, a succinic acid moiety remains, i.e., a -C(O)OH group.
  • the relative amounts of the first and second components are such that the ratio in parts by weight of the succinate ester first component to phosphite diester second component is from about 2:1 to 1:2, preferably 1:1.
  • hydrocarbyl-succinic acids or anhydrides for preparing the first component are per se known in the art and the commonly used anhydride may be represented by the formula: wherein R'" is a C lf -C so aliphatic hydrocarbon group, such as an alkyl, alkenyl, isoalkyl, isoalkenyl or cycloalkyl hydrocarbyl group. Oligomers containing 12 to 50 carbon atoms are also suitable as the aliphatic hydrocarbyl group, such as oligomers of C 2 -C S monoolefins, such as isobutene.
  • the aliphatic hydrocarbon group may be an unsubstituted hydrocarbon group or it may contain substituents such as chlorine, bromine, sulfur, phosphorous, nitrogen or oxygen which will not affect the utility of the final mono- or di- ester product.
  • a preferred substituent is sulfur as exemplified by 2-octadecylthio succinic anhydride.
  • the thio-bis-alkanols useful in forming the succinate ester first component are those ester-forming diol comoounds of the formula: wherein R and R' each independently may be hydrogen, methyl or ethyl, x may be 1-4, a, b, c and d each independently may be 1-3. If b or d are greater than 1, then the formula is meant to express ethoxylated derivatives of such alcohols.
  • Preferred embodiments are those thio-bis-alkanols within the foregoing formula herein a, b, c and d are each 1 or 2 and R is H or CH 3 .
  • Specific compounds include 2,2'-dithiodiethanol 2,2'-thiodiethanol, di (2-hydroxypropyl) disulfide and 3,3'-thiodipropanol.
  • Formation of these mono and di-esters proceeds by reacting the appropriate quantities of anhydride (or acid) and thio-bis-alkanol with or without an inert organic solvent diluent and heating and stirring the mixture at about 50 to 150°C until esterification of the anhydride is complete.
  • Equimolar quantities of each reactant will provide mainly the mono- (or hemi-) ester and reaction of 2 moles of hydrocarbon substituted succinic acid or anhydride per mole of thio-bis-alkanol will provide the di-ester material.
  • products useful in the present invention encompass mixtures of such mono- and di- esters.
  • the reaction of an equimolar ratio of thio-bis-alkanol and hydrocarbon succinic anhydride will provide a product containing about 80% mono-ester and about 20% di-ester.
  • the di-ester is produced in somewhat higher yields, about 90% of the product being di-ester and about 10% mono-ester when the mole ratio of succinic anhydride to thio-bis-alkanol is 2:1.
  • the di-ester compounds exhibit generally better friction properties.
  • succinic anhydrides having less than C 12 hydrocarbon substituent so long as the total number of carbon atoms of the hydrocarbon substituents on the succinic moiety of the ester compounds is at least C 12 since oil solubility of the finished compound is the important property.
  • the second component of the friction modifier additive of the present invention is a phosphite diester of the formula (R"0) Z P(:0)H where R" may be an alkyl or alkenyl group having about 6 to 20 carbon atoms and preferably about 12 to 18 carbon atoms. Particularly preferred is dioleyl phosphite. These phosphite ester compounds are, per se, well known in the art, and may be prepared by conventional techniques.
  • phosphite di-esters examples include distearyl phosphite, di-2-ethylhexyl phosphite, dicyclodecyl phosphite as well as phosphite diesters of mixed fatty alcohols, such as cetyl, stearyl and oleyl alcohols, or tallow alcohols (C 16 -C 18 fatty alcohols).
  • the particularly preferred embodiment of the present invention is a two component system composed of about equal parts by weight of 2,2'-thiodiethylbis (octadecenylsuccinic acid ester) as the first component and dioleyl phosphite as the second component.
  • the two-component system of the present invention has been found to exhibit a synergistic effect upon friction characteristics compared with either component used separately at equivalent additive concentration levels.
  • the additive system of this invention is especially useful in functional fluids such as tractor hydraulic fluids which use oil-immersed brakes and power takeoffciutches running in common a oil supply with the transmission. Frictional characteristics of the fluid are important to meet the demands of noiseless braking and power takeoff clutch capacity to provide effective frictional coupling of two or more unconnected surfaces that are immersed or in contact with the functional fluid.
  • compositions of the present invention will contain the two-component additive in amounts effective to provide the desirable properties of friction modification or retention to the power transmitting fluid.
  • the two component additive Generally there will be present 0.05 to 2 wt% of the two component additive based on the total weight of the composition, preferably there is employed about 0.1 to 1.5 wt% of the two-component additive in the hydrocarbon mineral oil fluid, such as a tractor hydraulic fluid which is the preferred composition.
  • Power transmission shift fluids are those functional fluid compositions such as automatic transmission fluids, power steering and brake fluids, hydraulic fluids and such compositions contain a number of conventional additives providing their normal attendant functions and are typically blended into the mineral oil base in the following ranges:
  • Typical base oils for hydraulic and other power transmission shift fluids include a wide variety of light hydrocarbon mineral oils, such as, naphthenic base, paraffin base and mixtures thereof, having a lubricating viscosity range of about 34 to 45 SUS (Saybolt Universal Seconds) at 38°C.
  • Hydraulic fluids used in the following examples were formulated in accordance with the components and concentrations noted above and are referred to as Base Fluid.

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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)

Claims (8)

1. Kraftübertragungsflüssigkeitszusammensetzung auf Mineralölbasis, die ein Zweikomponentenadditiv in einer für die Verbesserung der Reibungseigenschaften der flüssigen Zusammensetzung wirksamen Menge enthält, wobei die erste Komponente (i) ein Bernsteinsäureester ist, der durch die Reaktion von (a) einem Thio-bis-alkanol der Formel:
Figure imgb0008
in der R und R' unabhängig voneinander Wasserstoff, Methyl oder Ethyl sein können, x 1 bis 4 sein kann und a, b, c und d unabhängig voneinander 1 bis 3 sein können, mit (b) 1 bis 2 Mol, pro Mol des Thio-bis-alkanols, einer mit einem aliphatischen Kohlenwasserstoff substituierten Bernsteinsäure oder eines entsprechenden Bernsteinsäureanhydrids, wobei die aliphatische Kohlenwasserstoffgruppe 12 bis 50 Kohlenstoffatomen enthält, gebildet wird, und die zweite Komponente (ii) ein Phosphitdiester der Formel (R"0)2P(:0)H ist, in der R" eine Alkyl- oder Alkenylgruppe mit 6 bis 20 Kohlenstoffatomen ist.
2. Zusammensetzung nach Anspruch 1, in der 0,05 bis 2,0 Gew.% des Zweikomponentenadditivs vorhanden sind und das Gewichtsverhältnis der ersten Komponente zu der zweiten Komponente etwa 1:2 bis 2:1 beträgt.
3. Zusammensetzung nach Anspruch 1, in der die erste Komponente durch die Reaktion von 1 Mol der Kohlenwasserstoffbernsteinsäure oder des Kohlenwasserstoffbernsteinsäureanhydrids pro Mol des Thio-bis-alkanols gebildet worden ist.
4. Zusammensetzung nach Anspruch 1, in der die erste Komponente durch die Reaktion von 2 Mol der Kohlenwasserstoffbernsteinsäure oder des Kohlenwasserstoffbernsteinsäureanhydrids pro Mol des Thio-bis-alkanols gebildet worden ist.
5. Zusammensetzung nach Anspruch 1, in der R" der zweiten Komponente 12 bis 18 Kohlenstoffatome aufweist.
6. Zusammensetzung nach Anspruch 2, bei der es sich um ein Traktorfluid handelt.
7. Zusammensetzung nach Anspruch 6, in der die erste Komponente 2,2'-Thiodiethyl-bis-(octadecenylbernsteinsäureester) ist und die zweite Komponente Dioleylphosphit ist.
8. Verwendung eines Zweikomponentenadditivs zur Verbesserung der Reibungseigenschaften eines Mineralöls, wobei die erste Komponente (i) ein Bernsteinsäureester ist, der durch die Reaktion von (a) einem Thio-bis-alkanol der Formel:
Figure imgb0009
in der R und R' unabhängig voneinander Wasserstoff, Methyl oder Ethyl sein können, x 1 bis 4 sein kann und a, b, c und d unabhängig voneinander 1 bis 3 sein können, mit (b) 1 bis 2 Mol, pro Mol des Thiobisalkanols, einer mit einem aliphatischen Kohlenwasserstoff substituierten Bernsteinsäure oder eines entsprechenden Bernsteinsäureanhydrids, wobei die aliphatischen Kohlenwasserstoffgruppe 12 bis 50 Kohlenstoffatome enthält, gebildet wird, und die zweite Komponente (ii) ein Phosphitdiester der Formel (R"0)2P(:0)H ist, in der R" eine Alkyl- oder Alkenylgruppe mit 6 bis 20 Kohlenstoffatomen ist.
EP83307345A 1982-12-27 1983-12-02 Reibungsmodifizierender Zweikomponentenzusatz eine Kraftübertragungsflüssigkeit enthaltend Expired EP0113199B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US45312182A 1982-12-27 1982-12-27
US453121 1982-12-27

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EP0113199A2 EP0113199A2 (de) 1984-07-11
EP0113199A3 EP0113199A3 (en) 1986-02-12
EP0113199B1 true EP0113199B1 (de) 1988-07-27

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Publication number Priority date Publication date Assignee Title
JPH0251591A (ja) * 1988-06-24 1990-02-21 Exxon Chem Patents Inc パワートランスミッティング組成物において有用な添加剤の相乗的組合せ
US5284591A (en) * 1991-05-15 1994-02-08 The Lubrizol Corporation Functional fluid with borated epoxides, carboxylic solubilizers, zinc salts, calcium complexes and sulfurized compositions
US5635459A (en) * 1995-10-27 1997-06-03 The Lubrizol Corporation Borated overbased sulfonates for improved gear performance in functional fluids

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US3583915A (en) * 1968-07-22 1971-06-08 Mobil Oil Corp Load carrying additives
US4344853A (en) * 1980-10-06 1982-08-17 Exxon Research & Engineering Co. Functional fluid containing metal salts of esters of hydrocarbyl succinic acid or anhydride with thio-bis-alkanols as antioxidants

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EP0113199A2 (de) 1984-07-11
EP0113199A3 (en) 1986-02-12
DE3377504D1 (en) 1988-09-01
CA1232263A (en) 1988-02-02

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