EP1148114A2 - Schmierölzusammensetzungen mit ausgezeichneten thermischen Eigenschaften, hohem Druckwiderstand und mit vebessertem Verschleissschutzverhalten - Google Patents

Schmierölzusammensetzungen mit ausgezeichneten thermischen Eigenschaften, hohem Druckwiderstand und mit vebessertem Verschleissschutzverhalten Download PDF

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Publication number
EP1148114A2
EP1148114A2 EP01303441A EP01303441A EP1148114A2 EP 1148114 A2 EP1148114 A2 EP 1148114A2 EP 01303441 A EP01303441 A EP 01303441A EP 01303441 A EP01303441 A EP 01303441A EP 1148114 A2 EP1148114 A2 EP 1148114A2
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EP
European Patent Office
Prior art keywords
lubricating oil
acid ester
oil composition
range
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01303441A
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English (en)
French (fr)
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EP1148114A3 (de
Inventor
Himiko Takayama
Katsumi Umehara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Oronite Japan Ltd
Original Assignee
Chevron Oronite Japan Ltd
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Filing date
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Application filed by Chevron Oronite Japan Ltd filed Critical Chevron Oronite Japan Ltd
Publication of EP1148114A2 publication Critical patent/EP1148114A2/de
Publication of EP1148114A3 publication Critical patent/EP1148114A3/de
Withdrawn legal-status Critical Current

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    • 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
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/95—Esters
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
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    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M2215/086—Imides
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    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to a lubricating oil composition for use in industrial oils such as hydraulic oils, bearing oils, industrial gear oils and sliding surface lubricating oils.
  • the lubricating oil composition of the present invention provides excellent thermal stability, extreme pressure resistance and anti-wear performance.
  • EP extreme pressure
  • ZnDTP zinc dithiophosphates
  • ZnDTP may decompose at high operating temperatures and produce sludge that can contribute to filter plugging and viscosity increase of the lubricating oil.
  • the other type of chemistry involves "ashless" sulfur and phosphorus chemistry.
  • the reference to ash containing or ashless chemistry is historical and there are now ashless alternatives to ZnDTP.
  • phosphorus-containing anti-wear agents have excellent thermal stability under conditions of high temperature operation as demanded, for instance, in industrial oils such as hydraulic oil, bearing oil, industrial gear oil and sliding surface lubricating oil. But, extreme pressure and anti-wear performance is relatively poor in comparison to ZnDTP.
  • ZnDTP-free lubricating oils combining thermal stability, extreme pressure resistance and anti-wear performance are rare. It is not easy to produce lubricating oils having thermal stability at high temperatures with concomitant extreme pressure and anti-wear performance.
  • Japanese Patent Provisional Publication No. 9-111277 describes an ashless hydraulic oil composition
  • Japanese Patent Provisional Publication No. 11-323365 describes a hydraulic oil using a mineral oil, a synthetic oil, or a mixture thereof, as a base oil, which further contains (A) 0.01-1 wt % of an alkenyl succinimide or its derivative, (B) 0.1-5 wt % of a phosphoric acid ester, (C) 0.05-0.5 wt % of an alkylated diphenylamine, and (D) 0.05-0.5 wt % of a hindered phenol.
  • A 0.01-1 wt % of an alkenyl succinimide or its derivative
  • B 0.1-5 wt % of a phosphoric acid ester
  • C 0.05-0.5 wt % of an alkylated diphenylamine
  • D 0.05-0.5 wt % of a hindered phenol.
  • the present invention relates to a lubricating oil composition for use in industrial oils such as hydraulic oils, bearing oils, industrial gear oils and sliding surface lubricating oils.
  • the lubricating oil composition of the present invention provides excellent thermal stability, extreme pressure resistance and anti-wear performance.
  • the present invention relates to a lubricating oil composition
  • a lubricating oil composition comprising a major amount of a base oil of lubricating viscosity and
  • the weight ratio between the compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof and the phosphorus acid ester and/or an amine thereof is in the range of 1:1 to 500:1.
  • the weight ratio between the phosphoric acid ester and/or an amine thereof and the compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof is in the range of 1:0.5 to 1:20.
  • the lubricating oil composition of the present invention has a total phosphorus content in the range of 50 to 5,000 mass ppm.
  • the present invention relates to a lubricating oil concentrate containing a compatible organic diluent and
  • the lubricating oil concentrate of the present invention has a total phosphorus content in the range of 5,000 to 80,000 mass ppm.
  • the present invention relates to a method of producing the lubricating oil composition of the present invention by blending the mixture of the components of the lubricating oil composition of the present invention.
  • the resulting lubricating oil composition having excellent thermal stability, extreme pressure resistance and anti-wear performance.
  • the present invention relates to a method of lubricating hydraulic systems, bearing systems, gear systems, or sliding systems with the lubricating oil composition of the present invention.
  • the present invention relates to a lubricating oil composition for use in industrial oils such as hydraulic oils, bearing oils, industrial gear oils and sliding surface lubricating oils.
  • the lubricating oil composition of the present invention provides excellent thermal stability, extreme pressure resistance and anti-wear performance.
  • the lubricating oil composition of the present invention described herein having thermal stability will minimize sludge formation and viscosity increase resulting from decomposition of the components in the present invention.
  • the base oil of lubricating viscosity used in the lubricating oil composition of the present invention may be mineral or synthetic base oil having a kinematic viscosity of 5 to 900 mm 2 /s, preferably 20 to 700 mm 2 /s at 40 °C.
  • a mineral oil employable for the invention can be obtained from crude oil by distillation (under atmospheric or reduced pressure) and purification such as solvent extraction, hydrocracking, solvent dewaxing or hydrogenation refining.
  • Particularly preferred is a highly hydrogenation-refined base oil having a viscosity index of 100 to 150, an aromatic content of 5 wt % or less, a nitrogen content of 50 ppm or less, and a sulfur content of 50 ppm or less.
  • the synthetic oil (i.e., synthetic lubricating base oil) can be poly- ⁇ -olefin which is a polymer of ⁇ -olefin having 3 to 12 carbon atoms; a dialkyl diester such as dioctyl sebacate, which is an ester of a dibasic acid (e.g., sebacic acid, azelaic acid, or adipic acid) and an alcohol having 4 to 12 carbon atoms; a polyol ester which is an ester of a monobasic acid having 3 to 18 carbon atoms and 1-trimethylolpropane or pentaerythritol, or an alkylbenzene having an alkyl group which contains 9 to 40 carbon atoms.
  • a dialkyl diester such as dioctyl sebacate, which is an ester of a dibasic acid (e.g., sebacic acid, azelaic acid, or adipic acid) and an alcohol having 4 to 12
  • the mineral oil and synthetic oil can be employed singly or blended in combination. Blends of mineral oils with synthetic oils are also useful.
  • the lubricating oil composition of the present invention contains 0.1 to 5.0 wt %, preferably 0.1 to 3.0 wt %, more preferably 0.1 to 1.0 wt % and most preferably 0.1 to 0.5 wt %, of at least one compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and an amine salt thereof.
  • the amount means a ratio based on the total amount of the lubricating oil, and each component of the indicated amount contains a small amount of hydrocarbon oil which is employed in the preparation of the component and remains in the component.
  • the phosphoric acid ester, thiophosphoric acid ester, and amine salt thereof functions to enhance the lubricating performances, and can be selected from known compounds conventionally employed as extreme pressure agents.
  • a phosphoric acid ester, a thiophosphoric acid ester, or an amine salt thereof which has an alkyl group, an alkenyl group, an alkylaryl group, or an aralkyl group, any of which contains approximately 3 to 30 carbon atoms.
  • phosphoric acid esters examples include aliphatic phosphoric acid esters such as triisopropyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, trilauryl phosphate, tristearyl phosphate, and trioleyl phosphate; and aromatic phosphoric acid esters such as benzyl phenyl phosphate, allyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, ethyl diphenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethylphenyl diphenyl phosphate, diethylphenyl phenyl phosphate, propylphenyl diphenyl phosphate, dipropylphenyl phenyl phosphate, triethyl
  • thiophosphoric acid esters examples include aliphatic thiophosphoric acid esters such as triisopropyl thiophosphate, tributyl thiophosphate, ethyl dibutyl thiophosphate, trihexyl thiophosphate, tri-2-ethylhexyl thiophosphate, trilauryl thiophosphate, tristearyl thiophosphate, and trioleyl thiophosphate; and aromatic thiophosphoric acid esters such as benzyl phenyl thiophosphate, allyl diphenyl thiophosphate, triphenyl thiophosphate, tricresyl thiophosphate, ethyl diphenyl thiophosphate, cresyl diphenyl thiophosphate, dicresyl phenyl thiophosphate, ethylphenyl diphenyl thiophosphate, diethylphenyl pheny
  • amine salts of the above-mentioned phosphates and thiophosphates are also employable.
  • the amine salt is an amine salt of trialkylphenyl phosphate or an amine salt of alkyl phosphate.
  • One or any combination of the compounds selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and an amine salt thereof may be used.
  • the content of the phosphoric acid ester, thiophosphoric acid ester, and/or their amine salts in the lubricating oil is less than 0.1 wt %; the lubricating oil composition of the present invention will have insufficient lubricating performance. If the content is more than 5.0 wt.%, no further improvement is expected and would not be cost-effective.
  • the lubricating oil composition of the present invention further contains 0.01 to 1.0 wt %, preferably 0.01 to 0.4 wt %, more preferably 0.01 to 0.2 wt %, and most preferably 0.01 to 0.1 wt %, of a phosphorus acid ester and/or an amine salt thereof.
  • the amount means a ratio based on the total amount of the lubricating oil, and each component of the indicated amount contains a small amount of hydrocarbon oil which is employed in the preparation of the component and remains in the component.
  • the weight ratio between the compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof and the phosphorus acid ester and/or an amine thereof is in the range of 1:1 to 500:1, preferably 1:1 to 50:1, more preferably 1:1 to 25:1, and most preferably 1:1 to 10:1.
  • the phosphorus acid ester and/or its amine salt function to enhance the lubricating performances, and can be selected from known compounds conventionally employed as extreme pressure agents. Generally employed are a phosphorus acid ester or an amine salt thereof which has an alkyl group, an alkenyl group, an alkylaryl group, or an aralkyl group, any of which contains approximately 3 to 30 carbon atoms.
  • phosphorus acid esters examples include aliphatic phosphorus acid esters such as triisopropyl phosphite, tributyl phosphite, ethyl dibutyl phosphite, trihexyl phosphite, tri-2-ethylhexylphosphite, trilauryl phosphite, tristearyl phosphite, and trioleyl phosphite; and aromatic phosphorus acid esters such as benzyl phenyl phosphite, allyl diphenylphosphite, triphenyl phosphite, tricresyl phosphite, ethyl diphenyl phosphite, tributyl phosphite, ethyl dibutyl phosphite, cresyl diphenyl phosphite, dicresyl phenyl
  • dilauryl phosphite dioleyl phosphite, dialkyl phosphites, and diphenyl phosphite.
  • the phosphorus acid ester is a dialkyl phosphite or a trialkyl phosphite.
  • Amine salts of these phosphorus acid esters are also employable and can be used singly or together in combination.
  • the lubricating oil composition of the present invention will have insufficient lubricating performance. If the content is more than 1.0 wt %, no further improvement is expected and would not be cost-effective.
  • the lubricating oil composition of the present invention further contains 0.01 to 2.0 wt %, preferably 0.01 to 1.0 wt %, more preferably 0.01 to 0.4 wt %, and most preferably 0.01 to 0.2 wt %, of a compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzyl amine, and derivatives thereof.
  • the amount means a ratio based on the total amount of the lubricating oil, and each component of the indicated amount contains a small amount of hydrocarbon oil which is employed in the preparation of the component and remains in the component.
  • the weight ratio between the phosphoric acid ester and/or an amine thereof and the compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof is in the range of 1:0.5 to 1:20, more preferably 1:1 to 1:3, and most preferably 1:1 to 1:2 wt %.
  • the alkenyl succinimide can be a monoimide or a bisimide, and can be prepared by reaction between a polybutenyl succinic anhydride and a polyamine.
  • the polybutenyl succinic anhydride can be produced by reaction of a polybutene having a mean molecular weight of 800 to 8,000 or a chlorinated polybutene having a mean molecular weight of 800 to 8,000 with maleic anhydride at a temperature of 100 to 200 °C.
  • the polyamines include diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and hexamethylene heptamine.
  • alkenyl succinimide derivatives examples include borated derivatives, organic phosphonate derivatives, and derivatives which is produced by reacting an alkenyl succinimide with aldehyde, ketone, carboxylic acid, sulfonic acid, alkylene oxide, sulfur, or polyhydric alcohol.
  • a preferred derivative is a borated derivative, which can be produced by reacting the polybutenyl succinic anhydride-polyamine reaction product with boric acid or a boric acid derivative.
  • the alkenyl succinic acid ester and its derivative can be an ester of the above-mentioned polybutenyl succinic anhydride which has been prepared by the reaction between a polybutene or a chlorinated polybutene and maleic anhydride, with a polyhydric alcohol such as pentaerythritol, and its derivative.
  • the benzylamine and its derivative can be prepared by reacting the above-mentioned polybutene with phenol, formaldehyde and polyamine.
  • One or any combination of the compounds selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzyl amine, and derivatives thereof may be used.
  • the content of the component in the lubricating oil is less than 0.01 wt %, sludge dispersing performance will be insufficient and, furthermore, the lubricating oil composition of the present invention will have poor water tolerance. If the content is more than 2.0 wt %, oxidation stability likely decreases.
  • the lubricating oil composition of the present invention has a total phosphorus content in the range of 50 to 5,000 mass ppm, preferably 50 to 2,500 mass ppm, and most preferably 50 to 1,000 mass ppm.
  • the lubricating oil composition of the present invention may contain a variety of other auxiliary additives that can be favorably employed in the present invention.
  • auxiliary additives include extreme pressure agents, corrosion inhibitors, rust inhibitors, friction modifiers, anti-foaming agents, viscosity index improvers and pour point depressants. These examples of additives are provided to illustrate the present invention, but they are not intended to limit it.
  • the lubricating oil composition of the present invention can be prepared by successively or simultaneously adding the additive components to a base oil of lubricating viscosity, or by beforehand preparing a lubricating oil concentrate, as herein described below, and then mixing it with a base oil of lubricating viscosity.
  • the components can be blended in any order and can be blended as combinations of components.
  • the present invention also involves a lubricating oil concentrate comprising 1.0 to 30 wt % of a compatible organic diluent and
  • the concentrates contain sufficient organic liquid diluent to make them easy to handle during shipping and storage.
  • the concentrate will contain from 1.0 to 30.0 wt %, preferably 3.0 to 20.0 wt %, more preferably 5.0 to 10.0 wt %, of a compatible organic diluent.
  • Suitable compatible organic diluents which can be used include, for example, solvent refined 100N, i.e., Cit-Con 100N, and hydrotreated 100N, i.e., Chevron 100N, and the like.
  • the organic diluent preferably has a viscosity of about from 1.0 to 20.0 cSt at 100°C.
  • the weight ratio between the compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof and the phosphorus acid ester and/or an amine thereof is in the range of 1:1 to 500:1, preferably 1:1 to 50:1, more preferably 1:1 to 25:1, and most preferably 1:1 to 10:1.
  • the weight ratio between the phosphoric acid ester and/or an amine thereof and the compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof is in the range of 1:0.5 to 1:20, more preferably 1:1 to 1:3, and most preferably 1:1 to 1:2 wt %.
  • the lubricating oil concentrate of the present invention has a total phosphorus content in the range of 50 to 5,000 mass ppm, more preferably 10,000 to 50,000 mass ppm, and most preferably 15,000 to 30,000 mass ppm.
  • the components were blended in amounts (wt %) set forth in Table I to prepare lubricating oil compositions.
  • the lubricating oil compositions were evaluated by a modified CM Thermal Stability Test that heated the composition at 150 °C rather than at 135 °C under the following conditions:
  • test oil was then filtered over a filter (pore size: 0.8 ⁇ m), washed with n-hexane, and dried.
  • the dry residue on the filter was weighed to determine the amount of sludge. The lower the number (mg), the lower the sludge.
  • the viscosity increase is also indicated. A viscosity increase lower than 5% is preferable.
  • the lubricating oil compositions were evaluated by the Shell Four-Ball Tester, which operated at 1,800 r.p.m., to determine an initial seizure load (ISL). The higher the number (kg), the better the extreme pressure resistance.
  • the Vickers 35VQ25A (M-3952-5) vane pump test is a common wear test to evaluate the anti-wear characteristics of hydraulic oil by means of weight loss on the cam ring and the vanes of a 35VQ25A pump. Test duration is 50 hours per cartridge with a pump outlet pressure of 3,000 psi and an inlet oil temperature of 93.3 °C. A low number indicates low wear.
  • the lubricating oil composition of the present invention produces sludge and viscosity increase less than the Comparative lubricating oil compositions, while also providing excellent extreme pressure resistance. That is, the lubricating oil compositions of the present invention showed a high initial seizure load in the Shell Four-Ball Test, which means excellent extreme pressure resistance. While some of the Comparative Examples gave modified CM Thermal Stability Test results comparable to the Examples, they did not provide favorable viscosity increase or extreme pressure resistance. See for example, Comparative Example E. Further, Comparative Examples C and D provided excellent extreme pressure resistance, but the thermal stability and viscosity increase were higher than the lubricating oil compositions of the present invention demonstrated by Examples 1-3. Additionally, the lubricating oil composition of the present invention (Example 4) also demonstrated excellent anti-wear performance in the Vicker 35VQ25A (M-3952-5) Test.
  • the lubricating oil composition of the present invention has a broader scope of lubricating performance than the comparative lubricating oil compositions.
  • the lubricating oil composition of the present invention provides an excellent combination of thermal stability, extreme pressure resistance and anti-wear performance all in one multi-functional package.

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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)
EP01303441A 2000-04-18 2001-04-12 Schmierölzusammensetzungen mit ausgezeichneten thermischen Eigenschaften, hohem Druckwiderstand und mit vebessertem Verschleissschutzverhalten Withdrawn EP1148114A3 (de)

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JP2001303086A (ja) 2001-10-31

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