EP2087086A1 - Composition lubrifiante - Google Patents

Composition lubrifiante

Info

Publication number
EP2087086A1
EP2087086A1 EP07822873A EP07822873A EP2087086A1 EP 2087086 A1 EP2087086 A1 EP 2087086A1 EP 07822873 A EP07822873 A EP 07822873A EP 07822873 A EP07822873 A EP 07822873A EP 2087086 A1 EP2087086 A1 EP 2087086A1
Authority
EP
European Patent Office
Prior art keywords
fatty acid
lubricating composition
resistance
acid esters
lubricating
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Withdrawn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
EP07822873A
Other languages
German (de)
English (en)
Inventor
Tetsuya Kato
Koichi Numazawa
Takahiro Ozaki
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.)
Showa Shell Sekiyu KK
Original Assignee
Showa Shell Sekiyu KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Showa Shell Sekiyu KK filed Critical Showa Shell Sekiyu KK
Publication of EP2087086A1 publication Critical patent/EP2087086A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • C10M2201/0856—Phosphorus oxides, acids or salts used as thickening agent
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/045—Polyureas; Polyurethanes
    • C10M2217/0456—Polyureas; Polyurethanes used as thickening agents
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/66—Hydrolytic stability
    • 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 an improvement to lubricating compositions, and in particular relates to a semi-solid lubricating composition with excellent heat resistance, mechanical stability, load resistance, water resistance, corrosion resistance and flame resistance.
  • Grease compositions using this tricalcium phosphate as a thickening agent have a high dropping point and excellent heat resistance, and also perform extremely well in respect of mechanical stability and load resistance from ordinary temperatures up to high temperatures. At present, they are considered one of the preferred lubricating compositions.
  • the manufacturing or working processes take place at elevated temperatures, and sparks may be scattered during these manufacturing and working processes, so that there is a risk that fly- off scale heated to high temperatures may come into contact with the grease and ignite it. To prevent such fires, it is desirable that the grease should have as much excellent flame resistance as possible.
  • This invention provides a high-performance lubricating composition which has excellent heat resistance, mechanical stability, load resistance, corrosion resistance and water resistance and so can overcome all these problems.
  • a lubricating composition which, because of the addition of a tricalcium phosphate to the base oil, which may be a mineral oil and/or synthetic oil, as well as addition of a surfactant, has excellent heat resistance, mechanical stability and load resistance, and at the same time has water resistance and corrosion resistance.
  • the aforementioned tricalcium phosphate is used m the proportion of from 2 to 68 % by weight relative to the total composition of the lubricating composition.
  • a non- ionic surfactant is suitable for the aforementioned surfactant, and m particular it is possible to use one of or a combination of the fatty acid esters glycerine fatty acid esters, sorbitan fatty acid esters and sucrose fatty acid esters.
  • This surfactant is preferably used in the proportion of from 0.2 to 18 % by weight relative to the total composition of the lubricating composition.
  • a urea compound may be used together with the aforementioned tricalcium phosphate as a thickening agent, and can lengthen bearing life and improve durability.
  • the amount used thereof is preferably not more than 8 % by weight relative to the total composition of the lubricating composition.
  • the lubricating composition has excellent heat resistance, mechanical stability and load resistance, and also has corrosion resistance, water resistance and flame resistance, and further it can engender a substantial improvement in bearing life under high temperatures. Accordingly, it can be used in environments subjected to great heat, and can also be used effectively in environments in contact with water such as the paper-making industry and iron and steelmaking plant without giving rise to corrosion.
  • base oils which belong to Group I, Group II, Group III, Group IV and so on of the API (American Petroleum Institute) base oil categories.
  • Group I base oils include, for example, paraffinic mineral oils obtained by appropriate use of a suitable combination of refining processes such as solvent refining, hydrorefining, and dewaxing in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil.
  • Group II base oils include, for example, paraffinic mineral oils obtained by appropriate use of a suitable combination of refining processes such as hydrorefining and dewaxing ⁇ in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil.
  • Group II base oils refined by hydrorefining methods such as the Gulf Company method have a total sulphur content of less than 10 ppm and an aromatic content of under 5% and so are suitable for this invention.
  • Group III base oils and Group 11+ base oils include, for example, paraffinic mineral oils manufactured by a high degree of hydrorefining in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil, base oils refined by the Isodewax process which dewaxes and substitutes the wax produced by the dewaxing process with isoparaffins, and base oils refined by the Mobil wax isomerisation process. These, too, are suitable for use in this invention.
  • synthetic oils mention may be made of polyolefins, diester oils of dibasic acids such as dioctyl sebacate, polyol ester oils, alkylbenzenes, alkylnaphthalenes, esters, polyoxyalkylene glycols, polyoxyalkylene glycol esters, polyoxyalkylene glycol ethers, polyphenyl ethers, dialkyldiphenyl ethers, fluorine-containing compounds (perfluoropolyethers, fluorinated polyolefins) and silicone oils.
  • diester oils of dibasic acids such as dioctyl sebacate, polyol ester oils, alkylbenzenes, alkylnaphthalenes, esters, polyoxyalkylene glycols, polyoxyalkylene glycol esters, polyoxyalkylene glycol ethers, polyphenyl ethers, dialkyldiphenyl ethers, fluorine-containing compounds (perfluoropoly
  • the above-mentioned polyolefins include polymers of various olefins or hydrides thereof. Any olefin may be used, and as examples mention may be made of ethylene, propylene, butene and ⁇ -olefins with five or more carbons. In the manufacture of polyolefins, one kind of the above-mentioned olefins may be used singly or two or more kinds may be used in combination. Particularly suitable are the polyolefins called poly- ⁇ -olefins (PAO) . These are base oils of Group IV.
  • PAO poly- ⁇ -olefins
  • GTLs gas to liquid derived base oils
  • GTLs gas to liquid derived base oils
  • Fischer-Tropsch method of converting natural gas to liquid fuel have a very low sulphur content and aromatic content compared with mineral oil base oils refined from crude oil and have a very high paraffin constituent ratio, and so have excellent oxidative stability, and because they also have extremely small evaporation losses, they are suitable as base oils for this invention.
  • the tricalcium phosphate used in this invention it is possible to use Ca 3 (PO 4 ) 2 but in general any may be used which has the chemical structure of a hydroxyapatite composition that can be expressed as [Ca 3 (PO 4 ) 2 ] 3 • Ca (OH) 2 . Wherever below there is a reference to the amount contained in, this invention, it is to be taken as referring to the weight based on [Ca 3 (PO 4 ) 2 ] 3 -Ca (OH) 2 .
  • This tricalcium phosphate is added to the aforementioned base oil, and is incorporated in the amount of from 2 to 68 % by weight relative to the total composition of the lubricating composition, but preferably in the amount of from 41 to 60 % by weight and more preferably in the amount of from 45 to 55 % by weight. If the amount of tricalcium phosphate in the blend is less than 2 % by weight, the lubricating composition softens and it is not possible to maintain hardness in a suitable semi-solid state. If the amount incorporated exceeds 68% by weight, the lubricating composition hardens and is not in a slippery semi-solid state, so that manufacture is too difficult.
  • Surfactants are used together with the tricalcium phosphate. These surfactants are preferably non-ionic surfactants and, in particular, it is possible to use fatty acid ester type surfactants. These fatty acid ester type surfactants include, for example, glycerine fatty acid esters, sorbitan fatty acid esters and sucrose fatty acid esters. The fatty acids used therein are preferably saturated or unsaturated fatty acids with from 12 to 22 carbons. They may be used singly or in mixtures.
  • glycerine fatty acid esters mention may be made of monoglyceride stearate, monoglyceride monooleate, and mono-diglycerides of stearic acid and oleic acid.
  • sorbitan fatty acid esters mention be made of sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate and sorbitan trioleate.
  • sucrose fatty acid esters mention be made of sucrose palmitic acid ester and sucrose stearic acid ester. These surfactants may also be used in suitable mixtures .
  • surfactants are used in the amount of from 0.2 to 18 % by weight relative to the total composition of the lubricating composition, but preferably in the amount of from 1 to 15 % by weight and more preferably from 2 to 10 % by weight. If the amount of these surfactants in the total composition is too much, the effect is either the same or may even be reversed.
  • the desired composition may be obtained in accordance with the usual method by adding the aforementioned tricalcium phosphate and one or more surfactants to the base oil, heating as appropriate and stirring, and then kneading well using, for example, a three-roll mill.
  • the tricalcium phosphate as mentioned above is barely soluble in water. In greases comprised only of base oil and tricalcium phosphate, when the grease mixes with water, the grease structure is normally destroyed within about 30 minutes, and it is not possible to maintain its gelled structure.
  • lubricating composition of this invention by virtue of the fact that the aforementioned surfactants have been added, even when water is added to the lubricating composition, water of from 50 to 60 % by volume can be held with a certain degree of stability while keeping it in a finely dispersed state, and so by this means it is possible to maintain the gelled structure without destroying the semi-solid structure.
  • Lubricating compositions which use diurea compounds, tetraurea compounds and other urea compounds as thickening agents generally have superior heat-resisting properties, and by combining these with the tricalcium phosphate it is possible to produce lubricating compositions which have not only heat resistance and water resistance but also long bearing life at high temperatures and excellent durability.
  • urea compounds are used by being incorporated in the amount of not more than 8 % by weight relative to the total composition. These urea compounds may be blended in suitable proportions with the tricalcium phosphate but normally it is more desirable if the amount of tricalcium phosphate is greater.
  • the lubricating composition may be formed by mixing these urea compounds with the tricalcium phosphate, surfactants and base oil together.
  • a lubricating composition may also be made by appropriately mixing together a lubricating composition containing mainly tricalcium phosphate and surfactants and a lubricating composition containing mainly a urea compound.
  • this lubricating composition may also be used in combination with additives such as anti-oxidants, anti-corrosion agents, extreme pressure .additives, anti- wear agents and solid lubricants.
  • Examples 1-4 were obtained in similar fashion, using the blend compositions shown in Table 3.
  • Mineral oil paraffinic mineral oil with viscosity of 33 mm 2 /s at 100 0 C
  • Poly- ⁇ -olefin oil poly- ⁇ -olefin oil with viscosity of 40 mm 2 /s at 100 0 C
  • Ether oil alkyldiphenyl ether oil with viscosity of 13 mm 2 /s at 100 0 C
  • Ester oil polyol ester oil with viscosity of 6 mm 2 /s at 100 0 C
  • Tricalcium phosphate [Ca 3 (PO 4 ) 2 13 -Ca (OH) 2
  • Example 14 was a lubricating composition which contained in Example 1, in the amount of 2 % by weight, the diphenylamine type of anti-oxidant used in Comparative Example 5.
  • Examples 15-17 were lubricating compositions with Example 14 and Comparative Example 5 mixed in the proportions shown in Table 4 Tests
  • Tests were carried out on the lubricating compositions of Examples 1-13 and Comparative Examples 1- 4 in respect Of penetration, dropping point, water resistance, mechanical stability and load resistance. Tests were also carried out on the lubricating compositions of Examples 14-17 and Comparative Example 5 in respect of flame resistance and bearing life at high temperatures .
  • Test item the weld load WL (units kgf) and last non-seizure load LSNL (units kgf) were obtained.
  • Examples 1-13 also had excellent heat resistance, with dropping points of not less than 250 0 C in each case.
  • the LNSL last non-seizure load
  • the WL welding load
  • Normally greases referred to as extreme- pressure greases would have an LSNL (last non-seizure load) of about 63 kg and WL (weld load) of about 250 kg, so that the examples have exhibited a high load resistance.
  • Comparative Examples 1-4 had no surfactants added yet the penetration was 267-272 and the EP2007/062988
  • dropping point was not less than 25O 0 C, whilst good results were obtained in respect of the semi-solid state and heat resistance.
  • Example 14 in Table 4 is a case of using a tricalcium phosphate as the thickening agent.
  • Examples 15-i7 are cases of using a tricalcium phosphate and a urea compound together as thickening agents.
  • Comparative Example 5 is a case of using a urea compound as the thickening agent .
  • Examples 14-17 and Comparative Example 5 showed roughly the same performance in respect of penetration, dropping point, which shows heat resistance, mechanical stability and water resistance, but in the four-ball extreme pressure test for load resistance a big difference was seen: the LNSL (last non-seizure load) was 160 kg for Example 14 and 50 kg for Comparative Example 5, and the WL (weld load) was 400 kg for Example 13 and 126 kg for Comparative Example 5. The trend was that load resistance performance decreased as the 'amount of tricalcium phosphate was reduced.
  • bearing life was 180 hours in the cases where tricalcium phosphate or a urea compound was used alone as a thickening agent, but when both were used together it was more than 300 hours, a satisfactory .result .
  • Example 5 did burn ( Figure 2B) . A clear difference could be seen and it is evident that flame resistance has been improved in comparison with Comparative Example 5 of the prior art .
  • Figure 1 is an exploded drawing of the various parts - cylinder, inside roll and top cover - in a shell roll tester for testing water resistance.
  • Figure IA shows the state with no rust generated and
  • Figure IB the state with rust generated.
  • Figure 2 is a drawing illustrating the test configurations in a flame resistance test.
  • Figure 2A shows the configuration with the match not burning the grease and
  • Figure 2B the configuration with the match burning the grease .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne une composition lubrifiante avec d'excellents résistance thermique, stabilité mécanique, résistance à l'eau, résistance à la corrosion, résistance à une charge et caractère ignifuge. À cet effet, la présente invention suggère d'ajouter de 2 à 68 % en poids de phosphate tricalcique par rapport à la composition totale à une huile de base, qui peut être une huile minérale et/ou une huile synthétique. Des agents tensioactifs sont également ajoutés, et le tout est vigoureusement mélangé et malaxé de façon à donner une composition lubrifiante semi-solide. En ce qui concerne les agents tensioactifs, les agents tensioactifs non ioniques sont les plus appropriés, et des esters d'acide gras tels que des esters d'acide gras de glycérine, des esters d'acide gras de sorbitane et des esters d'acide gras de saccharose peuvent être utilisés. La quantité utilisée va de 0,2 à 18 % en poids par rapport à la composition totale.
EP07822873A 2006-12-01 2007-11-29 Composition lubrifiante Withdrawn EP2087086A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006326098 2006-12-01
PCT/EP2007/062988 WO2008065158A1 (fr) 2006-12-01 2007-11-29 Composition lubrifiante

Publications (1)

Publication Number Publication Date
EP2087086A1 true EP2087086A1 (fr) 2009-08-12

Family

ID=38876749

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07822873A Withdrawn EP2087086A1 (fr) 2006-12-01 2007-11-29 Composition lubrifiante

Country Status (9)

Country Link
US (1) US20090305920A1 (fr)
EP (1) EP2087086A1 (fr)
JP (1) JP5363722B2 (fr)
CN (1) CN101558141A (fr)
AR (1) AR064021A1 (fr)
CA (1) CA2671199A1 (fr)
CL (1) CL2007003447A1 (fr)
TW (1) TW200835786A (fr)
WO (1) WO2008065158A1 (fr)

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EP3476922B1 (fr) 2016-06-23 2021-08-25 JXTG Nippon Oil & Energy Corporation Composition de graisse pour joints homocinétiques, et joint homocinétique dans lequel ladite composition de graisse est scellée
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AR064021A1 (es) 2009-03-04
CN101558141A (zh) 2009-10-14
CL2007003447A1 (es) 2008-07-04
JP5363722B2 (ja) 2013-12-11
US20090305920A1 (en) 2009-12-10
JP2008156624A (ja) 2008-07-10
TW200835786A (en) 2008-09-01
WO2008065158A1 (fr) 2008-06-05
CA2671199A1 (fr) 2008-06-05

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