EP1006173A1 - Lubricant compositions exhibiting extended oxidation stability - Google Patents

Lubricant compositions exhibiting extended oxidation stability Download PDF

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Publication number
EP1006173A1
EP1006173A1 EP98309774A EP98309774A EP1006173A1 EP 1006173 A1 EP1006173 A1 EP 1006173A1 EP 98309774 A EP98309774 A EP 98309774A EP 98309774 A EP98309774 A EP 98309774A EP 1006173 A1 EP1006173 A1 EP 1006173A1
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EP
European Patent Office
Prior art keywords
oils
use according
lubricant
group
antioxidant
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.)
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Application number
EP98309774A
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German (de)
English (en)
French (fr)
Inventor
Helen Theresa Ryan
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.)
Afton Chemical Ltd
Original Assignee
Afton Chemical Ltd
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 Afton Chemical Ltd filed Critical Afton Chemical Ltd
Priority to EP98309774A priority Critical patent/EP1006173A1/en
Priority to CA002287726A priority patent/CA2287726C/en
Priority to SG1999005402A priority patent/SG77271A1/en
Priority to AU59364/99A priority patent/AU5936499A/en
Priority to JP11332670A priority patent/JP2000160182A/ja
Priority to KR1019990053876A priority patent/KR20000035777A/ko
Priority to CN991228529A priority patent/CN1216134C/zh
Priority to BR9905759-0A priority patent/BR9905759A/pt
Publication of EP1006173A1 publication Critical patent/EP1006173A1/en
Withdrawn legal-status Critical Current

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    • 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
    • C10M141/00Lubricating 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
    • C10M141/10Lubricating 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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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
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    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04Hydroxy compounds
    • C10M129/10Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04Hydroxy compounds
    • C10M129/10Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/14Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring containing at least 2 hydroxy groups
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    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M135/06Esters, e.g. fats
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    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/16Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiourea type, i.e. containing the group
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    • C10M135/12Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • C10M137/10Thio derivatives
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
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    • C10M2207/024Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
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    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027Neutral salts thereof
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    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2219/088Neutral salts
    • 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
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089Overbased salts
    • 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
    • C10M2223/045Metal containing thio derivatives
    • 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

Definitions

  • the present invention relates to the use of certain additives to extend the thermal stability and oxidation stability of lubricant compositions, and to lubricant compositions exhibiting extended thermal stability and oxidation stability.
  • Lubricating compositions for antiwear hydraulic and industrial applications typically contain additive components to impart antiwear performance. Hydraulic grade zinc dialkyldithiophosphates are typically used in this respect. The compositions usually also contain antioxidant components.
  • the compositions have conventionally been formulated using Group I base oils. However, the use of hydrocracked and catalytically dewaxed Group II and Group III base oils is on the increase. The hydrogenation and dewaxing processes involved result in base oils of exceptionally low aromaticity and sulphur level. These Group II and Group III bases have been found to exhibit an improved response to antioxidant components when compared with Group I basestocks.
  • the present invention provides the use in a lubricant composition
  • a lubricant composition comprising a hydraulic antiwear component and a base oil of an additive comprising at least one amine antioxidant and at least one additional antioxidant selected from ashless dithiocarbamate, sulphurised olefin and phenolic, antioxidants to provide a lubricant having improved thermal stability and oxidative stability in all basestock types.
  • the performance of the combinations of antioxidants used in accordance with the present invention will vary depending, amongst other things, on the base oil type, the specific combination and the concentration of additive(s), used.
  • the additives used in accordance with the present invention enable formulation of lubricants which may avoid excessive sludge formation after a period of 10 days when the lubricant is tested in accordance with the NOC test and when the base oil used is a Group I basestock.
  • the amount of sludge produced after 10 days in this test is not more than 100 mg/100 ml, preferably not more than 25 mg/ 100 ml. A 10 day sludge result of less than 10 mg/100 ml is particularly preferred.
  • the additives used in accordance with the present invention typically enable formulation of lubricants which use a Group II or higher basestock and which give a result of at least 500 minutes, preferably at least 600 minutes, in the RBOT thermal stability test.
  • the present invention relates to combinations of antioxidants which may be used to achieve good oxidation performance in Group II or higher basestock without derating thermal stability performance when Group I or higher basestock is used, and vice versa.
  • the amine used in the present invention is selected from optionally alkylated diphenylamines, phenyl-naphthylamines and mixtures thereof.
  • examples of such components that may be used in this invention include, but are not limited to, diphenylamine, phenyl- ⁇ -naphthylamine, phenyl-beta-naphthylamine, butyldiphenylamine, dibutyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, nonyldiphenylamine, dinonyldiphenylamine, dioctyldiphenylamine, nonyldiphenylamine, dinonyldiphenylamine, heptyldiphenylamine, diheptyldiphenylamine, methylstyryldiphenylamine, mixed butyl/octyl alkylated diphenylamines, mixed but
  • Useful amine antioxidants are generally characterized by their nitrogen content and TBN as determined by ASTM D 2896. It is preferred that the nitrogen content of the amine antioxidants be between 3.0 and 7.0 wt% and the TBN be between 100 and 250 mg KOH/g of the neat, i.e. undiluted, component.
  • the concentration of amine antioxidant(s) in the finished composition varies depending upon the basestock used, customer requirements and applications. Typically, the total amount of amine antioxidant present in the finished composition is from 0.04 wt% to 0.4 wt%, preferably, from 0.05 wt% to 0.2 wt %.
  • the sulphur-containing compounds of the present invention are selected from the group consisting of sulphurized olefins, sulphurized fatty acids, ashless dithiocarbamates, tetraalkylthiuram disulphides and mixtures thereof.
  • the sulphurized olefins suitable for use in the present invention may be prepared by a number of known methods. They are typically characterized by the type of olefin used in their production and their final sulphur content. High molecular weight olefins (e.g., those having an average molecular weight (Mn) of from about 112 to about 351 g/mole) are preferred.
  • olefins examples include ⁇ -olefins, isomerized ⁇ -olefins, branched olefins, cyclic olefins, polymeric olefins and mixtures thereof
  • ⁇ -olefins examples include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene and mixtures thereof.
  • ⁇ -Olefins may be isomerized before the sulphurization reaction or during the sulphurization reaction.
  • Structural and/or conformational isomers of the ⁇ -olefins that contain internal double bonds or branching may also be used.
  • isobutylene is the branched olefin counterpart of the ⁇ -olefin 1-butene.
  • Sulphur sources that may be used in the sulphurization reaction can include, for example, elemental sulphur, sulphur monochloride, sulphur dichloride, sodium sulphide, sodium polysulphide, and mixtures thereof added together or at different stages of the sulphurization process.
  • Unsaturated fatty acids and oils because of their unsaturation, may also be sulphurized and used in this invention.
  • fatty acids that may be used include lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, gadoleic acid, arachidonic acid, erucic acid, and mixtures of these.
  • oils or fats that may be used include corn oil, cottonseed oil, grapeseed oil, olive oil, palm oil, peanut oil, rapeseed oil, safflower seed oil, sesame seed oil, soybean oil, sunflower oil, sunflower seed oil, and combinations thereof.
  • ashless dithiocarbamates examples include, but are not limited to, methylene-bis(dialkyldithiocarbamate), ethylene-bis(dialkyldithiocarbamate), and isobutyl disulphide-2,2'-bis(dialkyldithiocarbamate), where the alkyl groups of the dialkyldithiocarbamate can preferably have from 1 to 16 carbons.
  • Examples of preferred ashless dithiocarbamates are methylene-bis(dibutyldithiocarbamate), ethylene-bis (dibutyldithiocarbamate), and isobutyl disulphide-2,2 ' -bis(dibutyldithiocarbamate).
  • Examples of preferred tetraalkylthiuram disulphides that may be used include tetrabutylthiuram disulphide and tetraoctylthiuram disulphide.
  • the concentration of the sulphur-containing compound in the finished composition can vary depending upon the customers' requirements and applications.
  • the compound is typically used in an amount of upto 0.1% by weight, preferably upto 0.05% by weight based on the total weight of the lubricant composition.
  • An important criteria for selecting the concentration of the compound is the sulphur content.
  • the compound should typically deliver between 0.005 wt. % and 0.07 wt. % of sulphur to the finished composition.
  • a sulphurized olefin having 12 wt. % sulphur content should be used between 0.04 wt. % and 0.58 wt. % to deliver between 0.005 wt. % and 0.07 wt.
  • An ashless dithiocarbamate having 30 wt. % sulphur content should be used between 0.02 wt. % and 0.23 wt. % to deliver between 0.005 wt. % and 0.07 wt. % sulphur to the finished composition.
  • Another criterion useful for selecting the sulphur-containing compound is the content of active sulphur as determined by ASTM D 1662.
  • the presence of high levels of active sulphur can lead to significant corrosion and sludge problems in the finished lubricant.
  • the level of active sulphur in the compound is below 1.5 wt. % as determined by ASTM D 1662.
  • sulphurized olefin that may be used in this invention would contain approximately 12 wt. % total sulphur content and ⁇ 1 wt. % active sulphur.
  • examples of commercially available sulphurized fatty oils or mixtures of sulphurized fatty oils and olefins, that may be used in this invention include those having approximately 9.5 wt. % sulphur content and 1 wt. % active sulphur, approximately 12.5 wt. % sulphur content and 1.5 wt. % active sulphur, and approximately 10 wt. % sulphur content and ⁇ 1 wt. % active sulphur.
  • An example of an ashless dithiocarbamate that may be used in this invention would be one which has approximately 30 wt. % sulphur from a practical standpoint the sulphur-containing compound should contain a minimum of 8.0 wt% sulphur in order to minimize the amount of additive needed to deliver the required amount of sulphur.
  • Mixtures of sulphurized olefins, ashless dithiocarbamates and tetraalkylthiuram disulphides, in varying proportions, may also be used, as long as the desired total sulphur content, and active sulphur content are satisfied.
  • phenolic antioxidants which may be used include hindered phenolics such as 2,6-di-butylphenol, 4-methyl-2,6-di-t-butylphenol, 2,4,6-tributylphenol, 2-t-butylphenol, 2,6-diisopropylphenol, 2-methyl-6-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 4-(N,N-dimethylaminomethyl)-2,6-di-t-butylphenol, 4-ethyl-2,6-di-t-butylphenol, 2-methyl-6-styrylphenol, 2,6-di-styryl-nonylphenol and mixtures thereof.
  • hindered phenolics such as 2,6-di-butylphenol, 4-methyl-2,6-di-t-butylphenol, 2,4,6-tributylphenol, 2-t-butylphenol, 2,6-diisopropylphenol, 2-methyl-6-t-
  • methylene bridged alkyl phenols are also useful.
  • these may be used singly or in combination with each other or with sterically hindered unbridged phenols.
  • Examples include 4,4'-methylene-bis(2,6-di-butylphenol), 4,4'-methylene-bis (6-t-butyl-o-cresol), 4,4'-methylene-bis(2-t-amyl-o-cresol), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), methylene bridged t-butylphenol mixtures, iso-octyl-3,5-di-butyl-4-hydroxy hydrocinnamate and thiodiethylene-bis (3,5-di-butyl-4-hydroxy)hydrocinnamate.
  • phenolic antioxidant will be present in the finished lubricant in an amount of upto 0.4% by weight, preferably upto 0.15% by weight.
  • the present invention also provides lubricant compositions, as described herein, comprising a hydraulic antiwear component, a base oil, at least one amine antioxidant and at least one additional antioxidant.
  • antioxidants useful in the present invention are commercially available or may be prepared by the application or adaptation of known techniques.
  • the hydraulic antiwear additive used in the composition of the invention is a hydraulic grade zinc dialkyldithiophosphate (ZDDP).
  • ZDDP hydraulic grade zinc dialkyldithiophosphate
  • "Hydraulic grade” means that the antiwear component is suitable for use in hydraulic applications, particularly with respect to their thermal stability. (ZDDPs) which have insufficient thermal stability tend to degrade rapidly to breakdown products which can be corrosive, in particular towards copper. This is a serious problem as certain hydraulic system components are made of this metal. Furthermore, the breakdown products can cause sludge formation which in turn can result in filter blocking. Thus, not all types of ZDDPs are suitable for use in the present invention. Zinc dihydrocarbyl dithiophosphates which may be used in the present invention are well-known in the art (see for example U.S.
  • the zinc dihydrocarbyl dithiophosphate is a zinc dialkyl dithiophosphate typically containing about 4 to about 12 carbon atoms and more commonly about 6 to about 12 carbon atoms in each alkyl group.
  • each alkyl group contains about 8 to about 12 carbon atoms.
  • suitable alkyl moieties include butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl, 2-ethylhexyl, decyl and dodecyl.
  • each alkyl moiety is 2-ethylhexyl.
  • Zinc dialkyl dithiophosphates of this type are described in European patent application no. 95306722.0 and are commercially available.
  • the ZDDP may be used in the lubricant over a broad weight range. It is usual however that the lubricant contains about 0.4 to about 0.9% by weight ZDDP. Preferably, the fluid comprises 0.6% by weight ZDDP.
  • Useful ZDDPs typically exhibit an overbased to neutral ratio of from 0.3:1 to 2:1, preferably 0.5:1 to 2:1. ZDDPs having an overbased to neutral ratio of about 1:1 are more commonly used. The ratio in question is determined by 31 P nmr.
  • useful ZDDPs generally exhibit a minimum value of about 10 mgKOH/g and preferably about 12 mgKOH/g. ZDDPs having a TBN of about 15 mgKOH/g are more commonly used. TBN is determined in accordance with ASTM D664.
  • ZDDPs which may be used by reference to the thermal stability of the finished hydraulic fluid in which they are included.
  • ASTM D2619 and CCM "A" thermal stability tests To meet the requirements of the ASTM D2619 test the finished fluid should give a maximum copper loss of 0.2 mg. To pass the CMC "A” test the finished fluid should give a maximum copper rod rating of 5 and a maximum sludge deposit of 25 mg/100 ml.
  • the ASTM D2619 and CCM "A” tests are well known in the art.
  • the thermal stability of the lubricant composition by post-treatment of the ZDDP component using a zinc alkanoate.
  • the alkanoate is branched on its ⁇ -carbon atom.
  • Such components are also described in European patent application no. 95306722.0.
  • the use of zinc octanoate is preferred, especially an overbased zinc octanoate such as zinc octanoate 22% which is commercially available under this designation.
  • the amine antioxidant is phenyl- ⁇ -naphthylamine or 2,6-di-t-butyl- ⁇ -dimethylamino-p-cresol, alone or each in combination with diphenylamine. Combinations based on phenyl- ⁇ -naphthylamine and diphenylamine are preferred.
  • Preferred combinations of antioxidants include: phenyl- ⁇ -naphthylamine, diphenylamine and an ashless dithiocarbamate, such as methylene-bis(dibutyldithiocarbamate); phenyl- ⁇ -naphthylamine, diphenylamine and a phenolic antioxidant, such as 2,6-di-t-butylphenol; and phenyl- ⁇ -naphthylamine, diphenylamine and a sulphurised olefin, such as one derived from a mixture of C 16-18 isomerised ⁇ -olefins.
  • the phenyl- ⁇ -naphthylamine may be replaced by 2,6-di-t-butyl- ⁇ -dimethylamino-p-cresol.
  • Lubricating oils contemplated for use in this invention include natural lubricating oils, synthetic lubricating oils and mixtures thereof. Suitable lubricating oils also include basestocks obtained by isomerization of synthetic wax and slack wax, as well as basestocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of crude oil.
  • both the natural and synthetic lubricating oils will each have a kinematic viscosity ranging from about 1 x 10 -6 m 2 /s to about 40 x 10 -6 m 2 /s (about 1 to about 40 cSt) at 100°C, although typical applications will require each oil to have a viscosity ranging from about 2 x 10 -6 m 2 /s to about 8 x 10 -6 m 2 /s (about 2 to about 8 cSt) at 100°C.
  • Natural base oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal or shale.
  • the preferred natural base oil is mineral oil.
  • the mineral oils useful in this invention include all common mineral oil base stocks. This would include oils that are naphthenic or paraffinic in chemical structure. Oils that are refined by conventional methodology using acid, alkali, and clay or other agents such as aluminum chloride, or they may be extracted oils produced, for example, by solvent extraction with solvents such as phenol, sulphur dioxide, furfural, dichlordiethyl ether, etc. They may be hydrotreated or hydro-refined, dewaxed by chilling or catalytic dewaxing processes, or hydrocracked. The mineral oil may be produced from natural crude sources or be composed of isomerized wax materials or residues of other refining processes.
  • the mineral oils will have kinematic viscosities of from 2 x 10 -6 m 2 /s to 12 x 10 -6 m 2 /s (2 cSt to 12 cSt) at 100°C.
  • the preferred mineral oils have kinematic viscosities of from 3 x 10 -6 m 2 /s to 10 x 10 -6 m 2 /s (3 to 10 cSt), and most preferred are those mineral oils with viscosities of 5 x 10 -6 m 2 /s to 9 x 10 -6 m 2 /s (5 to 9 cSt) at 100°C.
  • Synthetic lubricating oils useful in this invention include hydrocarbon oils and halo-substituted hydrocarbon oils such as oligomerized, polymerized, and interpolymerized olefins [e.g., polybutylenes, polypropylenes, propylene, isobutylene copolymers, chlorinated polylactenes, poly(1-hexenes), poly(1-octenes), and mixtures thereof]; alkylbenzenes [e.g., polybutylenes, polypropylenes, propylene, isobutylene copolymers, chlorinated polylactenes, poly(1-hexenes), poly (1-octenes) and mixtures thereof]; alkylbenzenes [e.g., dodecyl-benzenes, tetradecylbenzenes, dinonyl-benzenes and di(2-ethylhexyl)benzene]; polypheny
  • Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof where the terminal hydroxyl groups have been modified by esterification or etherification.
  • This class of synthetic oils is exemplified by: polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polypropylene glycol having a molecular weight of 100-1500); and mono- and poly-carboxylic esters thereof (e.g., the acetic acid esters, mixed C 3 -C 8 fatty acid esters, and C 12 oxo acid diester of tetraethylene glycol).
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids and alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoethers and propylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, lino
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl isophthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid.
  • a preferred type of oil from this class of synthetic oils are adipates of C 4 to C 12 alcohols.
  • Esters useful as synthetic lubricating oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils. These oils include tetra-ethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(dimethyl)-siloxanes and poly (methylphenyl) siloxanes.
  • oils include tetra-ethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethyl
  • Other synthetic lubricating oils include liquid esters of phosphorus containing acids (e.g., tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid), polymeric tetra-hydrofurans and poly- ⁇ -olefins.
  • liquid esters of phosphorus containing acids e.g., tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid
  • polymeric tetra-hydrofurans e.g., tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid
  • polymeric tetra-hydrofurans e.g., polymeric tetra-hydrofurans and poly- ⁇ -olefins.
  • the lubricating base oils may be derived from refined, re-refined oils, or mixtures thereof.
  • Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment.
  • Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
  • Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties.
  • Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art.
  • Re-refined oils are obtained by treating used oils in processes similar to those used to obtain the refined oils. These re-refined oils are also known as reclaimed or reprocessed oils and are often additionally processed by techniques for removal of spent additives and oils breakdown products.
  • White oils, as taught in U.S. 5,736,490 may also be used as the base oil, especially for turbine applications.
  • the base oil is a Group I, Group II or Group III base oil.
  • the use of Group II or Group III base oils is preferred.
  • the American Petroleum Institute has categorized these different basestock types as follows: Group I, >0.03 wt% sulphur, and/or ⁇ 90 vol% saturates, viscosity index between 80 and 120; Group II, ⁇ 0.03 wt% sulphur, and ⁇ 90 vol% saturates, viscosity index between 80 and 120; Group III, ⁇ 0.03 wt% sulphur, and ⁇ 90 vol% saturates, viscosity index >120; Group IV, all polyalphaolefins. Hydrotreated basestocks and catalytically dewaxed basestocks, because of their low sulphur and aromatics content, generally fall into the Group II and Group III categories.
  • Polyalphaolefins (Group IV basestocks) are synthetic base oils prepared from various ⁇ -olefins and are substantially free of sulphur and aromatics.
  • the lubricant composition of the present invention may be prepared by simple blending of the various components with a suitable base oil.
  • the additive components used in practice of this invention may be provided as a concentrate for formulation into a lubricant composition ready for use.
  • the concentrate may comprise, in addition to the fluid components, a solvent or diluent for the fluid components.
  • the solvent or diluent should be miscible with and/or capable of dissolving in the base oil to which the concentrate is to be added. Suitable solvents and diluents are well known.
  • the solvent or diluent may be the base oil of the lubricating oil composition itself.
  • the concentrate may suitably include any of the conventional additives used in lubricating oils compositions. The proportions of each component in the concentrate are controlled by the intended degree of dilution, though top treatment of the formulated fluid is possible.
  • additives commonly used in lubricants/fluids for turbine, antiwear hydraulic and industrial applications may be included in the compositions or concentrates of the present invention. These include demulsifiers, corrosion inhibitors, dispersants, sulphur- and/or phosphorus-containing antiwear agents and rust inhibitors. These additives, when present, are used in amounts conventionally used in such applications. Some additives may be included in the concentrate and some added to the fully formulated lubricant/fluid as a top-treat.
  • a lubricant composition was prepared by blending components in the proportions specified in the following table.
  • Component % by weight Corrosion inhibitor 0.0085 Detergent 0.050 Rust inhibitor 0.051 Phenolic antioxidant 0.013 Demulsifier 0.0064 Process oil 0.0111 *ZDDP 0.510 Base oil Balance to 100%
  • the ZDDP was zinc di(2-ethylhexyl)dithiophosphate.
  • the base oil used was either a Group I or Group II base oil. Further details of this are given in the following table.

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EP98309774A 1998-11-30 1998-11-30 Lubricant compositions exhibiting extended oxidation stability Withdrawn EP1006173A1 (en)

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Application Number Priority Date Filing Date Title
EP98309774A EP1006173A1 (en) 1998-11-30 1998-11-30 Lubricant compositions exhibiting extended oxidation stability
CA002287726A CA2287726C (en) 1998-11-30 1999-10-28 Lubricant compositions exhibiting extended oxidation stability
SG1999005402A SG77271A1 (en) 1998-11-30 1999-11-01 Lubricant compositions exhibiting extended oxidation stability
AU59364/99A AU5936499A (en) 1998-11-30 1999-11-11 Lubricant compositions exhibiting extended oxidation stability
JP11332670A JP2000160182A (ja) 1998-11-30 1999-11-24 向上した酸化安定性を示す潤滑剤組成物
KR1019990053876A KR20000035777A (ko) 1998-11-30 1999-11-30 증대된 산화 안정성을 나타내는 윤활 조성물
CN991228529A CN1216134C (zh) 1998-11-30 1999-11-30 显示持久氧化稳定性的润滑剂组合物
BR9905759-0A BR9905759A (pt) 1998-11-30 1999-11-30 Composições lubrificantes exibindo estabilidade a oxidação prolongada

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US6852680B2 (en) 2001-10-26 2005-02-08 Ethyl Corporation Dithiocarbamates containing alkylthio and hydroxy substituents
WO2006065344A1 (en) 2004-12-10 2006-06-22 Chemtura Corporation Lubricant compositions stabilized with multiple antioxidants
WO2009009293A1 (en) * 2007-07-06 2009-01-15 Chemtura Corporation Lubricant compositions stabilized with styrenated phenolic antioxidant
WO2010008694A1 (en) 2008-07-14 2010-01-21 Chemtura Corporation Liquid additives for the stabilization of lubricant compositions
US20110030269A1 (en) * 2009-08-05 2011-02-10 David Eliezer Chasan Lubricant composition
WO2012058021A2 (en) * 2010-10-28 2012-05-03 Chevron U.S.A. Inc. Compressor oils having improved oxidation resistance
RU2505590C1 (ru) * 2012-09-06 2014-01-27 Общество с ограниченной ответственностью "ЛЛК-Интернешнл" Смазочное масло для газовых турбин
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US8748357B2 (en) 2008-07-15 2014-06-10 Exxonmobil Research And Engineering Company Method for stabilizing diesel engine lubricating oil against degradation by biodiesel fuel
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US20150133352A1 (en) * 2012-06-06 2015-05-14 Vanderbilt Chemicals, Llc Fuel efficient lubricating oils
RU2505590C1 (ru) * 2012-09-06 2014-01-27 Общество с ограниченной ответственностью "ЛЛК-Интернешнл" Смазочное масло для газовых турбин
WO2015085083A1 (en) * 2013-12-06 2015-06-11 Basf Se Composition and method of forming the same
US9982211B2 (en) 2013-12-06 2018-05-29 Basf Se Composition and method of forming the same
US10704007B2 (en) 2013-12-06 2020-07-07 Basf Se Composition and method of forming the same
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US9783759B2 (en) 2014-09-04 2017-10-10 Vanderbilt Chemicals, Llc Liquid ashless antioxidant additive for lubricating compositions
EP3189125A4 (en) * 2014-09-04 2018-01-24 Vanderbilt Chemicals, LLC Liquid ashless antioxidant additive for lubricating compositions
CN113913228A (zh) * 2021-11-12 2022-01-11 福建优立盛油脂有限公司 一种用于锂基润滑脂的抗氧化剂组合物
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JP2000160182A (ja) 2000-06-13
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CA2287726A1 (en) 2000-05-30
CA2287726C (en) 2003-07-08

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