US3193500A - Extreme pressure lubricant - Google Patents
Extreme pressure lubricant Download PDFInfo
- Publication number
- US3193500A US3193500A US202656A US20265662A US3193500A US 3193500 A US3193500 A US 3193500A US 202656 A US202656 A US 202656A US 20265662 A US20265662 A US 20265662A US 3193500 A US3193500 A US 3193500A
- Authority
- US
- United States
- Prior art keywords
- dithiophosphate
- carbon atoms
- molybdenum
- alkyl
- extreme pressure
- 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.)
- Expired - Lifetime
Links
- 239000000314 lubricant Substances 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims description 39
- 230000001050 lubricating effect Effects 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 32
- 125000000217 alkyl group Chemical group 0.000 description 27
- -1 caproylphenyl Chemical group 0.000 description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 22
- 229910052750 molybdenum Inorganic materials 0.000 description 22
- 239000011733 molybdenum Substances 0.000 description 22
- 239000010687 lubricating oil Substances 0.000 description 18
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 14
- 229910052721 tungsten Inorganic materials 0.000 description 13
- 239000010937 tungsten Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 11
- 239000003921 oil Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 125000000753 cycloalkyl group Chemical group 0.000 description 8
- 239000011593 sulfur Chemical group 0.000 description 8
- 229910052717 sulfur Chemical group 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000005037 alkyl phenyl group Chemical group 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000003657 tungsten Chemical class 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 231100000241 scar Toxicity 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000005069 Extreme pressure additive Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WIDQNNDDTXUPAN-UHFFFAOYSA-I tungsten(v) chloride Chemical compound Cl[W](Cl)(Cl)(Cl)Cl WIDQNNDDTXUPAN-UHFFFAOYSA-I 0.000 description 2
- 208000032544 Cicatrix Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- DXECDJILNIXBML-UHFFFAOYSA-N bis(6-methylheptoxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)CCCCCOP(S)(=S)OCCCCCC(C)C DXECDJILNIXBML-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- YHNUQWOWFPKIPU-UHFFFAOYSA-N cyclohexyloxy-cyclohexylsulfanyl-hydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound C1CCCCC1SP(=S)(O)OC1CCCCC1 YHNUQWOWFPKIPU-UHFFFAOYSA-N 0.000 description 1
- NFMSEGPNBWIRTB-UHFFFAOYSA-N decoxy-decylsulfanyl-hydroxy-sulfanylidene-lambda5-phosphane Chemical compound CCCCCCCCCCOP(O)(=S)SCCCCCCCCCC NFMSEGPNBWIRTB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000001545 dialkoxyaryl group Chemical group 0.000 description 1
- XPRULOZMJZDZEF-UHFFFAOYSA-N dibutoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCOP(S)(=S)OCCCC XPRULOZMJZDZEF-UHFFFAOYSA-N 0.000 description 1
- JWOPLIXEIJVTGP-UHFFFAOYSA-N dihexadecoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCCCCCCCCCOP(S)(=S)OCCCCCCCCCCCCCCCC JWOPLIXEIJVTGP-UHFFFAOYSA-N 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- GXUZYWRVKRMDJC-UHFFFAOYSA-N dodecoxy-dodecylsulfanyl-hydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCCCCCOP(O)(=S)SCCCCCCCCCCCC GXUZYWRVKRMDJC-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- QYLZRNUGXYADKP-UHFFFAOYSA-N hexadecoxy-hexadecylsulfanyl-hydroxy-sulfanylidene-lambda5-phosphane Chemical compound CCCCCCCCCCCCCCCCOP(O)(=S)SCCCCCCCCCCCCCCCC QYLZRNUGXYADKP-UHFFFAOYSA-N 0.000 description 1
- XVLAAJGISPCYOA-UHFFFAOYSA-N hydroxy-octadecoxy-octadecylsulfanyl-sulfanylidene-lambda5-phosphane Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(=S)SCCCCCCCCCCCCCCCCCC XVLAAJGISPCYOA-UHFFFAOYSA-N 0.000 description 1
- GSJYSUQLJKYYRS-UHFFFAOYSA-N hydroxy-octoxy-octylsulfanyl-sulfanylidene-lambda5-phosphane Chemical compound CCCCCCCCOP(O)(=S)SCCCCCCCC GSJYSUQLJKYYRS-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- DRWPVEQJXKTFFL-UHFFFAOYSA-M sodium;(4-methylphenoxy)-(4-methylphenyl)sulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Na+].C1=CC(C)=CC=C1OP([O-])(=S)SC1=CC=C(C)C=C1 DRWPVEQJXKTFFL-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- SXYOAESUCSYJNZ-UHFFFAOYSA-L zinc;bis(6-methylheptoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C.CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C SXYOAESUCSYJNZ-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
-
- 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
- C10M137/10—Thio derivatives
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
-
- 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
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
-
- 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
- C10M2223/045—Metal containing thio derivatives
-
- 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
- C10N2010/12—Groups 6 or 16
-
- 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
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- Patent No. 3,068,259 dated Dec. 11, 1962. Divided and this application .l'une 13, 1962, Ser. No. 202,656
- This invention relates to certain compounds of molybdenum and tungsten having particular utility as additives in lubricating oils and more particularly to lubricating oil compositions containing the same.
- This invention is based upon the discovery that certain compounds of molybdenum and tungsten which when blended in minor proportions with lubricating oils impart to the resulting composition significantly improved extreme pressure characteristics.
- the compounds which have been found particularly useful as addition agents in lubricating oils according to the invention are molybdenum and tungsten salts of organic substituted dithiophosphoric acids having the general formula:
- R is an oil-solubilizing organic radical such as aryl, alkyl, alkoxyalkyl, aralkyl, cycloalkyl, aryloxyalkyl, acylaryl and alkoxyaryl radicals; M is molybdenum or tungsten and X is a halogen or sulfur, y is the valency of the metal M, z is an integer of at least one but less than the valency of the metal M and represents the number of dithiophosphate ester groups in the product, and v is the valency of X.
- R is an oil-solubilizing organic radical such as aryl, alkyl, alkoxyalkyl, aralkyl, cycloalkyl, aryloxyalkyl, acylaryl and alkoxyaryl radicals
- M is molybdenum or tungsten and X is a halogen or sulfur
- y is the valency of the metal M
- z is an integer of
- R in the above general formula is selected from the group consisting of phenyl, caproylphenyl, alkyl, cycloalkyl, alkylphenyl, alkylphenoxyalkyl and alkoxyphenyl radicals wherein said alkyl radical contains 4 to 30 carbon atoms, said cycloalkyl phatic group are also useful such as for example diphenyl radical contains 5 to 6 carbon atoms, the alkyl portion of said alkylphenyl radical contains 1 to 8 carbon atoms, the alkyl portions of said alkylphenoxyalkyl radical contain 2 to 5 carbon atoms and the alkyl portion of said alkoxyphenyl radical contains 2 to 4 carbon atoms.
- compounds of this class include a molybdenum or tungsten salt of dialkyl dithiophosphates and dicycloalkyl dithiophosphates such as dibutyl dithiophosphate, butyl hexyl dithiophosphate, amyl octyl dithiophosphate, dihexyl dithiophosphate, di-n-octyl dithiophosphate, diisooctyl dithiophosphate, didecyl dithiophosphate, dilauryl dithiophosphate, dihexadecyl dithiophosphate, dioctadecyl dithiophosphate, dicyclopentyl dithiophosphate, dicyclohexyl dithiophosphate, and so forth.
- dialkyl dithiophosphates and dicycloalkyl dithiophosphates such as dibutyl dithiophosphate, butyl hexyl dithiophosphate, amyl
- dialkyl dithiophosphates in which the alkyl group has at least 4 carbon atoms and preferably more than 6 carbon atoms as for example from 6 to 30 are preferred since the longer alkyl chains tend to increase the solubility of the dithio phosphates in lubricating oils.
- the diaryloxyalkyl dithiophosphates such as di-2,4-dibutylphenoxyethyl dithiophosphate, di-2,4-diamylphen0xypropyl dithiophosphate; the diacylaryl dithiophosphates such as dicaproylphenyl dithiophosphate, and the dialkoxyaryl dithiophosphates such as diethoxyphenyl dithiophosphate, dibutoxyphenyl dithiophosphate and the like are likewise useful.
- the organic substituents of the compounds are not critical and can be selected from a variety of organic radicals on the basis of their ability to impart oil-solubility to the compounds.
- the halogen containing molybdenum and tungsten salts which are utilized in compositions of the invention are prepared by reacting the desired metal halide with an alkali metal salt of a partial ester of dithiophosphoric acid.
- Methods of preparing the partial esters of dithiophosphoric acids and the alkali metal salts thereof are known to the art.
- an alkali metal salt of an ester of dithiophosphoric acid can be prepared by first reacting an appropriate alcohol or hydroxyaromatic compound with phosphorus pentasulfide and then reacting the partially esterified acid thus formed with sodium or potassium hydroxide.
- the amounts of the alkali metal salt of the dithiophosphate ester and of the molybdenum or tungsten halide can be varied considerably; however, in all cases the mols of dithiophosphate compound employed will be less than the number required for reaction with all of the halogen atoms.
- the principal reaction involved in preparing the compounds useful in compositions of the invention can probably be expressed by the following illustrative equation, although it is understood that it is not desired to be bound by any theory of reaction:
- R, M, y and 1 have the meaning indicated previously and X is a halogen.
- Sulfur can be made to replace part or all of the halogen in the above reaction product simply by causing hydrogen sulfide to react therewith in the presence of a tertiary amine or other acid scavenger.
- EXAMPLE 1H Fifty grams (0.04 mol) of the molybdenum tris-(diisooctyl dithiophosphate) dichloride as prepared in Example I is dissolved in 100 milliliters of benzene containing approximately 0.08 mol of pyridine. Hydrogen sulfide is then bubbled slowly through the solution for about 1 hour. After standing for approximately one hour, the mixture is filtered and the solvent is removed from the filtrate under reduced pressure. Upon analysis of the final product the sulfur content was found to have increased from 13.06 percent to 16.57 percent while the chlorine content decreased from'9.70 percent to 3.58 percent. The product is a brown liquid, soluble in common organic solvents.
- the sodium chloride which is formed in the reaction is filtered 0d.
- the carbon tetrachloride is distilled ,oif to leave tungsten tris-(didecyl dithiophosphate) dichloride.
- EXAMPLE VI To a solution of 528 grams (1.0 mol) of sodium dioctylphenyl dithiophosphate in 1000 milliliters of carbon tetrachloride is added 110 grams (0.31 mol) of tungsten pentachloride in small portions over a two hour period. The temperature is maintained at approximately to C. during the addition. The reaction mixture is permitted to stand for a time and the sodium chloride which is formed in the reaction is filtered off. The carbon tetrachloride is distilled 01f to leave tungsten tris-(dioctylphenyl dithiophosphate) dichloride.
- EXAMPLE VII 4 EXAMPLE VIII Forty-seven grams (0.04 mol) of molybdenum tris- (dicresyl dithiophosphate) dichloride as prepared in Example IV is dissolved in milliliters of benzene containing approximately 0.08 mol of pyridine. Hydrogen sulfide is bubbled through the solution until precipitation of pyridine hydrochloride is cornplete. After standing for approximately one hour, the mixture is filtered and the solvent is removed from the filtrate under reduced pressure to leave molybdenum tris-(dicresyl dithiophosphate) sulfide.
- the molybdenum and tungsten organic substituted dithiophosphates disclosed hereinabove are particularly useful as additives to lubricating oils to improve the extreme pressure characteristics thereof.
- the .additives are employed in lubricating oil compositions preferably in amounts ranging from about 0.05 to about 5 percent or more by weight.
- the exact amount of the additives to be employed will depend to a great extent upon the purpose for which the oil is intended. For example, an oil intended for use at high temperatures and high pressures should contain more of the additive as compared to the amounts required for an oil intended for less severe usage.
- the lubricating oil to which the additives are added to form a lubricating composition having improved extreme pressure characteristics can be any mineral oil of lubricating viscosity such as naphthenic base, parafiinic base and mixed base lubricating oils.
- Synthetic lubricating oils such as polymerized olefins, organic esters such as di-Z-ethyl hexyl sebacate and di-Z-ethylhexyl azelate and the like, can also be used as the base oil to form a lubricating composition in accordance with the invention.
- blends of oils of suitable viscosity may be employed instead of a single oil.
- the additives disclosed herein can be added to the lubricating oil base directly or in the form of a mineral oil concentrate in an amount to give the desired concentration in the final lubricating composition. Slight heating of the mixture may be advantageously employed to facilitate blending of the additives in the composition.
- a fourth steel ball in a rotating spindle is placed so that itis entirely supported by the other three balls forming a pyramid.
- the three immobile steel balls and the rotating single steel ball are forced into contact with each other in response to a vertically applied load.
- Sufficient test lubricant is poured into a test cup to cover the three lower balls at a predetermined depth.
- the spindle is revolved at 1800 r.p.m. while electrical heating units heat the oil to a temperature of 248 F.
- wear is measured by examination of the scars on the clean surfaces of the three stationaryballs; the two maximum right angle diameters of each wear scar being measured to the closest 0.01 millimeter and averaged.
- the antiwear properties are rated by the difference in the scar diameters.
- curve A shows the results obtained with the oil alone.
- Curves B and C represent the results obtained with zinc diisooctyl dithiophosphate, a commercially available extreme pressure additive at concentrations of 0.5 and 1.0 percent respectively.
- Curves D and E represent the results obtained with the lubricating oil composition containing molybdenum tris-(diisooctyl dithiophosphate) dichloride at concentrations of 0.5 and 1.0 percent by Weight respectively.
- Curves and G represent the results obtained with a lubricating 011 composition containing the reaction product of Example IE1 at concentrations of 0.5 and 1.0 percent by Weight respectively.
- additives disclosed herein there may be present in the lubricating composition of this invention other conventional additives such as pour point depressants, anti-rust agents, antioxidants, viscosity index improvers and the like.
- R-O s X1 R-O S 1 wherein R is selected from the group consisting of phenyl, caproylphenyl, alkyl, cycloalkyl, alkyphenyl, alkylphenoxyalkyl and alkoxyphenyl radicals wherein said alkyl radical contains 4 to 30 carbon atoms, said cycloalkyl radical contains 5 to 6 carbon atoms, the alkyl portion of said alkylphenyl radical contains 1 to 8 carbon atoms, the alkyl portions of said alkylphenoxyalkyl radical contain 2 to 5 carbon atoms and the alkyl portion of said alkoxyphenyl radical contains 2 to 4 carbon atoms; M is a metal selected from the group consisting of molybdenum and tungsten; X is an element selected from the group consisting of chlorine and sulfur; y is the valency of the metal M; z is an integer of at least one but less than the valency of the metal M; and v is the valency of
- R is selected from the group consisting of phenyl, caproylphenyl, alkyl, cycloalkyl, alkylphenyl, alkylphenoxyalkyl and alkoxyphenyl radicals wherein said alkyl radical contains 4 to 30 carbon atoms, said cycloalkyl radical contains 5 to 6 carbon atoms, the alkyl portion of said alkylphenyl radical contains 1 to 8 carbon atoms, the alkyl portions of said alkylphenoxyalkyl radical contain 2 to 5 carbon atoms and the alkyl portion of said alkoxyphenyl radical contains 2 to 4 carbon atoms; M is molybdenum; X is sulfur; y is the valency of molybdenum; z is an integer of at least one but less than the valency of molybdenum; and v is the valency of sulfur.
- R is selected from the group consisting of phenyl, caproylphenyl, alkyl, cycloalkyl, alkylphenyl, alkylphenoxyalkyl and alkoxyphenyl radicals wherein said alkyl radical contains 4 to 30 carbon atoms, said cycloalkyl radical contains 5 to 6 carbon atoms, the alkyl portion of said alkylphenyl radical contains 1 to 8 carbon atoms, the alkyl portions of said alkylphenoxyalkyl radical contain 2 to 5 carbon atoms and the alkyl portion of said alkoxyphenyl radical contains 2 to 4 carbon atoms; M is tungsten; X is sulfur; y is the valency of tungsten; z is an integer of at least one but less than the valency of tungsten; and v is the valency of sulfur.
- a lubricating composition comprising a major proportion of a lubricating oil and a minor amount suificient to confer improved extreme pressure characteristics to the composition of a compound having the formula wherein R is selected from the group consisting of phenyl,
- R is selected from the group consisting of phenyl, caproylphenyl, alkyl, cycloalkyl, alkylphenyl, alkylphenoxyalkyl and alkoxyphenyl radicals wherein said alkyl radical contains 4 to 30 carbon atoms, said cycloalkyl radical contains 5 to 6 carbon atoms, the alkyl portion of said alkylphenyl radical contains 1 to 8 carbon atoms, the alkyl portions of said alkylphenoxyalkyl radical contain 2 to 5 carbon atoms and the alkyl portion of said alkoxyphenyl radical contains 2 to 4 carbon atoms; M is tungsten; X is chlorine; y is the valency of tungsten; z is an integer of at least one but less than the valency of tungsten; and v is the valency of chlorine;
- a lubricating composition comprising a major pro- 8 portion of a lubricating oil and a minor amount sufficient to confer improved extreme pressure characteristics to the composition of molybderiuni' tris-(diisooctyl dithiophosphate) dichloride.
- a lubricating composition comprising a major proportion of a lubricating oil and a minor amount sufiicient to confer improved extreme pressure characteristics to the composition of molybdenum tris-(diisooctyl dithiophos-' phate) sulfide.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Description
July 6, 1965 R. J. HARTLE EXTREME PRESSURE LUBRICANT Original Filed Feb. 12, 1959 0 6 6/8 0 E 6F M V w A 0 3 w m 0 6 4 2 0 4 2 0 0 0 0 0 0 WQHNNMQ 151/543 4040, x01. oaeAMs IN VENTOR. 05527 J. HARTLE ATTORNEY.
United States Patent 3,193,500 EXTREME PRESSURE LUBRICANT Robert J. l-llartle, Gihsonia, Pan, nssignor to Gulf Research & Development Company, Pittsburgh, Pa., a corporation of Delaware Original application Feb. 12, 1959, Ser. No. 792,883, new
Patent No. 3,068,259, dated Dec. 11, 1962. Divided and this application .l'une 13, 1962, Ser. No. 202,656
8 Claims. (Cl. 252-32.7)
This application is a division of application Serial No. 792,883, filed February 12, 1959, now US. Patent No. 3,068,259.
This invention relates to certain compounds of molybdenum and tungsten having particular utility as additives in lubricating oils and more particularly to lubricating oil compositions containing the same.
As is well known to those skilled in the art, uncompounded lubricating oils frequently fail to provide satisfactory lubrication to surfaces engaging under extreme pressure. The failure of lubricants to provide proper lubrication under high operating pressures results in the rubbing surfaces of machinery suffering considerable Wear even to such an extent where they must be replaced.
This invention is based upon the discovery that certain compounds of molybdenum and tungsten which when blended in minor proportions with lubricating oils impart to the resulting composition significantly improved extreme pressure characteristics.
The compounds which have been found particularly useful as addition agents in lubricating oils according to the invention are molybdenum and tungsten salts of organic substituted dithiophosphoric acids having the general formula:
RO\ s /P\ :IMX R-O S v in which R is an oil-solubilizing organic radical such as aryl, alkyl, alkoxyalkyl, aralkyl, cycloalkyl, aryloxyalkyl, acylaryl and alkoxyaryl radicals; M is molybdenum or tungsten and X is a halogen or sulfur, y is the valency of the metal M, z is an integer of at least one but less than the valency of the metal M and represents the number of dithiophosphate ester groups in the product, and v is the valency of X. More specifically, R in the above general formula is selected from the group consisting of phenyl, caproylphenyl, alkyl, cycloalkyl, alkylphenyl, alkylphenoxyalkyl and alkoxyphenyl radicals wherein said alkyl radical contains 4 to 30 carbon atoms, said cycloalkyl phatic group are also useful such as for example diphenyl radical contains 5 to 6 carbon atoms, the alkyl portion of said alkylphenyl radical contains 1 to 8 carbon atoms, the alkyl portions of said alkylphenoxyalkyl radical contain 2 to 5 carbon atoms and the alkyl portion of said alkoxyphenyl radical contains 2 to 4 carbon atoms. More specifically, compounds of this class include a molybdenum or tungsten salt of dialkyl dithiophosphates and dicycloalkyl dithiophosphates such as dibutyl dithiophosphate, butyl hexyl dithiophosphate, amyl octyl dithiophosphate, dihexyl dithiophosphate, di-n-octyl dithiophosphate, diisooctyl dithiophosphate, didecyl dithiophosphate, dilauryl dithiophosphate, dihexadecyl dithiophosphate, dioctadecyl dithiophosphate, dicyclopentyl dithiophosphate, dicyclohexyl dithiophosphate, and so forth. Those dialkyl dithiophosphates in which the alkyl group has at least 4 carbon atoms and preferably more than 6 carbon atoms as for example from 6 to 30 are preferred since the longer alkyl chains tend to increase the solubility of the dithio phosphates in lubricating oils. The molybdenum and tungsten diaryl dithiophosphates and the diaryl dithiophosphates in which the aryl group bears an alkyl or cycloalidithiophosphate, di-2,4-diamylphenyl dithiophosphate, di- 2,4dihexylphenyl dithiophosphate, and the various di-wax substituted diaryl dithiophosphates. The diaryloxyalkyl dithiophosphates such as di-2,4-dibutylphenoxyethyl dithiophosphate, di-2,4-diamylphen0xypropyl dithiophosphate; the diacylaryl dithiophosphates such as dicaproylphenyl dithiophosphate, and the dialkoxyaryl dithiophosphates such as diethoxyphenyl dithiophosphate, dibutoxyphenyl dithiophosphate and the like are likewise useful. The organic substituents of the compounds are not critical and can be selected from a variety of organic radicals on the basis of their ability to impart oil-solubility to the compounds.
The halogen containing molybdenum and tungsten salts which are utilized in compositions of the invention are prepared by reacting the desired metal halide with an alkali metal salt of a partial ester of dithiophosphoric acid. Methods of preparing the partial esters of dithiophosphoric acids and the alkali metal salts thereof are known to the art. For example, an alkali metal salt of an ester of dithiophosphoric acid can be prepared by first reacting an appropriate alcohol or hydroxyaromatic compound with phosphorus pentasulfide and then reacting the partially esterified acid thus formed with sodium or potassium hydroxide. With regard to the proportions of reactants em ployed in the preparation of the compounds useful in compositions of the invention, the amounts of the alkali metal salt of the dithiophosphate ester and of the molybdenum or tungsten halide can be varied considerably; however, in all cases the mols of dithiophosphate compound employed will be less than the number required for reaction with all of the halogen atoms. The principal reaction involved in preparing the compounds useful in compositions of the invention can probably be expressed by the following illustrative equation, although it is understood that it is not desired to be bound by any theory of reaction:
In the above equation, R, M, y and 1 have the meaning indicated previously and X is a halogen.
, Sulfur can be made to replace part or all of the halogen in the above reaction product simply by causing hydrogen sulfide to react therewith in the presence of a tertiary amine or other acid scavenger.
The synthesis of the oil-soluble molybdenum and tungsten salts useful in compositions of the invention will be better understood from the following illustrative examples.
EXAMPLE I To a solution of 376 grams (1 mol) of sodium diisooctyl dithiophosphate in 500 milliliters of carbon tetrachloride is added 84 grams (0.31 mol) of molybdenum pentachloride in small portions over a two hour period. The temperature is maintained at approximately 55 to 60 C. during the addition. The reaction mixture is permitted to stand for a time as for example overnight, and the sodium chloride which is formed in the reaction is filtered off. The carbon tetrachloride is distilled oif to leave approximately 390 grams of molybdenum trisdiisooctyl dithiophosphate) dichloride. The product is a viscous brown liquid which turns blue on exposure to air for several hours. It is soluble in the common organic solvents.
Analysis.Calculated for Mo: 7.82 percent. for Mo: 7.78 percent.
Found 3 EXAMPLE II EXAMPLE 1H Fifty grams (0.04 mol) of the molybdenum tris-(diisooctyl dithiophosphate) dichloride as prepared in Example I is dissolved in 100 milliliters of benzene containing approximately 0.08 mol of pyridine. Hydrogen sulfide is then bubbled slowly through the solution for about 1 hour. After standing for approximately one hour, the mixture is filtered and the solvent is removed from the filtrate under reduced pressure. Upon analysis of the final product the sulfur content was found to have increased from 13.06 percent to 16.57 percent while the chlorine content decreased from'9.70 percent to 3.58 percent. The product is a brown liquid, soluble in common organic solvents.
EXAMPLE IV To a solution of 330 grams (1.0 mol) of sodium dicresyl dithiophosphate in 1000 milliliters of carbon tetrachloride is added 84 grams (0.31 mol) of molybdenum To a solution'of 432 grams (1.0 mol) of sodium didecyl dithiophosphate in 1000 milliliters of carbon tetrachloride is added 110 grams (0.31 mol) of tungsten pentachloride in small portions over a two hour period. The temperature is maintained at approximately 55 to 60 C. during the addition. The reaction mixture is permitted to stand for atime, as for example overnight, and
the sodium chloride which is formed in the reaction is filtered 0d. The carbon tetrachloride is distilled ,oif to leave tungsten tris-(didecyl dithiophosphate) dichloride.
EXAMPLE VI To a solution of 528 grams (1.0 mol) of sodium dioctylphenyl dithiophosphate in 1000 milliliters of carbon tetrachloride is added 110 grams (0.31 mol) of tungsten pentachloride in small portions over a two hour period. The temperature is maintained at approximately to C. during the addition. The reaction mixture is permitted to stand for a time and the sodium chloride which is formed in the reaction is filtered off. The carbon tetrachloride is distilled 01f to leave tungsten tris-(dioctylphenyl dithiophosphate) dichloride.
EXAMPLE VII 4 EXAMPLE VIII Forty-seven grams (0.04 mol) of molybdenum tris- (dicresyl dithiophosphate) dichloride as prepared in Example IV is dissolved in milliliters of benzene containing approximately 0.08 mol of pyridine. Hydrogen sulfide is bubbled through the solution until precipitation of pyridine hydrochloride is cornplete. After standing for approximately one hour, the mixture is filtered and the solvent is removed from the filtrate under reduced pressure to leave molybdenum tris-(dicresyl dithiophosphate) sulfide.
The molybdenum and tungsten organic substituted dithiophosphates disclosed hereinabove are particularly useful as additives to lubricating oils to improve the extreme pressure characteristics thereof. When employed for this purpose, the .additives are employed in lubricating oil compositions preferably in amounts ranging from about 0.05 to about 5 percent or more by weight. The exact amount of the additives to be employed will depend to a great extent upon the purpose for which the oil is intended. For example, an oil intended for use at high temperatures and high pressures should contain more of the additive as compared to the amounts required for an oil intended for less severe usage.
The lubricating oil to which the additives are added to form a lubricating composition having improved extreme pressure characteristics can be any mineral oil of lubricating viscosity such as naphthenic base, parafiinic base and mixed base lubricating oils. Synthetic lubricating oils such as polymerized olefins, organic esters such as di-Z-ethyl hexyl sebacate and di-Z-ethylhexyl azelate and the like, can also be used as the base oil to form a lubricating composition in accordance with the invention. If desired, blends of oils of suitable viscosity may be employed instead of a single oil.
To prepare an improved lubricating composition in accordance with the invention the additives disclosed herein can be added to the lubricating oil base directly or in the form of a mineral oil concentrate in an amount to give the desired concentration in the final lubricating composition. Slight heating of the mixture may be advantageously employed to facilitate blending of the additives in the composition.
To demonstrate the effectiveness of the molybdenum and tungsten salts of the type described above in mineral oil compositions contemplated by this invention, several comparative tests were conducted with a mineral oil alone and with the same oil blended with a commercially available extreme pressure additive. The mineral :oil employed had the following inspection:
A four ball wear test was conducted as follows:
Three steel balls are securely fastened so that rotation is impossible. A fourth steel ball in a rotating spindle is placed so that itis entirely supported by the other three balls forming a pyramid. The three immobile steel balls and the rotating single steel ball are forced into contact with each other in response to a vertically applied load. Sufficient test lubricant is poured into a test cup to cover the three lower balls at a predetermined depth. The spindle is revolved at 1800 r.p.m. while electrical heating units heat the oil to a temperature of 248 F. At the conclusion of the test, wear is measured by examination of the scars on the clean surfaces of the three stationaryballs; the two maximum right angle diameters of each wear scar being measured to the closest 0.01 millimeter and averaged. The antiwear properties are rated by the difference in the scar diameters.
Table I Percent Lever load Average Compound added concen- (kilograms) scar tration diameter il lone O 10 0.56 None a 20 0.72
30 1. Z iisooct l dithio hosphate-.. 0.5 20 0.
m0 d y p 0.5 30 0. 40 0. 40 0. 65 0. 5 50 0. 89 1. 0 20 0. 30 1. 0 30 0. 35 1. O 40 0.68 a 3-22 Molybdenum tris-(diisooctyl- 0. 5
' te dichloride. 0.5 40 0.63 dithiophospha 0 5 5o 0' 70 1. 0 30 0. 65 1 0 40 0. 69 528 8'28 re ared in Exam le 0.5 i r ii p r p 0. 5 40 0. 43 0.5 50 0. 45 1. 0 30 0. 45 1. 0 40 0. 44 1. 0 50 0.48
The results recorded in Table I are shown graphically in the attached figure. Thus, curve A shows the results obtained with the oil alone. Curves B and C represent the results obtained with zinc diisooctyl dithiophosphate, a commercially available extreme pressure additive at concentrations of 0.5 and 1.0 percent respectively. Curves D and E represent the results obtained with the lubricating oil composition containing molybdenum tris-(diisooctyl dithiophosphate) dichloride at concentrations of 0.5 and 1.0 percent by Weight respectively. Curves and G represent the results obtained with a lubricating 011 composition containing the reaction product of Example IE1 at concentrations of 0.5 and 1.0 percent by Weight respectively.
The curves shown in the figure clearly show the superiority :of the lubricating compositions of this invention particularly in the upper pressure range. It will be seen also from the test results that only small amounts of the additives need be employed to obtain significant improvement in the extreme pressure characteristics of the lubricating composition.
In addition to the additives disclosed herein, there may be present in the lubricating composition of this invention other conventional additives such as pour point depressants, anti-rust agents, antioxidants, viscosity index improvers and the like.
It is apparent from the foregoing description that the invention provides novel lubricating compositions which are eminently satisfactory for use as lubricants in applications where high pressures and temperatures are encountered.
Those modifications and equivalents which fall within the spirit of the invention and the scope of the appended claims are to be considered part of the invention.
I claim: a;
1. A lubricating composition comprising a major proportion of a lubricating oil and a minor amount sufiicient to confer improved extreme pressure characteristics to the composition of a compound having the formula:
R-O s X1 R-O S 1 wherein R is selected from the group consisting of phenyl, caproylphenyl, alkyl, cycloalkyl, alkyphenyl, alkylphenoxyalkyl and alkoxyphenyl radicals wherein said alkyl radical contains 4 to 30 carbon atoms, said cycloalkyl radical contains 5 to 6 carbon atoms, the alkyl portion of said alkylphenyl radical contains 1 to 8 carbon atoms, the alkyl portions of said alkylphenoxyalkyl radical contain 2 to 5 carbon atoms and the alkyl portion of said alkoxyphenyl radical contains 2 to 4 carbon atoms; M is a metal selected from the group consisting of molybdenum and tungsten; X is an element selected from the group consisting of chlorine and sulfur; y is the valency of the metal M; z is an integer of at least one but less than the valency of the metal M; and v is the valency of X.
2. The lubricating composition of claim 1 wherein the said extreme pressure improvement additive is present in an amount from about 0.05 to about 5 percent by weight.
3. A lubricating composition comprising a major proportion of a lubricating oil and a minor amount suflicient to confer improved extreme pressure characteristics to the composition of a compound having the formula:
iii
wherein R is selected from the group consisting of phenyl, caproylphenyl, alkyl, cycloalkyl, alkylphenyl, alkylphenoxyalkyl and alkoxyphenyl radicals wherein said alkyl radical contains 4 to 30 carbon atoms, said cycloalkyl radical contains 5 to 6 carbon atoms, the alkyl portion of said alkylphenyl radical contains 1 to 8 carbon atoms, the alkyl portions of said alkylphenoxyalkyl radical contain 2 to 5 carbon atoms and the alkyl portion of said alkoxyphenyl radical contains 2 to 4 carbon atoms; M is molybdenum; X is sulfur; y is the valency of molybdenum; z is an integer of at least one but less than the valency of molybdenum; and v is the valency of sulfur.
4. A lubricating composition comprising a major proportion of a lubricating oil and a minor amount snfiicient to confer improved extreme pressure characteristics to the composition of a compound having the formula:
YIZ
wherein R is selected from the group consisting of phenyl, caproylphenyl, alkyl, cycloalkyl, alkylphenyl, alkylphenoxyalkyl and alkoxyphenyl radicals wherein said alkyl radical contains 4 to 30 carbon atoms, said cycloalkyl radical contains 5 to 6 carbon atoms, the alkyl portion of said alkylphenyl radical contains 1 to 8 carbon atoms, the alkyl portions of said alkylphenoxyalkyl radical contain 2 to 5 carbon atoms and the alkyl portion of said alkoxyphenyl radical contains 2 to 4 carbon atoms; M is tungsten; X is sulfur; y is the valency of tungsten; z is an integer of at least one but less than the valency of tungsten; and v is the valency of sulfur.
5. A lubricating composition comprising a major proportion of a lubricating oil and a minor amount suificient to confer improved extreme pressure characteristics to the composition of a compound having the formula wherein R is selected from the group consisting of phenyl,
caproylphenyl, alkyl, cycloalkyl, alkylphenyl, alkylphenoxyalkyl and alkoxyphenyl radicals wherein said alkyl radical contains 4 to 30 carbon atoms, said cycloal'kyl radical contains 5 to 6 carbon atoms, the alkyl portion of said alkylphenyl radical contains 1 to 8 carbon atoms, the allryl portions of said alkylphenoxyalkyl radical contain 2 to 5 carbon atoms and the alkyl portion of said alkoxyphenyl radical contains 2 to 4 carbon atoms; M is molybdenum; X is chlorine; y is the valency of molybdenum; z is an integer of at least one but less than the valency of molybdenum; and v is the valency of chlorine.
composition of a compound having the formula:
wherein R is selected from the group consisting of phenyl, caproylphenyl, alkyl, cycloalkyl, alkylphenyl, alkylphenoxyalkyl and alkoxyphenyl radicals wherein said alkyl radical contains 4 to 30 carbon atoms, said cycloalkyl radical contains 5 to 6 carbon atoms, the alkyl portion of said alkylphenyl radical contains 1 to 8 carbon atoms, the alkyl portions of said alkylphenoxyalkyl radical contain 2 to 5 carbon atoms and the alkyl portion of said alkoxyphenyl radical contains 2 to 4 carbon atoms; M is tungsten; X is chlorine; y is the valency of tungsten; z is an integer of at least one but less than the valency of tungsten; and v is the valency of chlorine;
'7. A lubricating composition comprising a major pro- 8 portion of a lubricating oil and a minor amount sufficient to confer improved extreme pressure characteristics to the composition of molybderiuni' tris-(diisooctyl dithiophosphate) dichloride.
8. A lubricating composition comprising a major proportion of a lubricating oil and a minor amount sufiicient to confer improved extreme pressure characteristics to the composition of molybdenum tris-(diisooctyl dithiophos-' phate) sulfide. i 7
References Cited by the Examiner UNITED STATES PATENTS 2,346,155 4/44 Denison et a1. 25232.7 2,480,673 8/49 Reiff et al. 260429 XR 2,609,342 9/52 White et a1. 252-25 3,047,500 7/62 Maston Q 25246.4 3,050,538 '8/62 Hugel et al. 252-464 DANIEL E. WY MAN, Primary Examiner.
ALPHONSO D. SULLIVAN, Examiner.
Claims (1)
1. A LUBRICATING COMPOSITION COMPRISING A MAJOR PROPORTION OF A LUBICATING OIL AND A MINOR AMOUNT SUFFICIENT TO CONFER IMPROVED EXTREME PRESSURE CHARACTERISTICS TO THE COMPOSITION OF A COMPOUND HAVING THE FORMULA:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US202656A US3193500A (en) | 1959-02-12 | 1962-06-13 | Extreme pressure lubricant |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US792883A US3068259A (en) | 1959-02-12 | 1959-02-12 | Molybdenum and tungsten halides and sulfides of organic substituted dithiophosphoricacids |
US202656A US3193500A (en) | 1959-02-12 | 1962-06-13 | Extreme pressure lubricant |
Publications (1)
Publication Number | Publication Date |
---|---|
US3193500A true US3193500A (en) | 1965-07-06 |
Family
ID=26897907
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US202656A Expired - Lifetime US3193500A (en) | 1959-02-12 | 1962-06-13 | Extreme pressure lubricant |
Country Status (1)
Country | Link |
---|---|
US (1) | US3193500A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3440028A (en) * | 1964-11-24 | 1969-04-22 | Cities Service Oil Co | Organo metal halide orthophosphate gasoline additive |
US3446735A (en) * | 1962-07-30 | 1969-05-27 | Lubrizol Corp | Lubricants containing molybdenum phosphorodithioates |
DE1296139B (en) * | 1965-10-28 | 1969-05-29 | Vanderbilt Co R T | Process for the production of complex, salt-like molybdenum oxide-sulfur-dithiophosphoric acid-O, O-diesters |
US3664954A (en) * | 1968-09-05 | 1972-05-23 | Sylvania Electric Prod | Group vi{14 b transition metal-amino-phosphorodithioates in lubricating oil |
DE1794121B1 (en) * | 1966-08-10 | 1973-02-22 | Vanderbilt Co R T | LUBRICANT |
US4259192A (en) * | 1979-04-02 | 1981-03-31 | Chevron Research Company | Lubricating oil compositions containing polyether dithiophosphates |
FR2484442A1 (en) * | 1980-02-01 | 1981-12-18 | Lubrizol Corp | PROCESS FOR THE PREPARATION OF MOLYBDENE CONTAINING COMPOSITIONS USEFUL FOR BETTER ECONOMY OF THE FUEL OF INTERNAL COMBUSTION ENGINES |
EP0417972A1 (en) * | 1989-09-07 | 1991-03-20 | Exxon Research And Engineering Company | Lubricating oil composition |
US5919740A (en) * | 1998-05-29 | 1999-07-06 | Exxon Chemical Patents Inc | Alkylthiophosphate salts for lubricating oils |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2346155A (en) * | 1942-02-23 | 1944-04-11 | Standard Oil Co | Compounded oil |
US2480673A (en) * | 1945-10-06 | 1949-08-30 | Socony Vacuum Oil Co Inc | Mineral oil lubricants |
US2609342A (en) * | 1949-12-03 | 1952-09-02 | Socony Vacuum Oil Co Inc | Lubricant |
US3047500A (en) * | 1958-04-04 | 1962-07-31 | Sinclair Research Inc | Lubricant including a molybdenum-containing organic material |
US3050538A (en) * | 1957-04-19 | 1962-08-21 | Inst Francais Du Petrole | Molybdenum blue complexes |
-
1962
- 1962-06-13 US US202656A patent/US3193500A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2346155A (en) * | 1942-02-23 | 1944-04-11 | Standard Oil Co | Compounded oil |
US2480673A (en) * | 1945-10-06 | 1949-08-30 | Socony Vacuum Oil Co Inc | Mineral oil lubricants |
US2609342A (en) * | 1949-12-03 | 1952-09-02 | Socony Vacuum Oil Co Inc | Lubricant |
US3050538A (en) * | 1957-04-19 | 1962-08-21 | Inst Francais Du Petrole | Molybdenum blue complexes |
US3047500A (en) * | 1958-04-04 | 1962-07-31 | Sinclair Research Inc | Lubricant including a molybdenum-containing organic material |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3446735A (en) * | 1962-07-30 | 1969-05-27 | Lubrizol Corp | Lubricants containing molybdenum phosphorodithioates |
US3440028A (en) * | 1964-11-24 | 1969-04-22 | Cities Service Oil Co | Organo metal halide orthophosphate gasoline additive |
DE1296139B (en) * | 1965-10-28 | 1969-05-29 | Vanderbilt Co R T | Process for the production of complex, salt-like molybdenum oxide-sulfur-dithiophosphoric acid-O, O-diesters |
DE1794121B1 (en) * | 1966-08-10 | 1973-02-22 | Vanderbilt Co R T | LUBRICANT |
US3664954A (en) * | 1968-09-05 | 1972-05-23 | Sylvania Electric Prod | Group vi{14 b transition metal-amino-phosphorodithioates in lubricating oil |
US4259192A (en) * | 1979-04-02 | 1981-03-31 | Chevron Research Company | Lubricating oil compositions containing polyether dithiophosphates |
FR2484442A1 (en) * | 1980-02-01 | 1981-12-18 | Lubrizol Corp | PROCESS FOR THE PREPARATION OF MOLYBDENE CONTAINING COMPOSITIONS USEFUL FOR BETTER ECONOMY OF THE FUEL OF INTERNAL COMBUSTION ENGINES |
FR2484443A1 (en) * | 1980-02-01 | 1981-12-18 | Lubrizol Corp | PROCESS FOR THE PREPARATION OF MOLYBDENE CONTAINING COMPOSITIONS USEFUL FOR BETTER ECONOMY OF THE FUEL OF INTERNAL COMBUSTION ENGINES |
EP0417972A1 (en) * | 1989-09-07 | 1991-03-20 | Exxon Research And Engineering Company | Lubricating oil composition |
US5919740A (en) * | 1998-05-29 | 1999-07-06 | Exxon Chemical Patents Inc | Alkylthiophosphate salts for lubricating oils |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2689220A (en) | Lubricating oil compositions of mixed diester dithiophosphates | |
US2736737A (en) | Phosphate partial ester-aldehyde condensation product and lubricant containing the same | |
US2364284A (en) | Modified lubricating oil | |
US5531911A (en) | Metal free hydraulic fluid with amine salt | |
US2589326A (en) | Organic phosphorus ester-p2s5 reaction products and oil compositions containing the same | |
US3193500A (en) | Extreme pressure lubricant | |
US3068259A (en) | Molybdenum and tungsten halides and sulfides of organic substituted dithiophosphoricacids | |
USRE22830E (en) | Compounded oil | |
US3174931A (en) | Grease compositions | |
US2683691A (en) | Extreme pressure lubricants | |
US2373811A (en) | Complex dithiophosphoric acid esters | |
US3239464A (en) | Extreme pressure lubricant | |
US3357920A (en) | Non-ash containing lubricating oil compositions | |
US2765276A (en) | Lubricating compositions | |
US2686760A (en) | Hydraulic fluids and lubricating compositions | |
US3112267A (en) | Lubricating compositions | |
US2760937A (en) | Phosphorus-containing lubricant additives | |
US2599341A (en) | New phosphorus containing compounds | |
US2783203A (en) | Corrosion preventing agent | |
US3210275A (en) | Lubricating composition containing metal salts of hindered phosphorodithioates | |
US2948682A (en) | Formyl triesters of dithiophosphoric acid and lubricating oil compositions containing same | |
US2844616A (en) | Process for reacting di-organo substituted dithiophosphoric acid compounds and epoxides | |
US2361746A (en) | Crankcase lubricating oil composition | |
US3240704A (en) | Lubricating compositions having oilsoluble phosphorus-containing condensation products | |
US2767142A (en) | Lubricating compositions |