US3450634A - Extreme pressure additives prepared from overbased lead naphthenate and partially or unneutralized dialkyl dithiophosphoric acid - Google Patents
Extreme pressure additives prepared from overbased lead naphthenate and partially or unneutralized dialkyl dithiophosphoric acid Download PDFInfo
- Publication number
- US3450634A US3450634A US711138A US3450634DA US3450634A US 3450634 A US3450634 A US 3450634A US 711138 A US711138 A US 711138A US 3450634D A US3450634D A US 3450634DA US 3450634 A US3450634 A US 3450634A
- Authority
- US
- United States
- Prior art keywords
- acid
- lead
- extreme pressure
- reaction
- lead naphthenate
- 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
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- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 title description 18
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 title description 13
- 239000005069 Extreme pressure additive Substances 0.000 title description 5
- 239000002253 acid Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 19
- 229910052717 sulfur Inorganic materials 0.000 description 19
- 239000011593 sulfur Substances 0.000 description 19
- 239000007795 chemical reaction product Substances 0.000 description 18
- 239000000314 lubricant Substances 0.000 description 18
- 150000002148 esters Chemical class 0.000 description 16
- 239000000654 additive Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- 239000002199 base oil Substances 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 229910000464 lead oxide Inorganic materials 0.000 description 9
- 230000001050 lubricating effect Effects 0.000 description 9
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- -1 citric Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 125000005608 naphthenic acid group Chemical group 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- NDLNTMNRNCENRZ-UHFFFAOYSA-N 2-[2-hydroxyethyl(octadecyl)amino]ethanol Chemical compound CCCCCCCCCCCCCCCCCCN(CCO)CCO NDLNTMNRNCENRZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 150000001261 hydroxy acids Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical class S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- ZUNYMXPJGBXUCI-UHFFFAOYSA-N dioctoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCOP(S)(=S)OCCCCCCCC ZUNYMXPJGBXUCI-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- RWQFRHVDPXXRQN-UHFFFAOYSA-N phosphorus sesquisulfide Chemical compound P12SP3SP1P2S3 RWQFRHVDPXXRQN-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- AQFWNELGMODZGC-UHFFFAOYSA-N o-ethylhydroxylamine Chemical compound CCON AQFWNELGMODZGC-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- 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
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/56—Acids of unknown or incompletely defined constitution
- C10M129/58—Naphthenic 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
- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/123—Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/108—Residual fractions, e.g. bright stocks
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/16—Naphthenic 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
- C10M2207/26—Overbased carboxylic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
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- 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
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- 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
- C10M2207/40—Fatty vegetable or animal oils
-
- 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
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/402—Castor oils
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- 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
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
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- 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
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- 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
- C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- 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
- C10N2010/08—Groups 4 or 14
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- the present invention relates to extreme pressure additives and a method for their preparation, and more particularly, is concerned with certain phosphosulfurized materials and metal derivatives thereof useful as additives in lubricants which are required to operate under extreme load conditions.
- This invention is concerned with certain compounds which, when added in small amounts to base lubricating oils, provide a lubricant composition with improved antiwear and extreme pressure characteristics.
- the compounds of this invention form three classes of extreme pressure agents which can be generally described as follows: Firstly, the class of materials produced by reacting a hydroxy dibasic acid and an ethoxy amine, which is then treated with phosphorus and sulfur, followed by subsequent neutralization with an alcohol and a metal oxide. Secondly, the class of materials produced by reacting an unsaturated dibasic acid and an alcohol, treating with phosphorus and sulfur, followed by subsequent 'ice neutralization with a metal oxide. Thirdly, the class of materials produced by reacting an overbased lead naphthenate with a dialkyl dithiophosphoric acid or a partially neutralized dialkyl dithiophosphoric acid.
- Suitable hydroxy dibasic acids for use in producing the additives of the first class described above generally include those corresponding to the general formula (CHOH) (CH (COOH) where x is about 1 to 4 and y is about 0 to 6.
- Preferred dibasic acids include, among other, tartaric, mucic and malic acids.
- Monobasic hydroxy acids such as glycolic and tribasic hydroxy acids such as citric, may also be employed.
- dibasic hydroxy-acids are preferred.
- Suitable ethoxy amines include those of the general formula .zisO.
- the reaction of the acid and amine can be conveniently carried out by heating a fluid mixture of the components containing about 1 to 1.5, preferably about 1.1 to 1.2 mols of amine per mol of acid at a temperature and for a time sufficient to completely react the acid and amine, e.g., until the theoretical amount of water is recovered from the reaction mixture.
- Suitable temperatures are from about 60 to 200 C., preferably about to 150 C.
- the time required for complete reaction will vary depending upon the temperature and particular reactants but usually falls in the range of about 1 to 20 hours.
- a preferred process is to reflux the acid and a small molecular excess of amine in a suitable solvent, e.g., toluene, until the theoretical amount of water is recovered.
- the sulfurization and phosphorization of the resulting reaction product can be accomplished by any of the various methods employed in the art but in each case should be conducted in a manner that provides the mixture with about 5 to 15% by weight of combined sulfur, preferably about 8 to 12%, and about 2 to 8%, preferably about 4 to 6% by weight of combined phosphorus.
- a particularly preferred method of conducting the sulfurization-phosphorization is phosphosulfurization which can conveniently be performed by adding a suitable amount, usually about 30 to 70 mol percent based on the acid component, of phosphorus sesquisulfide or phosphorus pentasulfide to the reaction product and heating the resulting mixture at a temperature and for a time suflicient to provide the aforementioned amounts of sulfur and phosphorus. Suitable temperatures are between about 100 and 200 C., preferably about to C. Again the reaction time will vary with the reaction temperature selected but will usually fall in the range of about 2 to 10 hours.
- the sulfur can be added by first sulfurizing the reaction product with a sulfurizing agent such as sulfur flour or lump sulfur at a suitable temperature, e.g., about 150 to 250 C. and preferably about to 180 C.
- a sulfurizing agent such as sulfur flour or lump sulfur
- sulfur flour When sulfur flour is employed as the sulfurizing agent, it is preferred to actually add the desired amount of sulfur flour to the mixture and conduct the sulfurizing reaction so as to react substantially all of the sulfur with the mixture.
- the time required for complete reaction of the sulfur will vary depending upon the reaction temperature selected but usually falls in the range of about 3 to 15 hours. About 5 to 10 hours at C. is a preferred sulfurizing condition.
- the sulfurized product can then be phosphorized employing a suitable phosphorizing agent such as a phosphosulfurizing agent.
- Phosphosulfurizing agents are the phosphorus sulfides such as P 8 P 5 etc., phosphorus sequisulfide (P 8 being particularly preferred. Since, when employing the phosphorus sulfides, the treatment is a phosphosulfurization, it may act to provide the reaction product with sulfur as well as phosphorus.
- the phosphosulfurized reaction product of the hydroxy dibasic acid and ethoxylated amine is then treated with an alcohol to improve oil solubility.
- Suitable alcohols include alkanols having from about 5 to 24 carbon atoms.
- Fatty alcohols e.g., lauryl alcohol, oleyl alcohol, etc., having from 10 to 24 carbon atoms are preferred.
- the treatment with alcohol is preferably carried out by heating, e.g., refluxing a fluid mixture of the phosphosulfurized reaction product and alcohol at a temperature of from about 80 to 170 0, preferably about 110 to 150 C., for a time suflicient to improve the solubility of the reaction product which time will vary depending upon the temperature and reactants but is usually within the range of about 5 to hours.
- the reaction is terminated when no further water is evolved.
- a preferable method of carrying out this reaction is to reflux the reactants in a solvent such as toluene.
- the alcohol is used in a slight excess, about 101 to 105 percent, referred to the acidic reaction component.
- the phosphosulfurized reaction product, as treated with an alcohol, can be further neutralized or partially neutralized by methods employed in the art using, for example, metal oxides.
- Neutralization can be accomplished by heating a fluid mixture of the reaction product with a metal oxide such as lead or zinc oxide at a temperature of from about 100 to 200 C., preferably about 130 to 170 C., for a time sufficient to neutralize the alcoholtreated, phosphosulfurized reaction product the desired degree.
- the final product will generally have an acid number of less than about 100, preferably 60, and contain about 2 to 5 weight percent metal.
- the time for this neutralization required will vary depending upon the reactants and temperature, but usually is within the range of about 5 to 15 hours.
- the second class of additives referred to above are the reaction products of unsaturated dibasic acids and an alcohol, treated with phosphorus and sulfur and followed by subsequent neutralization with a metal oxide.
- the reaction is accomplished by heating a fluid mixture of the unsaturated dibasic acid and alcohol in about a 1:1 mol ratio so that the desired partial ester, e.g., the half ester, reaction product predominates.
- the acid and alcohol can be refluxed in a suitable solvent, e.g., toluene, with removal of water until no further water is evolved.
- Suitable acids are maleic, fumaric, citraconic, mesaconic as well as high molecular weight materials such as linoleic dimer acids.
- Suitable alcohols are alkanols having about 4 to 24 carbon atoms and preferably about 6 to 18 carbon atoms.
- the ester, e.g., half ester, of the acid is neutralized with 9, metal oxide such as lead oxide.
- the neutralized ester e.g.
- the lead salt or soap is then phosphorized and sulfurized, more accurately phosphosulfurized, for example, according to the procedure described above to produce a final product containing about 0.5 to 2% by weight, preferably about 0.75 to 1%, sulfur and about 0.5 to 5% by weight, preferably about 1 to 3%, phosphorus, and about 15 to 25% by weight metal, e.g., lead depending on the degree of esterification in making the partial ester and the molecular weight of the alcohol portion of the partial ester.
- lead content will be about 18 to 22%.
- the third class of additives encompassed by this invention are the reaction products of an Overbased lead naphthenate with a dialkyl dithiophosphoric acid or a partially neutralized dialkyl dithiophosphoric acid.
- Overbased lead naphthenate is produced by reacting naphthenic acids with an excess of lead oxide over the amount required for neutralizing the naphthenic acids.
- the lead naphthenate will contain about 35 to 50% by weight lead and preferably about twice the amount of lead calculated for theoretical neutralization of the naphthenic acids.
- the lead content preferably will be about 39 to 46%.
- the lead oxide is generally used in an excess of from about 50 to preferably about 75 to 125%.
- Suitable naphthenic acids are those having an acid number of about to 250, preferably about to 220 and an average molecular weight of about 220 to 320, preferably about 250 to 290 as calculated from the acid number.
- the basic lead naphthenate is reacted with a dialkyl dithiophosphoric acid in an amount suflicient to neutralize the excess basicity of the lead naphthenate.
- the basic lead naphthenate may be similarly reacted with a partially zincneutralized dialkyl dithiophosphoric acid, again in an amount calculated to neutralize the excess basicity of the lead naphthenate.
- the alkyl group of the dialkyl dithiophosphoric acid may have from about 4 to 24 carbon atoms, preferably about 6 to 18 carbon atoms.
- the lubricating oil base stock used in the present invention is of lubricating viscosity and can be, for instance, a solvent extracted or solvent refined oil obtained in accordance with conventional methods of solvent refining lubricating oils. Often, lubricating oils have viscosities from about 20 to 250 SUS at 210 F.
- the base oil can be derived from paraffinic, naphthenic, asphaltic or mixed base crudes, and if desired, a blend of solventtreated Mid-Continent neutrals and Mid-Continent bright stocks may be employed.
- the oils can be thickened to grease consistency.
- the base oil of the fluid lubricant or grease can also be a synthetic oil of lubricating viscosity.
- One type of synthetic oleaginous base which can be used is an ester synthetic oil of lubricating viscosity which consists essentially of carbon, hydrogen and oxygen, e.g., di-2-ethylhexyl sebacate.
- ester synthetic oil of lubricating viscosity which consists essentially of carbon, hydrogen and oxygen, e.g., di-2-ethylhexyl sebacate.
- Various of these lubricating materials have been described in the literature and generally their vicosity ranges from the light to heavy oils, e.g., about 50 SUS at 100 F. to 250 SUS at 210 F. and preferably 30 to 150 SUS at 210 F.
- These esters are of improved thermal stability, low acid number and high flash and fire points.
- complex esters, diesters, monoesters and polyesters can be used alone, or, to achieve the most desirable viscosity characteristics, complex esters, diesters and polyesters can be blended with each other or with naturally-occurring esters like castor oil to produce lubricating compositions of wide viscosity ranges which can be tailor-made to meet various specifications. This blending is performed, for example, by stirring together a quantity of diester and complex ester at an elevated temperature, altering the proportions of each component until the desired viscosity is reached.
- compositions of this invention incorporate into the base oil a small, minor amount of one of the above described additives sufficient to provide the base oil of lubricating viscosity (which is the major portion of the composition) with improved anti-wear and extreme pressure properties.
- This amount is generally about 0.01 to 15 or 20 or more percent by weight of the lubricant depending on the particular base oil used and its application.
- the preferred concentration should be the minimum amount to give the desired properties for the particular application and usually will be about 0.2 to 20 percent by weight of the lubricant.
- dispersants may be used to increase the concentration. In these cases, it has been found that increased solubility is best obtained in highly refined oils by dissolving the dispersant in the oil before dissolving the additive.
- compositions of this invention Materials normally incorporated in lubricating oils and greases to impart special characteristics can be added to the composition of this invention. These include corrosion inhibitors, additional extreme pressure agents, antiwear agents, etc.
- the amount of additives included in the composition usually ranges from about 0.01 weight percent up to about 20 or more weight percent of the lubricant and, in general, they can be employed in any amount desired as long as the composition is not unduly deleteriously affected.
- Ethomeen 18/12 (0.67 mol) and Ethomeen T/ 12 (0.73 mol) were reacted with tartaric acid (1.3 mols) by refluxing in toluene until the theoretical 2.6 mols of water were recovered from the reaction mixture.
- 'Ethomeen 18/ 12 and T/l2 are tertiary amines containing one fatty alkyl group and two dioxyethylene groups, having the formula RN[(CH CH O),,H]
- the Ethomeens are commercial materials available from Armour Chemical Co.
- Ethomeen T/12 is derived from a mixture of amines having an average carbon chain ranging from C to C
- the predominant alkyl group in Ethomeen 18/12 is C
- This reaction product was then treated with 0.65 mol of P S for four hours at 110 C. and for 2 hours at 130 C.
- the solid amber product analyzed: sulfur, 10.1%; phosphorous, 5.20%; acid No. 169. This product was found to be soluble in naphthenic-type lubricating oil base stocks, but to have limited solubility in paraffinic-type base stocks.
- EXAMPLE II 640 grams of the product of Example I (1.94 acid number equivalents) were reacted with 400 grams (2 mols) lauryl alcohol by refluxing in toluene for 12 hours, recovering 11 ml. water of reaction. 200 grams of maleic acid (1.5 mols) were then added and the reaction was continued until approximately 68 ml. of water were collected and no further water was being evolved. After removal of toluene solvent, the dark amber fluid product analyzed: sulfur, 4.34%; phosphorus, 2.72%; acid No. 139.
- EXAMPLE III 500 grams of the product of Example II were treated with 50 grams of zinc oxide at 150 C. for 8 hours. 200 grams of a 50 vis. 95 VI mineral oil were added to reduce viscosity, and the product filtered to remove unreacted zinc oxide and insoluble reaction products. The 600 gram yield of product analyzed: sulfur, 3.24%; phosphorus, 1.8%; zinc, 2.82%; acid No. 50.6.
- EXAMPLE V 406 grams (1.9 mols est.) of the Example IV half ester reaction product were treated with 210 grams (0.95 mol) of lead oxide at 120 C. for one hour. The product was then diluted with approximately two volumes of benzene and filtered to remove unreacted lead oxide and insoluble lead salt of unreacted maleic acid. The fluid filtrate was treated with 77 grams (0.35 mol) of phosphorus sesquisulfide at C. for one hour, filtered, and the solvent removed by vacuum stripping. The resultant product analyzed: sulfur, 0.84%; phosphorus, 1.46%; and lead, 21.0%
- a solution of basic lead naphthenate was prepared by reacting 260 grams of naphthenic acids (acid No. 212, avg. MW 260) with 223 grams (1 mol or 2 equiv.) of lead oxide in 1600 grams of 100 vis. naphthenic neutral oil.
- the resultant 22% lead naphthenate solution in oil analyzed 9.70% lead, equivalent to approximately 44% lead content in the lead naphthenate, or approximately twice the lead content required for neutralization of the naphthenic acid.
- 300 grams of the basic lead naphthenate solution were diluted with 200 grams of toluene, and to this mixture were added 48 grams of dioctyl dithiophosphoric acid (acid No. 181), and the reaction mixture refluxed for six hours with water of reaction being removed via a Dean-Stark trap. After removal of solvent by vacuum stripping, the resultant product analyzed; sulfur 2.94%; phosphorus, 1.53%; and lead, 7.57%
- EXAMPLE VII 300 grams of the basic lead naphthenate solution prepared as in Example VI were treated with 262 grams of a partially zinc-neutralized dioctyl dithiophosphoric acid EXAMPLE VIII
- Table I show performance in the Falex load test, the Four-Ball EP and wear tests, the SAE load test, and the Timken load and wear tests.
- the tests used in evaluating these lubricants are well known in the art and their description is not considered essential to this invention.
- the Timken wear test is run using the Timken machine described in CRC procedure L-18-545, modified so that the test block is continuously moved back and forth for a distance of about 0.13 inch approximately every 15 seconds.
- Example II wt. percent
- Example III wt. percent
- Example V wt. percent
- Example VI wt. percent
- Example VII wt. percent. Falex max. load, lbs
- Timken machine safe lbs- Four-ball weld point, kg MHL Four ball wear scar, mm., at;
- Norm-Base oils A and B are solvent refined neutral oils, having 100 F. vlscosities of about 500 and 200 SUS, respectively.
- Base oil 0 is a solvent refined bright stock having a viscosity of SUS at 210 F.
- An extreme pressure additive comprising the reaction product of over-based lead naphthenates containing about 35 to 50 percent by weight lead with a compound selected from the group consisting of dialkyl dithiophosphoric acid and partially zinc-neutralized dialkyl dithiophosphoric acid, the alkyl group of the dialkyl dithiophosphoric acid having from 4 to 24 carbon atoms, said ovrebased lead naphthenate being produced by reaction of naphthenic acid having an acid number of about 175 to 250 and an average molecular weight of about 220 to 320 as calculated from the acid number with an excess of lead oxide over the amount required for neurtalization of the acid, said compound being used in an amount sufficient to neutralize the excess basicity of said overbased lead naphthenate.
- An oleaginous lubricant composition consisting essentially of a base oil of lubricating viscosity and an amount sufiicient to give improved extreme pressure properties to the composition of the additive of claim 1.
- composition of claim 3 wherein said amount is from about 0.01 to 20 percent by weight of the lubricant composition.
- An oleaginous lubricant composition consisting essentially of a base oil of lubrictaing viscosity and an amount sufiicient to give improved extreme pressure properties to the composition of the additive of claim 2.
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Description
United States Patent US. Cl. 25232.7 6 Claims ABSTRACT OF THE DISCLOSURE Extreme pressure additives, especially for use with a lubricant composition comprising the class of materials produced by reacting an overbased lead naphthenate with a dialkyl dithiophosphoric acid or a partially neutralized dialkyl dithiophosphoric acid.
This application is a continuation of application Ser. No. 553,316, filed May 27, 1966, now abandoned.
The present invention relates to extreme pressure additives and a method for their preparation, and more particularly, is concerned with certain phosphosulfurized materials and metal derivatives thereof useful as additives in lubricants which are required to operate under extreme load conditions.
The need for extreme pressure lubricants and additives for the production of such lubricants is well known. When a lubricating film that separates two moving surfaces is subjected to increased pressure as a result of high load conditions, the lubricant tends to be squeezed out. The compression action of the high loads also tends to cause an increase in the internal heat of the lubricating film, resulting in a thinning out of the film due to its decreased viscosity. This combined squeezing and thinning of lubricant film permits the metal surfaces to make point contacts and generate friction which augments the heat effect on the film. Continued movement of the surfaces under these conditions results in high wear and ultimately in seizure and destruction of the surfaces under severe conditions.
It has been repeatedly observed that lubricating oil fractions alone do not have the required film strength to prevent excessive wear and seizure of highly loaded parts such as gears. It has been further observed, however, that certain materials, i.e., extreme pressure agents, can be added to lubricants to improve film strength and thus prevent wear and destruction of metal parts which are under high loads. A number of such agents have been found suitable for this purpose in the past, but there is a continuing search for new additives which are more effective or equally effective at lower cost, since such additives are usually more expensive than the equivalent amount of lubricant base that they replace.
This invention is concerned with certain compounds which, when added in small amounts to base lubricating oils, provide a lubricant composition with improved antiwear and extreme pressure characteristics. :In general, the compounds of this invention form three classes of extreme pressure agents which can be generally described as follows: Firstly, the class of materials produced by reacting a hydroxy dibasic acid and an ethoxy amine, which is then treated with phosphorus and sulfur, followed by subsequent neutralization with an alcohol and a metal oxide. Secondly, the class of materials produced by reacting an unsaturated dibasic acid and an alcohol, treating with phosphorus and sulfur, followed by subsequent 'ice neutralization with a metal oxide. Thirdly, the class of materials produced by reacting an overbased lead naphthenate with a dialkyl dithiophosphoric acid or a partially neutralized dialkyl dithiophosphoric acid.
Suitable hydroxy dibasic acids for use in producing the additives of the first class described above generally include those corresponding to the general formula (CHOH) (CH (COOH) where x is about 1 to 4 and y is about 0 to 6. Preferred dibasic acids include, among other, tartaric, mucic and malic acids. Monobasic hydroxy acids such as glycolic and tribasic hydroxy acids such as citric, may also be employed. However, dibasic hydroxy-acids are preferred. Suitable ethoxy amines include those of the general formula .zisO.
The reaction of the acid and amine can be conveniently carried out by heating a fluid mixture of the components containing about 1 to 1.5, preferably about 1.1 to 1.2 mols of amine per mol of acid at a temperature and for a time sufficient to completely react the acid and amine, e.g., until the theoretical amount of water is recovered from the reaction mixture. Suitable temperatures are from about 60 to 200 C., preferably about to 150 C. The time required for complete reaction will vary depending upon the temperature and particular reactants but usually falls in the range of about 1 to 20 hours. A preferred process is to reflux the acid and a small molecular excess of amine in a suitable solvent, e.g., toluene, until the theoretical amount of water is recovered.
The sulfurization and phosphorization of the resulting reaction product can be accomplished by any of the various methods employed in the art but in each case should be conducted in a manner that provides the mixture with about 5 to 15% by weight of combined sulfur, preferably about 8 to 12%, and about 2 to 8%, preferably about 4 to 6% by weight of combined phosphorus. A particularly preferred method of conducting the sulfurization-phosphorization is phosphosulfurization which can conveniently be performed by adding a suitable amount, usually about 30 to 70 mol percent based on the acid component, of phosphorus sesquisulfide or phosphorus pentasulfide to the reaction product and heating the resulting mixture at a temperature and for a time suflicient to provide the aforementioned amounts of sulfur and phosphorus. Suitable temperatures are between about 100 and 200 C., preferably about to C. Again the reaction time will vary with the reaction temperature selected but will usually fall in the range of about 2 to 10 hours.
Alternatively, the sulfur can be added by first sulfurizing the reaction product with a sulfurizing agent such as sulfur flour or lump sulfur at a suitable temperature, e.g., about 150 to 250 C. and preferably about to 180 C. When sulfur flour is employed as the sulfurizing agent, it is preferred to actually add the desired amount of sulfur flour to the mixture and conduct the sulfurizing reaction so as to react substantially all of the sulfur with the mixture. The time required for complete reaction of the sulfur will vary depending upon the reaction temperature selected but usually falls in the range of about 3 to 15 hours. About 5 to 10 hours at C. is a preferred sulfurizing condition. After sulfurization of the reaction product, the sulfurized product can then be phosphorized employing a suitable phosphorizing agent such as a phosphosulfurizing agent. Phosphosulfurizing agents are the phosphorus sulfides such as P 8 P 5 etc., phosphorus sequisulfide (P 8 being particularly preferred. Since, when employing the phosphorus sulfides, the treatment is a phosphosulfurization, it may act to provide the reaction product with sulfur as well as phosphorus.
The phosphosulfurized reaction product of the hydroxy dibasic acid and ethoxylated amine is then treated with an alcohol to improve oil solubility. Suitable alcohols include alkanols having from about 5 to 24 carbon atoms. Fatty alcohols e.g., lauryl alcohol, oleyl alcohol, etc., having from 10 to 24 carbon atoms are preferred. The treatment with alcohol is preferably carried out by heating, e.g., refluxing a fluid mixture of the phosphosulfurized reaction product and alcohol at a temperature of from about 80 to 170 0, preferably about 110 to 150 C., for a time suflicient to improve the solubility of the reaction product which time will vary depending upon the temperature and reactants but is usually within the range of about 5 to hours. Conveniently, the reaction is terminated when no further water is evolved. A preferable method of carrying out this reaction is to reflux the reactants in a solvent such as toluene. In general, the alcohol is used in a slight excess, about 101 to 105 percent, referred to the acidic reaction component.
The phosphosulfurized reaction product, as treated with an alcohol, can be further neutralized or partially neutralized by methods employed in the art using, for example, metal oxides. Neutralization can be accomplished by heating a fluid mixture of the reaction product with a metal oxide such as lead or zinc oxide at a temperature of from about 100 to 200 C., preferably about 130 to 170 C., for a time sufficient to neutralize the alcoholtreated, phosphosulfurized reaction product the desired degree. The final product will generally have an acid number of less than about 100, preferably 60, and contain about 2 to 5 weight percent metal. The time for this neutralization required will vary depending upon the reactants and temperature, but usually is within the range of about 5 to 15 hours.
The second class of additives referred to above are the reaction products of unsaturated dibasic acids and an alcohol, treated with phosphorus and sulfur and followed by subsequent neutralization with a metal oxide. In general, the reaction is accomplished by heating a fluid mixture of the unsaturated dibasic acid and alcohol in about a 1:1 mol ratio so that the desired partial ester, e.g., the half ester, reaction product predominates. Conveniently, the acid and alcohol can be refluxed in a suitable solvent, e.g., toluene, with removal of water until no further water is evolved. However, the means by which this esterification is carried out in no way limits the scope of this invention, since the partial ester product is desired only as an intermediate reaction material and can be prepared in a variety of ways well known to the art. Suitable acids are maleic, fumaric, citraconic, mesaconic as well as high molecular weight materials such as linoleic dimer acids. Suitable alcohols are alkanols having about 4 to 24 carbon atoms and preferably about 6 to 18 carbon atoms. The ester, e.g., half ester, of the acid is neutralized with 9, metal oxide such as lead oxide. The neutralized ester, e.g. the lead salt or soap is then phosphorized and sulfurized, more accurately phosphosulfurized, for example, according to the procedure described above to produce a final product containing about 0.5 to 2% by weight, preferably about 0.75 to 1%, sulfur and about 0.5 to 5% by weight, preferably about 1 to 3%, phosphorus, and about 15 to 25% by weight metal, e.g., lead depending on the degree of esterification in making the partial ester and the molecular weight of the alcohol portion of the partial ester. Using a preferred alcohol of about 116 to 158 molecular weight for example, lead content will be about 18 to 22%.
The third class of additives encompassed by this invention are the reaction products of an Overbased lead naphthenate with a dialkyl dithiophosphoric acid or a partially neutralized dialkyl dithiophosphoric acid. Overbased lead naphthenate is produced by reacting naphthenic acids with an excess of lead oxide over the amount required for neutralizing the naphthenic acids. Generally, the lead naphthenate will contain about 35 to 50% by weight lead and preferably about twice the amount of lead calculated for theoretical neutralization of the naphthenic acids. For the usual naphthenic acids having an acid number in the range of about 190-220 the lead content preferably will be about 39 to 46%. The lead oxide is generally used in an excess of from about 50 to preferably about 75 to 125%. Suitable naphthenic acids are those having an acid number of about to 250, preferably about to 220 and an average molecular weight of about 220 to 320, preferably about 250 to 290 as calculated from the acid number. The basic lead naphthenate is reacted with a dialkyl dithiophosphoric acid in an amount suflicient to neutralize the excess basicity of the lead naphthenate. The basic lead naphthenate may be similarly reacted with a partially zincneutralized dialkyl dithiophosphoric acid, again in an amount calculated to neutralize the excess basicity of the lead naphthenate. The alkyl group of the dialkyl dithiophosphoric acid may have from about 4 to 24 carbon atoms, preferably about 6 to 18 carbon atoms.
The lubricating oil base stock used in the present invention is of lubricating viscosity and can be, for instance, a solvent extracted or solvent refined oil obtained in accordance with conventional methods of solvent refining lubricating oils. Often, lubricating oils have viscosities from about 20 to 250 SUS at 210 F. The base oil can be derived from paraffinic, naphthenic, asphaltic or mixed base crudes, and if desired, a blend of solventtreated Mid-Continent neutrals and Mid-Continent bright stocks may be employed. The oils can be thickened to grease consistency.
The base oil of the fluid lubricant or grease can also be a synthetic oil of lubricating viscosity. One type of synthetic oleaginous base which can be used is an ester synthetic oil of lubricating viscosity which consists essentially of carbon, hydrogen and oxygen, e.g., di-2-ethylhexyl sebacate. Various of these lubricating materials have been described in the literature and generally their vicosity ranges from the light to heavy oils, e.g., about 50 SUS at 100 F. to 250 SUS at 210 F. and preferably 30 to 150 SUS at 210 F. These esters are of improved thermal stability, low acid number and high flash and fire points. The complex esters, diesters, monoesters and polyesters can be used alone, or, to achieve the most desirable viscosity characteristics, complex esters, diesters and polyesters can be blended with each other or with naturally-occurring esters like castor oil to produce lubricating compositions of wide viscosity ranges which can be tailor-made to meet various specifications. This blending is performed, for example, by stirring together a quantity of diester and complex ester at an elevated temperature, altering the proportions of each component until the desired viscosity is reached.
The compositions of this invention incorporate into the base oil a small, minor amount of one of the above described additives sufficient to provide the base oil of lubricating viscosity (which is the major portion of the composition) with improved anti-wear and extreme pressure properties. This amount is generally about 0.01 to 15 or 20 or more percent by weight of the lubricant depending on the particular base oil used and its application. The preferred concentration should be the minimum amount to give the desired properties for the particular application and usually will be about 0.2 to 20 percent by weight of the lubricant. In some cases where oil solubility might limit the amount of additive employed, dispersants may be used to increase the concentration. In these cases, it has been found that increased solubility is best obtained in highly refined oils by dissolving the dispersant in the oil before dissolving the additive.
Materials normally incorporated in lubricating oils and greases to impart special characteristics can be added to the composition of this invention. These include corrosion inhibitors, additional extreme pressure agents, antiwear agents, etc. The amount of additives included in the composition usually ranges from about 0.01 weight percent up to about 20 or more weight percent of the lubricant and, in general, they can be employed in any amount desired as long as the composition is not unduly deleteriously affected.
The following examples are'included to illustrate the advantages of the compounds of the present composition in lubricant compositions.
EXAMPLE I Ethomeen 18/12 (0.67 mol) and Ethomeen T/ 12 (0.73 mol) were reacted with tartaric acid (1.3 mols) by refluxing in toluene until the theoretical 2.6 mols of water were recovered from the reaction mixture.'Ethomeen 18/ 12 and T/l2 are tertiary amines containing one fatty alkyl group and two dioxyethylene groups, having the formula RN[(CH CH O),,H] The Ethomeens are commercial materials available from Armour Chemical Co. Ethomeen T/12 is derived from a mixture of amines having an average carbon chain ranging from C to C The predominant alkyl group in Ethomeen 18/12 is C This reaction product was then treated with 0.65 mol of P S for four hours at 110 C. and for 2 hours at 130 C. After removal of toluene solvent, the solid amber product analyzed: sulfur, 10.1%; phosphorous, 5.20%; acid No. 169. This product was found to be soluble in naphthenic-type lubricating oil base stocks, but to have limited solubility in paraffinic-type base stocks.
EXAMPLE II 640 grams of the product of Example I (1.94 acid number equivalents) were reacted with 400 grams (2 mols) lauryl alcohol by refluxing in toluene for 12 hours, recovering 11 ml. water of reaction. 200 grams of maleic acid (1.5 mols) were then added and the reaction was continued until approximately 68 ml. of water were collected and no further water was being evolved. After removal of toluene solvent, the dark amber fluid product analyzed: sulfur, 4.34%; phosphorus, 2.72%; acid No. 139.
EXAMPLE III 500 grams of the product of Example II were treated with 50 grams of zinc oxide at 150 C. for 8 hours. 200 grams of a 50 vis. 95 VI mineral oil were added to reduce viscosity, and the product filtered to remove unreacted zinc oxide and insoluble reaction products. The 600 gram yield of product analyzed: sulfur, 3.24%; phosphorus, 1.8%; zinc, 2.82%; acid No. 50.6.
EXAMPLE IV The half ester of maleic acid was prepared by refluxing 4 mols of maleic acid with 4 mols of mixed 0;
alcohols in the presence of toluene solvent until 73 mols of water were recovered and no further water was evolved. The product was filtered to remove traces of solid contaminants and the toluene solvent was removed by vacuum stripping.
EXAMPLE V 406 grams (1.9 mols est.) of the Example IV half ester reaction product were treated with 210 grams (0.95 mol) of lead oxide at 120 C. for one hour. The product was then diluted with approximately two volumes of benzene and filtered to remove unreacted lead oxide and insoluble lead salt of unreacted maleic acid. The fluid filtrate was treated with 77 grams (0.35 mol) of phosphorus sesquisulfide at C. for one hour, filtered, and the solvent removed by vacuum stripping. The resultant product analyzed: sulfur, 0.84%; phosphorus, 1.46%; and lead, 21.0%
EXAMPLE VI A solution of basic lead naphthenate was prepared by reacting 260 grams of naphthenic acids (acid No. 212, avg. MW 260) with 223 grams (1 mol or 2 equiv.) of lead oxide in 1600 grams of 100 vis. naphthenic neutral oil. The resultant 22% lead naphthenate solution in oil analyzed 9.70% lead, equivalent to approximately 44% lead content in the lead naphthenate, or approximately twice the lead content required for neutralization of the naphthenic acid. 300 grams of the basic lead naphthenate solution were diluted with 200 grams of toluene, and to this mixture were added 48 grams of dioctyl dithiophosphoric acid (acid No. 181), and the reaction mixture refluxed for six hours with water of reaction being removed via a Dean-Stark trap. After removal of solvent by vacuum stripping, the resultant product analyzed; sulfur 2.94%; phosphorus, 1.53%; and lead, 7.57%
EXAMPLE VII 300 grams of the basic lead naphthenate solution prepared as in Example VI were treated with 262 grams of a partially zinc-neutralized dioctyl dithiophosphoric acid EXAMPLE VIII The eflicacy of the compounds of this invention as extreme pressure and anti-Wear additives is demonstrated by the data of Table I, which show performance in the Falex load test, the Four-Ball EP and wear tests, the SAE load test, and the Timken load and wear tests. The tests used in evaluating these lubricants are well known in the art and their description is not considered essential to this invention. The Timken wear test is run using the Timken machine described in CRC procedure L-18-545, modified so that the test block is continuously moved back and forth for a distance of about 0.13 inch approximately every 15 seconds.
TABLE Composition No Blank 1 2 Base oil A, wt. percent Base oil B, wt. percent Base oil 0, wt. percent...
Example II, wt. percent Example III, wt. percent. Example V, wt. percent Example VI, wt. percent... Example VII, wt. percent. Falex max. load, lbs
SAE machine, lbs. at 300 r.p.m .I
Timken machine, safe lbs- Four-ball weld point, kg MHL Four ball wear scar, mm., at;
7 kg. for 2 hrs 14 kg. for 1 hr Timken wear at 100 lbs, mg
1 Falls at break-1n:
Norm-Base oils A and B are solvent refined neutral oils, having 100 F. vlscosities of about 500 and 200 SUS, respectively. Base oil 0 is a solvent refined bright stock having a viscosity of SUS at 210 F.
It is claimed:
1. An extreme pressure additive comprising the reaction product of over-based lead naphthenates containing about 35 to 50 percent by weight lead with a compound selected from the group consisting of dialkyl dithiophosphoric acid and partially zinc-neutralized dialkyl dithiophosphoric acid, the alkyl group of the dialkyl dithiophosphoric acid having from 4 to 24 carbon atoms, said ovrebased lead naphthenate being produced by reaction of naphthenic acid having an acid number of about 175 to 250 and an average molecular weight of about 220 to 320 as calculated from the acid number with an excess of lead oxide over the amount required for neurtalization of the acid, said compound being used in an amount sufficient to neutralize the excess basicity of said overbased lead naphthenate.
2. The additive of claim 1 wherein the lead oxide is used in an excess of from about 50 to 150 percent.
3. An oleaginous lubricant composition consisting essentially of a base oil of lubricating viscosity and an amount sufiicient to give improved extreme pressure properties to the composition of the additive of claim 1.
4. The composition of claim 3 wherein said amount is from about 0.01 to 20 percent by weight of the lubricant composition.
5. An oleaginous lubricant composition consisting essentially of a base oil of lubrictaing viscosity and an amount sufiicient to give improved extreme pressure properties to the composition of the additive of claim 2.
6. The additive of claim 2 wherein the alkyl group of said compound is from about 6 to 18 carbon atoms.
References Cited UNITED STATES PATENTS 2,364,283 12/1944 Freuler. 3,222,280 12/1'965 Wolfram.
PATRICK P. GARVIN, Primary Examiner.
US. Cl. X.R
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US71113868A | 1968-03-06 | 1968-03-06 |
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Publication Number | Publication Date |
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US3450634A true US3450634A (en) | 1969-06-17 |
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Application Number | Title | Priority Date | Filing Date |
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US711138A Expired - Lifetime US3450634A (en) | 1968-03-06 | 1968-03-06 | Extreme pressure additives prepared from overbased lead naphthenate and partially or unneutralized dialkyl dithiophosphoric acid |
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US (1) | US3450634A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4804489A (en) * | 1987-10-29 | 1989-02-14 | The Lubrizol Corporation | Low molecular weight viscosity modifying compositions |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2364283A (en) * | 1941-10-21 | 1944-12-05 | Union Oil Co | Modified lubricating oil |
US3222280A (en) * | 1961-12-26 | 1965-12-07 | Union Oil Co | Lubricants having improved cohesiveness and adhesiveness |
-
1968
- 1968-03-06 US US711138A patent/US3450634A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2364283A (en) * | 1941-10-21 | 1944-12-05 | Union Oil Co | Modified lubricating oil |
US3222280A (en) * | 1961-12-26 | 1965-12-07 | Union Oil Co | Lubricants having improved cohesiveness and adhesiveness |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4804489A (en) * | 1987-10-29 | 1989-02-14 | The Lubrizol Corporation | Low molecular weight viscosity modifying compositions |
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