US3245979A - Phosphorus phenol condensation compounds - Google Patents
Phosphorus phenol condensation compounds Download PDFInfo
- Publication number
- US3245979A US3245979A US345825A US34582564A US3245979A US 3245979 A US3245979 A US 3245979A US 345825 A US345825 A US 345825A US 34582564 A US34582564 A US 34582564A US 3245979 A US3245979 A US 3245979A
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- US
- United States
- Prior art keywords
- product
- oil
- phenol
- viscosity
- hours
- 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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- 150000001875 compounds Chemical class 0.000 title description 6
- XAVGNEJDRLVNOO-UHFFFAOYSA-N [P].OC1=CC=CC=C1 Chemical compound [P].OC1=CC=CC=C1 XAVGNEJDRLVNOO-UHFFFAOYSA-N 0.000 title description 2
- 238000009833 condensation Methods 0.000 title description 2
- 230000005494 condensation Effects 0.000 title description 2
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 21
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 18
- 239000007859 condensation product Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000000314 lubricant Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 239000002199 base oil Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- -1 thiophenols Chemical class 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid ester group Chemical class C(CCCCCCCCCCC)(=O)O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012065 filter cake Substances 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
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 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
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
Classifications
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- 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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl 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
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- 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
- C10M137/105—Thio derivatives not containing metal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- 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
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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- 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
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- 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
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- 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
- C10M2207/304—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 derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
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- 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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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/102—Polyesters
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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
-
- 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
- C10M2223/041—Triaryl phosphates
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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
- C10M2223/042—Metal salts thereof
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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
- C10M2223/047—Thioderivatives not containing metallic elements
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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
- C10M2223/121—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy of alcohols or phenols
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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
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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
- C10N2010/02—Groups 1 or 11
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol fueled engines
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
Definitions
- the present invention relates to oleaginous base lubricants having increased load carrying capacity and improved resistance to oxidation. More particularly, it relates to lubricants containing a novel condensation product as an extreme pressure agent and anti-oxidant.
- Mineral oil and synthetic lubricants in the form of greases or free-flowing liquids, are called upon to ease friction and prevent damage to machinery operated at temperatures to as high as about 450 F. At elevated temperatures an internal combustion engine using these lubricants is an ideal oxidizing machine since the lubricant is violently agitated in the presence of air for long periods of time. In addition the stability of the lubricants is further drastically reduced due to contact with metallic surfaces which give up metallic particles to the lubricant that act as powerful oxidation catalysts. Furthermore, water also causes corrosion of metallic surfaces and accentuates oxidation of the lubricant. Aside from being stable under conditions of use the lubricant must exhibit anti-wear and load carrying or extreme pressure characteristics.
- an oil-soluble condensation product of an alkylated phenol, phosphorous trichloride and hydroquinone is an excellent extreme pressure agent and when added in small effective amounts to oleaginous base lubricating oils provides a lubricant -composition improved in oxidation resistance and antiwear and extreme pressure characteristics.
- the alkyl-substituted phenols, including thiophenols, which are employed in the preparation of the condensation product are the monohydric phenols having at least one alkyl group, for instance, in an orthoor para-position, i.e., non-meta position.
- Representative alkyl phenols are those in which the alkyl group contains 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms, for example, amyl phenol, octyl phenol, nonyl phenol, p-ternbutyl phenol, p-tert-octyl phenol, the corresponding thiophenols, .a mixture of phenols and the like.
- the alkylated phenol is one that gives an oil-soluble product in the condensation reaction.
- the alkyl-substituted phenol, phosphorous trichloride and hydroquinone are reacted to provide an oil-soluble product.
- the alkylated phenol to phosphorous trichloride to :hydroquinone molar ratio is about 4:2:1, although slightly less or greater amounts of a given component may be used.
- Any method may be employed to produce the condensation product, but the preferred method comprises the following: a twostep procedure wherein (1) a stoichiometric amount of the alkyl-substituted phenol dissolved in a suitable solvent is slowly added to the phosphorous trichloride in the presence of a hydrogen chloride acceptor such as pyridine.
- sulfurizing the condensation product or treating the condensation product with a phosphorous sulfide also gives products having the desired properties.
- Sulfurizing of the condensation product can be accomplished in accordance with methods well-known in the art, as for instance, heating one mole of condensation product with about 1 to 3 moles of sulfur.
- the phosphorous sulfide-treated derivative can be obtained by heating the condensation product with about 0.01 to 5.0 weight percent of phosphorous sulfide, for example, phosphorous pentasulfide, preferably about 0.05 to 0.5%. These reactions are usually conducted at temperatures of about to 200 C., for say from about 2 to 50 or more hours.
- condensation product of an alkylated phenol, phosphorous tric-hloride and hydroquinone may be represented structurally as follows:
- the sulfurized derivative of the above product can be represented structurally as follows:
- R in the above structural formulae is an alkyl group of 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms.
- the formula of the phosphosulfurized i.e., phosphorous sulfide-treated) derivative is conjectural. At the low temperatures employed and since hydrogen sulfide is evolved during the reaction, one would expect the phosphorous sulfide to add on the aliphatic chain via the sulfur atom.
- 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.
- lubricating oils have viscosities from about 20 to 250 SUS at 210 F.
- the base oil may be derived from parafiinic, naphthenic, asphaltic or mixed base crudes, and if desired, a blend of solventtreated Mid-Continent neutrals and Mid-Continent bright stocks may be employed.
- a particularly suitable base oil used in the preparation of the composition may be described as a liquid mineral oil fraction having a viscosity index of about 100.
- Grease compositions may be prepared by the incorporation or formation in the oleaginous base of vgrease-thickening fatty acid soaps of metals such as the alkaline metals of group I and II of the periodic table.
- the soap content of the grease is generally about 2-25%.
- the soaps are usually the alkali metal or alkaline earth metal, e.g., lithium, barium, calcium, etc.; salts of natural or synthetic long-chain carboxylic acids, such as stearic, lhydroxy stearic or lauric acids, say of 12 to 20 carbon atoms.
- alkali metal or alkaline earth metal e.g., lithium, barium, calcium, etc.
- salts of natural or synthetic long-chain carboxylic acids such as stearic, lhydroxy stearic or lauric acids, say of 12 to 20 carbon atoms.
- the base oil of the fluid lubricant or grease may be a synthetic oil of lubricating viscosity.
- One type of synthetic oleaginous base 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.
- these lubricating materials have been described in the literature and generally their viscosity ranges from the light to heavy oils, e.g., about 50 S.U.S. at 100 F. to 250 S.U.S. at 210 F. and preferably 30 to S.U.S. at 210 F.
- These esters are of improved thermal stability, low acid number, and high flash and fire points.
- complex esters, diesters, mon-oesters and polyesters may be used alone or to achieve the most desirable viscosity characteristics, complex esters, diesters and polyesters may be blended with each other or with naturallyoccurring esters like castor oil to produce lubricating compositions of wide viscosity ranges which can be tailormade 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.
- esters are prepared fundamentally by the action of acids on alcohols. The mere mixture of an alcohol and acid at the proper temperature will react to produce an equilibrium mixture which includes the monoeste'r. The same is true for the reactions of organic dibasic acids and glycols to produce synthetic lubricant polyester bright stock.
- the diesters are frequently of the type alcoholdicarboxylic acid-alcohol, while complex esters are generally of the type X-YZYX in which X represents a monoalcohol residue, Y represents a dicarboxylic acid residue and Z represents a glycol residue and the linkages are ester linkages.
- esters have been found to be es eciall adaptable to the conditions to which turbine engines are exposed, since they can be formulated to give a desirable combination of high flash point, low pour point, and high viscosity at elevated temperature, and need contain no additives which might leave a residue upon volatilization.
- many complex esters have shown good stability to shear. Greases which use these esters as the oleaginous base also have most of these characteristics.
- Suitable monoand dicarboxylic acids used to make synthetic ester lubricant bases can be branched or straight chain and saturated or unsaturated and they frequently contain from about 2 to 12 carbons atoms. usually contain from about 4 to 12 carbon atoms.
- the useful glycols include the aliphatic monoglycols of 4 to 20 or 30 carbon atoms, preferably 4 to 12.
- compositions of this invention incorporate a small amount of the condensation products sufficient to inhibit oxidation in the base oil of lubricating viscosity which is the major portion of the composition. This amount is generally about 0.1 to 10% or more.
- the preferred concentration should be the minimum amount to give adequate protection for the particular application desired and usually will be about 0.25 to 5%.
- 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, and in general they can be employed in any amounts desired as long as the composition is not unduly deleteri-ously affected.
- Example I.Cndensation product of paratertiary octyl phenol, PCl and hydroquinone A liter, fluted, 4-necked flask, equipped with a power- :stat controlled heating mantle, thermometer, motor driven paddle stirrer and nitrogen inlet tube was used. The flask was flushed with nitrogen and a blanket of nitrogen continued during the addition of octyl phenol. The flask was then charged with 514 g. (6.5 moles) pyridine followed by 274 g. (2 moles) of PCl in 500 g. toluene. The PCl was weighed directly into the toluene to minimize .contact with air and hydrolysis with the moisture in the The alcohols air.
- the flask contents had a white precipitate, but the mixture was fluid enough for good mixing. After 1.3 hours and at a temperature of 102 C. the contents of the flask had turned to a tan color. One and a quarter hours later at 116 C. the toluene was refluxing and some of it was removed periodically through the trap. Some pyridine was lost in this process. After about 3.5 hours and the temperature still at 116 C. the nun was shut down for overnight. The reaction mass now had an orange color. The next morning, g. (1 mole) pyridine was added to insure the presence of enough pyridine to take up the hydrogen chloride formed in the next step. Then g. (1 mole) of hydroquinone dissolved in 800 g.
- the mass was then transferred to a beaker and allowed to stand overnight. The next day it was filtered through a Biichner funnel and the filter cake washed with ether and toluene and discarded. The filtrate weighed 2837 g. and 1987 g. of this were washed with a dilute solution of NaHCO using ether and methanol to break the emulsion formed. This was followed by 3 washes with 1:2 parts of water and methanol. The crude undried product was then topped to 185 C. at 10 mm. The product weighed 632 g, representing a 91.5% yield. It was a cloudy off white viscous liquid and analyzed 5.79% P, 0.0% Cl and acid number 0.5.
- Example Il.-Sulfurization of condensation product Example I To a one liter, fluted, 4-necked flask equipped with a reflux condenser mot-or driven stirrer, thermometer, and powerstat controlled heating mantle were charged 297 g. (0.3 mole) of the product described in Example I, 19.2 g. (0.6 mole) flowers of sulfur and 100 g. toluene. After heating and stirring the mixture for one hour the temperature was C. and the toluene was not refluxing. One hundred grams of toluene were then added to obtain refluxing at lower temperature. This occurred at 123 C. The mixture was then refluxed and stirred for 27 hours and a clear yellow solution resulted. It was then topped to 195 C at 12 mm. The clear yellow product weighed 314 g. It analyzed 5.52% P, 5.25% S and 0.0% Cl.
- Example III -Ph0sph0rus pentasulfide treatment of the condensation product of octylphenol, phosphorus trichloride and hydroquinone
- a similar condensation product prepared as in Example I having 6.16% P, 0.0% Cl was treated with 0.28% P 5 with agitation at about C. for 5.5 hours in an open flask. The odor of H 5 was evident during the first 2 hours.
- Example I V.C0ndensati0n product of para tertiary butyl phenol, phosphorus trichloride, and Izyrlroquinone This product was prepared in the same manner as Example I. After addition of the butyl phenol the reaction mass was maintained at toluene reflux temperature for 6.5 hours. After the addition of the hydroquinone-ether solution and removal of the ether the mass was refluxed at 114 C. for 3.25 hours. Part of the product was washed the same as Example I and then dried. It was topped to 175 C. at 13 mm. The yield was 80% of the theoretical. The viscous, cloudy off white product analyzed 7.22% P and 0.0% Cl.
- Example V Sulfurizatin of the condensation product of p.-tert.-butyl phenol, phosphorus trichloride and hydroquinone
- a product similar to that prepared in Example IV was sulfurized for 24 hours at 118 C, in Example II procedure. It was topped to 186 C. at 12 mm. The product was a soft solid and analyzed 6.98% P, 7.21% S and had an acid number of 14.9.
- Example VI Various amounts of the compounds of Examples I through IV were incorporated in an oil blend (identified in Table I below) and the lubricant compositions were subjected to a modified railroad oxidation test. For purposes of comparison a run without the additive of the present invention was included. In this test, 350 cc. of the oil are charged to a large tube and maintained at 285 F. in an oil bath for 1 44 hours while introducing 5 liters of oxygen per hour at the bottom 'of the tube in the presence of a copper on lead coupon measuring 1 x 3 inches.
- Oil Blend B consisted of a 30/70 blend of Solvent Refined Mid-Gontinent Neutrals, having viscosity indices of 95 and viscosities of about 80 and 160 SUS at 100 F., respectively, plus 1% of a methacrylate ester polymer which is a commercial ashless detergent.
- Example VII One weight percent of the compounds of Examples II and III and a mixture of .5 weight percent of the compound of Example I and .5 weight percent of the compound of Example II were each incorporated into a base oil B (identified in Table I) and the lubricant compositions were subjected to Shell 4-ball extreme pressure and 6 wear tests. For purposes of comparison base oil A (identified in Table II) and base oil B without the additives of the present invention were also tested. The results of the tests are shown in Table II.
- Base 011 (B) is Base Oil (A) plus 1% ashless detergent as in tests of Table I.
- R is an alkyl radical of 1 to 18 carbon atoms.
- R is an alkyl radical of 4 to 12 carbon atoms.
- R is an alkyl group of 1 to 18 carbon atoms.
- R is an alkyl radical of 4 to 12 carbon atoms.
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Description
United States Patent Office 3,245,979 Patented Apr. 12, 1966 3,245,979 PHOSPHORUS PHENOL CONDENSATION COMPOUNDS John W. Nelson, Lansing, Howard J. Maison, Harvey, and David W. Young, Homewoorl, liL, assignors to Sinclair Refining Company No Drawing. Original application Jan. 30, 1961, der. No. 85,453. Divided and this application Jan. 23, 1964, Ser. No. 345,325
Claims. (Cl. 260125) This is a division of co-pending application Serial No. 85,453, filed January 30, 1961.
The present invention relates to oleaginous base lubricants having increased load carrying capacity and improved resistance to oxidation. More particularly, it relates to lubricants containing a novel condensation product as an extreme pressure agent and anti-oxidant.
Mineral oil and synthetic lubricants, in the form of greases or free-flowing liquids, are called upon to ease friction and prevent damage to machinery operated at temperatures to as high as about 450 F. At elevated temperatures an internal combustion engine using these lubricants is an ideal oxidizing machine since the lubricant is violently agitated in the presence of air for long periods of time. In addition the stability of the lubricants is further drastically reduced due to contact with metallic surfaces which give up metallic particles to the lubricant that act as powerful oxidation catalysts. Furthermore, water also causes corrosion of metallic surfaces and accentuates oxidation of the lubricant. Aside from being stable under conditions of use the lubricant must exhibit anti-wear and load carrying or extreme pressure characteristics.
It has now been discovered that an oil-soluble condensation product of an alkylated phenol, phosphorous trichloride and hydroquinone is an excellent extreme pressure agent and when added in small effective amounts to oleaginous base lubricating oils provides a lubricant -composition improved in oxidation resistance and antiwear and extreme pressure characteristics. The alkyl-substituted phenols, including thiophenols, which are employed in the preparation of the condensation product are the monohydric phenols having at least one alkyl group, for instance, in an orthoor para-position, i.e., non-meta position. Representative alkyl phenols are those in which the alkyl group contains 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms, for example, amyl phenol, octyl phenol, nonyl phenol, p-ternbutyl phenol, p-tert-octyl phenol, the corresponding thiophenols, .a mixture of phenols and the like. The alkylated phenol is one that gives an oil-soluble product in the condensation reaction.
In the preparation of the condensation product of the present invention, the alkyl-substituted phenol, phosphorous trichloride and hydroquinone are reacted to provide an oil-soluble product. -In the reaction the alkylated phenol to phosphorous trichloride to :hydroquinone molar ratio is about 4:2:1, although slightly less or greater amounts of a given component may be used. Any method may be employed to produce the condensation product, but the preferred method comprises the following: a twostep procedure wherein (1) a stoichiometric amount of the alkyl-substituted phenol dissolved in a suitable solvent is slowly added to the phosphorous trichloride in the presence of a hydrogen chloride acceptor such as pyridine. In this finst step (RO) PCl is formed, wherein R represents the alkyl-substituted phenyl radical of the phenol. (2) In the second step the pro-per amount of hydroquinone dissolved in a suitable solvent is then slowly added and allowed to react with the remaining chlorine atom to couple the two (RO) PCl molecules and form the condensation product of the present invention.
It has also been found that sulfurizing the condensation product or treating the condensation product with a phosphorous sulfide also gives products having the desired properties. Sulfurizing of the condensation product can be accomplished in accordance with methods well-known in the art, as for instance, heating one mole of condensation product with about 1 to 3 moles of sulfur. The phosphorous sulfide-treated derivative can be obtained by heating the condensation product with about 0.01 to 5.0 weight percent of phosphorous sulfide, for example, phosphorous pentasulfide, preferably about 0.05 to 0.5%. These reactions are usually conducted at temperatures of about to 200 C., for say from about 2 to 50 or more hours.
The condensation product of an alkylated phenol, phosphorous tric-hloride and hydroquinone may be represented structurally as follows:
The sulfurized derivative of the above product can be represented structurally as follows:
R in the above structural formulae is an alkyl group of 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms. The formula of the phosphosulfurized i.e., phosphorous sulfide-treated) derivative is conjectural. At the low temperatures employed and since hydrogen sulfide is evolved during the reaction, one would expect the phosphorous sulfide to add on the aliphatic chain via the sulfur atom.
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. Generally, lubricating oils have viscosities from about 20 to 250 SUS at 210 F. The base oil may be derived from parafiinic, naphthenic, asphaltic or mixed base crudes, and if desired, a blend of solventtreated Mid-Continent neutrals and Mid-Continent bright stocks may be employed. A particularly suitable base oil used in the preparation of the composition may be described as a liquid mineral oil fraction having a viscosity index of about 100.
Grease compositions may be prepared by the incorporation or formation in the oleaginous base of vgrease-thickening fatty acid soaps of metals such as the alkaline metals of group I and II of the periodic table. The soap content of the grease is generally about 2-25%. Although the use of high viscosity oils (above 100 S.U.S. at 100 F.) gives harder greases, the use of a low viscosity non-naphthenic 100% solvent refined neutral Mid-Continent base lubricating oil provides a grease having better low temperature pumpability. The soaps are usually the alkali metal or alkaline earth metal, e.g., lithium, barium, calcium, etc.; salts of natural or synthetic long-chain carboxylic acids, such as stearic, lhydroxy stearic or lauric acids, say of 12 to 20 carbon atoms.
The base oil of the fluid lubricant or grease may be a synthetic oil of lubricating viscosity. One type of synthetic oleaginous base 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 viscosity ranges from the light to heavy oils, e.g., about 50 S.U.S. at 100 F. to 250 S.U.S. at 210 F. and preferably 30 to S.U.S. at 210 F. These esters are of improved thermal stability, low acid number, and high flash and fire points. The complex esters, diesters, mon-oesters and polyesters may be used alone or to achieve the most desirable viscosity characteristics, complex esters, diesters and polyesters may be blended with each other or with naturallyoccurring esters like castor oil to produce lubricating compositions of wide viscosity ranges which can be tailormade 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.
These esters are prepared fundamentally by the action of acids on alcohols. The mere mixture of an alcohol and acid at the proper temperature will react to produce an equilibrium mixture which includes the monoeste'r. The same is true for the reactions of organic dibasic acids and glycols to produce synthetic lubricant polyester bright stock. The diesters are frequently of the type alcoholdicarboxylic acid-alcohol, while complex esters are generally of the type X-YZYX in which X represents a monoalcohol residue, Y represents a dicarboxylic acid residue and Z represents a glycol residue and the linkages are ester linkages. These esters have been found to be es eciall adaptable to the conditions to which turbine engines are exposed, since they can be formulated to give a desirable combination of high flash point, low pour point, and high viscosity at elevated temperature, and need contain no additives which might leave a residue upon volatilization. In addition, many complex esters have shown good stability to shear. Greases which use these esters as the oleaginous base also have most of these characteristics.
Suitable monoand dicarboxylic acids used to make synthetic ester lubricant bases can be branched or straight chain and saturated or unsaturated and they frequently contain from about 2 to 12 carbons atoms. usually contain from about 4 to 12 carbon atoms. In general, the useful glycols include the aliphatic monoglycols of 4 to 20 or 30 carbon atoms, preferably 4 to 12.
The compositions of this invention incorporate a small amount of the condensation products sufficient to inhibit oxidation in the base oil of lubricating viscosity which is the major portion of the composition. This amount is generally about 0.1 to 10% or more. The preferred concentration should be the minimum amount to give adequate protection for the particular application desired and usually will be about 0.25 to 5%. In some oases 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, and in general they can be employed in any amounts desired as long as the composition is not unduly deleteri-ously affected.
The following examples are included to further illustrate the present invention but are not to be considered limiting.
Example I.Cndensation product of paratertiary octyl phenol, PCl and hydroquinone A liter, fluted, 4-necked flask, equipped with a power- :stat controlled heating mantle, thermometer, motor driven paddle stirrer and nitrogen inlet tube was used. The flask was flushed with nitrogen and a blanket of nitrogen continued during the addition of octyl phenol. The flask was then charged with 514 g. (6.5 moles) pyridine followed by 274 g. (2 moles) of PCl in 500 g. toluene. The PCl was weighed directly into the toluene to minimize .contact with air and hydrolysis with the moisture in the The alcohols air. After mixing the flasks contents thoroughly, 824 g. (4 moles) parate'rtiary octyl phenol dissolved in1000 g. toluene were added dropwise over 2.5 hours. During this addition 400 g. toluene were added to reduce the viscosity of the agitating mass, and the temperature rose from room temperature to 53 C. Some cooling was employed by blowing a stream of air on the outside of the flask. After the addition of the phenol, a Dean-Stark trap, and water cooled reflux condenser capped with a drying tube were attached to the flask. The nitrogen blanket was discontinued and entrance neck of the flask plugged. Agitation was continued and heat was applied to the mantle. The flask contents had a white precipitate, but the mixture was fluid enough for good mixing. After 1.3 hours and at a temperature of 102 C. the contents of the flask had turned to a tan color. One and a quarter hours later at 116 C. the toluene was refluxing and some of it was removed periodically through the trap. Some pyridine was lost in this process. After about 3.5 hours and the temperature still at 116 C. the nun was shut down for overnight. The reaction mass now had an orange color. The next morning, g. (1 mole) pyridine was added to insure the presence of enough pyridine to take up the hydrogen chloride formed in the next step. Then g. (1 mole) of hydroquinone dissolved in 800 g. of ether was added while stirring the mass. The heat was turned on and after 15 minutes and at 55 C. ether was removed periodically to raise the temperature of the refluxing mixture. After 3.25 hours the removal of ether was discontinued since the pot temperature was 113 C. The removed ether contained no HCl when tested with a few drops of NaOH and phenophthalein indicator. The reaction was allowed to continue for 4.25 hours at 112- 113 C.
The mass was then transferred to a beaker and allowed to stand overnight. The next day it was filtered through a Biichner funnel and the filter cake washed with ether and toluene and discarded. The filtrate weighed 2837 g. and 1987 g. of this were washed with a dilute solution of NaHCO using ether and methanol to break the emulsion formed. This was followed by 3 washes with 1:2 parts of water and methanol. The crude undried product was then topped to 185 C. at 10 mm. The product weighed 632 g, representing a 91.5% yield. It was a cloudy off white viscous liquid and analyzed 5.79% P, 0.0% Cl and acid number 0.5.
Example Il.-Sulfurization of condensation product Example I To a one liter, fluted, 4-necked flask equipped with a reflux condenser mot-or driven stirrer, thermometer, and powerstat controlled heating mantle were charged 297 g. (0.3 mole) of the product described in Example I, 19.2 g. (0.6 mole) flowers of sulfur and 100 g. toluene. After heating and stirring the mixture for one hour the temperature was C. and the toluene was not refluxing. One hundred grams of toluene were then added to obtain refluxing at lower temperature. This occurred at 123 C. The mixture was then refluxed and stirred for 27 hours and a clear yellow solution resulted. It was then topped to 195 C at 12 mm. The clear yellow product weighed 314 g. It analyzed 5.52% P, 5.25% S and 0.0% Cl.
Example III.-Ph0sph0rus pentasulfide treatment of the condensation product of octylphenol, phosphorus trichloride and hydroquinone A similar condensation product prepared as in Example I having 6.16% P, 0.0% Cl was treated with 0.28% P 5 with agitation at about C. for 5.5 hours in an open flask. The odor of H 5 was evident during the first 2 hours. The product analyzed, 6.20% P and had an acid number of 1.4.
Example I V.C0ndensati0n product of para tertiary butyl phenol, phosphorus trichloride, and Izyrlroquinone This product was prepared in the same manner as Example I. After addition of the butyl phenol the reaction mass was maintained at toluene reflux temperature for 6.5 hours. After the addition of the hydroquinone-ether solution and removal of the ether the mass was refluxed at 114 C. for 3.25 hours. Part of the product was washed the same as Example I and then dried. It was topped to 175 C. at 13 mm. The yield was 80% of the theoretical. The viscous, cloudy off white product analyzed 7.22% P and 0.0% Cl.
Example V.Sulfurizatin of the condensation product of p.-tert.-butyl phenol, phosphorus trichloride and hydroquinone A product similar to that prepared in Example IV was sulfurized for 24 hours at 118 C, in Example II procedure. It was topped to 186 C. at 12 mm. The product was a soft solid and analyzed 6.98% P, 7.21% S and had an acid number of 14.9.
Example VI Various amounts of the compounds of Examples I through IV were incorporated in an oil blend (identified in Table I below) and the lubricant compositions were subjected to a modified railroad oxidation test. For purposes of comparison a run without the additive of the present invention was included. In this test, 350 cc. of the oil are charged to a large tube and maintained at 285 F. in an oil bath for 1 44 hours while introducing 5 liters of oxygen per hour at the bottom 'of the tube in the presence of a copper on lead coupon measuring 1 x 3 inches.
TABLE I.MODIFIED RAILROAD OXIDATION TEST [Oil Blend 13*] Additive:
Example None I II III IV Concentration, percent" 0.5 1.0 1.0 1.0 Sample No. 803 6,065 6,089 6,088 6,079 Oil Blend:
Sam No. 750 6, 041 6,032 6, 054 6, 053 6,050 KV. 100 F 27. 63 27. 38 28. 44 28. 46 28. 06 RR Oxidation Test:
Kv./100 F 34. 6 27. 45 28.80 28.2 28.0 Viscosity Rise, percent 25 0.26 0. 13 0. 9 0.0 Catalyst Wt. Chge., mg. 5. 7 +1.0 +0. 5 +0.7 5. 1 Acid Number 1. 30 0. 90 0.72 1. 93 1.69 Pentane Insol., percent 0. 033 0.013 0.006 0.011 0.005 Initial pH 2.7 1.8 2. 3 1. 9 1.6
*Oil Blend B consisted of a 30/70 blend of Solvent Refined Mid-Gontinent Neutrals, having viscosity indices of 95 and viscosities of about 80 and 160 SUS at 100 F., respectively, plus 1% of a methacrylate ester polymer which is a commercial ashless detergent.
The data of Table I demonstrate that the addition of small amounts of the additives of the present invention improves the oxidative stability of the oil remarkably with reference to percent viscosity change, metal corrosiveness and pentane insolubles formation.
Example VII One weight percent of the compounds of Examples II and III and a mixture of .5 weight percent of the compound of Example I and .5 weight percent of the compound of Example II were each incorporated into a base oil B (identified in Table I) and the lubricant compositions were subjected to Shell 4-ball extreme pressure and 6 wear tests. For purposes of comparison base oil A (identified in Table II) and base oil B without the additives of the present invention were also tested. The results of the tests are shown in Table II.
The data of Table II demonstrate that the additives of the present invention in addition to being excellent antioxidants also possess extreme pressure and antiwear properties.
TABLE II.SHELL FOUR BALL TESTS Base Oil (A) is a 30/70 blend of Solvent Refining Mid-Continent Neutrals, having V.I.s of about and viseosities of about 80 and 160 SUS at F., respectively.
Base 011 (B) is Base Oil (A) plus 1% ashless detergent as in tests of Table I.
We claun:
1. The product having the structural formula:
wherein R is an alkyl radical of 1 to 18 carbon atoms.
2. The product of claim 1 wherein R is an alkyl radical of 4 to 12 carbon atoms.
3. The product of claim 1 phosphosulfurized with about 0.01 to 5% of phosphorus sulfide.
4. The product having the structural formula:
wherein R is an alkyl group of 1 to 18 carbon atoms.
5. The product of claim 4 wherein R is an alkyl radical of 4 to 12 carbon atoms.
References Cited by the Examiner UNITED STATES PATENTS 2,234,379 3/1941 Martin 260461.303 X 2,520,090 4/1950 Barrett 260461.303 X 2,642,461 6/1953 Morris et a1. 260-461.303 X 2,820,766 1/1958 Elliott et a1. 260-461.303 X 2,952,701 9/1960 McConnell et al. 26046l.303 X OTHER REFERENCES Kosolapotf, Organo-Phosphorus Compounds, John Wiley and Sons, New York, New York (1950), p. 184.
CHARLES B. PARKER, Primary Examiner.
FRANK M. SIKORA, DELBERT R. PHILLIPS,
Assistant Examiners.
Claims (2)
1. THE PRODUCT HAVING THE STRUCTURAL FORMULA:
3. THE PRODUCT OF CLAIM 1 PHOSPHOSULFURIZED WITH ABOUT 0.01 TO 5% OF PHOSPHORUS SULFIDE.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US345825A US3245979A (en) | 1961-01-30 | 1964-01-23 | Phosphorus phenol condensation compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US85453A US3240704A (en) | 1961-01-30 | 1961-01-30 | Lubricating compositions having oilsoluble phosphorus-containing condensation products |
US345825A US3245979A (en) | 1961-01-30 | 1964-01-23 | Phosphorus phenol condensation compounds |
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US3245979A true US3245979A (en) | 1966-04-12 |
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US345825A Expired - Lifetime US3245979A (en) | 1961-01-30 | 1964-01-23 | Phosphorus phenol condensation compounds |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3536623A (en) * | 1968-01-05 | 1970-10-27 | Exxon Research Engineering Co | Organic halo phosphite ester reaction products and hydrocarbon oil compositions containing the same |
US3867367A (en) * | 1971-12-20 | 1975-02-18 | Texaco Inc | Sulfurized oligomeric phosphorodiamidate |
EP0049166A1 (en) * | 1980-10-01 | 1982-04-07 | Uniroyal, Inc. | Hydrolytically stable diphosphites useful as antioxidants |
US4463112A (en) * | 1980-02-13 | 1984-07-31 | Leistner William E | Phenylethylidene-substituted phenyl polyphosphites |
US4800030A (en) * | 1985-12-28 | 1989-01-24 | Idemitsu Kosan Company Limited | Refrigerator oil composition |
US6069267A (en) * | 1997-07-29 | 2000-05-30 | E. I. Du Pont De Nemours And Company | Selective synthesis of organodiphosphite compounds |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2234379A (en) * | 1938-03-25 | 1941-03-11 | Monsanto Chemicals | Preservation of soap |
US2520090A (en) * | 1947-12-30 | 1950-08-22 | Monsanto Chemicals | Polyphosphates of divalent aryl hydrocarbons |
US2642461A (en) * | 1952-03-29 | 1953-06-16 | Shell Dev | Organodiphosphine oxides and sulfides |
US2820766A (en) * | 1953-09-17 | 1958-01-21 | Wakefield & Co Ltd C C | Lubricating compositions |
US2952701A (en) * | 1957-04-15 | 1960-09-13 | Eastman Kodak Co | Organophosphorus derivatives of 2, 2-dimethyl-1, 3-propanediol |
-
1964
- 1964-01-23 US US345825A patent/US3245979A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2234379A (en) * | 1938-03-25 | 1941-03-11 | Monsanto Chemicals | Preservation of soap |
US2520090A (en) * | 1947-12-30 | 1950-08-22 | Monsanto Chemicals | Polyphosphates of divalent aryl hydrocarbons |
US2642461A (en) * | 1952-03-29 | 1953-06-16 | Shell Dev | Organodiphosphine oxides and sulfides |
US2820766A (en) * | 1953-09-17 | 1958-01-21 | Wakefield & Co Ltd C C | Lubricating compositions |
US2952701A (en) * | 1957-04-15 | 1960-09-13 | Eastman Kodak Co | Organophosphorus derivatives of 2, 2-dimethyl-1, 3-propanediol |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3536623A (en) * | 1968-01-05 | 1970-10-27 | Exxon Research Engineering Co | Organic halo phosphite ester reaction products and hydrocarbon oil compositions containing the same |
US3867367A (en) * | 1971-12-20 | 1975-02-18 | Texaco Inc | Sulfurized oligomeric phosphorodiamidate |
US4463112A (en) * | 1980-02-13 | 1984-07-31 | Leistner William E | Phenylethylidene-substituted phenyl polyphosphites |
EP0049166A1 (en) * | 1980-10-01 | 1982-04-07 | Uniroyal, Inc. | Hydrolytically stable diphosphites useful as antioxidants |
US4800030A (en) * | 1985-12-28 | 1989-01-24 | Idemitsu Kosan Company Limited | Refrigerator oil composition |
US6069267A (en) * | 1997-07-29 | 2000-05-30 | E. I. Du Pont De Nemours And Company | Selective synthesis of organodiphosphite compounds |
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