US3536623A - Organic halo phosphite ester reaction products and hydrocarbon oil compositions containing the same - Google Patents
Organic halo phosphite ester reaction products and hydrocarbon oil compositions containing the same Download PDFInfo
- Publication number
- US3536623A US3536623A US695893A US3536623DA US3536623A US 3536623 A US3536623 A US 3536623A US 695893 A US695893 A US 695893A US 3536623D A US3536623D A US 3536623DA US 3536623 A US3536623 A US 3536623A
- Authority
- US
- United States
- Prior art keywords
- phosphite
- chloro
- sulfur
- sludge
- polyhydric
- 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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- 239000000203 mixture Substances 0.000 title description 38
- -1 halo phosphite ester Chemical class 0.000 title description 36
- 239000007795 chemical reaction product Substances 0.000 title description 17
- 229930195733 hydrocarbon Natural products 0.000 title description 13
- 239000004215 Carbon black (E152) Substances 0.000 title description 9
- 150000002430 hydrocarbons Chemical class 0.000 title description 9
- 239000010802 sludge Substances 0.000 description 29
- 125000001309 chloro group Chemical group Cl* 0.000 description 26
- 239000000654 additive Substances 0.000 description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 24
- 229910052717 sulfur Inorganic materials 0.000 description 21
- 239000011593 sulfur Substances 0.000 description 20
- 239000010687 lubricating oil Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 239000000446 fuel Substances 0.000 description 14
- 150000004820 halides Chemical class 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- 239000000376 reactant Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000002401 inhibitory effect Effects 0.000 description 11
- 150000008301 phosphite esters Chemical class 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 239000007859 condensation product Substances 0.000 description 9
- 150000005690 diesters Chemical class 0.000 description 8
- 239000010688 mineral lubricating oil Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 239000002199 base oil Substances 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 125000002877 alkyl aryl group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 5
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- NPXUKNQBFIIIDW-UHFFFAOYSA-N dichlorophosphinite Chemical compound [O-]P(Cl)Cl NPXUKNQBFIIIDW-UHFFFAOYSA-N 0.000 description 4
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000010763 heavy fuel oil Substances 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002367 Polyisobutene Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000006422 bromocycloalkyl group Chemical group 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 150000000218 1-tetradecanols Chemical class 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- MWCBGWLCXSUTHK-UHFFFAOYSA-N 2-methylbutane-1,4-diol Chemical compound OCC(C)CCO MWCBGWLCXSUTHK-UHFFFAOYSA-N 0.000 description 1
- ZBCATMYQYDCTIZ-UHFFFAOYSA-N 4-methylcatechol Chemical compound CC1=CC=C(O)C(O)=C1 ZBCATMYQYDCTIZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N Trimethylene glycol Natural products OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical group [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols 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
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- YKUQQHYAEQIQHO-UHFFFAOYSA-N dichloro (2-nonylphenyl) phosphite Chemical compound P(OCl)(OCl)OC1=C(C=CC=C1)CCCCCCCCC YKUQQHYAEQIQHO-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HQPMKSGTIOYHJT-UHFFFAOYSA-N ethane-1,2-diol;propane-1,2-diol Chemical compound OCCO.CC(O)CO HQPMKSGTIOYHJT-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
-
- 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
- C07F9/201—Esters of thiophosphorus acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2691—Compounds of uncertain formula; reaction of organic compounds (hydrocarbons acids, esters) with Px Sy, Px Sy Halz or sulfur and phosphorus containing 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
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
-
- 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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- 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
- C10M2209/086—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 polycarboxylic, e.g. maleic acid
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
- C10M2215/065—Phenyl-Naphthyl amines
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
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- 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
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- 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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- 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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- 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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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
- C10M2225/041—Hydrocarbon polymers
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- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
Definitions
- the present invention relates to organic halophosphite mono or diesters reacted with halides of sulfur and with either an alkylene glycol or other polyhydric alkylene or aromatic hydrocarbon to produce novel additives for lubricating oils, middle distillate fuels and residual fuels.
- novel condensation products have been found to inhibit oxidation, inhibit sludge formation, act as sludge dispersants to a certain degree, and to be good antiwear agents.
- the additives are not only useful in lubricating oils but also fuels derived from mineral oils because it has been found that they have a certain degree of flowability improvement and, at the same time, they minimize wear on pumps used to transfer fuels through conduits and other types of fuel supply lines. These novel additives tend to minimize fouling and plugging difficulties in the transportation of fuels through pipes and the like where pumps are required to be the prime movers for such articles of commerce.
- novel organic halophosphite ester reaction products are ashless in nature which means that they tend to eliminate the formation of deposits on the internal surfaces of the combustion engines when added to lubricating oils used in those engines, Whereas, sludge inhibitors and sludge dispersants containing metal ions, upon their breakdown, tend to deposit the metals in one form or another on the internal surfaces of such engines thus leaving a residue of ash-forming deposits which is considered to be undesirable. Many of the heretofore used sludge inhibitors and sludge dispersants not only are ash forming but tend to be too corrosive for practical purposes when coming in contact with the conventionally used copper-lead bearing employed in automotive and diesel engines.
- the heretofore employed dispersants oftentimes do exhibit certain desirable properties but they may lack suflicient antioxidant and antiwear properties thus making it necessary to employ still other additives in association with these dispersants in order to impart additional desirable properties to the fuels and lubricating oils.
- the organic halophosphite mono and diesters herein employed in producing condensation products are, for the most part, not new in and of themselves but the resultant condensation reaction products are believed to be novel and are designed to impart antioxidant, rust preventive, antiwear, sludge inhibiting and sludge dispersing characteristics to the fuels and lubricating oils to which they are added to a much greater degree than has heretofore been thought possible
- the novel condensation products which offer enhanced utilities in connection with their use in lubricating oils and mineral oil fuels are produced by reacting organic halophosphite mono or diesters with a halide of sulfur and with an alkylene glycol or other polyhydric alkylene or aromatic hydrocarbon.
- these halophosphite esters may be reacted with a preformed reaction product of a halide of sulfur with an alkylene glycol or with another polyhydric alkylene or aromatic hydrocarbon.
- the final condensation product appears to be substantially the same regardless of whether or not the halides of sulfur and the polyhydric compounds are reacted sequentially with the phosphite esters, are first reacted with each other, or are simultaneously added to the phosphite ester reactants.
- organic halophosphite esters used as reactants are represented by the formula:
- R is selected from the group consisting of alkyl, chloro and bromo alkyl, aryl, chloro and bromo aryl, aralkyl, chloro and bromo aralkyl, cycloalkyl, chloro and bromo cycloalkyl, alkenyl, chloro and bromo alkenyl, alkaryl, and chloro and bromo alkaryl;
- X is selected from the group consisting of chloro and bromo and CR and X is selected from the group consisting of chloro and bromo.
- the polyphosphite prepared from polyhydric compounds may be used as well.
- Phosphite ester compounds as defined, are reacted then with a halide of sulfur followed by a reaction with a polyhydric organic compound or they are reacted simultaneously with an admixture of the halide of sulfur and the polyhydric compound.
- these phosphite esters may also be reacted with the reaction product of a halide of sulfur with a polyhydric compound of the type more fully described hereinafter.
- Typical phosphite esters which may be employed are as follows:
- the lorol radicals mentioned above in connection with the specific phosphites named are derived from the corresponding primary alcohols obtained by the reaction of carboxylic acid mixtures obtained from coconut or palm kernel oils. They are largely composed of lauryl alcohol together with minor amounts of octyl, decyl, and myristyl alcohols. Typically, this alcohol mixture boils between about 140 C. and about 190 C. at 50 mm. mercury pressure.
- the phosphite ester compounds are conventionally prepared by reacting the corresponding phenol or alcohol with the desired phosphorus trihalide, i.e., phosphorus trichloride or phosphorus tribromide. The particular method of preparation is immaterial since the mono and dihalo phosphite esters are, for the most part, old and well known and for the purposes of the present invention they are simply employed as one of the reactants to produce the novel additive compounds.
- Any halide of sulfur will be suitable for use as the second reactant employed in effecting the production of the novel condensation products, for example, sulfur monochloride, sulfur dichloride and sulfuryl chloride may be employed as a reactant.
- the final reactant is an organic compound containing two or more hydroxyl groups attached to carbon atoms, i.e., the final reactant employed may be an alkylene glycol or other polyhydric alkylene or aromatic hydrocarbon.
- the final reactant employed may be an alkylene glycol or other polyhydric alkylene or aromatic hydrocarbon.
- Specific compounds which are suitable examples of polyhydric reactants in the instant invention are as follows:
- reaction of the organic halo phosphite mono or diester with the other reactants is carried out in liquid phase either in the presence or absence of inert solvents such as normally liquid hydrocarbon petroleum solvents, petroleum ether, hexane, cyclohexane, heptane, benzene, toluene middle distillate fractions, residual fuel oils or lubricating oil fractions.
- inert solvents such as normally liquid hydrocarbon petroleum solvents, petroleum ether, hexane, cyclohexane, heptane, benzene, toluene middle distillate fractions, residual fuel oils or lubricating oil fractions.
- the last named solvent is particularly desirable for example, in cases where the final product is to be used in lubricating oils because the reacted mixture, upon purification, serves as a concentrate containing any-where from 50% to 75% of the active 4 phosphite sulfurized condensation product as the active ingredient and constitutes a convenient method of marketing the novel additive compound.
- the reaction is carried out in a temperature range between about 0 C. and about 100 C., preferably between about 20 C. and about C.
- the reaction time varies depending upon the reaction temperature employed. Generally, for the addition of the polyhydric compound, from between about 1 and about 10 hours, preferably between about 3 and about 6 hours are used. In any event, a sufficient length of time of reaction is maintained so that the evolution of hydrogen halide has completely ceased. The end of the evolution of the hydrogen halide is an indication of the completion of the reaction.
- the residual traces of hydrogen halide are stripped from the reacted mixture by means of an inert carrier gas stream, such as nitrogen. During this stripping operation, if desired, a slight vacuum may be applied in order to hasten the stripping operation.
- the mole ratio of reactants is as follows: the ratio of the halide of sulfure to the phosphite ester will range between about 2:1 and about 1:2 moles, in the case of a monoester being used, and between about 2:1 and about 1:4 moles in the case of a diester being used.
- polyhydric compound employcd per unit of phosphite ester this will usually be about one equivalent of hydroxyl per halide attached to a phosphorus or sulfur atom. It is also possible to use larger amounts of polyhydric compounds, particularly if a chloro or bromo-substituted constituent for R is used. Also, if a polyphosphite ester is used, up to 4 times the number of moles of polyhydric compound may be employed over that used in the case of the corresponding phosphite ester as represented by the foregoing structural formula. In the case of the pre-reaction of a halide of sulfur with the polyhydric compounds, a temperature of between about 10 and about 40 C. is used and an equi-molar amount of sulfur halide per hydroxyl compound is used.
- the molar ratio of phosphorus trihalide to glycol or to polyhydric aromatic hydrocarbon is between about 2:1 and about 4:1, also depending upon whether diesters or monoesters are desired to be the predominant component of the resultant reactant mixture.
- a mole ratio of alcohol to phosphorus trihalide of be tween about 0.75:1 and about 2.5 :1 is maintained and preferably a mole ratio of glycol or other polyhydric alkylene or aromatic hydrocarbon to phosphorus trihalide of between about 1.511 and about 5:1 is maintained.
- Any solvents which are employed in effectuating the reaction are distilled off at atmospheric pressures or under slight vacuum.
- novel sulfurized phosphite-polyhydric condensation products are useful in lubricating oil compositions of the type customarily employed in internal combustion engines of either the gasoline or diesel fuel type as well as in the lubrication of heavy duty gas engines.
- the amounts incorporated into such lubricating oils range between about 0.01 and about 10.0 wt. percent, preferably between about 0.1 and about 5 .0 wt. percent.
- the novel additives are also useful in middle distillate fuels and residual fuel oils because they impart antirust, anti-1 corrosive and sludge inhibiting properties to such materials into which the additives are incorporated.
- these hydrocarbon compositions include gasoline, jet furl, kerosene, heating oil, heavy residual fuels such as Bunker C, and the like.
- the additives are incorporated into amounts ranging between about 0.01 and about 5.0 wt. percent, preferably between about 0.05 and about 2.0 wt. percent, all percentages being based on the total weight of the composition.
- the fuels and lubricating oil compositions described may also include other conventional additives present in like or smaller amounts.
- they may contain oxidation inhibitors such as phenyl alpha naphthylarnine; rust inhibitors such as the over-based alkaline earth metal petroleum sulfonates; detergent additives such as overbased calcium petroleum sulfonate, zinc dialkyl dithiophosphates, phosphosulfurized polyisobutylene, barium phenate sulfide, phenol sulfonates; viscosity index improvers such as the polymers and copolymers of long chain alkyl acrylates and methacrylates, the polymers and copolymers of long chain alkyl fumarates, polyisobutylene, the aryl and alkyl phosphates; the four point depressants such as wax-alkylated naphthalenes, and the like.
- they may contain other ashless dispersants such as polyisobutyl
- a typical lubricating oil fraction of the SAE 10W30 grade is representative of automotive lubricating oils conventionally available. This was employed in carrying out certain of the tests described in the examples.
- the base oil was composed of about 90% of a solvent-extracted, dewaxed, neutral oil from Mid-Continent paraffinic crude. It had a viscosity of 105-115 SUS (Saybolt Universal Seconds) at 100 F. and a pour point of about F. The remaining of the base oil blend was the same type of oil but had a viscosity of about 450-500 SUS at 100 F.
- the oil also contained, in all tests, approximately 10% of a viscosity index improver, namely, polyisobutylene and about 3.75% of an ashless dispersant, i.e., the polyisobutenyl succinic anhydride imide of tetraethylene pentamine. Minor amounts, i.e., less than 1%, of over-based calcium petroleum sulfonate and wax-alkylated naphthalene were also present.
- the amount of novel additive employed in the base oil for test purposes was, in all cases, about 1 wt. percent based upon the total weight of the composition.
- Falex wear test Two types of tests were carried out to test the efficacy of the herein described novel additives.
- a Falex wear test machine was operated with the test oils for minutes under 500 lbs. per square inch direct pressure gauge reading on a hearing having a rotating steel pin and then determining, at the end of this time, the milligrams of wear on the steel pin used in the test. The test was conducted for the purpose of measuring the amount of wear which the bearings would encounter under extremely severe conditions and while using the test oil compositions.
- cyclic temperature sludge test which evaluated the sludge-handling ability of the tested lubricating oil compositions.
- the temperature of the oil was cyclically raised and lowered over a period of stated hours in order to determine the oxidation stability and the sludge inhibiting or sludge forming tendencies of the novel additives in the oil compositions.
- a 6 cylinder Ford engine was used which employed a standard carburetor. It was operated at a standard speed of 1,500 r.p.m.::15 r.p.m. under a constant load of 140:2 foot lbs. of torque.
- the oil sump temperature was maintained in the cold phase at 150 F.i-'5 F. and in the hot phase at 215 F.i5 F.
- the cold phase operation was for a period of 5 hours and alternated with a hot phase operation of 2 hours.
- EXAMPLE 1 600 grams of nonylphenol were gradually added to 414 grams of phosphorus trichloride at ambient or room tem perature. The admixture (after 3 hours) ceased evolving hydrogen chloride gas. An aliquot constituting 158 grams of the nonylphenol dichloro phosphite ester was then mixed with about 51 grams of sulfur dichloride. After the addition of the sulfur dichloride, the mixture was then gradually added to about 62 grams of ethylene glycol. After completion of the addition, the reaction temperature of the reacting mixture was increased from ambient temperature to about C. and kept at this temperature for about 3 hours with stirring and agitation. In the final stages of the final 3-hour period, the mixture was stripped with a stream of nitrogen gas for about 2 hours. The product had a phosphorus content of about 7.95 wt. percent and a sulfur content of about 9.33 wt. percent.
- EXAMPLE 3 200 grams of nonylphenol was added, dropwise, to 137 grams of phosphorus trichloride at room temperature. The mixture was stirred constantly until evolution of hydrogen chloride gas had completely stopped. This reaction mixture was then admixed, dropwise, with about 76 grams of sulfur monochloride and the resultant mixture added, dropwise, to about 62 grams of ethylene glycol while maintaining the mixture at about room temperature. The reaction mixture was stirred for 3 hours and was then stripped with a stream of nitrogen gas for 2 hours at room temperature. The product showed a phosphorus content of about 4.16 wt. percent and a sulfur content of about 4.48 wt. percent.
- a test carried out on the base oil but containing no zinc di-(C -C alkyl)- dithiophosphate and no additive resulted in a broken pin Falex test,
- brorno cycloalkyl alkenyl, chloro and bromo alkenyl, alkaryl, and chloro and brorno alkaryl;
- X is selected from the group consisting of chloro, brorno and CR and X is selected from the group consisting of chloro and bromo,
- R is selected from the group consisting of alkyl, chloro and brorno alkyl, aryl, chloro and bromo aryl, aralkyl, chloro and bromo aralkyl, cycloalkyl, chloro and bromo cycloalkyl, alkenyl, chloro and brorno alkenyl, alkaryl, and chloro and brorno alkaryl;
- X is selected from the group consisting of chloro, brorno and 0R and X is selected from the group consisting of chloro and brorno, with a halide of sulfur and with a polyhydric hydrocarbon selected from the group consisting of polyhydric alkylene hydrocarbons and polyhydric arylene hydrocarbons.
- chloro and brorno alkyl aryl, chloro and brorno aryl, aralkyl, chloro and bromo aralkyl, cycloalkyl, chloro and with the reaction product of halide of sulfur and a polyhydric hydrocarbon selected from the group consisting of polyhydric alkylene hydrocarbons and polyhydric arylene hydrocarbons.
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Description
United States Patent ORGANIC HALO PHOSPHITE ESTER REACTION PRODUCTS AND HYDROCARBON OIL COMPO- SITIONS CONTAINING THE SAME Shih-En Hu, Roselle, N.J., assignor to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed Jan. 5, 1968, Ser. No. 695,893
Int. Cl. Cm 1/48 U.S. Cl. 25246.7 8 Claims ABSTRACT OF THE DISCLOSURE Organic halophosphite mono or diesters are reacted with a halide of sulfur and alkylene glycols or other polyhydric alkylene or aromatic compounds. These novel condensation products exhibit sludge inhibition, sludge dispersancy, rust inhibition, and antiwear properties when admixed at between about 0.1 and about 10.0 wt. percent, in lubricating mineral oils, middle distillate hydrocarbon fuels, and residual hydrocarbon fuels The present invention relates to organic halophosphite mono or diesters reacted with halides of sulfur and with either an alkylene glycol or other polyhydric alkylene or aromatic hydrocarbon to produce novel additives for lubricating oils, middle distillate fuels and residual fuels. These novel condensation products have been found to inhibit oxidation, inhibit sludge formation, act as sludge dispersants to a certain degree, and to be good antiwear agents. The additives are not only useful in lubricating oils but also fuels derived from mineral oils because it has been found that they have a certain degree of flowability improvement and, at the same time, they minimize wear on pumps used to transfer fuels through conduits and other types of fuel supply lines. These novel additives tend to minimize fouling and plugging difficulties in the transportation of fuels through pipes and the like where pumps are required to be the prime movers for such articles of commerce.
Various phoshite derivatives have, in the past, been produced and used as additives in both hydrocarbon fuel compositions and in lubricating oil compositions. Usually such phosphite derivatives, as employed in the past, suffer from one or more deficiencies with respect to the aforementioned properties so that it has *become a major undertaking of many persons working in the art to find novel additives which will impart additional characteristics, in one or more respects, to these mineral oil fractions by the incorporation of novel additives thereto. Such incorporation serves a combination of functions. High operating temperatures in internal combustion engines tend to accelerate the deterimental oxidative influences on lubricating oils and this, in turn, tends to result in the early breakdown of these oils with the resultant formation of acids and other sludge type materials which generally gum-up, clog and corrode bearings, pumps and the like, and deposit sludge-like materials on the internal surfaces of internal combustion engines. This, in turn, leads to excessive bearing wear, plugging difficulties in oil circulation systems, and a general fouling of the moving parts of such engines because of excessive sludge formation.
The novel organic halophosphite ester reaction products, hereinafter described, are ashless in nature which means that they tend to eliminate the formation of deposits on the internal surfaces of the combustion engines when added to lubricating oils used in those engines, Whereas, sludge inhibitors and sludge dispersants containing metal ions, upon their breakdown, tend to deposit the metals in one form or another on the internal surfaces of such engines thus leaving a residue of ash-forming deposits which is considered to be undesirable. Many of the heretofore used sludge inhibitors and sludge dispersants not only are ash forming but tend to be too corrosive for practical purposes when coming in contact with the conventionally used copper-lead bearing employed in automotive and diesel engines. The heretofore employed dispersants oftentimes do exhibit certain desirable properties but they may lack suflicient antioxidant and antiwear properties thus making it necessary to employ still other additives in association with these dispersants in order to impart additional desirable properties to the fuels and lubricating oils. The organic halophosphite mono and diesters herein employed in producing condensation products are, for the most part, not new in and of themselves but the resultant condensation reaction products are believed to be novel and are designed to impart antioxidant, rust preventive, antiwear, sludge inhibiting and sludge dispersing characteristics to the fuels and lubricating oils to which they are added to a much greater degree than has heretofore been thought possible The novel condensation products which offer enhanced utilities in connection with their use in lubricating oils and mineral oil fuels are produced by reacting organic halophosphite mono or diesters with a halide of sulfur and with an alkylene glycol or other polyhydric alkylene or aromatic hydrocarbon. Alternatively, these halophosphite esters may be reacted with a preformed reaction product of a halide of sulfur with an alkylene glycol or with another polyhydric alkylene or aromatic hydrocarbon. The final condensation product appears to be substantially the same regardless of whether or not the halides of sulfur and the polyhydric compounds are reacted sequentially with the phosphite esters, are first reacted with each other, or are simultaneously added to the phosphite ester reactants.
The organic halophosphite esters used as reactants are represented by the formula:
wherein R is selected from the group consisting of alkyl, chloro and bromo alkyl, aryl, chloro and bromo aryl, aralkyl, chloro and bromo aralkyl, cycloalkyl, chloro and bromo cycloalkyl, alkenyl, chloro and bromo alkenyl, alkaryl, and chloro and bromo alkaryl; X is selected from the group consisting of chloro and bromo and CR and X is selected from the group consisting of chloro and bromo. The polyphosphite prepared from polyhydric compounds may be used as well.
Phosphite ester compounds, as defined, are reacted then with a halide of sulfur followed by a reaction with a polyhydric organic compound or they are reacted simultaneously with an admixture of the halide of sulfur and the polyhydric compound. As before stated, these phosphite esters may also be reacted with the reaction product of a halide of sulfur with a polyhydric compound of the type more fully described hereinafter. Typical phosphite esters which may be employed are as follows:
nonylphenyl, dichloro phosphite normal propyl dichloro phosphite isopropyl, butylhexyl chloro phosphite cyclohexyl dichloro phosphite decyl dichloro phosphite lorol dichloro phosphite cetyl dichloro phosphite phenyl dichloro phosphite cresyl dichloro phosphite tolyl dichloro phosphite 3 dinonylphenyl chloro phosphite diphenyl chloro phosphite dicresyl chloro phosphite ditolyl chloro phosphite dicyclohexyl chloro phosphite ethylbenzyl dichloro phosphite nonyl, phenyl chloro phosphite dioctadecyl chloro phosphite polyisobutenylphenyl dichloro phosphite dipolyisobutenyl chloro phosphite diethylbenzyl chloro phosphite chloroctyl dichloro phosphite chlorbenzyl dichloro phosphite chlorpolyisobutenyl, nonylphenyl chloro phosphite Each of the above named specific compounds may have the chlorine atom substituted with a bromine atom and serve equally as well as the reactant. The lorol radicals mentioned above in connection with the specific phosphites named are derived from the corresponding primary alcohols obtained by the reaction of carboxylic acid mixtures obtained from coconut or palm kernel oils. They are largely composed of lauryl alcohol together with minor amounts of octyl, decyl, and myristyl alcohols. Typically, this alcohol mixture boils between about 140 C. and about 190 C. at 50 mm. mercury pressure. The phosphite ester compounds are conventionally prepared by reacting the corresponding phenol or alcohol with the desired phosphorus trihalide, i.e., phosphorus trichloride or phosphorus tribromide. The particular method of preparation is immaterial since the mono and dihalo phosphite esters are, for the most part, old and well known and for the purposes of the present invention they are simply employed as one of the reactants to produce the novel additive compounds.
Any halide of sulfur will be suitable for use as the second reactant employed in effecting the production of the novel condensation products, for example, sulfur monochloride, sulfur dichloride and sulfuryl chloride may be employed as a reactant.
The final reactant is an organic compound containing two or more hydroxyl groups attached to carbon atoms, i.e., the final reactant employed may be an alkylene glycol or other polyhydric alkylene or aromatic hydrocarbon. Specific compounds which are suitable examples of polyhydric reactants in the instant invention are as follows:
ethylene glycol propylene glycol 1,2 trimethylene glycol Z-methyl propylene glycol 2-methyl butylene glycol catechol glycerol pentaerythritol diethylene glycol resorcinol hydroquinone para, para-dihydroxy diphenol methyl hydroquinone 4-methyl catechol triethylene glycol polyethylene glycol polypropylene glycol The reaction of the organic halo phosphite mono or diester with the other reactants is carried out in liquid phase either in the presence or absence of inert solvents such as normally liquid hydrocarbon petroleum solvents, petroleum ether, hexane, cyclohexane, heptane, benzene, toluene middle distillate fractions, residual fuel oils or lubricating oil fractions. The last named solvent is particularly desirable for example, in cases where the final product is to be used in lubricating oils because the reacted mixture, upon purification, serves as a concentrate containing any-where from 50% to 75% of the active 4 phosphite sulfurized condensation product as the active ingredient and constitutes a convenient method of marketing the novel additive compound.
The reaction is carried out in a temperature range between about 0 C. and about 100 C., preferably between about 20 C. and about C. The reaction time varies depending upon the reaction temperature employed. Generally, for the addition of the polyhydric compound, from between about 1 and about 10 hours, preferably between about 3 and about 6 hours are used. In any event, a sufficient length of time of reaction is maintained so that the evolution of hydrogen halide has completely ceased. The end of the evolution of the hydrogen halide is an indication of the completion of the reaction. The residual traces of hydrogen halide are stripped from the reacted mixture by means of an inert carrier gas stream, such as nitrogen. During this stripping operation, if desired, a slight vacuum may be applied in order to hasten the stripping operation.
In general, the mole ratio of reactants is as follows: the ratio of the halide of sulfure to the phosphite ester will range between about 2:1 and about 1:2 moles, in the case of a monoester being used, and between about 2:1 and about 1:4 moles in the case of a diester being used.
In the case of the amount of polyhydric compound employcd per unit of phosphite ester employed, this will usually be about one equivalent of hydroxyl per halide attached to a phosphorus or sulfur atom. It is also possible to use larger amounts of polyhydric compounds, particularly if a chloro or bromo-substituted constituent for R is used. Also, if a polyphosphite ester is used, up to 4 times the number of moles of polyhydric compound may be employed over that used in the case of the corresponding phosphite ester as represented by the foregoing structural formula. In the case of the pre-reaction of a halide of sulfur with the polyhydric compounds, a temperature of between about 10 and about 40 C. is used and an equi-molar amount of sulfur halide per hydroxyl compound is used.
Many of the halophosphite mono and diesters above mentioned are available commercially. For those enumerated above which are not available commercially, it is a simple matter to effect a reaction between phosphorus trichloride or tribromide and the corresponding monohydric alcohol or phenol or between the phosphorus trihalides and the corresponding polyhydric alkylenes or aromatic hydrocarbons in which the molar ratios of the alcohol to phosphorus compound are maintained at between about 111 and about 2:1 depending upon whether or not it is desired to produce a mixture predominating in mono or diphosphite ester. In the case of the polyhydric compounds, the molar ratio of phosphorus trihalide to glycol or to polyhydric aromatic hydrocarbon is between about 2:1 and about 4:1, also depending upon whether diesters or monoesters are desired to be the predominant component of the resultant reactant mixture. Preferably a mole ratio of alcohol to phosphorus trihalide of be tween about 0.75:1 and about 2.5 :1 is maintained and preferably a mole ratio of glycol or other polyhydric alkylene or aromatic hydrocarbon to phosphorus trihalide of between about 1.511 and about 5:1 is maintained. Any solvents which are employed in effectuating the reaction are distilled off at atmospheric pressures or under slight vacuum.
The novel sulfurized phosphite-polyhydric condensation products are useful in lubricating oil compositions of the type customarily employed in internal combustion engines of either the gasoline or diesel fuel type as well as in the lubrication of heavy duty gas engines. The amounts incorporated into such lubricating oils range between about 0.01 and about 10.0 wt. percent, preferably between about 0.1 and about 5 .0 wt. percent. As before stated, the novel additives are also useful in middle distillate fuels and residual fuel oils because they impart antirust, anti-1 corrosive and sludge inhibiting properties to such materials into which the additives are incorporated. Specifically, these hydrocarbon compositions include gasoline, jet feul, kerosene, heating oil, heavy residual fuels such as Bunker C, and the like. When used in these particular petroleum fuel fractions, the additives are incorporated into amounts ranging between about 0.01 and about 5.0 wt. percent, preferably between about 0.05 and about 2.0 wt. percent, all percentages being based on the total weight of the composition.
The fuels and lubricating oil compositions described may also include other conventional additives present in like or smaller amounts. For example, they may contain oxidation inhibitors such as phenyl alpha naphthylarnine; rust inhibitors such as the over-based alkaline earth metal petroleum sulfonates; detergent additives such as overbased calcium petroleum sulfonate, zinc dialkyl dithiophosphates, phosphosulfurized polyisobutylene, barium phenate sulfide, phenol sulfonates; viscosity index improvers such as the polymers and copolymers of long chain alkyl acrylates and methacrylates, the polymers and copolymers of long chain alkyl fumarates, polyisobutylene, the aryl and alkyl phosphates; the four point depressants such as wax-alkylated naphthalenes, and the like. In addition, they may contain other ashless dispersants such as polyisobutylene-substituted succinic anhydride condensation reaction products with polyethylene polyamine such as tetraethylene pentamine.
A typical lubricating oil fraction of the SAE 10W30 grade is representative of automotive lubricating oils conventionally available. This was employed in carrying out certain of the tests described in the examples. The base oil was composed of about 90% of a solvent-extracted, dewaxed, neutral oil from Mid-Continent paraffinic crude. It had a viscosity of 105-115 SUS (Saybolt Universal Seconds) at 100 F. and a pour point of about F. The remaining of the base oil blend was the same type of oil but had a viscosity of about 450-500 SUS at 100 F. The oil also contained, in all tests, approximately 10% of a viscosity index improver, namely, polyisobutylene and about 3.75% of an ashless dispersant, i.e., the polyisobutenyl succinic anhydride imide of tetraethylene pentamine. Minor amounts, i.e., less than 1%, of over-based calcium petroleum sulfonate and wax-alkylated naphthalene were also present. The amount of novel additive employed in the base oil for test purposes was, in all cases, about 1 wt. percent based upon the total weight of the composition.
Two types of tests were carried out to test the efficacy of the herein described novel additives. In one test known as the Falex wear test, a Falex wear test machine was operated with the test oils for minutes under 500 lbs. per square inch direct pressure gauge reading on a hearing having a rotating steel pin and then determining, at the end of this time, the milligrams of wear on the steel pin used in the test. The test was conducted for the purpose of measuring the amount of wear which the bearings would encounter under extremely severe conditions and while using the test oil compositions.
Another test was carried out known as the cyclic temperature sludge test which evaluated the sludge-handling ability of the tested lubricating oil compositions. In this test the temperature of the oil was cyclically raised and lowered over a period of stated hours in order to determine the oxidation stability and the sludge inhibiting or sludge forming tendencies of the novel additives in the oil compositions. A 6 cylinder Ford engine was used which employed a standard carburetor. It was operated at a standard speed of 1,500 r.p.m.::15 r.p.m. under a constant load of 140:2 foot lbs. of torque. The oil sump temperature was maintained in the cold phase at 150 F.i-'5 F. and in the hot phase at 215 F.i5 F. The cold phase operation was for a period of 5 hours and alternated with a hot phase operation of 2 hours.
The invention will be more completely understood by reference to the following examples but it is not intended that the invention be limited to these examples since they are only representative in nature. All percentages given are in terms of weight percent of the total composition.
EXAMPLE 1 600 grams of nonylphenol were gradually added to 414 grams of phosphorus trichloride at ambient or room tem perature. The admixture (after 3 hours) ceased evolving hydrogen chloride gas. An aliquot constituting 158 grams of the nonylphenol dichloro phosphite ester was then mixed with about 51 grams of sulfur dichloride. After the addition of the sulfur dichloride, the mixture was then gradually added to about 62 grams of ethylene glycol. After completion of the addition, the reaction temperature of the reacting mixture was increased from ambient temperature to about C. and kept at this temperature for about 3 hours with stirring and agitation. In the final stages of the final 3-hour period, the mixture was stripped with a stream of nitrogen gas for about 2 hours. The product had a phosphorus content of about 7.95 wt. percent and a sulfur content of about 9.33 wt. percent.
EXAMPLE 2 About 400 grams of nonyl phenol was added, dropwise, to 137 grams of phosphorus trichloride at room temperature. The mixture was stirred constantly until all evolution of hydrogen chloride gas had ceased. This took about 3 hours.
An additional 200 grams of nonylphenol was added, dropwise, to about 103 grams of sulfur dichloride at room temperature and the mixture was constantly stirred until the evolution of all hydrogen chloride gas had ceased. This again took about 3 hours.
An admixture of the foregoing mixtures of nonylphenolphosphorus trichloride reaction product and the nonylphenol-sulfur dichloride reacted mixture was prepared. This admixture was added, dropwise, to 62 grams of ethylene glycol at room temperature and was stirred for 3 hours followed by stripping with a stream of nitrogen gas at room temperature for an additional 2 hours. The final product had a phosphorus content of 3.49 wt. percent and a sulfur content of 4.41 wt. percent.
EXAMPLE 3 200 grams of nonylphenol was added, dropwise, to 137 grams of phosphorus trichloride at room temperature. The mixture was stirred constantly until evolution of hydrogen chloride gas had completely stopped. This reaction mixture was then admixed, dropwise, with about 76 grams of sulfur monochloride and the resultant mixture added, dropwise, to about 62 grams of ethylene glycol while maintaining the mixture at about room temperature. The reaction mixture was stirred for 3 hours and was then stripped with a stream of nitrogen gas for 2 hours at room temperature. The product showed a phosphorus content of about 4.16 wt. percent and a sulfur content of about 4.48 wt. percent.
EXAMPLE 4 Each of the products of each of the preceding examples were subjected to either the Falex test or the Cyclic Temperature Sludge Test, both tests having been hereinbefore described. The data obtained are set forth in the hereinafter set forth table.
The base oil employed, in the tests set forth in the table, was previously described as an SA-E l0W-30 oil blend. It contained about 1.2 wt. percent of zinc di-(C C alkyl)-dithiophosphate, which additive was omitted from the base oil when the additives prepared in accordance with Examples 1, 2 and 3 were employed. A test carried out on the base oil but containing no zinc di-(C -C alkyl)- dithiophosphate and no additive resulted in a broken pin Falex test,
brorno cycloalkyl, alkenyl, chloro and bromo alkenyl, alkaryl, and chloro and brorno alkaryl; X is selected from the group consisting of chloro, brorno and CR and X is selected from the group consisting of chloro and bromo,
Cyclic temperature sludge test demerit rating, hours 500 p.S.l., Wt. percent 30 min., bearing Number Additive of additive wt. loss, mg. 63
None F ZDDP l 1 Zinc di-(Ci-Cs alkyl) dithipl10sphate.
It is readily apparent, from the foregoing data, that the novel additives exhibit marked antiwear and sludge inhibition characteristics when used in lubricating oils.
A comparison of the results of the Cyclic Temperature Sludge Test (Run A vs. Run B) shows that the base oil above exhibited excessive sludge formation at 105 hours whereas use of the sulfurized-phosphite ester condensation product of Example 1 was still better than the control even after 168 hours. Also in the Falex test, the novel additives were superior to the conventional antiwear additives of Run F.
Having now thus fully described and illustrated the nature of the invention, what is desired to be secured by Letters Patent is:
I claim:
1. A mineral lubricating oil composition containing a sludge inhibiting amount of the reaction product of:
X2 wherein R is selected from the group consisting of alkyl, chloro and brorno alkyl, aryl, chloro and bromo aryl, aralkyl, chloro and bromo aralkyl, cycloalkyl, chloro and bromo cycloalkyl, alkenyl, chloro and brorno alkenyl, alkaryl, and chloro and brorno alkaryl; X is selected from the group consisting of chloro, brorno and 0R and X is selected from the group consisting of chloro and brorno, with a halide of sulfur and with a polyhydric hydrocarbon selected from the group consisting of polyhydric alkylene hydrocarbons and polyhydric arylene hydrocarbons.
2. A mineral lubricating oil composition containing a sludge inhibiting amount of the reaction product of:
chloro and brorno alkyl, aryl, chloro and brorno aryl, aralkyl, chloro and bromo aralkyl, cycloalkyl, chloro and with the reaction product of halide of sulfur and a polyhydric hydrocarbon selected from the group consisting of polyhydric alkylene hydrocarbons and polyhydric arylene hydrocarbons.
3. A mineral lubricating oil composition containing a sludge inhibiting amount of the reaction product of claim 1 wherein the phosphite ester is mono nonylphenyl dichloro phosphite ester and the polyhydric compound is ethylene glycol.
4. A mineral lubricating oil composition containing a sludge inhibiting amount of the reaction product of claim 3 wherein the sulfur halide is sufur dichloride.
5. A mineral lubricating oil composition containing a sludge inhibiting amount of the reaction product of claim 3 wherein the sulfur halide is sulfur monochloride.
6. A mineral lubricating oil composition containing a sludge inhibiting amount of the reaction product of claim 2 wherein the phosphite ester is mono nonylphenyl dichloro phosphite ester and the polyhydric compound is ethylene glycol.
7. A mineral lubricating oil composition containing a sludge inhibiting amount of the reaction product of claim 6 wherein the sulfur halide is sulfur dichloride.
8. A mineral lubricating oil composition containing a sludge inhibiting amount of the reaction product of claim 6 wherein the sulfur halide is sulfur monochloride.
References Cited UNITED STATES PATENTS 2,242,260 5/1941 Prutton 25248 2,506,344 5/1950 Cleary 260-985 X 3,240,704 3/1966 Nelson et a1. 25246.6 3,245,979 4/1966 Nelson et al. 25246.6 3,435,097 3/1969 Bottomley et al. 260-985 X DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner US. Cl. X.R.
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US5030368A (en) * | 1988-08-24 | 1991-07-09 | Mobil Oil Corporation | N,N-diorganodithiocarbamate derivatives and lubricant compositions containing same |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US2242260A (en) * | 1937-01-22 | 1941-05-20 | Lubri Zol Dev Corp | Lubricating composition |
US2506344A (en) * | 1948-03-09 | 1950-05-02 | Piant Products Corp | Method for making thiophosphates |
US3240704A (en) * | 1961-01-30 | 1966-03-15 | Sinclair Research Inc | Lubricating compositions having oilsoluble phosphorus-containing condensation products |
US3245979A (en) * | 1961-01-30 | 1966-04-12 | Sinclair Refining Co | Phosphorus phenol condensation compounds |
US3435097A (en) * | 1965-03-26 | 1969-03-25 | Nat Poly Chem Inc | Phenolic-sulfide-phosphite compounds |
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1968
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US2242260A (en) * | 1937-01-22 | 1941-05-20 | Lubri Zol Dev Corp | Lubricating composition |
US2506344A (en) * | 1948-03-09 | 1950-05-02 | Piant Products Corp | Method for making thiophosphates |
US3240704A (en) * | 1961-01-30 | 1966-03-15 | Sinclair Research Inc | Lubricating compositions having oilsoluble phosphorus-containing condensation products |
US3245979A (en) * | 1961-01-30 | 1966-04-12 | Sinclair Refining Co | Phosphorus phenol condensation compounds |
US3435097A (en) * | 1965-03-26 | 1969-03-25 | Nat Poly Chem Inc | Phenolic-sulfide-phosphite compounds |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US5030368A (en) * | 1988-08-24 | 1991-07-09 | Mobil Oil Corporation | N,N-diorganodithiocarbamate derivatives and lubricant compositions containing same |
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