CA2139438A1 - Use of adducts of 0, 0-dialkyldithiophosphoric acids - Google Patents
Use of adducts of 0, 0-dialkyldithiophosphoric acidsInfo
- Publication number
- CA2139438A1 CA2139438A1 CA002139438A CA2139438A CA2139438A1 CA 2139438 A1 CA2139438 A1 CA 2139438A1 CA 002139438 A CA002139438 A CA 002139438A CA 2139438 A CA2139438 A CA 2139438A CA 2139438 A1 CA2139438 A1 CA 2139438A1
- Authority
- CA
- Canada
- Prior art keywords
- adducts
- carbon atoms
- chain
- unsaturated
- straight
- 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.)
- Abandoned
Links
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 150000007513 acids Chemical class 0.000 title claims abstract description 16
- 150000001298 alcohols Chemical class 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007866 anti-wear additive Substances 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- -1 2-ethylhexyl group Chemical group 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 2
- 239000005068 cooling lubricant Substances 0.000 claims 1
- 239000010687 lubricating oil Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 239000003879 lubricant additive Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 5
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical class CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229940055577 oleyl alcohol Drugs 0.000 description 4
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- SZXCCXFNQHQRGF-UHFFFAOYSA-N di(propan-2-yloxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)OP(S)(=S)OC(C)C SZXCCXFNQHQRGF-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- YGMLOGWOEDZXIJ-UHFFFAOYSA-N 2-ethylhexylsulfanyl-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCC(CC)CSP(O)(O)=S YGMLOGWOEDZXIJ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 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
- 125000001117 oleyl 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])/C([H])=C([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])[H] 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- CAGSQBQWMHFMKE-UHFFFAOYSA-L zinc;2-ethylhexylsulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCC(CC)CSP([O-])([O-])=S CAGSQBQWMHFMKE-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/123—Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C07F9/165—Esters of thiophosphoric acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/06—Hydroxy compounds having hydroxy 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
- 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
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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
- 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
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/36—Polyoxyalkylenes etherified
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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
- C10M153/00—Lubricating compositions characterised by the additive being a macromolecular compound containing phosphorus
- C10M153/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy 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
- 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
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—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
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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
- 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
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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
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
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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
- C10N2040/02—Bearings
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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
- C10N2040/135—Steam engines or turbines
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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
- C10N2040/20—Metal working
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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
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
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Abstract
The invention concerns adducts of O,O-dialkyldithiophosphoric acids, in which the alkvl groups have 4 to 18 carbon at-oms, with long-chain unsaturated monohydric alcohols or with addition products of ethylene oxide and/or propylene oxide with such alcohols. These adducts are suitable for use as metal-free. hydrolysis-stable anti-wear additives for lubricants.
Description
2~ ~4 ~3~
USE OF ADDUCTS OF O,O-DIALKYLDITHIOPHOSPHORIC ACIDS
Use of adducts of O,O-dialkyldithiophosphoric acids with unsaturated monohydric alcohols or ethoxylates and/or proproxylates of the same as lubricant additives.
5The invention relates to the use of adducts of O,O-dialkyldithiophosphoric acids of the general formula (RlO)(R20)P(S)-SH (I) where Rl and R2 are identical or different and are a straight-chain or branched alkyl group having from 4 to 18 carbon atoms, with unsaturated compounds selected from the group consisting of a) unsaturated, straight-chain or branched monohydric alcohols having from 10 to 24 carbon 15atoms and an iodine number in the range from 45 to 180, and b) addition products of ethylene oxide and/or propylene oxide with unsaturated, straight-chain or branched, monohydric alcohols having from 10 20to 24 carbon atoms, having iodine numbers in the range from 30 to 160, as anti-wear additives (AW additives) for lubricants.
A typical example of hitherto customary AW
additives are zinc salts of alkyldithiophosphoric acids (zinc alkyldithiophosphates). Although these additives have satisfactory properties in the relevant tests, e.g.
in accordance with DIN 51350 (weld load; wear diameter), and are accordingly widely used in lubricants, they do at the same time have the disadvantage that they are not stable to hydrolysis and have an unpleasant odor;
furthermore their metal content is undesired for reasons of environmental protection.
;~13~3~;3~
US-A 2 528 732 describes the uæe of adducts of O,O-dialkyldithiophosphoric acids with oleyl alcohol as stabilizers for mineral oils; however no reference is made to lubricant properties of these adducts. The same applies to analogous adducts with terpenes as described in US-A 2 665 295 and US-A 2 689 258.
Furthermore, US-A 3 574 795 describes adducts of O,O-dialkyldithiophosphoric acids with conjugated dienes and their use as lubricant additives. However, the achievable AW and EP (extreme pressure) effects change greatly even if adducts with butadiene are compared with those with chloroprene, so that no predictions are possible herefrom for the behavior of adducts with unsaturated alcohols.
Furthermore, the previously known adducts are lacking a free OH group which is very advantageously noticeable in the adducts to be used according to the invention.
Furthermore, GB-A 700 530 describes adducts of dialkyl-dithiophosphoric acids with succinic acid and the use of the metal salts derived from the adducts as lubricant additives which are, however, then no longer metal-free.
Although metal-free analogous adducts with maleic and fumaric esters are known from US-A 3 359 203, these adducts have esterified carboxylic acid functions which can be destroyed by hydrolysis and, in addition, give downstream products having unpleasant smells.
There is therefore a need for lubricant additives which have equally good properties in the appropriate tests and are odor-free and metal-free and are furthermore stable to hydrolysis and have an improved thermal stability.
These requirements are met by the adducts of the inven-tion to be used according to the invention.
Typical examples of the radicals R1 and R2 in the O,O-dialkyldithiophosphoric acids of the general formula I
are butyl, pentyl, hexyl, methylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, 2~3~
heYA~ecyl and octadecyl, with isobutyl, isoamyl and 2-ethylhexyl being particularly advantageous. The compounds of the $ormula I are commercially available or can be prepared by conventional methods.
Typical examples of unsaturated, straight-chain or br~nche~ monohydric alcohols to be used according to the invention are olefinically unsaturated fatty alcohols having from 10 to 24 carbon atoms and an iodine number in the range from 45 to 180, which are commercial products and which are obtainable from animal and/or plant fats and oils or else by a synthetic route, e.g. lauroleyl, myristoleyl, palmitoleyl, oleyl, gadoleinyl, erucyl, linoyl, and linoleyl alcohols, including industrial mix-tures of these fatty alcohols; particular preference is given to industrial oleyl alcohol mixtures having a high content of oleyl alcohol.
Addition products of ethylene oxide and/or propylene oxide with unsaturated, straight-chain or br~nche~
monohydric alcohols, in particular olefinically unsa-turated fatty alcohols having from 10 to 24 carbon atomsas in the above examples,-having iodine numbers in the range from 30 to 160, can also be used according to the lnvention .
Preferred adducts to be used according to the invention are those of 0,0-dialkyldithiophosphoric acids in which the radicals R1 and R2 are a straight-chain or branched alkyl group having from 4 to 12, in particular from 4 to 8, carbon atoms.
Adducts to be preferably used can furthermore also be obtained using addition products of ethylene oxide and/or propylene oxide with unsaturated fatty alcohols having from 16 to 22 carbon atoms; typical examples of such fatty alcohols have already been mentioned above.
The adducts to be used according to the invention have an X~3~3~
OH group originating from the monohydric alcohols or alkoxylates thereof which has a surprisingly favorable effect on the AW properties. Although these adducts have a lower sulfur and phosphorus content than comparable adducts obtained using olefins without an OH group, in tests they show essentially the same AW properties.
The adducts of the invention can be used as wear-reducing additives in water-miscible and water-immiscible lubricants containing mineral oils or free of mineral oils. Typical examples of such lubricants, which include metal forming fluids, are the following:
motor oil, gearbox oil, diesel motor oil, turbine oil, greases, hydraulic oils;
for non-cutting metal forming: drawing oils, stamping oils, rolling oils;
for cutting metal forming: cutting oils, ho~;ng oils, gr; n~; ng oils, reaming oils, deep-well drilling oils.
Adducts having relatively short alkyl groups, in parti-cular those having from 4 to 6 carbon atoms such as butyl or isobutyl and pentyl or isoamyl and also hexyl are here particularly suitable as additives for water-containing lubricants. Adducts having longer alkyl groups, e.g.
having 8 or more than 8 carbon atoms, are particularly suitable as additives for water-free lubricants.
The invention further relates to adducts of O,O-dialkyl-dithiophosphoric acids of the above general formula I, in where R1 and R2 are each straight-chain or branched alkyl groups having from 4 to 6 carbon atoms, with unsaturated compounds as defined above.
The adducts of the invention can be prepared in a manner known per se by addition of O,O-dialkyldithiophosphoric acids to monohydric alcohols having olefinic double bonds X~.t39~
or to ethylene oxide and/or propylene oxide adducts of the same, generally at elevated temperatures, preferably from 110 to 150C, in particular from 125 to 140C. At these reaction temperatures the use of catalysts i8 generally not necessary.
The reaction times required are in the order of a few hours. If the reaction times at a certain reaction temperature become too long, the temperatures can be increased to a certain extent, as long as no decom position pheno~en~ occur in the reaction mixture. Shorter reaction times are also achieved by using the dialkyl-dithiophosphoric acids of the formula I in a small excess, e.g. up to 10 %, based on unsaturated compound8 used. The excess mercapto groups then contained in the reaction mixture are advantageously neutralized after the reaction is complete with bases, in particular amines, to a pH in the range from 7 to 8; amines particularly suitable for this purpose are mono-, di- or, if steri-cally possible, tri-(C4-C18)- alkylamines having straight-chain, branched or cyclic alkyl groups; furthermore alsoalkanolamines such as ethanolamine, diethanolamine or triethanolamine, but these- only if the compounds to be used according to the invention are intended for water-miscible lubricants. Furthermore, the treatment with the abovementioned amines is also advisable as deodorisation for adducts prepared from equimolar amounts of monoal-cohols and dialkyldithiophosphoric acids.
The invention is illustrated below by means of examples of preferred embodiments; the Comparative Examples 1, 2 and 3 are not according to the invention. Comparative Example 3 shows, by use of diisopropyldithiophosphoric acid, a good WSD value which results from this product decomposing rapidly owing to its low thermal stability and thus the high proportion of S and P being reacted.
Even the use of relatively long-chain alcohols as in Examples 3 and 4 shows that, owing to the free OH groups of the oleyl alcohols used, the polar properties ensure Xl;3~
a greater affinity for the metal surface, which leads to the same WSD values although the S and P available is ~ignificantly lower.
Comparative Example 1 Commercial zinc 2-ethylhexyldithiophosphate cont~;n;ng 9.5 % of zinc, 8 % of phosphorus and 16 % of sulfur.
Comparative Example 2 2-ethylhexylamine salt of 2-ethylhexyldithiophosphoric acid cont~;n;ng 16 % of mineral oil. Sulfur content:
about 11 %, phosphorus content: about 5.5 %.
Comparative Example 3 Reaction product of O,O-diisopropyldithiophosphoric acid with ethyl acrylate as described in DE-A 29 21 620; S
content: about 20 % by weight, P content: about 9.9 % by weight.
Example 1 354 g (1 mol) of O,O-bis(2-ethylhexyl)dithiopho~phoric acid were heated with 267 g (1 mol) of OcenolR 90/95 (industrial C18 fatty alcohol; IN 90-95; from Henkel) under nitrogen at 130C for 8 hours while stirring. The unreacted SH groups were neutralized with 30 g (0.23 mol) of 2-ethylhexylamine to pH 8.
This gave a clear, low-viscosity product having an acid number of 16.
Sulfur content: about 10.4 %, phosphorus content: about 5 %.
X~ 43~
Example 2 490 g (1 mol) of an adduct of oleyl alcohol with 5 mol of EO (IN 42-50) were heated with 354 g (1 mol) of O,O-bis(2-ethylhexyl)dithiophosphoric acid under nitrogen for 12 hours at from 125 to 130C while stirring.
This gave an intermediate-viscosity, clear product having an acid number of 27.
Sulfur content: about 7.6 %, phosphorus content: about 3.7 %.
Example 3 242 g (1 mol) of O,O-diisobutyldithiophosphoric acid were heated with 270 g (1 mol) of OcenolR 110/130 (IN 110-130;
from Henkel) under nitrogen at 120C for 9 hours while stirring. The remaining SH groups were neutralized with 20 g (0.15 mol) of 2-ethylhexylamine to pH 8.
This gave a clear, intermediate-viscosity product having an acid number of 15.
Sulfur content: about 12.5 %, phosphorus content: about 6.1 %.
Example 4 334 g (1 mol) of O,O-bis(2-ethylhexyl)dithiophosphoric acid were heated with 270 g (1 mol) of Ocenol 110/130 (IN
110-130; from Henkel) under nitrogen at 120C for 8 hours while stirring. The remaining SH groups were neutralized with 25 g (0.19 mol) of 2-ethylhexylamine to pH 8.
Thi~ gave a clear, intermediate-viscosity product having an acid number of 16.
Sulfur content: 10.3 %, phosphorus content: 5.0 %.
X1394 ;3~
The properties of the abovementioned adducts or compara-tive products as lubricant additives were determined in accordance with DIN 51350 (Tentative Method IP 239/69) in a Shell four-ball apparatus. In detail, the following were measured:
1. WL = weld load. This is the load at which the four balls of the apparatus weld together within 60 seconds.
2. WSD = wear scar diameter in mm. This is the 10mean wear diameter at a load of 800 N for one hour.
The base oil used was an undoped mixed basic spindle oil (Shell Gadus 22/40).
The load of 800 N was selected because no wear diameters 15could be determined at 150 or 300 N as prescribed by DIN.
Results of testing in the four-ball apparatus:
Lubricant Additive - WL WSD
Type Conc. in N mm % by weight Comparative Example 1 1 1800 2.3 Comparative Example 2 1 1800 2.3 Comparative Example 3 1 1800 0.9 Example 1 1 1800 2.3 Example 2 1 1800 2.3 Example 3 1 1800 0.9 ~xample 4 1 1800 0.9 As is shown by the above table, the adducts of the invention have the same lubricant properties as the comparative products. However, in contrast to these, they are stable to hydrolysis and metal-free.
USE OF ADDUCTS OF O,O-DIALKYLDITHIOPHOSPHORIC ACIDS
Use of adducts of O,O-dialkyldithiophosphoric acids with unsaturated monohydric alcohols or ethoxylates and/or proproxylates of the same as lubricant additives.
5The invention relates to the use of adducts of O,O-dialkyldithiophosphoric acids of the general formula (RlO)(R20)P(S)-SH (I) where Rl and R2 are identical or different and are a straight-chain or branched alkyl group having from 4 to 18 carbon atoms, with unsaturated compounds selected from the group consisting of a) unsaturated, straight-chain or branched monohydric alcohols having from 10 to 24 carbon 15atoms and an iodine number in the range from 45 to 180, and b) addition products of ethylene oxide and/or propylene oxide with unsaturated, straight-chain or branched, monohydric alcohols having from 10 20to 24 carbon atoms, having iodine numbers in the range from 30 to 160, as anti-wear additives (AW additives) for lubricants.
A typical example of hitherto customary AW
additives are zinc salts of alkyldithiophosphoric acids (zinc alkyldithiophosphates). Although these additives have satisfactory properties in the relevant tests, e.g.
in accordance with DIN 51350 (weld load; wear diameter), and are accordingly widely used in lubricants, they do at the same time have the disadvantage that they are not stable to hydrolysis and have an unpleasant odor;
furthermore their metal content is undesired for reasons of environmental protection.
;~13~3~;3~
US-A 2 528 732 describes the uæe of adducts of O,O-dialkyldithiophosphoric acids with oleyl alcohol as stabilizers for mineral oils; however no reference is made to lubricant properties of these adducts. The same applies to analogous adducts with terpenes as described in US-A 2 665 295 and US-A 2 689 258.
Furthermore, US-A 3 574 795 describes adducts of O,O-dialkyldithiophosphoric acids with conjugated dienes and their use as lubricant additives. However, the achievable AW and EP (extreme pressure) effects change greatly even if adducts with butadiene are compared with those with chloroprene, so that no predictions are possible herefrom for the behavior of adducts with unsaturated alcohols.
Furthermore, the previously known adducts are lacking a free OH group which is very advantageously noticeable in the adducts to be used according to the invention.
Furthermore, GB-A 700 530 describes adducts of dialkyl-dithiophosphoric acids with succinic acid and the use of the metal salts derived from the adducts as lubricant additives which are, however, then no longer metal-free.
Although metal-free analogous adducts with maleic and fumaric esters are known from US-A 3 359 203, these adducts have esterified carboxylic acid functions which can be destroyed by hydrolysis and, in addition, give downstream products having unpleasant smells.
There is therefore a need for lubricant additives which have equally good properties in the appropriate tests and are odor-free and metal-free and are furthermore stable to hydrolysis and have an improved thermal stability.
These requirements are met by the adducts of the inven-tion to be used according to the invention.
Typical examples of the radicals R1 and R2 in the O,O-dialkyldithiophosphoric acids of the general formula I
are butyl, pentyl, hexyl, methylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, 2~3~
heYA~ecyl and octadecyl, with isobutyl, isoamyl and 2-ethylhexyl being particularly advantageous. The compounds of the $ormula I are commercially available or can be prepared by conventional methods.
Typical examples of unsaturated, straight-chain or br~nche~ monohydric alcohols to be used according to the invention are olefinically unsaturated fatty alcohols having from 10 to 24 carbon atoms and an iodine number in the range from 45 to 180, which are commercial products and which are obtainable from animal and/or plant fats and oils or else by a synthetic route, e.g. lauroleyl, myristoleyl, palmitoleyl, oleyl, gadoleinyl, erucyl, linoyl, and linoleyl alcohols, including industrial mix-tures of these fatty alcohols; particular preference is given to industrial oleyl alcohol mixtures having a high content of oleyl alcohol.
Addition products of ethylene oxide and/or propylene oxide with unsaturated, straight-chain or br~nche~
monohydric alcohols, in particular olefinically unsa-turated fatty alcohols having from 10 to 24 carbon atomsas in the above examples,-having iodine numbers in the range from 30 to 160, can also be used according to the lnvention .
Preferred adducts to be used according to the invention are those of 0,0-dialkyldithiophosphoric acids in which the radicals R1 and R2 are a straight-chain or branched alkyl group having from 4 to 12, in particular from 4 to 8, carbon atoms.
Adducts to be preferably used can furthermore also be obtained using addition products of ethylene oxide and/or propylene oxide with unsaturated fatty alcohols having from 16 to 22 carbon atoms; typical examples of such fatty alcohols have already been mentioned above.
The adducts to be used according to the invention have an X~3~3~
OH group originating from the monohydric alcohols or alkoxylates thereof which has a surprisingly favorable effect on the AW properties. Although these adducts have a lower sulfur and phosphorus content than comparable adducts obtained using olefins without an OH group, in tests they show essentially the same AW properties.
The adducts of the invention can be used as wear-reducing additives in water-miscible and water-immiscible lubricants containing mineral oils or free of mineral oils. Typical examples of such lubricants, which include metal forming fluids, are the following:
motor oil, gearbox oil, diesel motor oil, turbine oil, greases, hydraulic oils;
for non-cutting metal forming: drawing oils, stamping oils, rolling oils;
for cutting metal forming: cutting oils, ho~;ng oils, gr; n~; ng oils, reaming oils, deep-well drilling oils.
Adducts having relatively short alkyl groups, in parti-cular those having from 4 to 6 carbon atoms such as butyl or isobutyl and pentyl or isoamyl and also hexyl are here particularly suitable as additives for water-containing lubricants. Adducts having longer alkyl groups, e.g.
having 8 or more than 8 carbon atoms, are particularly suitable as additives for water-free lubricants.
The invention further relates to adducts of O,O-dialkyl-dithiophosphoric acids of the above general formula I, in where R1 and R2 are each straight-chain or branched alkyl groups having from 4 to 6 carbon atoms, with unsaturated compounds as defined above.
The adducts of the invention can be prepared in a manner known per se by addition of O,O-dialkyldithiophosphoric acids to monohydric alcohols having olefinic double bonds X~.t39~
or to ethylene oxide and/or propylene oxide adducts of the same, generally at elevated temperatures, preferably from 110 to 150C, in particular from 125 to 140C. At these reaction temperatures the use of catalysts i8 generally not necessary.
The reaction times required are in the order of a few hours. If the reaction times at a certain reaction temperature become too long, the temperatures can be increased to a certain extent, as long as no decom position pheno~en~ occur in the reaction mixture. Shorter reaction times are also achieved by using the dialkyl-dithiophosphoric acids of the formula I in a small excess, e.g. up to 10 %, based on unsaturated compound8 used. The excess mercapto groups then contained in the reaction mixture are advantageously neutralized after the reaction is complete with bases, in particular amines, to a pH in the range from 7 to 8; amines particularly suitable for this purpose are mono-, di- or, if steri-cally possible, tri-(C4-C18)- alkylamines having straight-chain, branched or cyclic alkyl groups; furthermore alsoalkanolamines such as ethanolamine, diethanolamine or triethanolamine, but these- only if the compounds to be used according to the invention are intended for water-miscible lubricants. Furthermore, the treatment with the abovementioned amines is also advisable as deodorisation for adducts prepared from equimolar amounts of monoal-cohols and dialkyldithiophosphoric acids.
The invention is illustrated below by means of examples of preferred embodiments; the Comparative Examples 1, 2 and 3 are not according to the invention. Comparative Example 3 shows, by use of diisopropyldithiophosphoric acid, a good WSD value which results from this product decomposing rapidly owing to its low thermal stability and thus the high proportion of S and P being reacted.
Even the use of relatively long-chain alcohols as in Examples 3 and 4 shows that, owing to the free OH groups of the oleyl alcohols used, the polar properties ensure Xl;3~
a greater affinity for the metal surface, which leads to the same WSD values although the S and P available is ~ignificantly lower.
Comparative Example 1 Commercial zinc 2-ethylhexyldithiophosphate cont~;n;ng 9.5 % of zinc, 8 % of phosphorus and 16 % of sulfur.
Comparative Example 2 2-ethylhexylamine salt of 2-ethylhexyldithiophosphoric acid cont~;n;ng 16 % of mineral oil. Sulfur content:
about 11 %, phosphorus content: about 5.5 %.
Comparative Example 3 Reaction product of O,O-diisopropyldithiophosphoric acid with ethyl acrylate as described in DE-A 29 21 620; S
content: about 20 % by weight, P content: about 9.9 % by weight.
Example 1 354 g (1 mol) of O,O-bis(2-ethylhexyl)dithiopho~phoric acid were heated with 267 g (1 mol) of OcenolR 90/95 (industrial C18 fatty alcohol; IN 90-95; from Henkel) under nitrogen at 130C for 8 hours while stirring. The unreacted SH groups were neutralized with 30 g (0.23 mol) of 2-ethylhexylamine to pH 8.
This gave a clear, low-viscosity product having an acid number of 16.
Sulfur content: about 10.4 %, phosphorus content: about 5 %.
X~ 43~
Example 2 490 g (1 mol) of an adduct of oleyl alcohol with 5 mol of EO (IN 42-50) were heated with 354 g (1 mol) of O,O-bis(2-ethylhexyl)dithiophosphoric acid under nitrogen for 12 hours at from 125 to 130C while stirring.
This gave an intermediate-viscosity, clear product having an acid number of 27.
Sulfur content: about 7.6 %, phosphorus content: about 3.7 %.
Example 3 242 g (1 mol) of O,O-diisobutyldithiophosphoric acid were heated with 270 g (1 mol) of OcenolR 110/130 (IN 110-130;
from Henkel) under nitrogen at 120C for 9 hours while stirring. The remaining SH groups were neutralized with 20 g (0.15 mol) of 2-ethylhexylamine to pH 8.
This gave a clear, intermediate-viscosity product having an acid number of 15.
Sulfur content: about 12.5 %, phosphorus content: about 6.1 %.
Example 4 334 g (1 mol) of O,O-bis(2-ethylhexyl)dithiophosphoric acid were heated with 270 g (1 mol) of Ocenol 110/130 (IN
110-130; from Henkel) under nitrogen at 120C for 8 hours while stirring. The remaining SH groups were neutralized with 25 g (0.19 mol) of 2-ethylhexylamine to pH 8.
Thi~ gave a clear, intermediate-viscosity product having an acid number of 16.
Sulfur content: 10.3 %, phosphorus content: 5.0 %.
X1394 ;3~
The properties of the abovementioned adducts or compara-tive products as lubricant additives were determined in accordance with DIN 51350 (Tentative Method IP 239/69) in a Shell four-ball apparatus. In detail, the following were measured:
1. WL = weld load. This is the load at which the four balls of the apparatus weld together within 60 seconds.
2. WSD = wear scar diameter in mm. This is the 10mean wear diameter at a load of 800 N for one hour.
The base oil used was an undoped mixed basic spindle oil (Shell Gadus 22/40).
The load of 800 N was selected because no wear diameters 15could be determined at 150 or 300 N as prescribed by DIN.
Results of testing in the four-ball apparatus:
Lubricant Additive - WL WSD
Type Conc. in N mm % by weight Comparative Example 1 1 1800 2.3 Comparative Example 2 1 1800 2.3 Comparative Example 3 1 1800 0.9 Example 1 1 1800 2.3 Example 2 1 1800 2.3 Example 3 1 1800 0.9 ~xample 4 1 1800 0.9 As is shown by the above table, the adducts of the invention have the same lubricant properties as the comparative products. However, in contrast to these, they are stable to hydrolysis and metal-free.
Claims (10)
1. Use of adducts of O,O-dialkyldithiophosphoric acids of the general formula I
(R1O)(R2O)P(S)-SH (I) where R1 and R2 are identical or different and are a straight-chain or branched alkyl group having from 4 to 18 carbon atoms, with unsaturated compounds selected from the group consisting of a) unsaturated, straight-chain or branched monohydric alcohols having from 10 to 24 carbon atoms and an iodine number in the range from 45 to 180, and b) addition products of ethylene oxide and/or propylene oxide with unsaturated, straight-chain or branched, monohydric alcohols having from 10 to 24 carbon atoms, having iodine numbers in the range from 30 to 160, as anti-wear additives for lubricants.
(R1O)(R2O)P(S)-SH (I) where R1 and R2 are identical or different and are a straight-chain or branched alkyl group having from 4 to 18 carbon atoms, with unsaturated compounds selected from the group consisting of a) unsaturated, straight-chain or branched monohydric alcohols having from 10 to 24 carbon atoms and an iodine number in the range from 45 to 180, and b) addition products of ethylene oxide and/or propylene oxide with unsaturated, straight-chain or branched, monohydric alcohols having from 10 to 24 carbon atoms, having iodine numbers in the range from 30 to 160, as anti-wear additives for lubricants.
2. Use of adducts as claimed in claim 1, wherein R1 and R2 are each a straight-chain or branched alkyl group having from 4 to 12 carbon atoms.
3. Use of adducts as claimed in claim 1 or 2, wherein R1 and R2 are each a straight-chain or branched alkyl group having from 4 to 8 carbon atoms.
4. Use of adducts as claimed in at least one of claims 1 to 3, wherein R1 and R2 are each an isobutyl, isoamyl or 2-ethylhexyl group.
5. An adduct as claimed in at least one of claims 1 to 4 with an unsaturated fatty alcohol having from 16 to 22 carbon atoms.
6. An adduct as claimed in at least one of claims 1 to 4 with addition products of ethylene oxide and/or propylene oxide with an unsaturated fatty alcohol having from 16 to 22 carbon atoms.
7. Use of the adducts as claimed in at least one of claims 1 to 6 in water-miscible or water-immiscible cooling lubricants.
8. Use of the adducts as claimed in at least one of claims 1 to 6 in hydraulic fluids.
9. Use of the additives as claimed in at least one of claims 1 to 6 in lubricating oils.
10. An adduct of an O,O-dialkyldithiophosphoric acid of the general formula I
(R1O)(R2O)P(S)-SH (I) where Rl and R2 are each an alkyl group having from 4 to 6 carbon atoms, in particular an isobutyl or isoamyl group, with an unsaturated compound selected from the group consisting of a) unsaturated, straight-chain or branched monohydric alcohols having from 10 to 24 carbon atoms and an iodine number in the range from 45 to 180, and b) addition products of ethylene oxide and/or propylene oxide with unsaturated, straight-chain or branched monohydric alcohols having from 10 to 24 carbon atoms, having iodine numbers in the range from 30 to 160.
(R1O)(R2O)P(S)-SH (I) where Rl and R2 are each an alkyl group having from 4 to 6 carbon atoms, in particular an isobutyl or isoamyl group, with an unsaturated compound selected from the group consisting of a) unsaturated, straight-chain or branched monohydric alcohols having from 10 to 24 carbon atoms and an iodine number in the range from 45 to 180, and b) addition products of ethylene oxide and/or propylene oxide with unsaturated, straight-chain or branched monohydric alcohols having from 10 to 24 carbon atoms, having iodine numbers in the range from 30 to 160.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4221858.6 | 1992-07-03 | ||
| DE4221858A DE4221858A1 (en) | 1992-07-03 | 1992-07-03 | Adducts of 0,0-dialkyldithiophosphoric acids with unsaturated compounds, process for their preparation and their use as lubricant additives |
| PCT/EP1993/001688 WO1994001441A1 (en) | 1992-07-03 | 1993-06-30 | Use of adducts of o,o-dialkyldithiophosphoric acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2139438A1 true CA2139438A1 (en) | 1994-01-20 |
Family
ID=6462395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002139438A Abandoned CA2139438A1 (en) | 1992-07-03 | 1993-06-30 | Use of adducts of 0, 0-dialkyldithiophosphoric acids |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0648216B1 (en) |
| JP (1) | JPH07508526A (en) |
| KR (1) | KR100249443B1 (en) |
| AT (1) | ATE144518T1 (en) |
| AU (1) | AU674153B2 (en) |
| BR (1) | BR9306662A (en) |
| CA (1) | CA2139438A1 (en) |
| DE (2) | DE4221858A1 (en) |
| ES (1) | ES2095062T3 (en) |
| WO (1) | WO1994001441A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100461096B1 (en) * | 1997-05-02 | 2005-04-06 | 주식회사 엘지생활건강 | Manufacturing method of ultra high concentration powder detergent |
| JP2006071104A (en) * | 1997-07-02 | 2006-03-16 | Nsk Ltd | Rolling bearing |
| KR100564221B1 (en) * | 1998-09-29 | 2006-09-20 | 주식회사 엘지생활건강 | Method for producing a novel anionic sugar-based surfactant having a polyol group and a carboxyl group in the molecule |
| CA2451026C (en) | 2001-06-22 | 2013-12-10 | Health Protection Agency | Mycobacterial antigens expressed under low oxygen tension |
| EP2196473A1 (en) | 2001-07-04 | 2010-06-16 | Health Protection Agency | Mycobacterial antigens expressed during latency |
| DE102005026405A1 (en) * | 2005-06-08 | 2006-12-14 | Lehmann & Voss & Co. Kg | Polymers Dithiophosphorsäurehydroxyfettsäureester, process for their preparation and their use as a lubricant additive |
| JP7288320B2 (en) * | 2019-03-15 | 2023-06-07 | 株式会社Adeka | Method for producing zinc dithiophosphate and method for improving odor of zinc dithiophosphate |
| JP7253863B2 (en) * | 2019-03-15 | 2023-04-07 | 株式会社Adeka | Method for producing zinc dithiophosphate and method for improving corrosion resistance of zinc dithiophosphate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2528732A (en) * | 1947-01-31 | 1950-11-07 | Socony Vacuum Oil Co Inc | Reaction products of diesters of dithiophosphoric acid and mineral oil compositions containing the same |
| US5037567A (en) * | 1988-12-30 | 1991-08-06 | Mobil Oil Corporation | Phosphorus-sulfur olefinic derivatives as multifunctional lubricants and multifunctional additives for lubricants |
| JP2502532Y2 (en) * | 1990-05-30 | 1996-06-26 | 日産自動車株式会社 | Striker mounting structure for automobile door lock device |
-
1992
- 1992-07-03 DE DE4221858A patent/DE4221858A1/en not_active Withdrawn
-
1993
- 1993-06-30 KR KR1019940704850A patent/KR100249443B1/en not_active IP Right Cessation
- 1993-06-30 AT AT93915754T patent/ATE144518T1/en not_active IP Right Cessation
- 1993-06-30 BR BR9306662A patent/BR9306662A/en not_active IP Right Cessation
- 1993-06-30 DE DE59304313T patent/DE59304313D1/en not_active Expired - Fee Related
- 1993-06-30 WO PCT/EP1993/001688 patent/WO1994001441A1/en active IP Right Grant
- 1993-06-30 CA CA002139438A patent/CA2139438A1/en not_active Abandoned
- 1993-06-30 JP JP6502905A patent/JPH07508526A/en active Pending
- 1993-06-30 EP EP93915754A patent/EP0648216B1/en not_active Expired - Lifetime
- 1993-06-30 ES ES93915754T patent/ES2095062T3/en not_active Expired - Lifetime
- 1993-06-30 AU AU45622/93A patent/AU674153B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07508526A (en) | 1995-09-21 |
| AU674153B2 (en) | 1996-12-12 |
| BR9306662A (en) | 1998-12-08 |
| WO1994001441A1 (en) | 1994-01-20 |
| DE59304313D1 (en) | 1996-11-28 |
| KR100249443B1 (en) | 2000-04-01 |
| AU4562293A (en) | 1994-01-31 |
| ES2095062T3 (en) | 1997-02-01 |
| KR957002199A (en) | 1995-06-19 |
| EP0648216A1 (en) | 1995-04-19 |
| EP0648216B1 (en) | 1996-10-23 |
| DE4221858A1 (en) | 1994-01-05 |
| ATE144518T1 (en) | 1996-11-15 |
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| EEER | Examination request | ||
| FZDE | Discontinued |