EP0684979B1 - Lubricant compositions containing complexes of alkoxylated amine, acid, and adenine - Google Patents
Lubricant compositions containing complexes of alkoxylated amine, acid, and adenine Download PDFInfo
- Publication number
- EP0684979B1 EP0684979B1 EP94909035A EP94909035A EP0684979B1 EP 0684979 B1 EP0684979 B1 EP 0684979B1 EP 94909035 A EP94909035 A EP 94909035A EP 94909035 A EP94909035 A EP 94909035A EP 0684979 B1 EP0684979 B1 EP 0684979B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- composition
- complex
- carbon atoms
- adenine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002253 acid Substances 0.000 title claims abstract description 66
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229930024421 Adenine Natural products 0.000 title claims abstract description 49
- 229960000643 adenine Drugs 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 150000001412 amines Chemical class 0.000 title claims abstract description 37
- 239000000314 lubricant Substances 0.000 title description 11
- 239000010687 lubricating oil Substances 0.000 claims abstract description 30
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 26
- 238000002485 combustion reaction Methods 0.000 claims abstract description 16
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 claims description 13
- 230000007797 corrosion Effects 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000000446 fuel Substances 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 235000019198 oils Nutrition 0.000 description 39
- 239000000654 additive Substances 0.000 description 19
- -1 hydrocarbyl dihydrogen phosphates Chemical class 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 230000000996 additive effect Effects 0.000 description 12
- 125000002723 alicyclic group Chemical group 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 238000000746 purification Methods 0.000 description 7
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000010689 synthetic lubricating oil Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229960004889 salicylic acid Drugs 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical compound SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- FCEWRLVEPKVKBU-UHFFFAOYSA-N 2-[2-(tert-butylamino)-1-hydroxyethyl]phenol Chemical compound CC(C)(C)NCC(O)C1=CC=CC=C1O FCEWRLVEPKVKBU-UHFFFAOYSA-N 0.000 description 1
- HHXCMCNHNPGJNS-UHFFFAOYSA-N 3,5-ditert-butyl-4-hydroxybenzenecarbodithioic acid Chemical compound CC(C)(C)C1=CC(C(S)=S)=CC(C(C)(C)C)=C1O HHXCMCNHNPGJNS-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C1*)=C(*)C(C)=C(*)C1C(S)=S Chemical compound CC(C1*)=C(*)C(C)=C(*)C1C(S)=S 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UIJGNTRUPZPVNG-UHFFFAOYSA-N benzenecarbothioic s-acid Chemical compound SC(=O)C1=CC=CC=C1 UIJGNTRUPZPVNG-UHFFFAOYSA-N 0.000 description 1
- DXECDJILNIXBML-UHFFFAOYSA-N bis(6-methylheptoxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)CCCCCOP(S)(=S)OCCCCCC(C)C DXECDJILNIXBML-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
-
- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/16—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiourea type, i.e. containing the group
-
- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/123—Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
-
- 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
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
-
- 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
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- 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
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
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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
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- C10N2040/26—Two-strokes or two-cycle engines
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Definitions
- This invention relates to a composition of matter containing a complex being the reaction product of alkoxylated amine, acid and adenine and to an improved lubricating oil composition containing the reaction product and to the use of such complexes to reduce friction and/or improve fuel economy and/or inhibit copper corrosion in an internal combustion engine.
- U.S. Patent, 4,575,431 discloses a lubricating oil additive composition containing dihydrocarbyl hydrogen dithiophosphates and a sulfur-free of hydrocarbyl dihydrogen phosphates and dihydrocarbyl hydrogen phosphates, said composition being at least 50% neutralized by a hydrocarbyl amine having 10 to 30 carbons in said hydrocarbyl group.
- ZDDP zinc dialkyldithiophosphate
- Patent 4,089,790 discloses an extreme-pressure lubricating oil containing (1) hydrated potassium borate, (2) an antiwear agent selected from (a) ZDDP, (b) an ester, an amide or an amine salt of a dihydrocarbyl dithiophosphoric acid or (c) a zinc alkyl aryl sulfonate and (3) an oil-soluble organic sulfur compound.
- Oil formulations containing ZDDP require friction modifiers in order to reduce energy losses in overcoming friction. Such energy losses results in lower fuel economy.
- oil additive packages containing ZDDP have environmental drawbacks. ZDDP adds to engine deposits which can lead to increased oil consumption and emissions. Moreover, ZDDP is not ash-free.
- U.S. Patent No. 5,076,945 discloses a lubricating oil composition containing an amine salt of a dithiobenzoic acid.
- the amines used to prepare salts are long chain hydrocarbyl amines.
- U.S. Patents 3,849,319 and 3,951,973 describe lubricant compositions containing di- and tri(hydrocarbylammonium)trithiocyanurates.
- the hydrocarbyl radicals include alkyl, aralkyl, aryl, alkaryl and cycloalkyl and the examples are directed to alkylamines. These lubricant compositions were stated to have improved load-carrying properties.
- a lubricating oil additive which provides excellent antiwear, antioxidation, friction reducing, fuel economy and environmentally beneficial (less fuel, less phosphorus, i.e., less exhaust emissions) properties. It is also desirable to find additives which inhibit copper corrosion. It would be a further benefit if these additives do not contribute phosphorous to the lubricating oil composition.
- This invention relates to a novel composition of matter containing alkoxylated amine, acid, and adenine. It also relates to an improved lubricating oil composition which reduces friction and/or improves fuel economy in an internal combustion engine and in some cases exhibit improved copper corrosion inhibition and/or antiwear and antioxidant properties.
- the present invention provides a composition of matter which comprises the reaction product of alkoxylated amine, acid and adenine wherein said reaction product is a complex having the following formula (I) wherein Z is derived from either a hydrocarbylsalicylic acid, trithiocyanuric acid, a hydrocarbylsulfonic acid, a dihydrocarbyldithiophosphoric acid or a dihydrocarbyldithiobenzoic acid and wherein R is a hydrocarbyl group of 2 to 22 carbon atoms, R 1 is hydrogen or a hydrocarbyl group of 1 to 20 carbon atoms, x and y are each independently integers of from 1 to 15 with the proviso that the sum of x + y is from 2 to 20, and a, b and c are independent numbers from 1.0 to 3.0 wherein the ratios of a:b, a:c and b:c range from 1.0:3.0 to 3.0:1.0.
- Z is derived from either a
- a lubricant composition comprising a major amount of a lubricating oil basestock and a minor amount of a complex having the formula (I).
- the present invention provides for the use of a complex having the formula (I) set forth above for inhibiting copper corrosion associated with the use of lubricating oil compositions in an internal combustion engine.
- the present invention provides for the use of a complex having the formula (I) set forth above for reducing friction and/or improving fuel economy in an internal combustion engine.
- the present invention also provides for the use of a complex having the formula (I) set forth above for reducing wear in an internal combustion engine.
- the lubricating oil will contain a major amount of a lubricating oil basestock.
- the lubricating oil basestocks are well known in the art and can be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof.
- the lubricating oil basestock will have a kinematic viscosity ranging from about 5 to about 10,000 cSt at 40°C.
- Natural lubricating oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal and shale.
- Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologues thereof, and the like.
- Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc.
- Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids with a variety of alcohols. Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers.
- Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils.
- Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, polyalphaolefins, and the like.
- the lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof.
- Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment.
- Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
- Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties.
- Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art.
- Rerefined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
- R is preferably a hydrocarbyl group of from 2 to 18 carbon atoms, especially 6 to 18 carbon atoms, and R 1 is preferably hydrogen or a hydrocarbyl group of from 1 to 16 carbon atoms, most preferably hydrogen.
- Such hydrocarbyl groups includes aliphatic (alkyl or alkenyl) and alicyclic groups.
- the aliphatic or alicyclic groups may be substituted with amino, hydroxy, mercapto and the like and may be interrupted by O, S or N.
- the sum of x+y is preferably 2 to 15.
- the complexes of the present invention are prepared from the reaction of alkoxylated, preferably a propoxylated or ethoxylated, especially ethoxylated amines with acid and adenine.
- Adenines are commercially available or may be prepared by methods known in the art. Adenine may be purchased from Aldrich Chemical Company. Ethoxylated and/or propoxylated amines are commercially available from Sherex Chemicals under the trade name Varonic and from Akzo Corporation under the trade names Ethomeen®, Ethoduomeen® and Propomeen®.
- Examples of preferred amines include ethoxylated (5) cocoalkylamine, ethoxylated (2) tallowalkylamine, ethoxylated (15) cocoalkylamine and ethoxylated (5) soyaalkylamine and ethoxylated (10) stearylamine. Propoxylated may be substituted for ethoxylated amines.
- the complexes of the present invention are the reaction product of:
- Preferred hydrocarbylsalicylic acids used to react with alkoxylated amines and adenines to form the complexes of the present invention have the following formula: wherein R 1 is a hydrocarbyl group of from 2 to 30 carbon atoms preferably a hydrocarbyl group of from 2 to 26 carbon atoms.
- Such hydrocarbyl groups include aliphatic (alkyl or alkenyl) and alicyclic group.
- the aliphatic and alicyclic groups may be substituted with hydroxy, alkoxy, cyano, nitro, and the like and the alicyclic groups may contain O, S, or N as hetero atoms.
- These substituted salicylic acids are commercially available or may be prepared by methods known in the art, e.g. U.S. Patent 5,023,366.
- Trithiocyanuric acid may exist in different tautomeric forms represented by formulas II, III or mixtures thereof:
- Trithiocyanuric acid is prepared by methods well known in the art. These methods involve the treatment of cyanuric chloride with sulfur nucleophiles according to the following reaction scheme:
- sulfur nucleophiles which may be employed in the above reaction scheme include sodium sulfide, thiourea and thioacetic acid.
- Preferred hydrocarbylsulfonic acids used to react with alkoxylated amines and adenines to form the complexes of the present invention have the following formula: wherein R 1 is a hydrocarbyl group of from 2 to 30 carbon atoms preferably a hydrocarbyl group of from 2 to 26 carbon atoms.
- Such hydrocarbyl groups include aliphatic (alkyl or alkenyl) and alicyclic group.
- the aliphatic and alicyclic groups may be substituted with hydroxy, alkoxy, cyano, nitro, and the like and the alicyclic groups may contain O, S, or N as hetero atoms.
- These sulfonic acids are commercially available or may be prepared by methods well known in the art.
- Preferred dihydrocarbyldithiophosphoric acids used to react with alkoxylated amines and adenines to form the complexes of the present invention have the following formula: wherein R 2 and R 3 are each independently hydrocarbyl groups having from 3 to 30 carbon atoms preferably 3 to 20 carbon atoms.
- Such hydrocarbyl groups include aliphatic (alkyl or alkenyl) and alicyclic group.
- the aliphatic and alicyclic groups may be substituted with hydroxy, alkoxy, cyano, nitro, and the like and the alicyclic groups may contain O, S, or N as hetero atoms.
- dialkyldithiophosphoric acids are made from mixed (85%) 2-butyl alcohol and (15%) isooctyl alcohol (mixed primary and secondary alcohols).
- Dihydrocarbyldithiophosphoric acids may be purchased from Exxon Chemical Company
- Preferred dihydrocarbyldithiobenzoic acids used to react with alkoxylated amines and adenines to form the complexes of the present invention have the following formula: wherein R 2 to R 6 are each preferably hydrogen; a hydrocarbyl group containing from 1 to 18 carbon atoms; or a hydroxy group with the proviso that at least one of R 2 to R 5 is a hydrocarbyl, preferably an alkyl group containing 1 to 18 carbon atoms, more preferably 1 to 6 carbon atoms. R 3 and R 5 are most preferably t-butyl groups and R 4 is preferably hydroxy. The sum of x + y is preferably 2 to 15.
- the hydrocarbyl groups include aliphatic (alkyl or alkenyl) and alicyclic groups which may be substituted by hydroxy, amino, cyano and the like and may be interrupted by O, S or N.
- Dithiobenzoic acids may be prepared from a phenol according to the following method.
- a Phenol of the formula: is dissolved in a solvent such as dimethylsulfoxide and treated under nitrogen with potassium hydroxide dissolved in a minimum amount of water. Carbon disulfide is then added under nitrogen to this mixture which is maintained at about room temperature.
- the resulting reaction mixture is heated at between 25 to 100°C for 1-3 hours and then added to an acidified water solution.
- the resulting dithiobenzoic acid can be isolated by solvent extraction using, e.g. ether and the solvent evaporated.
- the complexes of the present invention are derived from a hydrocarbylsalicylic acid they are prepared by adding the salicylic acid to a mixture of adenine and alkoxylated amine. Because of the exothermic nature of the reaction, the reaction mixture should be stirred during addition of salicylic acid.
- the complexes of the present invention are derived from trithiocyanuric acid they are prepared by adding trithiocyanuric acid to a mixture of adenine and alkoxylated amine. Because of the exothermic nature of the reaction, the reaction mixture should be stirred during addition of trithiocyanuric acid.
- the amounts of reactants are approximately stoichiometic, although a slight excess of trithiocyanuric acid, which has three reactive hydrogens, may be employed.
- the complexes of the present invention are derived from a dihydrocarbyldithiobenzoic acid they are prepared as described below. This preparation is based on an approximate 1:1:1 mole ratio although this ratio may vary. About 10 to 20% of the required amount of alkoxylated amine (based on the thiobenzoic acid) is added to the dithiobenzoic acid with heating and stirring. Temperatures may range from about 25 to about 180°C. About 10 to 20% of the required amount of adenine is then added. This sequential addition process is repeated until the required amount (based on the above approximate 1:1:1 of amine:acid:adenine) is reached. A precipitate (polymeric and unidentified material) forms if this alternative additional procedure is not employed.
- the complexes of the present invention are derived from a hydrocarbylsulfonic acid they are prepared by adding the sulfonic acid to a mixture of adenine and alkoxylated amine. Because of the exothermic nature of the reaction, the reaction mixture should be stirred during addition of sulfonic acid.
- the complexes of the present invention are derived from a dihydrocarbyldithiophosphoric acid they are prepared as described below. This preparation is based on an approximate 1:1:1 mole ratio although this ratio may vary. About 10 to 20% of the required amount of alkoxylated amine (based on the phosphoric acid) is added to the dihydrocarbyldithiophosphoric acid with heating and stirring. Temperatures may range from about 25 to about 180°C. About 10 to 20% of the required amount of adenine is then added. This sequential addition process is repeated until the required stoichiometic amounts (1:1:1 of amine :acid:adenine) is reached. A precipitate (polymeric and unidentified material) forms if this sequential addition procedure is not employed.
- a:b:c may be 1:2:1 or 1:1:3.
- the lubricant oil composition according to the invention comprises a major amount of lubricating oil basestock and a minor amount. of the alkoxylated amine:acid:adenine complex.
- the acid is either trithiocyanuric acid, hydrocarbylsulfonic acid or hydrocarbylsalicylic acid typically, the amount of complex will be from about 0.001 wt% to about 5 wt%, based on oil basestock.
- the amount of amine salt is from about 0.05 wt% to about 1.0 wt%.
- the concentration of the complex of general formula (I) may typically range from 0.1 to 5 wt% based on oil and preferably from 0.5 to 1.5 wt%.
- the amount of complex is such that there is an effective amount to achieve one or more of improved fuel economy, reduced friction, inhibition of copper corrosion, antiwear properties and antioxidant properties when the lubricant oil composition is used in an internal combustion engine.
- additives known in the art may be added to the lubricating oil basestock.
- additives include dispersants, antiwear agents, antioxidants, rust inhibitors, other corrosion inhibitors, detergents, pour point depressants, extreme pressure additives, viscosity index improvers, other friction modifiers, hydrolytic stabilizers and the like. These additives are typically disclosed, for example, in "Lubricant Additives” by C. V. Smalhear and R. Kennedy Smith, 1967, pp. 1-11 and in U.S. Patent 4,105,571.
- the lubricating oil composition of this invention can be used in the lubrication system of essentially any internal combustion engine, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad engines, and the like. Also contemplated are lubricating oils for gas-fired engines, alcohol (e.g., methanol) powered engines, stationary powered engines, turbines, and the like.
- alcohol e.g., methanol
- This Example illustrates the preparation of a complex containing ethoxylated amine, trithiocyanuric acid and adenine according to the invention.
- 68 g of ethoxylated(5)cocoalkylamine and 13 g of adenine was heated to 70°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser.
- 14 g of trithiocyanuric acid was added gradually to the stirred amine solution. During addition, the temperature rose to 105°C due to an exothermic reaction between acid and amine adenine components. The reaction mixture was used without further purification.
- the complex containing ethoxylated amine, trithiocyanuric acid and adenine is an effective friction modifier as shown in this example.
- the Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described by S. Jahanmir and M. Beltzer in ASLE Transaction, Vol. 29, No. 3, p. 425 (1985) using a force of 0.8 Newtons (1 Kg) applied to a 12.5 mm steel ball in contact with a rotating steel cylinder that has a 43.9 mm diameter.
- the cylinder rotates inside a cup containing a sufficient quantity of lubricating oil to cover 2 mm of the bottom of the cylinder.
- the cylinder was rotated at 0.25 RPM.
- the friction force was continuously monitored by means of a load transducer.
- This Example illustrates the preparation of a complex containing an ethoxylated amine, alkylsalicylic acid and adenine according to the invention.
- 101 g of ethoxylated(5)cocoalkylamine and 4 g of adenine were heated to 80°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser.
- 100 g of salicylic acid having the formula was added gradually to the stirred amine/adenine solution. During addition, the temperature rose to 104°C due to the exothermic reaction between acid and amine.
- the reaction mixture was maintained at 104°C for 1.5 hours and then cooled to room temperature.
- the reaction mixture was a complex according to the invention and was used without further purification.
- the complex containing ethoxylated amine, alkylsalicylic acid, adenine is an effective friction modifier as shown in this example.
- the Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described in Example 2.
- Various amounts of complex prepared in Example 3 were added to solvent 150 N.
- the results of BOC friction tests are shown in Table 2.
- TABLE 2 Wt% of Ethoxylated(5)Cocoalkylamine, Alkyl Salicylic Acid and Adenine Complex in Solvent 150N Coefficient of Friction 0.00 0.32 0.1 0.07 0.2 0.05 0.3 0.035 0.5 0.03 0.8 0.03 1.0 0.02
- a solution of 3 g ethoxylated (5) cocoalkylamine was heated to 50-110°C with stirring.
- 0.5 g of 4-hydroxy-3,5-ditertiarybutyldithiobenzoic acid was then added to the heated and stirred solution following by 125 mg of adenine.
- This procedure of sequentially adding the dithiobenzoic and adenine was repeated until 2 g of the acid and 500 mg of adenine have been added to the solution. The sequential procedure was employed to prevent precipitation of by-product polymeric materials.
- the adenine-containing complex achieves lower coefficient of friction than can be obtained from the comparable complex without adenine or a Primene JMT:DTB complex.
- This Example illustrates the preparation of a complex containing ethoxylated amine, alkylsulfonic acid and adenine according to the invention.
- 41 g of ethoxylated(2)tallowamine and 1 g of adenine were heated to 60°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser.
- 58 g of alkylsulfonic acid having the formula was added gradually to the stirred amine/adenine solution. During addition, the temperature rose to 105°C due to the exothermic reaction between acid and amine.
- the reaction mixture was maintained at 105°C for 1.5 hours and then cooled to room temperature.
- the reaction mixture was a complex according to the invention and was used without further purification.
- the complex containing ethoxylated amine, alkylsulfonic acid and adenine is an effective friction modifier as shown in this example.
- the Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described in Example 2.
- Various amounts of complex prepared in Example 7 were added to solvent 150 N.
- the results of BOC friction tests are shown in Table 4.
- TABLE 4 Wt% of Ethoxylated(2)Tallowamine, Alkylsulfonic Acid and Adenine Complex in Solvent 150N Coefficient of Friction 0.00 0.32 0.1 0.20 0.2 0.18 0.3 0.13 0.5 0.10 0.8 0.07 1.0 0.06
- This Example illustrates the preparation of the novel complex of the invention.
- a solution of 80 g of diisooctyldithiophosphoric acid was heated to 50-100°C with stirring.
- 10 g of ethoxylated(5)cocoalkylamine was then added to the heated and stirred solution followed by 1 g of adenine.
- This procedure of sequentially adding ethoxylated amine and adenine was repeated until 75 g of ethoxylated (5) cocoalkylamine and 7 g of adenine have been added to the solution.
- the sequential addition procedure was employed to prevent precipitation of byproduct.
- the complex was then collected on cooling and used without further purification.
- Example 9 illustrates the superior copper corrosion protection provided by the complex of the invention as prepared in Example 9.
- the test for copper corrosion were run as follows. Copper corrosion tests were based on ASTM D-2440. 25 g of oil sample is placed in a 0.5" test tube with 30 cm of copper wire coiled to 0.5" and stretched to a finished length of 2". The test tube is then heated at 110°C for 120 hours. Nitrogen is bubbled through the oil at 17 cc/min during the test period. A 5 g sample of oil is removed at the end of the test and analyzed for copper content. Results of the copper corrosion are shown in Table 5.
- Antiwear properties are measured by the four-ball wear test as follows.
- the Four Ball test used in described in detail in ASTM method D-2266. In this test, three balls are fixed in a lubricating cup and an upper rotating ball is pressed against the lower three balls.
- the test balls utilized were made of AISI 52100 steel with a hardness of 65 Rockwell C (840 Vickers) and a centerline roughness of 25 mm. Prior to the tests, the test cup, steel balls, and all holders were washed with 1,1,1 trichloroethane. The steel balls subsequently were washed with a laboratory detergent to remove any solvent residue, rinsed with water, and dried under nitrogen.
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Abstract
Description
- This invention relates to a composition of matter containing a complex being the reaction product of alkoxylated amine, acid and adenine and to an improved lubricating oil composition containing the reaction product and to the use of such complexes to reduce friction and/or improve fuel economy and/or inhibit copper corrosion in an internal combustion engine.
- There are many instances, as is well known, particularly under "Boundary Lubrication" conditions where two rubbing surfaces must be lubricated, or otherwise protected, so as to prevent wear and to insure continued movement. Moreover, where, as in most cases, friction between the two surfaces will increase the power required to effect movement and where the movement is an integral part of an energy conversion system, it is most desirable to effect the lubrication in a manner which will minimise this friction. As is also well known, both wear and friction can be reduced, with various degrees of success, through the addition of a suitable additive or combination thereof, to a natural or synthetic lubricant. Similarly, continued movement can be insured, again with varying degrees of success, through the addition of one or more appropriate additives.
- In order to protect internal combustion engines from wear, engine lubricating oils have been provided with antiwear and antioxidant additives. The primary oil additive for the past 40 years for providing antiwear and antioxidant properties has been zinc dialkyldithiophosphate (ZDDP). For example, U.S. Patent, 4,575,431 discloses a lubricating oil additive composition containing dihydrocarbyl hydrogen dithiophosphates and a sulfur-free of hydrocarbyl dihydrogen phosphates and dihydrocarbyl hydrogen phosphates, said composition being at least 50% neutralized by a hydrocarbyl amine having 10 to 30 carbons in said hydrocarbyl group. U.S. Patent 4,089,790 discloses an extreme-pressure lubricating oil containing (1) hydrated potassium borate, (2) an antiwear agent selected from (a) ZDDP, (b) an ester, an amide or an amine salt of a dihydrocarbyl dithiophosphoric acid or (c) a zinc alkyl aryl sulfonate and (3) an oil-soluble organic sulfur compound. Oil formulations containing ZDDP, however, require friction modifiers in order to reduce energy losses in overcoming friction. Such energy losses results in lower fuel economy. Moreover, oil additive packages containing ZDDP have environmental drawbacks. ZDDP adds to engine deposits which can lead to increased oil consumption and emissions. Moreover, ZDDP is not ash-free. Various ashless oil additive packages have been developed recently due to such environmental concerns. However, many ashless additive packages tend to be corrosive to copper which leads to additional components in the additive package to protect against corrosion. Most current commercial engine oils contain reduced phosphorus due to the poisoning of the catalytic converters by phosphorus.
- U.S. Patent No. 5,076,945 discloses a lubricating oil composition containing an amine salt of a dithiobenzoic acid. The amines used to prepare salts are long chain hydrocarbyl amines.
- U.S. Patents 3,849,319 and 3,951,973 describe lubricant compositions containing di- and tri(hydrocarbylammonium)trithiocyanurates. The hydrocarbyl radicals include alkyl, aralkyl, aryl, alkaryl and cycloalkyl and the examples are directed to alkylamines. These lubricant compositions were stated to have improved load-carrying properties.
- It would be desirable to have a lubricating oil additive which provides excellent antiwear, antioxidation, friction reducing, fuel economy and environmentally beneficial (less fuel, less phosphorus, i.e., less exhaust emissions) properties. It is also desirable to find additives which inhibit copper corrosion. It would be a further benefit if these additives do not contribute phosphorous to the lubricating oil composition.
- This invention relates to a novel composition of matter containing alkoxylated amine, acid, and adenine. It also relates to an improved lubricating oil composition which reduces friction and/or improves fuel economy in an internal combustion engine and in some cases exhibit improved copper corrosion inhibition and/or antiwear and antioxidant properties.
- The present invention provides a composition of matter which comprises the reaction product of alkoxylated amine, acid and adenine wherein said reaction product is a complex having the following formula (I)
- In a further aspect of the present invention there is provided a lubricant composition comprising a major amount of a lubricating oil basestock and a minor amount of a complex having the formula (I).
- In a further aspect the present invention provides for the use of a complex having the formula (I) set forth above for inhibiting copper corrosion associated with the use of lubricating oil compositions in an internal combustion engine.
- In a further aspect the present invention provides for the use of a complex having the formula (I) set forth above for reducing friction and/or improving fuel economy in an internal combustion engine.
- The present invention also provides for the use of a complex having the formula (I) set forth above for reducing wear in an internal combustion engine.
- In the lubricating oil composition of the present invention, the lubricating oil will contain a major amount of a lubricating oil basestock. The lubricating oil basestocks are well known in the art and can be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof. In general, the lubricating oil basestock will have a kinematic viscosity ranging from about 5 to about 10,000 cSt at 40°C.
- Natural lubricating oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal and shale.
- Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologues thereof, and the like. Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc. Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids with a variety of alcohols. Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers.
- Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, polyalphaolefins, and the like.
- The lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art. Rerefined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
- In the oil soluble complexes of the present invention having the formula (I), R is preferably a hydrocarbyl group of from 2 to 18 carbon atoms, especially 6 to 18 carbon atoms, and R1 is preferably hydrogen or a hydrocarbyl group of from 1 to 16 carbon atoms, most preferably hydrogen. Such hydrocarbyl groups includes aliphatic (alkyl or alkenyl) and alicyclic groups. The aliphatic or alicyclic groups may be substituted with amino, hydroxy, mercapto and the like and may be interrupted by O, S or N. The sum of x+y is preferably 2 to 15.
- The complexes of the present invention are prepared from the reaction of alkoxylated, preferably a propoxylated or ethoxylated, especially ethoxylated amines with acid and adenine. Adenines are commercially available or may be prepared by methods known in the art. Adenine may be purchased from Aldrich Chemical Company. Ethoxylated and/or propoxylated amines are commercially available from Sherex Chemicals under the trade name Varonic and from Akzo Corporation under the trade names Ethomeen®, Ethoduomeen® and Propomeen®. Examples of preferred amines include ethoxylated (5) cocoalkylamine, ethoxylated (2) tallowalkylamine, ethoxylated (15) cocoalkylamine and ethoxylated (5) soyaalkylamine and ethoxylated (10) stearylamine. Propoxylated may be substituted for ethoxylated amines.
- The complexes of the present invention are the reaction product of:
- (a) an alkoxylated, preferably a propoxylated or ethoxylated , especially an ethoxylated amine of the formula:
- (b) an acid being either a hydrocarbylsalicylic acid, trithiocyanuric acid, a hydrocarbylsulfonic acid, a dihydrocarbyldithiophosphoric acid or a dihydrocarbyldithiobenzoic acid, and
- (c) an adenine of the formula:
- Preferred hydrocarbylsalicylic acids used to react with alkoxylated amines and adenines to form the complexes of the present invention have the following formula:
-
-
- Other sulfur nucleophiles which may be employed in the above reaction scheme include sodium sulfide, thiourea and thioacetic acid.
- Preferred hydrocarbylsulfonic acids used to react with alkoxylated amines and adenines to form the complexes of the present invention have the following formula:
- Preferred dihydrocarbyldithiophosphoric acids used to react with alkoxylated amines and adenines to form the complexes of the present invention have the following formula:
- Preferred dihydrocarbyldithiobenzoic acids used to react with alkoxylated amines and adenines to form the complexes of the present invention have the following formula:
- Dithiobenzoic acids may be prepared from a phenol according to the following method. A Phenol of the formula:
- When the complexes of the present invention are derived from a hydrocarbylsalicylic acid they are prepared by adding the salicylic acid to a mixture of adenine and alkoxylated amine. Because of the exothermic nature of the reaction, the reaction mixture should be stirred during addition of salicylic acid.
- When the complexes of the present invention are derived from trithiocyanuric acid they are prepared by adding trithiocyanuric acid to a mixture of adenine and alkoxylated amine. Because of the exothermic nature of the reaction, the reaction mixture should be stirred during addition of trithiocyanuric acid. The amounts of reactants are approximately stoichiometic, although a slight excess of trithiocyanuric acid, which has three reactive hydrogens, may be employed.
- When the complexes of the present invention are derived from a dihydrocarbyldithiobenzoic acid they are prepared as described below. This preparation is based on an approximate 1:1:1 mole ratio although this ratio may vary. About 10 to 20% of the required amount of alkoxylated amine (based on the thiobenzoic acid) is added to the dithiobenzoic acid with heating and stirring. Temperatures may range from about 25 to about 180°C. About 10 to 20% of the required amount of adenine is then added. This sequential addition process is repeated until the required amount (based on the above approximate 1:1:1 of amine:acid:adenine) is reached. A precipitate (polymeric and unidentified material) forms if this alternative additional procedure is not employed.
- When the complexes of the present invention are derived from a hydrocarbylsulfonic acid they are prepared by adding the sulfonic acid to a mixture of adenine and alkoxylated amine. Because of the exothermic nature of the reaction, the reaction mixture should be stirred during addition of sulfonic acid.
- When the complexes of the present invention are derived from a dihydrocarbyldithiophosphoric acid they are prepared as described below. This preparation is based on an approximate 1:1:1 mole ratio although this ratio may vary. About 10 to 20% of the required amount of alkoxylated amine (based on the phosphoric acid) is added to the dihydrocarbyldithiophosphoric acid with heating and stirring. Temperatures may range from about 25 to about 180°C. About 10 to 20% of the required amount of adenine is then added. This sequential addition process is repeated until the required stoichiometic amounts (1:1:1 of amine :acid:adenine) is reached. A precipitate (polymeric and unidentified material) forms if this sequential addition procedure is not employed.
- The precise stoichiometry of the bonding in the complexes of the formula (I) is not known since each molecule in the complex may have several sites which can take part in the hydrogen bonding process either as an acceptor or donor. Because of the multiplicity of bonding possibilities, the molar ratios a:b:c can be varied over a wide range based on the donor/acceptor sites on each of the three molecules and therefore a, b and c in formula (I) are numbers which are not necessarily integral. When the acid is trithiocyanuric acid there exist a total of forty-five combinations of interaction sites between the three molecules comprising the complex of the formula (I). When the acid is hydrocarbylsulfonic or hydrocarbylsalicylic acid there exist a total of thirty combinations of interaction sites between the three molecules comprising the complex of the formula (I). When the acid is dihydrocarbyldithiobenzoic or dihydrocarbyldithiophosphoric acid there exist a total of fifteen combinations of interaction sites between the three molecules comprising the complex of the formula (I). For example a:b:c may be 1:2:1 or 1:1:3.
- The lubricant oil composition according to the invention comprises a major amount of lubricating oil basestock and a minor amount. of the alkoxylated amine:acid:adenine complex. When the acid is either trithiocyanuric acid, hydrocarbylsulfonic acid or hydrocarbylsalicylic acid typically, the amount of complex will be from about 0.001 wt% to about 5 wt%, based on oil basestock. Preferably, the amount of amine salt is from about 0.05 wt% to about 1.0 wt%. When the acid is either dihydrocarbyldithiobenzoic acid or dihydrocarbyldithiophosphoric acid the concentration of the complex of general formula (I) may typically range from 0.1 to 5 wt% based on oil and preferably from 0.5 to 1.5 wt%. The amount of complex is such that there is an effective amount to achieve one or more of improved fuel economy, reduced friction, inhibition of copper corrosion, antiwear properties and antioxidant properties when the lubricant oil composition is used in an internal combustion engine.
- If desired, other additives known in the art may be added to the lubricating oil basestock. Such additives include dispersants, antiwear agents, antioxidants, rust inhibitors, other corrosion inhibitors, detergents, pour point depressants, extreme pressure additives, viscosity index improvers, other friction modifiers, hydrolytic stabilizers and the like. These additives are typically disclosed, for example, in "Lubricant Additives" by C. V. Smalhear and R. Kennedy Smith, 1967, pp. 1-11 and in U.S. Patent 4,105,571.
- The lubricating oil composition of this invention can be used in the lubrication system of essentially any internal combustion engine, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad engines, and the like. Also contemplated are lubricating oils for gas-fired engines, alcohol (e.g., methanol) powered engines, stationary powered engines, turbines, and the like.
- This invention may be further understood by reference to the following example, which includes a preferred embodiment of the invention.
- This Example illustrates the preparation of a complex containing ethoxylated amine, trithiocyanuric acid and adenine according to the invention. 68 g of ethoxylated(5)cocoalkylamine and 13 g of adenine was heated to 70°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser. 14 g of trithiocyanuric acid was added gradually to the stirred amine solution. During addition, the temperature rose to 105°C due to an exothermic reaction between acid and amine adenine components. The reaction mixture was used without further purification.
- The complex containing ethoxylated amine, trithiocyanuric acid and adenine is an effective friction modifier as shown in this example. The Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described by S. Jahanmir and M. Beltzer in ASLE Transaction, Vol. 29, No. 3, p. 425 (1985) using a force of 0.8 Newtons (1 Kg) applied to a 12.5 mm steel ball in contact with a rotating steel cylinder that has a 43.9 mm diameter. The cylinder rotates inside a cup containing a sufficient quantity of lubricating oil to cover 2 mm of the bottom of the cylinder. The cylinder was rotated at 0.25 RPM. The friction force was continuously monitored by means of a load transducer. In the tests conducted, friction coefficients attained steady state values after 7 to 10 turns of the cylinder. Friction experiments were conducted with an oil temperature of 100°C. Various amounts of the complex prepared in Example 1 were added to solvent 150 N. The results of BOC friction tests are shown in Table 1.
- As can be seen from the results in Table 1, as little as 0.05 wt% of complex shows 79% decrease in the coefficient of friction. These results demonstrate that present complexes are capable of significant reductions in the coefficient of friction of a lubricant basestock which results in less friction and hence greater fuel economy when the lubricant oil is used in an internal combustion engine.
- This Example illustrates the preparation of a complex containing an ethoxylated amine, alkylsalicylic acid and adenine according to the invention. 101 g of ethoxylated(5)cocoalkylamine and 4 g of adenine were heated to 80°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser. 100 g of salicylic acid having the formula
- The complex containing ethoxylated amine, alkylsalicylic acid, adenine is an effective friction modifier as shown in this example. The Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described in Example 2. Various amounts of complex prepared in Example 3 were added to solvent 150 N. The results of BOC friction tests are shown in Table 2.
TABLE 2 Wt% of Ethoxylated(5)Cocoalkylamine, Alkyl Salicylic Acid and Adenine Complex in Solvent 150N Coefficient of Friction 0.00 0.32 0.1 0.07 0.2 0.05 0.3 0.035 0.5 0.03 0.8 0.03 1.0 0.02 - As can be seen from the results in Table 2, as little as 0.1 wt% of complex shows a 78% decrease in the coefficient of friction. These results demonstrate that the present complexes are capable of significant reductions in the coefficient of friction of a lubricant basestock which results in less friction and hence greater fuel economy when the lubricated oil is used in an internal combustion engine.
- A solution of 3 g ethoxylated (5) cocoalkylamine was heated to 50-110°C with stirring. 0.5 g of 4-hydroxy-3,5-ditertiarybutyldithiobenzoic acid was then added to the heated and stirred solution following by 125 mg of adenine. This procedure of sequentially adding the dithiobenzoic and adenine was repeated until 2 g of the acid and 500 mg of adenine have been added to the solution. The sequential procedure was employed to prevent precipitation of by-product polymeric materials.
- Ball on Cylinder (BOC) friction tests were performed on the ethoxylated(5)cocoalkylamine:dithiobenzoate:adenine complex from Example 5 in solvent 150N base oil using several concentrations of the additive. The BOC tests were performed using the experimental procedure described in Example 2. The data is shown in Table 3.
TABLE 3 Concentration (wt.%) in solvent 150N Coefficient of Friction Ethoxylated (5) cocoamine:DTB:Adenine Ethoxylated (5) cocoamine:DTB Primene** JMT:DTB 1 0 0.37 0.37 0.37 2 0.05 0.22 0.121 -- 3 0.1 0.17 0.107 0.3 4 0.2 0.13 -- -- 5 0.4 -- 0.107 -- 6 0.5 0.07 -- 0.21 7 0.6 -- 0.107 -- 8 0.8 0.06 0.107 0.177 ** Primene JMT is predominantly a C18 t-alkyl primary amine manufactured by Rohm & Haas. - As can be seen from the data in Table 3, the adenine-containing complex achieves lower coefficient of friction than can be obtained from the comparable complex without adenine or a Primene JMT:DTB complex.
- This Example illustrates the preparation of a complex containing ethoxylated amine, alkylsulfonic acid and adenine according to the invention. 41 g of ethoxylated(2)tallowamine and 1 g of adenine were heated to 60°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser. 58 g of alkylsulfonic acid having the formula
- The complex containing ethoxylated amine, alkylsulfonic acid and adenine is an effective friction modifier as shown in this example. The Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described in Example 2. Various amounts of complex prepared in Example 7 were added to solvent 150 N. The results of BOC friction tests are shown in Table 4.
TABLE 4 Wt% of Ethoxylated(2)Tallowamine, Alkylsulfonic Acid and Adenine Complex in Solvent 150N Coefficient of Friction 0.00 0.32 0.1 0.20 0.2 0.18 0.3 0.13 0.5 0.10 0.8 0.07 1.0 0.06 - As can be seen from the results in Table 4, as little as 1.0 wt% of complex shows an 81% decrease in the coefficient of friction. These results demonstrate that the present complexes are capable of significant reductions in the coefficient of friction of a lubricant basestock which results in less friction and hence greater fuel economy when the lubricated oil is used in an internal combustion engine.
- This Example illustrates the preparation of the novel complex of the invention. A solution of 80 g of diisooctyldithiophosphoric acid was heated to 50-100°C with stirring. 10 g of ethoxylated(5)cocoalkylamine was then added to the heated and stirred solution followed by 1 g of adenine. This procedure of sequentially adding ethoxylated amine and adenine was repeated until 75 g of ethoxylated (5) cocoalkylamine and 7 g of adenine have been added to the solution. The sequential addition procedure was employed to prevent precipitation of byproduct. The complex was then collected on cooling and used without further purification.
- This Example illustrates the superior copper corrosion protection provided by the complex of the invention as prepared in Example 9. The test for copper corrosion were run as follows. Copper corrosion tests were based on ASTM D-2440. 25 g of oil sample is placed in a 0.5" test tube with 30 cm of copper wire coiled to 0.5" and stretched to a finished length of 2". The test tube is then heated at 110°C for 120 hours. Nitrogen is bubbled through the oil at 17 cc/min during the test period. A 5 g sample of oil is removed at the end of the test and analyzed for copper content. Results of the copper corrosion are shown in Table 5.
TABLE 5 Copper Corrosion (ppm) Base case - Lubricating oil 21 Base case +1% Ethoxylated(5)cocoamine:DDP(diisooctyl) 37 Base case +1% Ethoxylated(5)cocoamine:DDP(diisooctyl):Adenine 17 Base case +1.5% Ethoxylated(5)cocoamine:DDP(diisooctyl) 57 Base case +1.5% Ethoxylated(5)cocoamine:DDP(diisooctyl):Adenine 23 Base case +1% Ethoxylated(2)tallowamine:DDP(secondary)* 74 Base case +1% Ethoxylated(2)tallowamine:DDP(secondary):Adenine 18 Base case +1.5% Ethoxylated(2)tallowamine:DDP(secondary) 107 Base case +1.5% Ethoxylated(2)tallowamine:DDP(secondary):Adenine 23 * DDP (secondary) contains a mixture of isobutyl (85%) and isooctyl (15%) as the alkyl component. - This Example illustrates the superior antiwear properties of the complex of the invention. Antiwear properties are measured by the four-ball wear test as follows. The Four Ball test used in described in detail in ASTM method D-2266. In this test, three balls are fixed in a lubricating cup and an upper rotating ball is pressed against the lower three balls. The test balls utilized were made of AISI 52100 steel with a hardness of 65 Rockwell C (840 Vickers) and a centerline roughness of 25 mm. Prior to the tests, the test cup, steel balls, and all holders were washed with 1,1,1 trichloroethane. The steel balls subsequently were washed with a laboratory detergent to remove any solvent residue, rinsed with water, and dried under nitrogen.
- The Four Ball wear tests were performed at 100°C, 60 kg load, and 1200 rpm for 45 minutes duration. After each test, the balls were washed and the Wear Scar Diameter (WSD) on the lower balls measured using an optical microscope. Using the WSD's, the wear volume (WV) was calculated from standard equations (see Wear Control Handbook, edited by M. B. Peterson and W. O. Winer, p. 451, American Society of Mechanical Engineers [1980]). The percent wear reduction (% WR) for each oil tested was then calculated using the following formula.
- The result of the four-ball are set forth in Table 6.
TABLE 6 % Additive in Solvent 150N* Wear Scar Diameter (mm) Ethoxylated(5)cocoamine:DDP(isooctyl) Ethoxylated(5)cocoamine:DDP(isooctyl):Adenine % wear volume reduction % wear volume reduction 0 0.0 0.0 0.1 -7.3 15.5 0.2 45.5 88.1 0.4 41.1 -- 0.5 -- 96.4 0.6 -- 97.8 0.8 15.1 99.2 1.0 -7.3 99.5 1.5 96.1 99.5 * S150 is a solvent extracted, dewaxed, hydrofined neutral lube base stock obtained from approved paraffinic crudes (viscosity, 32 cSt at 40°C, 150 Saybolt seconds) - The data in Table 6 demonstrate that even at low concentration (<0.2%), the present adenine complex has superior antiwear properties over the corresponding amine salt without adenine.
Claims (19)
- A composition of matter comprising a complex which is the reaction product of alkoxylated amine, acid and adenine, said complex having the formula (I):
- A composition as claimed in claim 2 or claim 3 wherein R1 is a hydrocarbyl group having from 2 to 26 carbon atoms.
- A composition as claimed in claim 1 wherein Z is derived from a dihydrocarbyldithiobenzoic acid of the following formula:
- A composition as claimed in claim 5 wherein R4 is hydroxy.
- A composition as claimed in either claim 5 or claim 6 wherein at least one of R2 to R5 is alkyl containing from 1 to 18 carbon atoms.
- A composition as claimed in any of claims 5 to 7 wherein R3 and R5 are t-butyl.
- A composition as claimed in claim 9 wherein R2 and R3 are alkyl or alkenyl groups of from 3 to 20 carbon atoms.
- A composition as claimed in any of claims 1 to 10 wherein R is alkyl or alkenyl of from 6 to 18 carbon atoms.
- A composition as claimed in any of claims 1 to 11 wherein the sum of x+y is 2 to 15.
- A composition as claimed in any of claims 1 to 12 wherein in the adenine R1 is hydrogen.
- A lubricating oil composition for internal combustion engines which comprises(a) a major amount of a lubricating oil basestock and(b) a minor amount of a complex as claimed in any of claims 1 to 13.
- A composition as claimed in claim 14 wherein the complex is as claimed in any of claims 5 to 11 and wherein the amount of complex is from about 0.1 to about 5.0 wt.%, based on oil basestock.
- A composition as claimed in claim 14 wherein the complex is as claimed in any of claims 1 to 4 and wherein the amount of complex is from about 0.001 to about 5.0 wt.%, based on oil basestock.
- The use in a lubricating oil composition of a complex as claimed in any of claims 1 to 13 for improving fuel economy in an internal combustion engine.
- The use in a lubricating oil composition for reducing wear and/or inhibiting copper corrosion in an internal combustion engines of a composition as claimed in any of claims 1 .to 13.
- The use of a composition as claimed in any of claims 1 to 13 as a friction modifier in a lubricating oil composition for an internal combustion engine.
Applications Claiming Priority (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US21291 | 1987-03-03 | ||
US21296 | 1993-02-22 | ||
US21288 | 1993-02-22 | ||
US08/021,503 US5290462A (en) | 1993-02-22 | 1993-02-22 | Lubricant composition containing complexes of alkoxylated amine, hydrocarbylsulfonic acid and adenine |
US08/021,506 US5266226A (en) | 1993-02-22 | 1993-02-22 | Ashless lube additives containing complexes of alkoxylated amine, dithiobenzoic acid and adenine (PNE-639) |
US21503 | 1993-02-22 | ||
US08/021,296 US5308517A (en) | 1993-02-22 | 1993-02-22 | Ashless lube additives containing complexes of alkoxylated amines, dihydrocarbyldithiophosphoric acid, and adenine |
US08/021,291 US5290463A (en) | 1993-02-22 | 1993-02-22 | Lubricant composition containing complexes of alkoxylated amine, hydrocarbylsalicylic acid and adenine |
US08/021,288 US5290460A (en) | 1993-02-22 | 1993-02-22 | Lubricant composition containing complexes of alkoxylated amine, trithiocyanuric acid, and adenine |
PCT/EP1994/000522 WO1994019437A1 (en) | 1993-02-22 | 1994-02-22 | Lubricant compositions containing complexes of alkoxylated amine, acid, and adenine |
US21506 | 1998-02-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0684979A1 EP0684979A1 (en) | 1995-12-06 |
EP0684979B1 true EP0684979B1 (en) | 1997-07-23 |
Family
ID=27533904
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94909035A Expired - Lifetime EP0684979B1 (en) | 1993-02-22 | 1994-02-22 | Lubricant compositions containing complexes of alkoxylated amine, acid, and adenine |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0684979B1 (en) |
JP (1) | JPH09502422A (en) |
CA (1) | CA2156606A1 (en) |
DE (1) | DE69404447T2 (en) |
WO (1) | WO1994019437A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070093395A1 (en) * | 2005-10-21 | 2007-04-26 | Habeeb Jacob J | Antiwear inhibiting and load enhancing additive combinations for lubricating oils |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3849319A (en) * | 1973-11-19 | 1974-11-19 | Texaco Inc | Di and tri(hydrocarbylammonium)trithiocyanurate and lubricating oil compositions containing same |
US4367152A (en) * | 1981-07-02 | 1983-01-04 | Exxon Research And Engineering Co. | Selected heteroaromatic nitrogen compounds as antioxidant/metal deactivators/electrical insulators in lubricating oils and petroleum liquid fuels |
US4501677A (en) * | 1983-11-02 | 1985-02-26 | Exxon Research & Engineering Co. | Heterocyclic nitrogen compounds--organometallic salt complexes as corrosion inhibitors in lubricating oils |
US5080813A (en) * | 1990-03-26 | 1992-01-14 | Ferro Corporation | Lubricant composition containing dialkyldithiophosphoric acid neutralized with alkoxylated aliphatic amines |
US5076945A (en) * | 1990-09-14 | 1991-12-31 | Exxon Research And Engineering Company | Lubricating oil containing ashless non-phosphorus additive |
US5085793A (en) * | 1990-11-19 | 1992-02-04 | Texaco Chemical Company | Corrosion-inhibited antifreeze/coolant composition |
-
1994
- 1994-02-22 EP EP94909035A patent/EP0684979B1/en not_active Expired - Lifetime
- 1994-02-22 WO PCT/EP1994/000522 patent/WO1994019437A1/en active IP Right Grant
- 1994-02-22 CA CA002156606A patent/CA2156606A1/en not_active Abandoned
- 1994-02-22 JP JP6518669A patent/JPH09502422A/en active Pending
- 1994-02-22 DE DE69404447T patent/DE69404447T2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CA2156606A1 (en) | 1994-09-01 |
DE69404447D1 (en) | 1997-08-28 |
JPH09502422A (en) | 1997-03-11 |
WO1994019437A1 (en) | 1994-09-01 |
EP0684979A1 (en) | 1995-12-06 |
DE69404447T2 (en) | 1998-01-15 |
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