EP0277729B1 - Lubricant compositions providing wear protection at reduced phosphorus levels - Google Patents
Lubricant compositions providing wear protection at reduced phosphorus levels Download PDFInfo
- Publication number
- EP0277729B1 EP0277729B1 EP88300500A EP88300500A EP0277729B1 EP 0277729 B1 EP0277729 B1 EP 0277729B1 EP 88300500 A EP88300500 A EP 88300500A EP 88300500 A EP88300500 A EP 88300500A EP 0277729 B1 EP0277729 B1 EP 0277729B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- additive composition
- lubricating oil
- additive
- present
- range
- 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
- 239000000203 mixture Substances 0.000 title claims description 177
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 52
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 51
- 239000011574 phosphorus Substances 0.000 title claims description 51
- 239000000314 lubricant Substances 0.000 title description 13
- 239000000654 additive Substances 0.000 claims description 118
- 230000000996 additive effect Effects 0.000 claims description 110
- 239000010687 lubricating oil Substances 0.000 claims description 86
- 239000003921 oil Substances 0.000 claims description 66
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 48
- 239000002270 dispersing agent Substances 0.000 claims description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 40
- 229910052725 zinc Inorganic materials 0.000 claims description 40
- 239000011701 zinc Substances 0.000 claims description 40
- -1 calcium sulfonates Chemical class 0.000 claims description 38
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 35
- 229910052796 boron Inorganic materials 0.000 claims description 34
- 229960002317 succinimide Drugs 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 230000001050 lubricating effect Effects 0.000 claims description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 14
- 239000001384 succinic acid Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 229920001281 polyalkylene Polymers 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002199 base oil Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 4
- BESRYENXPUCIID-CHHVJCJISA-N n-tert-butyl-1-(3,5,6-trimethylpyrazin-2-yl)methanimine oxide Chemical compound CC1=NC(C)=C(\C=[N+](/[O-])C(C)(C)C)N=C1C BESRYENXPUCIID-CHHVJCJISA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 31
- 239000002184 metal Substances 0.000 description 31
- 239000002585 base Substances 0.000 description 14
- 239000003112 inhibitor Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000003599 detergent Substances 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 229960005137 succinic acid Drugs 0.000 description 8
- 235000011044 succinic acid Nutrition 0.000 description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 150000003871 sulfonates Chemical class 0.000 description 7
- 230000003749 cleanliness Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 101000640743 Ralstonia solanacearum (strain GMI1000) Tryptophan 2,3-dioxygenase 2 Proteins 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000002939 deleterious effect Effects 0.000 description 4
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000003138 primary alcohols Chemical class 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 150000003333 secondary alcohols Chemical class 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006388 chemical passivation reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WZUVPPKBWHMQCE-UHFFFAOYSA-N Haematoxylin Chemical compound C12=CC(O)=C(O)C=C2CC2(O)C1C1=CC=C(O)C(O)=C1OC2 WZUVPPKBWHMQCE-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001638 boron Chemical class 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 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
- 230000000694 effects Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003879 lubricant additive Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- VZIQXGLTRZLBEX-UHFFFAOYSA-N 2-chloro-1-propanol Chemical compound CC(Cl)CO VZIQXGLTRZLBEX-UHFFFAOYSA-N 0.000 description 1
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 description 1
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
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- 150000003873 salicylate salts Chemical class 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 239000010706 single-grade lubricating oil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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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- 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
- C10M159/16—Reaction products obtained by Mannich reactions
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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- 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
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- 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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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
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- 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
- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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- 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
- C10M2215/28—Amides; Imides
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/043—Mannich bases
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- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
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- 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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- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol-fuelled engines
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
- C10N2040/253—Small diesel engines
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
Definitions
- the present invention is directed to a novel composition that is useful as a lubricant additive.
- the present invention relates to a lubricant additive composition that is characterized by antiwear and friction retention properties while providing reduced phosphorus levels.
- the invention relates to formulation of a so-called universal or mixed fleet lubricant oil additive composition (i.e. one that will result in a lubricant meeting the requirements of both heavy duty and passenger car engine tests) which has reduced phosphorus and which comprises zinc dialkyldithiophosphate having both primary and secondary character in combination with a succinimide dispersant.
- Lubricating oils particularly mineral oils, deteriorate under heavy loads and as a result of oxidation during their use in internal combustion engines to form products, some of which are corrosive and some of which agglomerate to form sludge-like deposits and varnish-like deposits.
- Such sludge-like material occurs when the crankcase lubricant is subjected to alternate hot and cold environments, which are present in ordinary stop-and-go driving.
- Sludge is a complex mixture of fuel combustion products, unburned fuel, carbon, lead anti-knock residues, and water and, if not maintained in fine suspension in the lubricating oil, will deposit on engine parts. Such deposits are deleterious to engine performance.
- additives and additive formulations have been added to lubricating oils to minimize deterioration and to enhance performance.
- Such materials as neutral and over-based metal long chain alkyl substituted sulfonates, phenates, salicylates, and phosphonates and thiophosphonates have been added as detergents and/or detergent-dispersants.
- Materials such as polymers and/or copolymers containing a carboxylate ester function and one or more polar functions, N-substituted long chain alkenyl succinimides, high-molecular weight amides and polyamides, high-molecular weight esters and polyesters, and amine salts of high-molecular weight organic acids, have been added as ashless dispersants to disperse the cold sludge formed under stop-and-go driving conditions.
- Materials such as metal dithiophosphates, metal dithiocarbamates, sulfurized terpenes, and phosphosulfurized terpenes, have been added as corrosion inhibitors.
- one or more additives are incorporated often into the lubricant composition to furnish or to enhance antiwear and friction retention properties of that composition. Examples of art describing such lubricating oil compositions are discussed hereinbelow.
- Rowe discloses lubricating oil compositions that contain a small amount of a mixture of a metal salt of an O,O-diorgano-phosphorodithioate and a boroaryl compound in synergistic proportions.
- An example of such mixture is a mixture of zinc, O,O-diisopropylphosphorodithioate and 9-hydroxy-9,10 boroxarophenanthrene. The amount of the mixture is sufficient to improve antiwear properties of the compositions.
- Braid discloses lubricant compositions containing esters of O,O-diorgano-S-(2-hydroxyalkyl) phosphorodithioates, which are antioxidants and corrosion inhibitors.
- Clark discloses a friction-reducing additive for use in lubricating oils.
- the additive comprises a hydrocarbon oil of lubricating viscosity, an extreme pressure antiwear agent, an alkaline material, such as an overbased calcium sulfonate, a viscosity index improving agent, and optionally an antifoam agent and an antioxidant agent.
- the antiwear agent comprises a mixture of an oil dispersion of solid, inorganic film-forming potassium borate, antimony dialkylphosphorodithioate, and a liquid chlorinated paraffin.
- Salentine discloses a lubricating oil composition having improved wear properties, which composition comprises an oil of lubricating viscosity having dispersed therein a hydrated alkali-metal borate extreme-pressure agent and an effective amount of a mixture of a non-sulfur-containing phosphate, a monothiophosphate, and a dithiophosphate, the mixture of phosphate, monothiophosphate, and dithiophosphate being in the ratio of 0.90-10:0.90-1.10:0.47-0.67.
- a lubricating oil composition comprising an oil of lubricating viscosity and a minor amount of a multifunctional additive consisting of the metal salt of a partially borated, partially phosphosulfurized hydroxyl-containing ester derived from a polyol, e.g., a zinc salt of borated, partially phosphosulfurized glycerol monooleate.
- the additive is an effective friction-reducing, antioxidant, and copper strip passivating additive in lubricants.
- Patent 4,483,775 Yamaguchi discusses this problem and suggests that the detrimental effect of the overbased calcium hydrocarbyl sulfonates on the wear of metal parts in the internal combustion engine can be overcome by adding to the lubricating oil containing these materials an effective amount of a complex prepared by reacting an insoluble metal salt of a diisopropyl dithiophosphoric acid with an oil-soluble alkenyl or alkyl mono- or bis-succinimide in specific amounts.
- Yamaguchi also points out that there is another problem that is associated with the use of phosphorus-containing additives in lubricating oils.
- the phosphorus can have a deleterious effect upon the catalysts that are employed in the emissions control systems of internal combustion engines of automobiles.
- the overbased metal hydrocarbyl sulfonates tend to offset the effectiveness of the metal dihydrocarbyldithiophosphates, additional amounts of the metal dihydrocarbyldithiophosphates must be employed and such increased amounts of these additives will introduce additional amounts of phosphorus into the lubricating oil.
- EP-A-020674 discloses a lubricating oil composition comprising
- an additive composition which is suitable for use in so-called universal or mixed fleet oils.
- Such an oil by definition, is one which is capable of passing a rigorous battery of engine tests which measure the performance of the oil for both passenger car and heavy duty (i.e. diesel) applications.
- pasenger car catalytic converters of phosphorus which is typically introduced into the oil via the anti-wear agent zinc dialkyldithiophosphate
- it would be particularly advantageous if an additive composition suitable for a universal oil could be formulated with reduced levels of phosphorus.
- a general object of the invention is to provide an additive composition which affords passing wear protection for a universal oil at reduced phosphorus levels.
- an additive composition for addition to an oil of lubricating viscosity suitable for passenger car and heavy duty use comprising: (a) zinc dialkyldithiophosphate having both primary and secondary character such that the primary to secondary ratio is 1:1 to 5:1, said mixed primary/secondary zinc dialkyldithiophosphate being present in the additive composition in amount such that a lubricating oil containing an effective amount of said additive composition has a phosphorus content of not greater than 0.1 wt %; (b) a succinimide dispersant in such amount that a lubricating oil containing 9 to 12 percent of said additive composition will comprise at least about 0.5 wt % succinimide; (c) a boron content such that a lubricating oil containing said additive composition contains at least 100 ppm boron; and (d) an effective amount of basic salts comprising high base magnesium sulfonates and high base calcium sulfonates such that a lubricating oil
- the molar ratio of primary to secondary alkyl groups in the zinc dialkyldithiophosphate (hereafter occasionaly referred to as "ZDDP") is within the range of about 1.7:1 to about 3.5:1 and preferably about 1.7:1 to about 4.5:1.
- the preferred amount of succinimide dispersant in the additive composition is such that will provide at least .5 wt. % of the succinimide in the finished oil and most preferably about .5 to about 3.5 wt. %.
- the preferred phosphorus level in the additive composition is such as will provide a phosphorus level of about .06 wt.% to about .09 wt.%.
- the preferred TBN of the additive is such as will provide a TBN in the finished oil within the range of about 8-12 and preferably about 9-11. It should be noted that all dispersant amounts are expressed in terms of active dispersant absent any diluent, except, however, in the examples where dispersant amounts are expressed in terms of a 40% active material containing added diluent.
- the additive composition of the present invention has a boron content sufficient to provide a boron level in the finished oil of within the range of about 100 ppm(wt) to about 600 ppm and preferably in the range of 150 ppm to 450 ppm.
- the advantages of the invention is the ability to reduce the level of phosphorus required in an additive composition for a mixed fleet oil despite the requirement of high TBN in such oils, which is necessary for passing heavy duty engine cleanliness tests, while at the same time obtaining passing wear peformance. Reducing the phosphorus in the oil composition benefits the catalytic converter in passenger cars.
- the succinimide dispersant required in the present invention is critical in accomplishing the reduction in phosphorus for the following reasons:
- increasing the secondary character of the ZDDP makes it possible to reduce the overall amount of ZDDP (and thus the total phosphorus required in the additive and resulting oil) without giving up passing wear performance.
- the additive composition of the present invention must comprise (a) zinc dialkyldithiophosphate having both primary and secondary character such that the primary to secondary ratio (expressed in moles) is within the range of from about 1:1 to about 5:1, and (b) succinimide dispersant.
- the total amount of phosphorus in the additive as provided by the ZDDP, must be such that the amount of phosphorus present in a lubricating oil containing an effective amount of the additive is not greater than about .1% by weight of the lubricating oil, and the TBN of the additive composition must be such that a lubricating oil containing an effective amount of the additive composition will have a TBN of at least 8.
- An effective amount of the additive composition of the present invention means a treat level in the lubricant which will allow the oil to pass both heavy duty and passenger car tests.
- additive composition optionally may be present in the additive composition.
- rust inhibitors such as normal or overbased sulfurized metal phenates or metal sulfonates.
- oxidation inhibitors such as normal or overbased sulfurized metal phenates or metal sulfonates.
- detergents such as normal or overbased sulfurized metal phenates or metal sulfonates.
- zinc dialkyldithiophosphate having both primary and secondary character for use in the present invention functions as a corrosion and wear inhibitor.
- zinc dialkyldithiophosphate is prepared by forming a dithiophosphoric acid via a reaction of a phenol or an alcohol with phosphorus pentasulfide and subsequently neutralizing the dithiophosphoric acid with a zinc compound, such as zinc oxide.
- a zinc compound such as zinc oxide.
- Such preparation is well known in the art and is presented, for example, in U.S. Patent 2,261,047 and U.S. Patent 4,483,775.
- This type of dialkyldithiophosphate can be identified by the alcohol that is employed in its preparation.
- a primary alcohol is employed, the product is referred to as a primary zinc dialkyldithiophosphate.
- the zinc dialkyldithiophosphate is identified as a secondary zinc dialkyldithiophosphate.
- Suitable primary alcohols for use in the preparation of the primary zinc dialkyldithiophosphate are n-butyl alcohol, n-octyl alcohol, isoamyl alcohol, isooctyl alcohol, and isobutyl alcohol.
- Suitable secondary alcohols are isopropyl alcohol, methyl isobutyl carbinol, 2-amyl alcohol, and 2-butyl alcohol.
- the resulting ZDDP is a hydrid having both primary and secondary character.
- the term "zinc dialkyldithiophosphate having both primary and secondary character” includes any of the following: (a) a zinc dialkyldithiophosphate preparation obtained by mixing a desired amount of primary zinc dialkyldithiophosphate with a desired amount of secondary zinc dialkyldithiophosphate; (b) a zinc dialkyldithiophosphate which results from employing a mixture of primary and secondary alcohols in the preparation of the zinc dialkyldithiophosphate; and (c) a zinc dialkyldithiophosphate obtained by mixing a primary or a secondary zinc dialkyldithiophosphate with a zinc dialkyldithiophosphate meeting the definition of (b).
- ratio of primary to secondary or “primary to secondary ratio” means the molar ratio of primary alkyl groups to
- the primary to secondary ratio in the zinc dialkyldithiophosphate is within the range of about 1:1 to about 5:1, preferably, within the range of about 1.7:1 to about 3.5:1, and more preferably, within the range of about 1.7:1 to about 2.5:1.
- the total amount of the mixed primary/secondary dialkyldithiophosphates should be an amount that will provide a phosphorus content in the lubricating oil composition not greater than 0.1 wt%, based upon the weight of the lubricating oil composition.
- the zinc dialkyldithiophosphate should be present in a total amount that will provide a phosphorus content in the lubricating oil composition that falls within the range of about 0.06 wt% to about 0.09 wt%, and most preferably within the range of about 0.06 wt% to about 0.08 wt%, based upon the weight of the lubricating oil composition.
- the prescribed 1°:2° molar ratio in the ZDDP used in the present invention is important when one considers the object of maintaining the phosphorus content in the additive composition at such a level that a finished oil containing an effective amount of the composition has a phosphorus content of not greater than about .1 wt % of the finished oil. If the total phosphorus is decreased, then in accordance with the present invention, passing wear can be maintained by increasing the 2° character of the ZDDP. Such an adjustment appears practicable where the phosphorus (in terms of the finished oil) is between about .06 and about 0.1 wt percent.
- the prescribed ratios of 1° to 2°character are based upon this fact, and the desirability of using the minimum amount of 2° character in the ZDDP to maintain wear protection (given the deleterious effect of the the 2° ZDDP on friction performance).
- the ratio will increase as the total phosphorus (in terms of the oil) approaches about .1 wt%, and will decrease as the phosphorus level approaches about .06 wt.%.
- a second required component of the additive composition of the present invention is a succinimide dispersant.
- Such succinimide is an N-substituted long chain-alkenyl succinimide.
- the alkenyl radical is derived from liquid polyisobutenes containing from 50 to 200 carbon atoms.
- Such a succinimide is an oil-soluble nitrogen containing composition.
- the preparation of succinimide dispersants is known in the art. Among such art are U.S. Patents 3,172,892; 3,272,746; and 3,219,666. The disclosures of these patents are incorporated herein by reference.
- an acylated nitrogen intermediate compound is formed by reacting a substantially aliphatic olefin polymer-substituted succinic-acid producing compount having at least about 50 aliphatic carbon atoms in the polymer substituent with at least about one half equivalent of an amine for each equivalent of acid-producing compound used, said reaction being carried out at a temperature within the range of about 80°C to about 250°C.
- the amine is selected from a group consisting of alkylene amines, hydroxysubstituted alkylene amines, and polyalkylene polyamines.
- the polymer substituent of the succinic acid-producing compound is derived conveniently from a polymer of isobutene.
- the polyisobutene has an average molecular weight that is within the range of about 700 to about 5,000.
- Suitable amines are alkylene amines, alkylene diamines having the structure NH2-R-NH2, wherein R is an alkylene group having from 2 to 24 carbon atoms, and the so-called polyalkyleneamines, sometimes referred to as alkylene polyamines or polyalkylene polyamines, which generally have the structure H2N--(R--NH) n H, where R is an aliphatic hydrocarbon group containing about 2 to about 4 carbon atoms and n is an integer from 1 to 10.
- Representative amines include methylene amines, ethylene amines, butylene amines, propylene amines, pentalene amines, ethylene diamine, triethylene tetraamine, propylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene)triamine, tripropylene tetramine, tetraethylene pentamene, trimethylene diamine, pentaethylene hexamine, di(trimethylene)triamine, etc.
- a preferred polyalkylene polyamine is tetraethylene pentamine (TEPA).
- the succinimide dispersant is present in the additive composition of the present invention in an amount sufficient to provide a lubricating oil containing an effective amount of the additive composition at least about .5 wt, % by weight of the lubricating oil. While a preferred range is about .5 to about 3.5 the maximum amount of succinimide is an economic consideration and is not critical in the present invention. However the requirement of at least .5 wt% is critical insofar as lesser amounts fail to provide the desired advantage of passing frictional tests, in particular the Allison C-3, when phosphorus levels of less than .1 by weight of the lube oil, in combination with the 1°/2° ratios discussed above, are employed.
- the additive composition of the present invention comprises sufficient TBN such that a universal oil comprising an effective treat level of said additive composition is provided with a TBN of at least 8, preferably, within the range of about 9 to about 11, and more preferably, about 10.
- Examples of components that are suitable for providing the required TBN in the additive composition of the present invention are overbased metal sulfonates and over based phenates.
- the sulfonates are normal or basic metal salts of petroleum ("mahogany") sulfonic acids and long chain alkyl substitued benzene sulfonic acids.
- the phenates are normal or basic salts of alkylphenols, alkylphenol sulfisides, and alkylphenol-aldehyde condensation products.
- a normal metal salt of an acid is a salt which contains the stoichiometric amount of metal required for the neutralization of the acidic group or groups present in the acid.
- a basic salt or overbased salt is a salt which contains more metal than is required to stoichiometrically neutralize the acidic group or groups present. While both normal and overbased sulfonates and phenates provide detergent properties for lubricating oil compositions, the overbased or superbasic or hyperbasic salts provide unusually high detergent power and, consequently, have a much greater capacity to neutralize acidic contaminants than do the normal sulfonates and phenates.
- an overbased sulfonate is prepared by mixing a promoter, catalyst or solvent with a normal sulfonate and a larger excess of metallic base, followed by heating, carbonation and filtration.
- Carbonation of the reaction mass is accomplished conveniently with carbon dioxide and is employed to increase the amount of metal base colloidally dispersed as metal carbonate in the filtered product.
- Phenols, trioacids, of phosphorus, alcoholates, alcohols, ketones, and alkanolamines can be used as promoters for catalysts.
- Typical metallic bases are basic compounds of alkaline earth metals, such as calcium, barium, or magnesium. Overbased metal sulfonates are discussed thoroughly in the prior art. Examples of such art are: United Kingdom Patent Application GB 2,082,619A and U.S. Patents 2,865,956; 2,956,018; 2,671,430; 3,779,920; 3,907,691; 4,137,184; 4,261,840; and 4,326,972.
- overbased metal phenates are presented in the prior art.
- Typical examples of the prior art are U.S. Patents 2,680,096; 3,036,917; 3,178,368; 3,194,761; 3,437,595; 3,464,910; 3,779,920; and 4,518,807.
- the reduced-phosphorus additive composition further comprises boron sufficient to provide within the range of from about 100 to about 600 ppm(wt.) boron in the finished oil containing the additive composition of the invention.
- the additive composition may contain an additional dispersant comprising at least on member of the group consisting of Mannich and succinate ester-amide (SEA) dispersant in an amount sufficient to provide preferably up to about 5 wt% of the second dispersant in the finished oil.
- SEA Mannich and succinate ester-amide
- the succinate ester-amide dispersant can be prepared in accordance with techniques which have been disclosed in the art (See for example U.S. Patent No. 4,426,305) by reacting an aliphatic hydrocarbon substituted succinic acid anhydride with an oxyalkylated amine.
- the long chain aliphatic hydrocarbon-substituted succinic acid compound that is used in the preparation of the second dispersant can be obtained by reacting an ethylenically unsaturated dicarboxylic acid compound (acid or anhydride), such as maleic acid, maleic anhydride, or fumeric acid, with a suitable olefin or halogenated olefin at a temperature within the range of about 100°C to 300°C. An alkenyl or alkyl substituted succinic acid or anhydride is produced.
- the unsaturated groups in the alkenyl group can be removed by standard hydrogenated techniques.
- the olefins or halosubstitued olefins contain from about 8 to about 500 carbon atoms, or more, and can include homopolymers and copolymers of monoolefins, such as ethylene, propylene, l-butene, isobutene, and the like. However, any of the techniques known in the art can be employed to produce this long chain succinic acid compound.
- the oxyalkylated amine suitable for reaction with the above described long chain aliphatic hydrocarbon succinic acid compound can be prepared in accordance with known methods by reacting an alkylene oxide with an amine having primary or secondary amine groups.
- Suitable amines are alkylene diamines having the structure NH2-R-NH2, wherein R is an alkylene group having from 2 to 24 carbon atoms, such as ethylene, 1, 2-propylene, trimethylene, hexamethylene, dodecamethylene, tetracosene, etc.
- polyalkyleneamines sometimes referred to as alkylene polyamines or polyalkylene polyamines.
- R is an aliphatic hydrocarbon group containing about 2 to about 4 carbon atoms and n is an integer from 1 to 6.
- Representative examples include ethylenediamine, 1,2-propylenediamine, 1,2-butylenediamine, 1,3-propanediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine (TEPA), etc.
- Suitable hydroxyalkylating reactants include halohydrins and vicinal epoxies (olefin oxides) having from 2 to 4 carbon atoms in the alkylating agent, such as ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, 2-chloro-l, ethanol, 2-chloro-l-propanol, 3-bromo-l-prophanol, and 4-chloro-butanol.
- the hydroxyalkylating agents can be used in a concentration of about 2.0 to 6 moles per mole of amine, and hydroxyalkylation can be carried out under conventional conditions, i.e., by reaction at 50°C to 300°C for a period of time within the range of 1 to 10 hours.
- the long chain aliphatic succinic acid compound is reacted with the N-substituted hydroxy alkyl diamine under conditions that are normally employed in the art and at a temperature within the range of about 0°C to about 250°C.
- a solvent such as benzene, toluene, naphtha, lube oil, xylene, and normal hexane, can be used to facilitate the control reaction.
- the optional second dispersant may also be a Mannich dispersant.
- Mannich dispersants made from hydrocarbon substituted phenols, formaldehyde and amines are well known in the patent literature. See U.S. Patent Nos. 3,413,347; 3,725,277; 3,368,972; 3,798,165; 3,697,574, and 4,426,305. These patents are incorporated by reference.
- the optional second dispersant can be present in the lubricating oil composition in an amount within the range of about 0 wt % to about 5 wt%, preferably, within the range of about 0 wt% to about 3 wt%.
- the additive composition of the present invention preferably contains boron in an amount such that a lubricating oil containing an effective amount of the additive composition, will have a boron content within the range of about 100 ppm(wt) to about 600 ppm(wt) boron.
- the preferred boron level is about 150 to about 450 ppm(wt) in the finished oil.
- the presence of boron is preferred for the protection of fluorinated elastomer hydrocarbon seals, and also enhances the anti-wear properties of the additive composition, especially where TBN is supplied by high-based calcium sulfonate. The latter is known to deleteriously effect the wear protection afforded by zinc dialkyldithiophosphate.
- boron is preferably present in an amount sufficient to provide about 150 ppm(wt) to about 450 ppm(wt) in the finished oil.
- Boron may be introduced into the additive composition in accordance with conventional techniques.
- a boron compound such as boron oxide, boron dihalides (boron trifluoride, boron tribromide, boron tricholoride), boron acids, such as tetraboric acid and metaboric acid, and simple esters of the boron acids, can be reacted with the succinimide, SEA or Mannich dispersants discussed above at a temperature within the range of about 50°C to about 250°C, preferably from about 100°C to about 170°C, with a sufficient concentration of boron compound to yield a boronated dispersant product containing at least 0.15% by weight boron (excluding lube oil).
- the boron compound can be reacted in a ratio within the range of about 0.1 to 10 moles of boron compound for equivalent of dispersant compound.
- the reaction can be carried out in the presence of diluent or solvent.
- a portion of the succinimide, Mannich or SEA dispersant intended for the additive composition of the invention may be segregated and heated with a boronating agent to introduce a higher level of boron than would be desired in the final dispersant. This overboronated product can then be blended back into the unboronated dispersant to achieve the desired level of boron.
- the additive composition of the present invention may contain other additive components, such as viscosity index improvers, pour point depressants, and antioxidants.
- the additive composition of the present invention comprises a mixture of several additive components, some of which are mandatory and some of which are optional.
- This blend or mixture is prepared easily by introducing one or more of the components into another component. It is not critical that a particular component be added to another particular component, i.e., there is no particular sequence which must be used when adding the various components in preparing the blend.
- the blend is a composition that will provide antiwear and friction retention properties to the lubricating oil to which it is added while minimizing the phosphorus level in that particular lubricating oil composition.
- the additive composition of the present invention can be added to a petroleum oil or synethetic oil of lubricating viscosity to provide antiwear and friction retention properties while minimizing the amount of phosphorus in the resulting lubricating oil composition.
- the additive composition of the present invention is quite suitable for addition to a lubricant that is being employed in heavy duty vehicles, such as those used in military operations.
- Lubricating oil compositions containing the additive composition of the present invention provide suitable anti-wear and friction retention properties. In addition, they contain only a limited amount of phosphorus and, consequently, minimize the phosphorus content in the engine and thus extend the life of the catalyst in the catalytic converter of the automobile.
- the additive composition of the present invention will be present in the lubricating oil composition in an amount that is within the range of about 9 wt% to about 12 wt%, based upon the weight of the lubricating oil composition. More particularly, the additive composition is present in the lubricating oil composition in an amount that is within the range of about 10% to about 11 wt%, based upon the weight of the lubricating oil composition.
- the scope of the present invention includes concentrates of the additive composition.
- concentrates are made up of about 90 wt% to about 10 wt% of an oil having lubricating viscosity.
- the concentrates contain the additive composition plus a suitable diluent.
- Typical diluents are inert diluents, preferably an oil of lubricating viscosity, so that the concentrate may be mixed conveniently with the lubricating oil that will make up the desired lubricating oil composition.
- Lubricating oils that are suitable as diluents typically will have viscosities that are within the range of about 35 Saybolt Universal Seconds (SUS) at 100°F (38°C) to about 1,000 SUS at 100°F (38°C).
- oil of lubricating viscosity can be used as the diluent for the concentrate of the present invention
- the oil of lubricating viscosity in the lubricating oil composition can be employed as the diluent in the concentrate.
- Lubricating oils that are suitable for use in the lubricating oil compositions and concentrates of the present invention are oils of lubricating viscosity and are either petroleum oils or synthetic oils.
- the petroleum oils can be paraffinic, naphthenic, or even halogen-substituted hydrocarbons.
- Typical synthetic oils are those comprising syntheticesters, diester, ethers, polyolefins, or combinations thereof.
- oils of lubricating viscosity will have viscosities that fall in the range of about 50 SUS to about 5,000 SUS at 100°F (38°C), preferably viscosities in the range of about 50 SUS to about 2,000 SUS at 100°F (38°C), and more preferably, viscosities in the range of about 80 SUS to about 1,000 SUS at 100°F (38°C).
- a lubricating oil composition which lubricating oil composition comprises a major portion of an oil having lubricating viscosity in combination with a minor portion of an additive composition as described above.
- a preferred embodiment of the lubricating oil additive composition of the present invention was prepared. This embodiment had the composition presented hereinbelow in Table I. This additive was then introduced into a Mid-East base stock. The resulting lubricating oil composition had an SAE grade of 15W-40. The additive composition made up 10.3 wt% of the lubricating oil composition, which had a TBN of about 10. The lubricating oil composition also contained 4.1 wt% Viscoplex 2-50 viscosity index improver obtained from Rohm-Darmstadt. The concentration of each of the components of the additive composition in the lubricating oil composition is also provided in Table I. The additive composition contained 1,700 ppm(wt) boron, while the SAE 15W-40 oil, identified hereinafter as Sample No. 1, contained 180 ppm(wt) boron. Furthermore, Sample No. 1 contained 784 ppm(wt) phosphorus. The molar ratio of primary to secondary in the zinc dialkyldithiophosphate was 4.4
- SAE 15W-40 Oil Sample No. 1 which contained a preferred embodiment of the additive composition of the present invention, met all performance criteria of the tests. It is particularly noteworthy that acceptable wear protection was provided in the Sequence IIID and V-D Tests while acceptable performance was provided in the Caterpillar TO-2 and Allison C-3 Tests. Sample No. 1 is a preferred embodiment of the lubricating oil composition of the present invention.
- Sample No. 1 was the formulation presented in Table I hereinabove.
- Sample No. 4 had a similar composition, but the alkyl diarylamine oxidation inhibitor was replaced by a sulfurized oxidation inhibitor.
- Sample No. 5 a North Sea base stock (less stable than the Mid-East stock) was employed. The results are presented hereinbelow in Table IV.
- the mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate provided acceptable wear protection.
- the preferred embodiments of the lubricating oil composition of the present invention were compared for diesel cleanliness to Sample No. 9, a similar additive composition but with a different detergent, and Sample No. 4, a similar additive composition but with a different oxidation inhibitor.
- the different detergent was a low base calcium sulfonate.
- the different oxidation inhibitor was a sulfurized oxidation inhibitor.
- the test method employed was the Caterpillar 1G2 Test. The results are presented hereinbelow in Table VI.
- Samples Nos. 1 and 6 embodiments of the lubricating oil composition of the present invention passed the specification for top groove fill; however, Sample No. 6 did not provide an acceptable value for weighted total demerits. On the other hand, the latter sample provided a small top groove fill. Each of the other two samples furnished acceptable diesel engine cleanliness response.
- Sample No. 10 employed an SAE 30 weight lubricating oil derived from the Mid-East base stock obtained from the British Petroleum Company.
- An Acryloid 150 pour point depressant obtained from Rohm & Haas was also a component of Sample No. 10. This sample was subjected to a Sequence V-D Test. The results are presented hereinbelow in Table VII. Also shown in Table VII are the results obtained with Sample No. 1, which is a multigrade oil containing a preferred embodiment of the additive composition of the present invention.
- Sample No. 11 Another embodiment of a lubricating oil composition of the present invention, Sample No. 11, was prepared and subjected to a Sequence V-D Test and a Caterpiller 1G2 Test. Results of these tests are presented hereinbelow in Table VIII.
- Sample No. 11 contained 795 ppm(wt) phosphorus and 190 ppm(wt) boron. The results obtained with Sample No. 1 are also provided in Table VIII.
- Each of these samples was a 15W-40 lubricating oil composition and each contained an embodiment of the additive composition of the present invention.
- Sample No. 1 contained Viscoplex 2-50, obtained from Rohm Darmstadt. Viscoplex 1-50 is a dispersant polymethacrylate viscosity index improver.
- Sample No. 11 contained ECA 6911, obtained from Paramins, a division of Exxon Corporation, as a viscosity index improver.
- Two additive compositions were prepared and were added to a Mid-East base stock to provide 15W-40 grade lubricating oil compositions.
- One additive composition was an embodiment of the present invention and, when added to the base oil, resulted in lubricating oil Sample No. 12.
- the other was a prior art additive composition and resulted in lubricating oil Sample No. 13.
- the primary to secondary molar ratio in the zinc dialkyldithiophosphate for Sample No. 12 was 1.7.
- Samples 13, 14 and 15 contained only primary zinc dialkyldithiophosphate.
- the SEA dispersant was prepared from propoxylated hexamethylenediamine and Indopol H-1500 polybutenes obtained from Amoco Chemicals Corporation.
- the succinimide dispersant was also prepared using Indopol H-1500 polybutenes.
- Samples Nos. 14, 15 and 17 contained the additive composition of the present invention. Of these, only Sample No. 17 provided unacceptable friction performance.
- Additional lubricating oil formulations containing embodiments of the additive composition of the present invention were prepared and tested for wear performance in the Sequence IIID and Sequence V-D Tests and for friction performance in the Detroit Diesel Allison C-3 Friction Test. The results of these tests are presented hereinbelow in Table XI.
- the molar ratio of 1°:2° in the zinc dialkyldithiophosphate to phosphorus from secondary zinc dialkyldithiophosphate is about 3.9.
- the results of the above examples indicate that the additive compositions of the present invention are effective in wear control while simultaneously accommodating friction response.
- the lubricating oils containing them i.e., the lubricating oils of the present invention, provide acceptable wear performance and friction performance while minimizing the amount of phosphorus in the engine emission system.
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Description
- The present invention is directed to a novel composition that is useful as a lubricant additive. In particular, the present invention relates to a lubricant additive composition that is characterized by antiwear and friction retention properties while providing reduced phosphorus levels. More particularly, the invention relates to formulation of a so-called universal or mixed fleet lubricant oil additive composition (i.e. one that will result in a lubricant meeting the requirements of both heavy duty and passenger car engine tests) which has reduced phosphorus and which comprises zinc dialkyldithiophosphate having both primary and secondary character in combination with a succinimide dispersant.
- Internal combustion engines, both gasoline and diesel, have many moving metal parts wherein metal slides against metal, resulting in metal wear. Since wear is a continuing problem that is associated with moving parts that contact one another, lubricants are used to provide a reduction in such wear. However, high rates of wear are found in internal combustion engines in crankcase bearings and on piston ring and cylinder wall surfaces of internal combustion engines. Relatively high rates of wear can take place in heavy duty engines, such as marine diesel engines, and engines employed in military vehicles.
- Lubricating oils, particularly mineral oils, deteriorate under heavy loads and as a result of oxidation during their use in internal combustion engines to form products, some of which are corrosive and some of which agglomerate to form sludge-like deposits and varnish-like deposits. Such sludge-like material occurs when the crankcase lubricant is subjected to alternate hot and cold environments, which are present in ordinary stop-and-go driving. Sludge is a complex mixture of fuel combustion products, unburned fuel, carbon, lead anti-knock residues, and water and, if not maintained in fine suspension in the lubricating oil, will deposit on engine parts. Such deposits are deleterious to engine performance.
- Various additives and additive formulations have been added to lubricating oils to minimize deterioration and to enhance performance. Such materials, as neutral and over-based metal long chain alkyl substituted sulfonates, phenates, salicylates, and phosphonates and thiophosphonates have been added as detergents and/or detergent-dispersants. Materials, such as polymers and/or copolymers containing a carboxylate ester function and one or more polar functions, N-substituted long chain alkenyl succinimides, high-molecular weight amides and polyamides, high-molecular weight esters and polyesters, and amine salts of high-molecular weight organic acids, have been added as ashless dispersants to disperse the cold sludge formed under stop-and-go driving conditions. Materials, such as metal dithiophosphates, metal dithiocarbamates, sulfurized terpenes, and phosphosulfurized terpenes, have been added as corrosion inhibitors. In addition, one or more additives are incorporated often into the lubricant composition to furnish or to enhance antiwear and friction retention properties of that composition. Examples of art describing such lubricating oil compositions are discussed hereinbelow.
- In U.S. Patent 3,532,626, Rowe discloses lubricating oil compositions that contain a small amount of a mixture of a metal salt of an O,O-diorgano-phosphorodithioate and a boroaryl compound in synergistic proportions. An example of such mixture is a mixture of zinc, O,O-diisopropylphosphorodithioate and 9-hydroxy-9,10 boroxarophenanthrene. The amount of the mixture is sufficient to improve antiwear properties of the compositions.
- In U.S. Patent 3,533,945, Vogel discloses the improvement of the lubricating properties of a lubricating oil by incorporating therein a boron-containing ester that is a combined boron esteralkenyl succinic acid ester of a polyhydric alcohol that is prepared by the process comprising the reaction of a polyhydroxy compound with a succinic acid-producing compound and a boron reactant. Vogel discloses that such boron-containing esters are useful, inter alia, as corrosion-inhibiting agents, extreme pressure agents, antiwear agents, and detergents.
- In U.S. Patent 3,544,465, Braid discloses lubricant compositions containing esters of O,O-diorgano-S-(2-hydroxyalkyl) phosphorodithioates, which are antioxidants and corrosion inhibitors.
- In U.S. Patent 4,557,844, Horodysky discloses the use of certain boron-, phosphorus-, and nitrogen-containing reaction products as antioxidants and antifriction agents in lubricants and fuels.
- In U.S. Patent 4,534,873, Clark discloses a friction-reducing additive for use in lubricating oils. The additive comprises a hydrocarbon oil of lubricating viscosity, an extreme pressure antiwear agent, an alkaline material, such as an overbased calcium sulfonate, a viscosity index improving agent, and optionally an antifoam agent and an antioxidant agent. Clark teaches that the antiwear agent comprises a mixture of an oil dispersion of solid, inorganic film-forming potassium borate, antimony dialkylphosphorodithioate, and a liquid chlorinated paraffin.
- In U.S. Patent 4,431,552, Salentine discloses a lubricating oil composition having improved wear properties, which composition comprises an oil of lubricating viscosity having dispersed therein a hydrated alkali-metal borate extreme-pressure agent and an effective amount of a mixture of a non-sulfur-containing phosphate, a monothiophosphate, and a dithiophosphate, the mixture of phosphate, monothiophosphate, and dithiophosphate being in the ratio of 0.90-10:0.90-1.10:0.47-0.67.
- In U.S. Patent 4,368,129, Hyrodysky, et al., disclose a lubricating oil composition comprising an oil of lubricating viscosity and a minor amount of a multifunctional additive consisting of the metal salt of a partially borated, partially phosphosulfurized hydroxyl-containing ester derived from a polyol, e.g., a zinc salt of borated, partially phosphosulfurized glycerol monooleate. The additive is an effective friction-reducing, antioxidant, and copper strip passivating additive in lubricants.
- Occasionally, certain additives will deleteriously affect the ability of certain other additives to perform their normal function. For example, overbased Group II metal hydrocarbyl sulfonates are effective detergents or dispersants and normal metal salts of dihydrocarbyldithiophosphoric acids are suitable antiwear additives. However, when these two additives appear in the same lubricating oil, the presence of an overbased Group II hydrocarbyl sulfonate will tend to deleteriously affect the effectiveness of the normal metal salts of the dihydrocarbyldithiophosphoric acids to provide sufficient wear protection in the internal combustion engine which employs that particular lubricating oil as its lubricant. In U.S. Patent 4,483,775, Yamaguchi discusses this problem and suggests that the detrimental effect of the overbased calcium hydrocarbyl sulfonates on the wear of metal parts in the internal combustion engine can be overcome by adding to the lubricating oil containing these materials an effective amount of a complex prepared by reacting an insoluble metal salt of a diisopropyl dithiophosphoric acid with an oil-soluble alkenyl or alkyl mono- or bis-succinimide in specific amounts.
- In U.S. Patent 4,483,775, Yamaguchi also points out that there is another problem that is associated with the use of phosphorus-containing additives in lubricating oils. The phosphorus can have a deleterious effect upon the catalysts that are employed in the emissions control systems of internal combustion engines of automobiles. Hence, if the overbased metal hydrocarbyl sulfonates tend to offset the effectiveness of the metal dihydrocarbyldithiophosphates, additional amounts of the metal dihydrocarbyldithiophosphates must be employed and such increased amounts of these additives will introduce additional amounts of phosphorus into the lubricating oil. While the effectiveness of the metal dihydrocarbyldithiophosphates relative to its antiwear performance is improved, the side result will be a reduced life for the catalytic converter system of the automobile. Consequently, the automobile manufacturers are interested in finding ways of minimizing the amount of the metal dihydrocarbyldithiophosphates in the lubricating oils without deleteriously affecting the antiwear performance provided by the lubricating oil.
- Other background art includes EP-A-020674 and EP-A-0131400 EP-A-020674 discloses a lubricating oil composition comprising
- (a) an oil of lubricating viscosity; and
- (b) an effective amount of each of the following
- 1. an alkenyl succinimide,
- 2. a Group II metal salt of a dihydrocarbyl dithiophosphoric acid,
- 3. a neutral or overbased alkali or alkaline earth metal hydrocarbyl sulfonate or mixture thereof,
- 4. a neutral or overbased alkali or alkaline earth metal alkylated phenate, or mixture thereof, and
- 5. a borated alkyl catechol friction modifier.
- A) the alkyl groups each contain from two to four carbon atoms and at least one alkyl group is a butyl group;
- B) the total number of carbon atoms per phosphorus atom is less than 8;
- C) from about 30 to 90 mole percent of the alkyl groups are primary alkyl groups;
- D) from about 10 to 70 mole percent of the alkyl groups are secondary alkyl groups; and
- E) the metal salt is a zinc, copper or iron salt mixtures thereof, or a mixture of calcium salt and one or more of said metal salts;
- It is generally desirable to formulate an additive composition which is suitable for use in so-called universal or mixed fleet oils. Such an oil, by definition, is one which is capable of passing a rigorous battery of engine tests which measure the performance of the oil for both passenger car and heavy duty (i.e. diesel) applications. However, given the harmful effect on pasenger car catalytic converters of phosphorus (which is typically introduced into the oil via the anti-wear agent zinc dialkyldithiophosphate) it would be particularly advantageous if an additive composition suitable for a universal oil could be formulated with reduced levels of phosphorus.
- Prior to the present invention, efforts to formulate a low phosphorus universal oil were unsuccessful primarily because of the difficulty encountered in balancing the often conflicting passing requirements of the various engine tests which the industry has established for passenger car and heavy duty oils. For example, heavy duty oils require a TBN of greater than about 8. However, because the detergent additives typically employed to impart TBN (i.e. overbased Group II metal hydrocarbyl sulfonates) tend to reduce the effectiveness of zinc dialkyldithiophosphates (ZDDP) wear inhibiting agents, a higher level of ZDDP--and thus a higher level of phosphorus--is required to pass the wear tests for passenger and heavy duty oils. To complicate matters, heavy duty oils must pass certain friction tests which measure the degree to which the oil impairs friction retention in the clutch, but as the phosphorus level (i.e as the zinc dialkyldithiphosphate) is increased to accomodate wear performance, passing these friction tests becomes increasingly difficult. Our work prior to the present invention determined that the minimum phosphorus level in a universal oil that would accomodate the industry's TBN, wear and friction requirements for a universal oil is about 0.1 wt %. Reducing the phosphorus level to below about 0.1 wt % (i.e. by reducing ZDDP wear inhibitor) resulted in failing engine wear tests.
- In light of the preceeding discussion, a general object of the invention is to provide an additive composition which affords passing wear protection for a universal oil at reduced phosphorus levels. Other objects will appear hereinafter.
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- According to the present invention there is provided an additive composition for addition to an oil of lubricating viscosity suitable for passenger car and heavy duty use comprising: (a) zinc dialkyldithiophosphate having both primary and secondary character such that the primary to secondary ratio is 1:1 to 5:1, said mixed primary/secondary zinc dialkyldithiophosphate being present in the additive composition in amount such that a lubricating oil containing an effective amount of said additive composition has a phosphorus content of not greater than 0.1 wt %; (b) a succinimide dispersant in such amount that a lubricating oil containing 9 to 12 percent of said additive composition will comprise at least about 0.5 wt % succinimide; (c) a boron content such that a lubricating oil containing said additive composition contains at least 100 ppm boron; and (d) an effective amount of basic salts comprising high base magnesium sulfonates and high base calcium sulfonates such that a lubricating oil containing an effective amount of said additive composition has a TBN within the range of 8 to 12. Preferably, the molar ratio of primary to secondary alkyl groups in the zinc dialkyldithiophosphate (hereafter occasionaly referred to as "ZDDP") is within the range of about 1.7:1 to about 3.5:1 and preferably about 1.7:1 to about 4.5:1. The preferred amount of succinimide dispersant in the additive composition is such that will provide at least .5 wt. % of the succinimide in the finished oil and most preferably about .5 to about 3.5 wt. %. The preferred phosphorus level in the additive composition is such as will provide a phosphorus level of about .06 wt.% to about .09 wt.%. The preferred TBN of the additive is such as will provide a TBN in the finished oil within the range of about 8-12 and preferably about 9-11. It should be noted that all dispersant amounts are expressed in terms of active dispersant absent any diluent, except, however, in the examples where dispersant amounts are expressed in terms of a 40% active material containing added diluent.
- In a preferred embodiment, the additive composition of the present invention has a boron content sufficient to provide a boron level in the finished oil of within the range of about 100 ppm(wt) to about 600 ppm and preferably in the range of 150 ppm to 450 ppm.
- Among the advantages of the invention is the ability to reduce the level of phosphorus required in an additive composition for a mixed fleet oil despite the requirement of high TBN in such oils, which is necessary for passing heavy duty engine cleanliness tests, while at the same time obtaining passing wear peformance. Reducing the phosphorus in the oil composition benefits the catalytic converter in passenger cars. Unexpectedly, the succinimide dispersant required in the present invention is critical in accomplishing the reduction in phosphorus for the following reasons: In accordance with the present invention, increasing the secondary character of the ZDDP makes it possible to reduce the overall amount of ZDDP (and thus the total phosphorus required in the additive and resulting oil) without giving up passing wear performance. However, in an additive composition having sufficient TBN to provide TBN of at least 8 in the finished oil and having a total phosphorus (as provided by primary ZDDP) to provide at least about .1 percent phosphorus in the finished oil, the combined effect of lowering the total phosphorus and simultaneously increasing the secondary character of the ZDDP, while acceptable from the standpoint of retaining engine wear performance, results in failing performance on the friction requirements applicable to heavy duty oils (i.e. the Allison C-3 and Caterpiller TO2 tests). This probelm was not entirely unexpected insofar as it is known that increasing the amount of secondary ZDDP will result in a debit in terms of frictional characteristics of the oil. Thus, reduction in the total amount of ZDDP coupled with an increase in the secondary character of the ZDDP, was not by itself an acceptable route to reduced phosphorus in an additive suitable for a universal oil, given the resulting debit in friction performance in the heavy duty tests. Surprisingly, in accordance with the present invention, it is only with addition of the succinimide dispersant that friction tests were passed. At the present time, the mechanism for this phenomenon is not well understood, however, without limitation, it is believed that the succinimide interacts in some manner with the secondary ZDDP so as to counteract the deleterious effects of the secondary ZDDP on the frictional performance of the additive composition.
- The additive composition of the present invention must comprise (a) zinc dialkyldithiophosphate having both primary and secondary character such that the primary to secondary ratio (expressed in moles) is within the range of from about 1:1 to about 5:1, and (b) succinimide dispersant. Also, the total amount of phosphorus in the additive, as provided by the ZDDP, must be such that the amount of phosphorus present in a lubricating oil containing an effective amount of the additive is not greater than about .1% by weight of the lubricating oil, and the TBN of the additive composition must be such that a lubricating oil containing an effective amount of the additive composition will have a TBN of at least 8. An effective amount of the additive composition of the present invention means a treat level in the lubricant which will allow the oil to pass both heavy duty and passenger car tests.
- Of course, other components optionally may be present in the additive composition. For example, there may also be present rust inhibitors, oxidation inhibitors, and one or more detergents, such as normal or overbased sulfurized metal phenates or metal sulfonates.
- The required zinc dialkyldithiophosphate having both primary and secondary character for use in the present invention functions as a corrosion and wear inhibitor. Typically, zinc dialkyldithiophosphate is prepared by forming a dithiophosphoric acid via a reaction of a phenol or an alcohol with phosphorus pentasulfide and subsequently neutralizing the dithiophosphoric acid with a zinc compound, such as zinc oxide. Such preparation is well known in the art and is presented, for example, in U.S. Patent 2,261,047 and U.S. Patent 4,483,775. This type of dialkyldithiophosphate can be identified by the alcohol that is employed in its preparation. If a primary alcohol is employed, the product is referred to as a primary zinc dialkyldithiophosphate. On the other hand, if the alcohol is a secondary alcohol, the zinc dialkyldithiophosphate is identified as a secondary zinc dialkyldithiophosphate. Suitable primary alcohols for use in the preparation of the primary zinc dialkyldithiophosphate are n-butyl alcohol, n-octyl alcohol, isoamyl alcohol, isooctyl alcohol, and isobutyl alcohol. Suitable secondary alcohols are isopropyl alcohol, methyl isobutyl carbinol, 2-amyl alcohol, and 2-butyl alcohol. If a mixture of primary and secondary alcohols is used, the resulting ZDDP is a hydrid having both primary and secondary character. In the present invention the term "zinc dialkyldithiophosphate having both primary and secondary character" includes any of the following: (a) a zinc dialkyldithiophosphate preparation obtained by mixing a desired amount of primary zinc dialkyldithiophosphate with a desired amount of secondary zinc dialkyldithiophosphate; (b) a zinc dialkyldithiophosphate which results from employing a mixture of primary and secondary alcohols in the preparation of the zinc dialkyldithiophosphate; and (c) a zinc dialkyldithiophosphate obtained by mixing a primary or a secondary zinc dialkyldithiophosphate with a zinc dialkyldithiophosphate meeting the definition of (b). Also, in the present invention the terminology "ratio of primary to secondary," or "primary to secondary ratio," means the molar ratio of primary alkyl groups to secondary alkyl groups in the zinc dialkyldithiophosphate.
- In the case of the additive composition of the present invention, the primary to secondary ratio in the zinc dialkyldithiophosphate is within the range of about 1:1 to about 5:1, preferably, within the range of about 1.7:1 to about 3.5:1, and more preferably, within the range of about 1.7:1 to about 2.5:1.
- The total amount of the mixed primary/secondary dialkyldithiophosphates should be an amount that will provide a phosphorus content in the lubricating oil composition not greater than 0.1 wt%, based upon the weight of the lubricating oil composition. Preferably, the zinc dialkyldithiophosphate should be present in a total amount that will provide a phosphorus content in the lubricating oil composition that falls within the range of about 0.06 wt% to about 0.09 wt%, and most preferably within the range of about 0.06 wt% to about 0.08 wt%, based upon the weight of the lubricating oil composition.
- The prescribed 1°:2° molar ratio in the ZDDP used in the present invention is important when one considers the object of maintaining the phosphorus content in the additive composition at such a level that a finished oil containing an effective amount of the composition has a phosphorus content of not greater than about .1 wt % of the finished oil. If the total phosphorus is decreased, then in accordance with the present invention, passing wear can be maintained by increasing the 2° character of the ZDDP. Such an adjustment appears practicable where the phosphorus (in terms of the finished oil) is between about .06 and about 0.1 wt percent. Other things being equal, as the total phosphorus decreases, increasing the secondary character of the ZDDP provides less and less of an effect in terms of counteracting the loss in wear protection brought about by the reduction in phosphorus. The prescribed ratios of 1° to 2°character are based upon this fact, and the desirability of using the minimum amount of 2° character in the ZDDP to maintain wear protection (given the deleterious effect of the the 2° ZDDP on friction performance). Within the prescribed ratio of 1°:2° character in the ZDDP (i.e. about 1:1 to about 5:1) the ratio will increase as the total phosphorus (in terms of the oil) approaches about .1 wt%, and will decrease as the phosphorus level approaches about .06 wt.%. At a 1°:2° ratio of greater than about 5:1, the presence of 2° character affords little if any ability to decrease the total phosphorus below about .1 wt percent of the finished oil. At the lower limit of 1°:2° of about 1:1, it becomes increasingly difficult to further reduce the total phosphorus, and still pass wear tests regardless how much 2° character is present in the ZDDP.
- A second required component of the additive composition of the present invention is a succinimide dispersant. Such succinimide is an N-substituted long chain-alkenyl succinimide. Typically, the alkenyl radical is derived from liquid polyisobutenes containing from 50 to 200 carbon atoms. Such a succinimide is an oil-soluble nitrogen containing composition. The preparation of succinimide dispersants is known in the art. Among such art are U.S. Patents 3,172,892; 3,272,746; and 3,219,666. The disclosures of these patents are incorporated herein by reference. For example, an acylated nitrogen intermediate compound is formed by reacting a substantially aliphatic olefin polymer-substituted succinic-acid producing compount having at least about 50 aliphatic carbon atoms in the polymer substituent with at least about one half equivalent of an amine for each equivalent of acid-producing compound used, said reaction being carried out at a temperature within the range of about 80°C to about 250°C. The amine is selected from a group consisting of alkylene amines, hydroxysubstituted alkylene amines, and polyalkylene polyamines.
- The polymer substituent of the succinic acid-producing compound is derived conveniently from a polymer of isobutene. Typically, the polyisobutene has an average molecular weight that is within the range of about 700 to about 5,000. Suitable amines are alkylene amines, alkylene diamines having the structure NH₂-R-NH₂, wherein R is an alkylene group having from 2 to 24 carbon atoms, and the so-called polyalkyleneamines, sometimes referred to as alkylene polyamines or polyalkylene polyamines, which generally have the structure H₂N--(R--NH)nH, where R is an aliphatic hydrocarbon group containing about 2 to about 4 carbon atoms and n is an integer from 1 to 10. Representative amines include methylene amines, ethylene amines, butylene amines, propylene amines, pentalene amines, ethylene diamine, triethylene tetraamine, propylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene)triamine, tripropylene tetramine, tetraethylene pentamene, trimethylene diamine, pentaethylene hexamine, di(trimethylene)triamine, etc. A preferred polyalkylene polyamine is tetraethylene pentamine (TEPA).
- Preferably the succinimide dispersant is present in the additive composition of the present invention in an amount sufficient to provide a lubricating oil containing an effective amount of the additive composition at least about .5 wt, % by weight of the lubricating oil. While a preferred range is about .5 to about 3.5 the maximum amount of succinimide is an economic consideration and is not critical in the present invention. However the requirement of at least .5 wt% is critical insofar as lesser amounts fail to provide the desired advantage of passing frictional tests, in particular the Allison C-3, when phosphorus levels of less than .1 by weight of the lube oil, in combination with the 1°/2° ratios discussed above, are employed.
- In addition to the requirements stated above, the additive composition of the present invention comprises sufficient TBN such that a universal oil comprising an effective treat level of said additive composition is provided with a TBN of at least 8, preferably, within the range of about 9 to about 11, and more preferably, about 10.
- Examples of components that are suitable for providing the required TBN in the additive composition of the present invention are overbased metal sulfonates and over based phenates. The sulfonates are normal or basic metal salts of petroleum ("mahogany") sulfonic acids and long chain alkyl substitued benzene sulfonic acids. The phenates are normal or basic salts of alkylphenols, alkylphenol sulfisides, and alkylphenol-aldehyde condensation products. A normal metal salt of an acid is a salt which contains the stoichiometric amount of metal required for the neutralization of the acidic group or groups present in the acid. A basic salt or overbased salt is a salt which contains more metal than is required to stoichiometrically neutralize the acidic group or groups present. While both normal and overbased sulfonates and phenates provide detergent properties for lubricating oil compositions, the overbased or superbasic or hyperbasic salts provide unusually high detergent power and, consequently, have a much greater capacity to neutralize acidic contaminants than do the normal sulfonates and phenates. Typically an overbased sulfonate is prepared by mixing a promoter, catalyst or solvent with a normal sulfonate and a larger excess of metallic base, followed by heating, carbonation and filtration. Carbonation of the reaction mass is accomplished conveniently with carbon dioxide and is employed to increase the amount of metal base colloidally dispersed as metal carbonate in the filtered product. Phenols, trioacids, of phosphorus, alcoholates, alcohols, ketones, and alkanolamines can be used as promoters for catalysts. Typical metallic bases are basic compounds of alkaline earth metals, such as calcium, barium, or magnesium. Overbased metal sulfonates are discussed thoroughly in the prior art. Examples of such art are: United Kingdom Patent Application GB 2,082,619A and U.S. Patents 2,865,956; 2,956,018; 2,671,430; 3,779,920; 3,907,691; 4,137,184; 4,261,840; and 4,326,972.
- The overbased metal phenates are presented in the prior art. Typical examples of the prior art are U.S. Patents 2,680,096; 3,036,917; 3,178,368; 3,194,761; 3,437,595; 3,464,910; 3,779,920; and 4,518,807.
- In a preferred embodiment of the present invention the reduced-phosphorus additive composition further comprises boron sufficient to provide within the range of from about 100 to about 600 ppm(wt.) boron in the finished oil containing the additive composition of the invention. Optionally, the additive composition may contain an additional dispersant comprising at least on member of the group consisting of Mannich and succinate ester-amide (SEA) dispersant in an amount sufficient to provide preferably up to about 5 wt% of the second dispersant in the finished oil.
- The succinate ester-amide dispersant can be prepared in accordance with techniques which have been disclosed in the art (See for example U.S. Patent No. 4,426,305) by reacting an aliphatic hydrocarbon substituted succinic acid anhydride with an oxyalkylated amine.
- The long chain aliphatic hydrocarbon-substituted succinic acid compound that is used in the preparation of the second dispersant can be obtained by reacting an ethylenically unsaturated dicarboxylic acid compound (acid or anhydride), such as maleic acid, maleic anhydride, or fumeric acid, with a suitable olefin or halogenated olefin at a temperature within the range of about 100°C to 300°C. An alkenyl or alkyl substituted succinic acid or anhydride is produced. The unsaturated groups in the alkenyl group can be removed by standard hydrogenated techniques. The olefins or halosubstitued olefins contain from about 8 to about 500 carbon atoms, or more, and can include homopolymers and copolymers of monoolefins, such as ethylene, propylene, l-butene, isobutene, and the like. However, any of the techniques known in the art can be employed to produce this long chain succinic acid compound.
- The oxyalkylated amine suitable for reaction with the above described long chain aliphatic hydrocarbon succinic acid compound can be prepared in accordance with known methods by reacting an alkylene oxide with an amine having primary or secondary amine groups. Suitable amines are alkylene diamines having the structure NH₂-R-NH₂, wherein R is an alkylene group having from 2 to 24 carbon atoms, such as ethylene, 1, 2-propylene, trimethylene, hexamethylene, dodecamethylene, tetracosene, etc. Also suitable are the so-called polyalkyleneamines, sometimes referred to as alkylene polyamines or polyalkylene polyamines. These generally have the structure H₂N--(R-NH)nH, where R is an aliphatic hydrocarbon group containing about 2 to about 4 carbon atoms and n is an integer from 1 to 6. Representative examples include ethylenediamine, 1,2-propylenediamine, 1,2-butylenediamine, 1,3-propanediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine (TEPA), etc.
- Suitable hydroxyalkylating reactants include halohydrins and vicinal epoxies (olefin oxides) having from 2 to 4 carbon atoms in the alkylating agent, such as ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, 2-chloro-l, ethanol, 2-chloro-l-propanol, 3-bromo-l-prophanol, and 4-chloro-butanol. The hydroxyalkylating agents can be used in a concentration of about 2.0 to 6 moles per mole of amine, and hydroxyalkylation can be carried out under conventional conditions, i.e., by reaction at 50°C to 300°C for a period of time within the range of 1 to 10 hours.
- Subsequently, the long chain aliphatic succinic acid compound is reacted with the N-substituted hydroxy alkyl diamine under conditions that are normally employed in the art and at a temperature within the range of about 0°C to about 250°C. A solvent, such as benzene, toluene, naphtha, lube oil, xylene, and normal hexane, can be used to facilitate the control reaction.
- As stated above, the optional second dispersant may also be a Mannich dispersant. Mannich dispersants made from hydrocarbon substituted phenols, formaldehyde and amines are well known in the patent literature. See U.S. Patent Nos. 3,413,347; 3,725,277; 3,368,972; 3,798,165; 3,697,574, and 4,426,305. These patents are incorporated by reference.
- The optional second dispersant (Mannich or SEA) can be present in the lubricating oil composition in an amount within the range of about 0 wt % to about 5 wt%, preferably, within the range of about 0 wt% to about 3 wt%.
- As stated above, the additive composition of the present invention preferably contains boron in an amount such that a lubricating oil containing an effective amount of the additive composition, will have a boron content within the range of about 100 ppm(wt) to about 600 ppm(wt) boron. The preferred boron level is about 150 to about 450 ppm(wt) in the finished oil. The presence of boron is preferred for the protection of fluorinated elastomer hydrocarbon seals, and also enhances the anti-wear properties of the additive composition, especially where TBN is supplied by high-based calcium sulfonate. The latter is known to deleteriously effect the wear protection afforded by zinc dialkyldithiophosphate. Provided a sufficiently low ratio of calcium to magnesium high base sulfonate is present in the additive formulation of the present invention, the presence of boron may not be required. However in the additive formulation of the present invention, boron is preferably present in an amount sufficient to provide about 150 ppm(wt) to about 450 ppm(wt) in the finished oil.
- Boron may be introduced into the additive composition in accordance with conventional techniques. For example, A boron compound, such as boron oxide, boron dihalides (boron trifluoride, boron tribromide, boron tricholoride), boron acids, such as tetraboric acid and metaboric acid, and simple esters of the boron acids, can be reacted with the succinimide, SEA or Mannich dispersants discussed above at a temperature within the range of about 50°C to about 250°C, preferably from about 100°C to about 170°C, with a sufficient concentration of boron compound to yield a boronated dispersant product containing at least 0.15% by weight boron (excluding lube oil). The boron compound can be reacted in a ratio within the range of about 0.1 to 10 moles of boron compound for equivalent of dispersant compound. The reaction can be carried out in the presence of diluent or solvent. Alternatively, a portion of the succinimide, Mannich or SEA dispersant intended for the additive composition of the invention may be segregated and heated with a boronating agent to introduce a higher level of boron than would be desired in the final dispersant. This overboronated product can then be blended back into the unboronated dispersant to achieve the desired level of boron.
- The additive composition of the present invention may contain other additive components, such as viscosity index improvers, pour point depressants, and antioxidants.
- The additive composition of the present invention comprises a mixture of several additive components, some of which are mandatory and some of which are optional. This blend or mixture is prepared easily by introducing one or more of the components into another component. It is not critical that a particular component be added to another particular component, i.e., there is no particular sequence which must be used when adding the various components in preparing the blend. As noted hereinabove, the blend is a composition that will provide antiwear and friction retention properties to the lubricating oil to which it is added while minimizing the phosphorus level in that particular lubricating oil composition.
- The additive composition of the present invention can be added to a petroleum oil or synethetic oil of lubricating viscosity to provide antiwear and friction retention properties while minimizing the amount of phosphorus in the resulting lubricating oil composition. The additive composition of the present invention is quite suitable for addition to a lubricant that is being employed in heavy duty vehicles, such as those used in military operations. Lubricating oil compositions containing the additive composition of the present invention provide suitable anti-wear and friction retention properties. In addition, they contain only a limited amount of phosphorus and, consequently, minimize the phosphorus content in the engine and thus extend the life of the catalyst in the catalytic converter of the automobile. Typically, the additive composition of the present invention will be present in the lubricating oil composition in an amount that is within the range of about 9 wt% to about 12 wt%, based upon the weight of the lubricating oil composition. More particularly, the additive composition is present in the lubricating oil composition in an amount that is within the range of about 10% to about 11 wt%, based upon the weight of the lubricating oil composition.
- The scope of the present invention includes concentrates of the additive composition. Such concentrates are made up of about 90 wt% to about 10 wt% of an oil having lubricating viscosity. The concentrates contain the additive composition plus a suitable diluent. Typical diluents are inert diluents, preferably an oil of lubricating viscosity, so that the concentrate may be mixed conveniently with the lubricating oil that will make up the desired lubricating oil composition. Lubricating oils that are suitable as diluents typically will have viscosities that are within the range of about 35 Saybolt Universal Seconds (SUS) at 100°F (38°C) to about 1,000 SUS at 100°F (38°C). While any oil of lubricating viscosity can be used as the diluent for the concentrate of the present invention, suitably, the oil of lubricating viscosity in the lubricating oil composition can be employed as the diluent in the concentrate.
- Lubricating oils that are suitable for use in the lubricating oil compositions and concentrates of the present invention are oils of lubricating viscosity and are either petroleum oils or synthetic oils. The petroleum oils can be paraffinic, naphthenic, or even halogen-substituted hydrocarbons. Typical synthetic oils are those comprising syntheticesters, diester, ethers, polyolefins, or combinations thereof. These oils of lubricating viscosity will have viscosities that fall in the range of about 50 SUS to about 5,000 SUS at 100°F (38°C), preferably viscosities in the range of about 50 SUS to about 2,000 SUS at 100°F (38°C), and more preferably, viscosities in the range of about 80 SUS to about 1,000 SUS at 100°F (38°C).
- Thus, in accordance with the present invention, there is also provided a lubricating oil composition, which lubricating oil composition comprises a major portion of an oil having lubricating viscosity in combination with a minor portion of an additive composition as described above.
- The following examples are being presented for the purpose of illustration only and are not intended to limit the scope of the present invention.
- A preferred embodiment of the lubricating oil additive composition of the present invention was prepared. This embodiment had the composition presented hereinbelow in Table I. This additive was then introduced into a Mid-East base stock. The resulting lubricating oil composition had an SAE grade of 15W-40. The additive composition made up 10.3 wt% of the lubricating oil composition, which had a TBN of about 10. The lubricating oil composition also contained 4.1 wt% Viscoplex 2-50 viscosity index improver obtained from Rohm-Darmstadt. The concentration of each of the components of the additive composition in the lubricating oil composition is also provided in Table I. The additive composition contained 1,700 ppm(wt) boron, while the SAE 15W-40 oil, identified hereinafter as Sample No. 1, contained 180 ppm(wt) boron. Furthermore, Sample No. 1 contained 784 ppm(wt) phosphorus. The molar ratio of primary to secondary in the zinc dialkyldithiophosphate was 4.4
- The SAE 15W-40 oil, Sample No. 1, was subjected to various standard tests, which included the Sequence IID Test to evaluate antitrust properties; the Sequence IIID Test to evaluate oxidation inhibition, oil consumption, and wear; the Sequence V-D Test to evaluate engine cleanliness and wear; the CRC L-38 Test to evaluate non-ferrous bearing corrosion and shear stability; the Caterpillar 1G2 Test to evaluate diesel piston cleanliness; the Caterpillar TO-2 Test to evaluate power shift transmission friction retention; the Detroit Diesel 6V-53T Test to evaluate piston deposits and wear; the Detroit Diesel Allison C-3/Friction Test to evaluate transmission friction retention; and the Detroit Diesel Allison C-3/Seals Test to evaluate seal compatibility. The results of these tests are presented hereinbelow in Table II.
- SAE 15W-40 Oil Sample No. 1, which contained a preferred embodiment of the additive composition of the present invention, met all performance criteria of the tests. It is particularly noteworthy that acceptable wear protection was provided in the Sequence IIID and V-D Tests while acceptable performance was provided in the Caterpillar TO-2 and Allison C-3 Tests. Sample No. 1 is a preferred embodiment of the lubricating oil composition of the present invention.
- Two other SAE 15W-40 oil formulations, which contained similar additive compositions, except for different amounts of the high-base magnesium sulfate rust inhibitor, were tested in a Sequence IID Test for rust inhibition response. These two oil formulations are identified hereinafter as Sample No. 2 and Sample No. 3. The results of these tests are presented hereinafter in Table III.
- These results demonstrate that a concentration of 1.10 wt% of this high-base magnesium sulfonate rust inhibitor was needed in the lubricating oil composition to provide acceptable Sequence IID performance.
- Three SAE 15W-40 oil formulations were compared for their oxidation inhibition responses when subjected to the Sequence IIID Test. Sample No. 1 was the formulation presented in Table I hereinabove. Sample No. 4 had a similar composition, but the alkyl diarylamine oxidation inhibitor was replaced by a sulfurized oxidation inhibitor. In Sample No. 5, a North Sea base stock (less stable than the Mid-East stock) was employed. The results are presented hereinbelow in Table IV.
- Neither Sample No. 4 nor Sample No. 5 provided acceptable Sequence IIID oxidation inhibition. Additional oxidation inhibitors would be required to obtain acceptable performance.
- In each sample, the mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate provided acceptable wear protection.
- The amount of borated succinimide dispersant was varied in additive compositions similar to that which was used in the Sample No. 1. Each of the oil compositions containing one of these additive compositions was subjected to a Sequence V-D Test to obtain the gasoline engine cleanliness response for that formulation. The results are presented hereinbelow in Table V.
- When the amount of the dispersant was reduced, poorer Sequence V-D sludge protection resulted. However, acceptable wear protection was obtained in each test.
- In this example, the preferred embodiments of the lubricating oil composition of the present invention, Sample No. 1 and Sample No. 6, were compared for diesel cleanliness to Sample No. 9, a similar additive composition but with a different detergent, and Sample No. 4, a similar additive composition but with a different oxidation inhibitor. The different detergent was a low base calcium sulfonate. The different oxidation inhibitor was a sulfurized oxidation inhibitor. The test method employed was the Caterpillar 1G2 Test. The results are presented hereinbelow in Table VI.
- Samples Nos. 1 and 6, embodiments of the lubricating oil composition of the present invention, passed the specification for top groove fill; however, Sample No. 6 did not provide an acceptable value for weighted total demerits. On the other hand, the latter sample provided a small top groove fill. Each of the other two samples furnished acceptable diesel engine cleanliness response.
- This example demonstrates the applicability of the additive composition of the present invention to a single-grade lubricant. Sample No. 10 employed an SAE 30 weight lubricating oil derived from the Mid-East base stock obtained from the British Petroleum Company. An Acryloid 150 pour point depressant obtained from Rohm & Haas was also a component of Sample No. 10. This sample was subjected to a Sequence V-D Test. The results are presented hereinbelow in Table VII. Also shown in Table VII are the results obtained with Sample No. 1, which is a multigrade oil containing a preferred embodiment of the additive composition of the present invention.
- These results shown an acceptable Sequence V-D performance for the single grade lubricating oil.
- Another embodiment of a lubricating oil composition of the present invention, Sample No. 11, was prepared and subjected to a Sequence V-D Test and a Caterpiller 1G2 Test. Results of these tests are presented hereinbelow in Table VIII. Sample No. 11 contained 795 ppm(wt) phosphorus and 190 ppm(wt) boron. The results obtained with Sample No. 1 are also provided in Table VIII. Each of these samples was a 15W-40 lubricating oil composition and each contained an embodiment of the additive composition of the present invention. Sample No. 1 contained Viscoplex 2-50, obtained from Rohm Darmstadt. Viscoplex 1-50 is a dispersant polymethacrylate viscosity index improver. Sample No. 11 contained ECA 6911, obtained from Paramins, a division of Exxon Corporation, as a viscosity index improver.
- Each of these embodiments of the lubricating oil composition of the present invention provided acceptable Sequence V-D test performance and Caterpillar 1G2 test performance.
- Two additive compositions were prepared and were added to a Mid-East base stock to provide 15W-40 grade lubricating oil compositions. One additive composition was an embodiment of the present invention and, when added to the base oil, resulted in lubricating oil Sample No. 12. The other was a prior art additive composition and resulted in lubricating oil Sample No. 13. The primary to secondary molar ratio in the zinc dialkyldithiophosphate for Sample No. 12 was 1.7. Samples 13, 14 and 15 contained only primary zinc dialkyldithiophosphate.
-
- The SEA dispersant was prepared from propoxylated hexamethylenediamine and Indopol H-1500 polybutenes obtained from Amoco Chemicals Corporation. The succinimide dispersant was also prepared using Indopol H-1500 polybutenes.
- These results demonstrate the superior wear performance and friction performance provided by the lubricating oil composition containing the embodiment of the additive composition of the present invention, i.e., Sample No. 12. When compared to Sample No. 13, its wear performance was equivalent to that of Sample No. 13 in the Sequence IIID Test and better than that of Sample No. 13 in the Sequence V-D Test and the Kombi Test. Furthermore, the friction performance of Sample No. 12 was equal to that of Sample No. 13 in the Caterpillar TO-2 Test and better than that of Sample No. 13 in the Detroit Diesel Allison C-3 Test.
- While the embodiment of the additive composition employed in Sample No. 12 contained both polyisobutenyl succinimide dispersant and the succinate ester-amide dispersant, use of the latter is optional in the additive composition of the present invention.
-
- Samples Nos. 14, 15 and 17 contained the additive composition of the present invention. Of these, only Sample No. 17 provided unacceptable friction performance.
- Additional lubricating oil formulations containing embodiments of the additive composition of the present invention were prepared and tested for wear performance in the Sequence IIID and Sequence V-D Tests and for friction performance in the Detroit Diesel Allison C-3 Friction Test. The results of these tests are presented hereinbelow in Table XI. The molar ratio of 1°:2° in the zinc dialkyldithiophosphate to phosphorus from secondary zinc dialkyldithiophosphate is about 3.9.
- The results of these tests show that the additive composition of the present invention provides acceptable wear performance and friction performance at substantially lower phosphorus levels and boron levels. In these tests, the Sequence V-D Test wear passes consistently. The Sequence IIID Test wear was obtained for two of the lubricating oil compositions and acceptable in each case. The Detroit Diesel Allison C-3 friction performance was obtained for Sample No. 21 and was found acceptable.
- The results of the above examples indicate that the additive compositions of the present invention are effective in wear control while simultaneously accommodating friction response. The lubricating oils containing them, i.e., the lubricating oils of the present invention, provide acceptable wear performance and friction performance while minimizing the amount of phosphorus in the engine emission system.
- As used herein 1° denotes primary and 2° denotes secondary.
Claims (11)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US600487A | 1987-01-21 | 1987-01-21 | |
US6004 | 2004-12-07 |
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EP0277729A1 EP0277729A1 (en) | 1988-08-10 |
EP0277729B1 true EP0277729B1 (en) | 1992-03-11 |
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ID=21718804
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EP88300500A Expired - Lifetime EP0277729B1 (en) | 1987-01-21 | 1988-01-21 | Lubricant compositions providing wear protection at reduced phosphorus levels |
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DE (1) | DE3868949D1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US7744660B2 (en) | 2003-06-25 | 2010-06-29 | The Lubrizol Corporation | Gel additives for fuel that reduce soot and/or emissions from engines |
CN101798545A (en) * | 2009-02-11 | 2010-08-11 | 中国石油天然气股份有限公司 | Lubricating oil composition |
US8088720B2 (en) | 2008-02-29 | 2012-01-03 | Exxonmobil Research And Engineering Company | Green lubricant compositions |
EP4306624A1 (en) * | 2022-07-14 | 2024-01-17 | Afton Chemical Corporation | Transmission lubricants containing molybdenum |
Families Citing this family (22)
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CA1337294C (en) * | 1987-11-20 | 1995-10-10 | Dale Robert Carroll | Lubricant compositions for enhanced fuel economy |
CA1337293C (en) * | 1987-11-20 | 1995-10-10 | Emil Joseph Meny | Lubricant compositions for low-temperature internal combustion engines |
EP0373454A1 (en) * | 1988-12-08 | 1990-06-20 | Idemitsu Kosan Company Limited | Lubricating oil composition for power control |
EP0444830A1 (en) * | 1990-02-26 | 1991-09-04 | Ethyl Petroleum Additives Limited | Succinimide composition |
US5202036A (en) * | 1990-06-28 | 1993-04-13 | The Lubrizol Corporation | Diesel lubricants and methods |
US5652201A (en) * | 1991-05-29 | 1997-07-29 | Ethyl Petroleum Additives Inc. | Lubricating oil compositions and concentrates and the use thereof |
CA2086970A1 (en) * | 1992-01-24 | 1993-07-25 | Michelle M. Cervenka | Low ash lubricating oil compositions |
GB9225337D0 (en) * | 1992-12-03 | 1993-01-27 | Exxon Chemical Patents Inc | Lubricating oil additives |
US5356552A (en) * | 1993-03-09 | 1994-10-18 | Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. | Chlorine-free lubricating oils having modified high molecular weight succinimides |
GB2280907B (en) * | 1993-08-13 | 1997-04-30 | Ethyl Petroleum Additives Ltd | Motor oil compositions,additive concentrates for producing such motor oils,and the use thereof |
JP4191795B2 (en) * | 1994-04-28 | 2008-12-03 | エクソンモービル・ケミカル・パテンツ・インク | Crankcase lubricant for modern heavy duty diesel and gasoline fuel engines |
US6004910A (en) * | 1994-04-28 | 1999-12-21 | Exxon Chemical Patents Inc. | Crankcase lubricant for modern heavy duty diesel and gasoline fueled engines |
GB9413976D0 (en) * | 1994-07-11 | 1994-08-31 | Exxon Chemical Patents Inc | Multigrade lubricating compositions |
EP0725129B1 (en) * | 1995-02-01 | 2001-12-12 | The Lubrizol Corporation | Low ash lubricant compositions |
GB2303378B (en) * | 1995-07-14 | 1999-02-24 | Ethyl Petroleum Additives Ltd | Crankcase lubricant compositions |
US5719107A (en) * | 1996-08-09 | 1998-02-17 | Exxon Chemical Patents Inc | Crankcase lubricant for heavy duty diesel oil |
US6649575B2 (en) | 2000-12-07 | 2003-11-18 | Infineum International Ltd. | Lubricating oil compositions |
EP1213341A1 (en) * | 2000-12-07 | 2002-06-12 | Infineum International Limited | Lubricating oil compositions |
US6767871B2 (en) * | 2002-08-21 | 2004-07-27 | Ethyl Corporation | Diesel engine lubricants |
JP6896384B2 (en) * | 2016-08-02 | 2021-06-30 | Emgルブリカンツ合同会社 | Lubricating oil composition |
CN113930271B (en) * | 2020-06-29 | 2022-08-02 | 中国石油天然气股份有限公司 | Hydraulic guide rail oil and additive composition thereof |
US11578287B1 (en) * | 2021-12-21 | 2023-02-14 | Afton Chemical Corporation | Mixed fleet capable lubricating compositions |
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EP0206748A2 (en) * | 1985-06-17 | 1986-12-30 | Chevron Research And Technology Company | Lubricating oil additive and lubricating oil composition containing the same |
Family Cites Families (4)
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US3190833A (en) * | 1961-04-14 | 1965-06-22 | Lubrizol Corp | Oxidation-resistant lubricating composition |
JPS59122597A (en) * | 1982-11-30 | 1984-07-16 | Honda Motor Co Ltd | Lubricating oil composition |
US4466895A (en) * | 1983-06-27 | 1984-08-21 | The Lubrizol Corporation | Metal salts of lower dialkylphosphorodithioic acids |
GB8414299D0 (en) * | 1984-06-05 | 1984-07-11 | Exxon Research Engineering Co | Lubricating compositions |
-
1988
- 1988-01-21 DE DE8888300500T patent/DE3868949D1/en not_active Revoked
- 1988-01-21 EP EP88300500A patent/EP0277729B1/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0206748A2 (en) * | 1985-06-17 | 1986-12-30 | Chevron Research And Technology Company | Lubricating oil additive and lubricating oil composition containing the same |
Cited By (5)
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US7744660B2 (en) | 2003-06-25 | 2010-06-29 | The Lubrizol Corporation | Gel additives for fuel that reduce soot and/or emissions from engines |
US8088720B2 (en) | 2008-02-29 | 2012-01-03 | Exxonmobil Research And Engineering Company | Green lubricant compositions |
CN101798545A (en) * | 2009-02-11 | 2010-08-11 | 中国石油天然气股份有限公司 | Lubricating oil composition |
CN101798545B (en) * | 2009-02-11 | 2013-07-31 | 中国石油天然气股份有限公司 | Lubricating oil composition |
EP4306624A1 (en) * | 2022-07-14 | 2024-01-17 | Afton Chemical Corporation | Transmission lubricants containing molybdenum |
Also Published As
Publication number | Publication date |
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EP0277729A1 (en) | 1988-08-10 |
DE3868949D1 (en) | 1992-04-16 |
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