EP2990469B1 - Utilisation dans des moteurs à essence à injection directe - Google Patents
Utilisation dans des moteurs à essence à injection directe Download PDFInfo
- Publication number
- EP2990469B1 EP2990469B1 EP15182399.4A EP15182399A EP2990469B1 EP 2990469 B1 EP2990469 B1 EP 2990469B1 EP 15182399 A EP15182399 A EP 15182399A EP 2990469 B1 EP2990469 B1 EP 2990469B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- olefin copolymer
- oil
- copolymer
- overbased
- pat
- 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.)
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- 239000003502 gasoline Substances 0.000 title claims description 8
- 238000002347 injection Methods 0.000 title claims description 8
- 239000007924 injection Substances 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 claims description 97
- 229920001577 copolymer Polymers 0.000 claims description 81
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 65
- 239000003921 oil Substances 0.000 claims description 57
- 239000002270 dispersing agent Substances 0.000 claims description 37
- 239000000314 lubricant Substances 0.000 claims description 34
- 239000010687 lubricating oil Substances 0.000 claims description 29
- 239000003607 modifier Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000011777 magnesium Substances 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 21
- 239000003599 detergent Substances 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 19
- 229910052791 calcium Inorganic materials 0.000 claims description 19
- 239000003112 inhibitor Substances 0.000 claims description 18
- 230000001050 lubricating effect Effects 0.000 claims description 17
- 239000005078 molybdenum compound Substances 0.000 claims description 16
- 239000004711 α-olefin Substances 0.000 claims description 16
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 229960002317 succinimide Drugs 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 6
- MQHWFIOJQSCFNM-UHFFFAOYSA-L Magnesium salicylate Chemical compound [Mg+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O MQHWFIOJQSCFNM-UHFFFAOYSA-L 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 claims description 3
- NFCPRRWCTNLGSN-UHFFFAOYSA-N 2-n-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC=C1NC1=CC=CC=C1 NFCPRRWCTNLGSN-UHFFFAOYSA-N 0.000 claims description 3
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 4
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 claims 2
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 claims 2
- 229940072082 magnesium salicylate Drugs 0.000 claims 2
- 229910052755 nonmetal Inorganic materials 0.000 claims 2
- 125000002524 organometallic group Chemical group 0.000 claims 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- -1 that is Chemical group 0.000 description 128
- 235000019198 oils Nutrition 0.000 description 53
- 239000000654 additive Substances 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 40
- 239000002904 solvent Substances 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 150000001412 amines Chemical class 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 21
- 230000000996 additive effect Effects 0.000 description 20
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 239000002199 base oil Substances 0.000 description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 18
- 125000001183 hydrocarbyl group Chemical group 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 229920002367 Polyisobutene Polymers 0.000 description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- 229930195733 hydrocarbon Natural products 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 14
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- 150000002752 molybdenum compounds Chemical class 0.000 description 13
- 239000000376 reactant Substances 0.000 description 13
- 229910052750 molybdenum Inorganic materials 0.000 description 12
- 239000011733 molybdenum Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 238000005576 amination reaction Methods 0.000 description 9
- 230000006870 function Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000010705 motor oil Substances 0.000 description 9
- 150000002989 phenols Chemical class 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 150000008064 anhydrides Chemical group 0.000 description 8
- 150000001993 dienes Chemical class 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 7
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000005453 pelletization Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 150000003609 titanium compounds Chemical class 0.000 description 7
- VVOIQBFMTVCINR-WWMZEODYSA-N 11-deoxycorticosterone pivalate Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)COC(=O)C(C)(C)C)[C@@]1(C)CC2 VVOIQBFMTVCINR-WWMZEODYSA-N 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 150000001639 boron compounds Chemical class 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920013639 polyalphaolefin Polymers 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 229920001897 terpolymer Polymers 0.000 description 6
- 239000003981 vehicle Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010688 mineral lubricating oil Substances 0.000 description 5
- 229920000307 polymer substrate Polymers 0.000 description 5
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- 230000009467 reduction Effects 0.000 description 5
- 239000004071 soot Substances 0.000 description 5
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 5
- 239000010689 synthetic lubricating oil Substances 0.000 description 5
- 238000013022 venting Methods 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
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- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 3
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Classifications
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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
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
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- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
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- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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- C10M2207/027—Neutral salts thereof
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- C10M2207/028—Overbased salts thereof
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- C10M2207/26—Overbased carboxylic acid salts
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- C10M2207/289—Partial esters containing free hydroxy groups
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- C10M2209/082—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type monocarboxylic
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- C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
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- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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- C10M2215/064—Di- and triaryl amines
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- C10M2215/066—Arylene diamines
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- C10M2215/22—Heterocyclic nitrogen compounds
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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
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/54—Fuel economy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/09—Treatment with nitrogen containing compounds
Definitions
- the disclosure relates to lubricant compositions for turbo charged gasoline direct injection (GDI) engines and in particular to lubricant compositions that provide reduced wear in turbo charged GDI engines.
- GDI turbo charged gasoline direct injection
- oil composition lubrication composition
- lubricating oil composition lubricating oil
- lubricant composition lubricating composition
- lubricating composition lubricating composition
- fully formulated lubricant composition lubricant
- lubricant crankcase oil
- crankcase lubricant engine oil
- engine lubricant motor oil
- motor lubricant are considered synonymous, fully interchangeable terminology referring to the finished lubrication product comprising a major amount of a base oil plus a minor amount of an additive composition.
- additive package As used herein, the terms “additive package,” “additive concentrate,” “additive composition,” “engine oil additive package,” “engine oil additive concentrate,” “crankcase additive package,” “crankcase additive concentrate,” “motor oil additive package,” “motor oil concentrate,” are considered synonymous, fully interchangeable terminology referring the portion of the lubricating composition excluding the major amount of base oil stock mixture.
- the additive package may or may not include the viscosity index improver or pour point depressant.
- hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
- hydrocarbyl groups include:
- percent by weight means the percentage the recited component represents to the weight of the entire composition.
- soluble oil-soluble
- dispenser dispensers
- soluble dissolvable, miscible, or capable of being suspended in the oil in all proportions.
- the foregoing terms do mean, however, that they are, for instance, soluble, suspendable, dissolvable, or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed.
- additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
- TBN Total Base Number in mg KOH/g as measured by the method of ASTM D2896 or ASTM D4739.
- alkyl refers to straight, branched, cyclic, and/or substituted saturated chain moieties of from about 1 to about 100 carbon atoms.
- alkenyl refers to straight, branched, cyclic, and/or substituted unsaturated chain moieties of from about 3 to about 10 carbon atoms.
- aryl refers to single and multi-ring aromatic compounds that may include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and/or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.
- chain stretch means cam chain wear as evidenced by a reduction in the metal to metal contact areas of the chain and sprocket in an engine.
- polymer is used generically to encompass ethylene copolymers, terpolymers or interpolymers. Such materials may contain amounts of other olefinic monomers so long as the basic characteristics of the polymers are not materially changed.
- Turbo-charged gasoline direct injection (GDI) engines are designed to provide improved fuel economy without sacrificing engine performance. While such GDI engines typically achieve outstanding performance and improved fuel economy, such engines generate soot at increased levels than in conventional engines. The soot accumulates in the lubricant and tends to increase engine wear. Evidence of engine wear may be evident by excessive cam chain "stretch.” Cam chain stretch is a term in the art used by automobile manufacturers to quantify the amount of wear exhibited by the cam chain. The cam chain does not actually stretch, but wear of the metal contacting parts causes the chain to loosen so that the timing of the engine is affected. Accordingly, there is a need for lubricant compositions which are effective to reduce engine wear in turbo-charged GDI engines.
- EP 2 083 024 A1 discloses a lubricating oil composition comprising a minor amount of at least one highly grafted, multi-functional olefin copolymer.
- the disclosure provides a use in a turbo-charged gasoline direct injection (GDI) engine of a lubricant composition to reduce engine wear.
- the lubricant composition includes a major amount of oil of lubricating viscosity, and a minor amount of at least one highly grafted, multi-functional olefin copolymer made by reacting an acylating agent with an olefin copolymer having a number average molecular weight greater than about 1,000 in the presence of a free radical initiator to provide an acylated olefin copolymer having a degree of grafting (DOG) of the acylating agent on the olefin copolymer of at least 0.5 wt.%, and reacting the acylated olefin copolymer with an amine to provide a highly grafted, multi-functional olefin copolymer.
- DOG degree of grafting
- the highly grafted, multi-functional olefin copolymer is effective to reduce engine wear in the turbo-charged GDI engine to below engine wear provided by a lubricant composition devoid of the highly grated, multi-functional olefin copolymer.
- a primary advantage of the exemplary embodiments may reduced engine wear as exhibited by a reduced iron content of the lubricant and/or reduced cam chain stretch.
- a lubricating oil for a turbo-charged GDI engine may be synergistically improved by the addition of a particular highly grafted, multi-functional olefin copolymer. More particularly, a lubricating oil containing a conventional dispersant/inhibitor (DI) package may be significantly improved for use in turbo-charged GDI engines by incorporating the highly grafted olefin copolymer as a dispersant/viscosity index improver. Such lubricating oil compositions, as described more fully herein, may be particularly useful for lubricating internal combustion gasoline engines that generate soot in excess of the amount of soot generated by a conventional gasoline engine.
- DI dispersant/inhibitor
- the lubricant composition described herein may be suitable for any engine lubricant irrespective of the sulfur, phosphorus, or sulfated ash (ASTM D-874) content.
- the sulfur content of the engine oil lubricant may be about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less, or about 0.3 wt% or less. In one embodiment the sulfur content may be in the range of about 0.001 wt% to about 0.5 wt%, or about 0.01 wt% to about 0.3 wt%.
- the phosphorus content may be about 0.2 wt% or less, or about 0.1 wt% or less, or about 0.085 wt% or less, or about 0.08 wt% or less, or even about 0.06 wt% or less, about 0.055 wt% or less, or about 0.05 wt% or less. In one embodiment the phosphorus content may be about 50 ppm to about 1000 ppm, or about 325 ppm to about 850 ppm.
- the total sulfated ash content may be about 2 wt% or less, or about 1.5 wt% or less, or about 1.1 wt% or less, or about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less.
- the sulfated ash content may be about 0.05 wt% to about 0.9 wt%, or about 0.1 wt% or about 0.2 wt% to about 0.45 wt%.
- the sulfur content may be about 0.4 wt% or less, the phosphorus content may be about 0.08 wt% or less, and the sulfated ash is about 1 wt% or less.
- the sulfur content may be about 0.3 wt% or less, the phosphorus content is about 0.05 wt% or less, and the sulfated ash may be about 0.8 wt% or less.
- the lubricating composition is an engine oil, wherein the lubricating composition may have (i) a sulfur content of about 0.5 wt% or less, (ii) a phosphorus content of about 0.1 wt% or less, and (iii) a sulfated ash content of about 1.5 wt% or less.
- the base oil used in the lubricating oil compositions herein may be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
- the five base oil groups are as follows: Table 1 Base oil Category Sulfur (%) Saturates (%) Viscosity Index Group I > 0.03 and/or ⁇ 90 80 to 120 Group II ⁇ 0.03 and ⁇ 90 80 to 120 Group III ⁇ 0.03 and ⁇ 90 ⁇ 120 Group IV All poly alpha ole fins (PAOs) Group V All others not included in Groups I, II, III, or IV
- Groups I, II, and III are mineral oil process stocks.
- Group IV base oils contain true synthetic molecular species, which are produced by polymerization of olefinically unsaturated hydrocarbons.
- Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and/or polyphenyl ethers, and the like, but may also be naturally occurring oils, such as vegetable oils.
- Group III base oils are derived from mineral oil, the rigorous processing that these fluids undergo causes their physical properties to be very similar to some true synthetics, such as PAOs. Therefore, oils derived from Group III base oils may be referred to as synthetic fluids in the industry.
- the base oil used in the disclosed lubricating oil composition may be a mineral oil, animal oil, vegetable oil, synthetic oil, or mixtures thereof.
- Suitable oils may be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined, and re-refined oils, and mixtures thereof.
- Unrefined oils are those derived from a natural, mineral, or synthetic source without or with little further purification treatment. Refined oils are similar to the unrefined oils except that they have been treated in one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like. Oils refined to the quality of an edible may or may not be useful. Edible oils may also be called white oils. In some embodiments, lubricant compositions are free of edible or white oils.
- Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often these oils are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
- Mineral oils may include oils obtained by drilling or from plants and animals or any mixtures thereof.
- oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types.
- Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.
- Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(1-hexenes), poly(1-octenes), trimers or oligomers of 1-decene, e.g., poly(1-decenes), such materials being often referred to as ⁇ -olefins, and mixtures thereof; alkyl-benzenes (e.g.
- dodecylbenzenes dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof or mixtures thereof.
- Polyalphaolefins are typically hydrogenated materials.
- oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans.
- Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
- the amount of the oil of lubricating viscosity present may be the balance remaining after subtracting from 100 wt% the sum of the amount of the performance additives inclusive of viscosity index improver(s) and/or pour point depressant(s) and/or other top treat additives.
- the oil of lubricating viscosity that may be present in a finished fluid may be a major amount, such as greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, greater than about 80 wt%, greater than about 85 wt%, or greater than about 90 wt%.
- the dissolved pelletized copolymer intermediate possessing carboxylic acid acylating functions subsequently reacted with an amine compound.
- the highly grafted, multi-functional olefin copolymer product is added to lubricating compositions in an amount sufficient to reduce cam chain wear in a turbo-charged GDI engine.
- the highly grafted, multi-functional olefin copolymer is provided as the reaction product of a previously dehydrated copolymer substrate that is derived from a polymer of ethylene and one or more C 3 to C 23 alpha-olefins.
- the copolymer is acylated with an acylating agent and is further reacted with an amine to provide the multi-functional product.
- the foregoing multi-functional product may be used in lubrication compositions to provide one or more functions including as a viscosity index (VI) modifier, dispersant, film formation improver, deposit controller, as well engine wear reduction.
- VI viscosity index
- the polymer substrate starting material for multi-functional olefin copolymer is derived from copolymers of ethylene and one or more C 3 to C 23 alpha-olefins. Copolymers of ethylene and propylene are suitably used to make the copolymer.
- Copolymers herein may include without limitation blends or reacted products of ethylene and one or more C 3 to C 23 alpha-olefins, and additionally optionally other dienes or polyenes. Thus, “copolymers” herein also includes terpolymers, and other higher forms.
- alpha-olefins suitable in place of propylene to form the copolymer or to be used in combination with ethylene and propylene to form a terpolymer include 1-butene, 1-pentene, 1-hexene, 1-octene and styrene; .alpha,co-diolefins such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene; branched chain alpha-olefins such as 4-methylbutene-1,5-methylpentene-1 and 6-methylheptene-1; and mixtures thereof.
- More complex polymer substrates also may be used as the olefin polymer starting material, which may be prepared using a third component.
- the third component generally used to prepare an interpolymer substrate is a polyene monomer selected from nonconjugated dienes and trienes.
- The-non-conjugated diene component is one having from 5 to 14 carbon atoms in the chain.
- the diene monomer may be characterized by the presence of a vinyl group in its structure and can include cyclic and bicyclo compounds.
- dienes include 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, vinylnorbornene, 5-methylene-2-norborene, 1,5-heptadiene, and 1,6-octadiene.
- a mixture of more than one diene may be used in the preparation of the interpolymer.
- a suitable nonconjugated diene for preparing a terpolymer or interpolymer substrate is 1,4-hexadiene.
- the triene component may have at least two nonconjugated double bonds, and up to about 30 carbon atoms in the chain.
- Typical trienes that may be used to prepare the interpolymer of the disclosure are 1-isopropylidene-3 ⁇ ,4,7,7 ⁇ -tetrahydroindene, 1-isopropylidenedicyclopentadiene, dihydro-isodicyclopentadiene, and 2-(2-methylene-4methyl-3-pentenyl)[2.2.1]bicyclo-5-heptene.
- Ethylene-propylene or higher alpha-olefin copolymers may consist of from about 15 to 80 mole percent ethylene and from about 85 to 20 mole percent C 3 to C 23 alpha-olefin with the mole ratios in one embodiment being from about 35 to 75 mole percent ethylene and from about 65 to 25 mole percent of a C 3 to C 23 alpha-olefin, with the proportions in another embodiment being from 50 to 70 mole percent ethylene and 50 to 30 mole percent C 3 to C 23 alpha-olefin, and the proportions in yet another embodiment being from 55 to 65 mole percent ethylene and 45 to 35 mole percent C 3 to C 23 alpha-olefin.
- Terpolymer variations of the foregoing polymers may contain from about 0 to 10 mole percent of a nonconjugated diene or triene. Other termonomer levels are less than 1 mole percent.
- the starting polymer that is acylated is desirably an oil-soluble, linear or branched polymer having a number average molecular weight from about 1,000 to 500,000, and for example a number average molecular weight of 50,000 to 250,000, as determined by gel permeation chromatography and universal calibration standardization.
- the polymerization reaction used to form an ethylene olefin copolymer may be conducted in the presence of a conventional Ziegler-Natta or metallocene catalyst system.
- the polymerization medium is not specific and may include solution, slurry, or gas phase processes, as known to those skilled in the art.
- the solvent may be any suitable inert hydrocarbon solvent that is liquid under reaction conditions for polymerization of alpha-olefins; examples of satisfactory hydrocarbon solvents include straight chain paraffins having from 5 to 8 carbon atoms, with hexane being preferred.
- Aromatic hydrocarbons for example, aromatic hydrocarbon having a single benzene nucleus, such as benzene, toluene and the like; and saturated cyclic hydrocarbons having boiling point ranges approximating those of the straight chain paraffinic hydrocarbons and aromatic hydrocarbons described above are particularly suitable.
- the solvent selected may be a mixture of one or more of the foregoing hydrocarbons.
- the liquid phase for polymerization is preferably liquid propylene. It is desirable that the polymerization medium be free of substances that will interfere with the catalyst components.
- the polymer described above i.e., the olefin polymer component, may be conveniently obtained in the form of ground or pelletized polymer.
- the olefin polymer may also be supplied as either a pre-mixed bale or a pre-mixed friable chopped agglomerate form.
- ground polymer bales or other forms of the olefin copolymer are fed to an extruder, e.g., a single or twin screw extruder, or a Banbury or other mixer having the capability of heating and effecting the desired level of mechanical work (agitation) on the polymer substrate for the dehydration step.
- a nitrogen blanket can be maintained at the feed section of the extruder to minimize the introduction of air.
- the olefin copolymer is initially heated before being admixed with any other reactants in the extruder or other mixer with venting to eliminate moisture content in the feed material.
- the dried olefin copolymer is in one embodiment then fed into another extruder section or separate extruder in series for conducting the grafting reaction.
- a graft monomer is next grafted onto the polymer backbone of the polymer olefin copolymer to form an acylated ethylene-alphaolefin polymer.
- Suitable graft monomers include ethylenically unsaturated carboxylic acid materials, such as unsaturated dicarboxylic acid anhydrides and their corresponding acids. Examples of these graft monomers are set forth, for example, in U.S. Pat. No. 5,837,773 , Carboxylic reactants which are suitable for grafting onto the ethylene-alphaolefin interpolymers contain at least one ethylenic bond and at least one carboxylic acid or its anhydride groups or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis.
- the carboxylic reactants are selected from the group consisting of acrylic, methacrylic, cinnamic, crotonic, maleic, fumaric and itaconic reactants or a mixture of two or more of these.
- itaconic acid or its anhydride is useful due to its reduced tendency to form a cross-linked structure during the free-radical grafting process.
- the ethylenically unsaturated carboxylic acid materials typically may provide one or two carboxylic groups per mole of reactant to the grafted copolymer. That is, methyl methacrylate may provide one carboxylic group per molecule to the grafted copolymer while maleic anhydride may provide two carboxylic groups per molecule to the grafted copolymer.
- the grafting reaction to form the acylated olefin copolymers is generally carried out with the aid of a free-radical initiator either in bulk or in solution.
- the grafting may be carried out in the presence of a free-radical initiator dissolved in oil.
- the use of a free-radical initiator dissolved in oil results in a more homogeneous distribution of acylated groups over the olefin copolymer molecules.
- the free-radical initiators which may be used to graft the ethylenically unsaturated carboxylic acid material to the polymer backbone include peroxides, hydroperoxides, peresters, and also azo compounds and preferably those which have a boiling point greater than 100° C. and decompose thermally within the grafting temperature range to provide free radicals.
- Representatives of these free-radical initiators are azobutyronitrile, dicumyl peroxide, 2,5-dimethylhexane-2,5-bis-tertiarybutyl peroxide and 2,5-dimethylhex-3-yne-2,5-bis-tertiary-butyl peroxide.
- the initiator may be used in an amount ranging from about 0.005% to about 1% by weight based on the weight of the reaction mixture.
- the graft monomer and olefin copolymer are in one embodiment fed to an extruder, e.g., a single or twin screw extruder e.g. Werner & Pfleiderer's ZSK series, or a Banbury or other mixer, having the capability of heating and effecting the desired level of mechanical work (agitation) on the reactants for the grafting step.
- grafting is conducted in an extruder, and particularly a twin screw extruder. A nitrogen blanket is maintained at the feed section of the extruder to minimize the introduction of air.
- Grafting may also be conducted in an extruder, such as a twin-screw extruder.
- a nitrogen blanket is maintained at the feed section of the extruder to minimize the introduction of air.
- the olefinic carboxylic acylating agent may be injected at one injection point, or is alternatively injected at two injection points in a zone of the extruder without significant mixing e.g. a transport zone. Such injection may result in an improved efficiency of the grafting and leads to a lower gel content.
- Suitable extruders are generally known available for conducting grafting, and the prior dehydration procedure.
- the dehydration of the polymer substrate and subsequent grafting procedures may be performed in separate extruders set up in series.
- a single extruder having multiple treatment or reaction zones may be used to sequentially conduct the separate operations within one piece of equipment. Illustrations of suitable extruders are set forth, e.g., in U.S. Pat. No. 3,862,265 and U.S. Pat. No. 5,837,773 .
- the olefin copolymer In forming the acylated olefin copolymers, the olefin copolymer generally is fed to plastic processing equipment such as an extruder, intensive mixer or masticator, heated to a temperature of at least 60°, for example, 150° to 240° C., and the ethylenically unsaturated carboxylic acid reagent and free-radical initiator are separately co-fed to the molten copolymer to effect grafting. The reaction is carried out optionally with mixing conditions to effect grafting of the olefin copolymers. If molecular weight reduction and grafting are performed simultaneously, illustrative mixing conditions are described in U.S. Pat. No. 5,075,383 .
- the processing equipment is generally purged with nitrogen to prevent oxidation of the copolymer and to aid in venting unreacted reagents and byproducts of the grafting reaction.
- the residence time in the processing equipment is controlled to provide for the desired degree of acylation and to allow for purification of the acylated copolymer via venting.
- Mineral or synthetic lubricating oil may optionally be added to the processing equipment after the venting stage to dissolve the acylated copolymer.
- the grafting reaction may also be carried out in solvent-free or essentially solvent free environment. Accordingly, the grafting reaction may be performed in the absence of hydrocarbon solvents.
- hydrocarbon solvents such as alkanes (e.g., hexane)
- alkanes e.g., hexane
- reduce amounts of transient unfunctionalized polymer are present after grafting in solventless grafting reactions, which results in a more active product. Therefore, the resulting copolymer intermediate is a more active product.
- a reduction is achieved in levels of undesirable grafted solvent (i.e., grafted hexyl succinic anhydride) and transient unfunctionalized (nongrafted) copolymer.
- Hydrocarbon solvents that may be omitted according to certain embodiments of the present disclosure include solvents that generally are more volatile than the reactants of the grafting reaction described herein, for example, solvents having a boiling point less than about 150° C. under standard atmospheric pressure conditions (i.e., approximately 14.7 lb./in 2 absolute).
- the solvents that may be omitted include, for example, open-chain aliphatic compounds such as C 9 or lower alkanes, alkenes and alkynes (e.g., C 5 to C 8 alkanes such as hexane); aromatic hydrocarbons (e.g., compounds having a benzene nucleus such as benzene and toluene); alicyclic hydrocarbons such as saturated cyclic hydrocarbons (e.g., cyclohexane); ketones; or any combinations of these.
- Some conventional grafting reactions have been performed in the presence of considerable amounts of hydrocarbon solvent, such as approximately 15% to 60% hexane content.
- the total amount of these types of such solvents in the grafting reaction mass does not exceed 0.5 wt. % content thereof.
- the grafted copolymer intermediate exits from the die face of the extruder either immediately after grafting, or after shearing and vacuum stripping (discussed below in more detail) if performed in different sections of the same extruder or a separate extruder arranged in series with the extruder in which grafting is conducted.
- the resulting copolymer intermediate comprises an acylated olefin copolymer characterized by having carboxylic acid acylating functionality randomly within its structure.
- the amount of carboxylic acid acylating agent e.g., maleic anhydride
- This parameter is referred to herein as the degree of grafting (DOG), further described as the mass percentage of acylating agent on the acylated copolymer.
- the DOG generally is in the range of 0.5 to 3.0 wt. %, particularly in the range of 1.5 to 2.5 wt. %, and more particularly in the range of 1.7 to 2.3 wt. %, of carboxylic acid acylating agent grafted on the copolymer backbone.
- the DOG value of a particular additive reaction product may be determined either by infrared peak ratio analysis of acid or anhydride moiety versus copolymer alkyl functionality or by titration (Total Acid/Anhydride Number) (TAN) of the additive reaction product.
- TAN Total Acid/Anhydride Number
- the TAN value in turn can be used to estimate the degree of grafting (DOG).
- the carboxylic reactant is grafted onto the prescribed copolymer backbone to provide 0.15 to 0.75 carboxylic groups per 1000 number average molecular weight units (Mn) of the copolymer backbone, desirably 0.2 to 0.5 carboxylic groups per 1000 number average molecular weight.
- Mn number average molecular weight units
- a copolymer substrate with M n of 20,000 is grafted with 3 to 15 carboxylic groups per copolymer chain or 1.5 to 7.5 moles of maleic anhydride per mole of copolymer.
- a copolymer with M n of 100,000 is grafted with 15 to 75 carboxylic groups per copolymer chain or 7.5 to 37.5 moles of maleic anhydride per copolymer chain.
- the minimum level of functionality is the level needed to achieve the minimum satisfactory dispersancy performance.
- the molecular weight of the acylated olefin copolymer may be reduced by mechanical, thermal, or chemical means, or a combination thereof. Techniques for degrading or reducing the molecular weight of such copolymers are generally known in the art. The number average molecular weight is reduced to suitable level for use in single grade or multigrade lubricating oils.
- the initial copolymer intermediate has an initial number average molecular weight ranging from about 1,000 to about 500,000 upon completion of the grafting reaction. In one embodiment, to prepare an additive intended for use in multigrade oils, the copolymer intermediate's number average molecular weight is reduced down to a range of about 1,000 to about 80,000.
- grafting and reduction of the high molecular weight olefin copolymer may be done simultaneously.
- the high molecular weight olefin copolymer may be first reduced to the prescribed molecular weight before grafting.
- the olefin copolymer's average molecular weight is reduced before grafting, its number average molecular weight is sufficiently reduced to a value below about 80,000, e.g., in the range of about 1,000 to 80,000.
- Reduction of the molecular weight of the copolymer intermediate, or the olefin copolymer feed material during or prior to grafting, to a prescribed lower molecular weight typically is conducted in the absence of a solvent or in the presence of a base oil, using either mechanical, thermal, or chemical means, or combination of these means.
- the copolymer intermediate, or olefin copolymer is heated to a molten condition at a temperature in the range of about 250° C. to about 350° C. and it is then subjected to mechanical shear, thermally or chemical induced cleavage or combination of said means, until the copolymer intermediate (or olefin copolymer) is reduced to the prescribed molecular weight.
- the shearing may be effected within an extruder section, such as described, e.g., in U.S. Pat. No. 5,837,773 .
- mechanical shearing may be conducted by forcing the molten copolymer intermediate (or olefin copolymer) through fine orifices under pressure or by other mechanical means.
- unreacted carboxylic reactant and free radical initiator usually are removed and separated from the copolymer intermediate before further functionalization is performed on the copolymer intermediate.
- the unreacted components may be eliminated from the reaction mass by vacuum stripping, e.g., the reaction mass may be heated to temperature of about 150° C. to about 450° C. under agitation with a vacuum applied for a period sufficient to remove the volatile unreacted graft monomer and free radical initiator ingredients.
- Vacuum stripping may be performed in an extruder section equipped with venting means.
- the copolymer intermediate may be pelletized before further processing in accordance with embodiments of the disclosure herein. Pelletization of the copolymer intermediate helps to isolate the intermediate product and reduce contamination thereof until further processing is conducted thereon at a desired time.
- the copolymer intermediate may be formed into pellets by a variety of process methods commonly practiced in the art of plastics processing. Such techniques include underwater pelletization, ribbon or strand pelletization or conveyor belt cooling. When the strength of the copolymer is inadequate to form into strands, the preferred method is underwater pelletization. Temperatures during pelletization should not exceed 30° C. Optionally, a surfactant can be added to the cooling water during pelletization to prevent pellet agglomeration.
- the mixture of water and quenched copolymer pellets is conveyed to a dryer such as a centrifugal drier for removal of water.
- Pellets may be collected in a box or plastic bag at any volume for storage and shipment. Under some conditions of storage and/or shipment at ambient conditions, pellets may tend to agglomerate and stick together.
- the pellets may be ground by mechanical methods to provide high surface area solid pieces for easy and quick dissolution into oil.
- the pelletized copolymer intermediate may be supplied as an unground or ground form of the pellets.
- the pelletized acylated copolymer intermediate is dissolved in solvent neutral oil.
- the pellets generally are dissolved in the solvent at an introduction level of from about 5 wt. % to about 25 wt. %, particularly about 10 wt. % to about 15 wt. %, and more particularly about 12 wt. % to about 13 wt. %, based on the resulting solution (solute and solvent) viscosity.
- the pelletized copolymer intermediate can be dissolved in the solvent neutral at temperature of, for example, about 135° C. to about 165° C. with mechanical stirring under a nitrogen blanket.
- the dissolving mixture may be sparged with inert gas during the dissolution for about 4 to 16 hours.
- Such treatment may be performed in a continuous stirred process vessel of suitable capacity.
- the inert sparging gas may be nitrogen.
- the dissolution and sparging, if used, may be prior to the subsequent amination procedure.
- One or more spargers are located within the vessel at locations submerged beneath the surface of the solution, preferably near the bottom of the solution, and bubble inert gas through the solution. Nitrogen sparging removes moisture from the dissolved copolymer intermediate and solvent oil. Importantly, the removal of moisture from the copolymer intermediate may act to convert any polymeric dicarboxylic diacids present back to the desired copolymeric dicarboxylic anhydride form.
- some portion of the pelletized copolymer intermediate may inadvertently transform to a copolymeric succinic diacid form.
- this change is more apt to occur as a function of a longer shelf life.
- the conducting of nitrogen sparging during dissolution of the copolymer intermediate and prior to amination has the benefit of converting the copolymeric succinic diacid back into the desired active polymeric succinic anhydride form before the copolymer intermediate is further reacted and functionalized (e.g., aminated). Consequently, a more highly functionalized and active aminated product may be obtained in subsequent processing.
- the conversion of polymeric succinic diacid back into the active polymeric succinic anhydride form can be monitored by measuring the viscosity of the solution.
- the solution viscosity decreases significantly from an initial higher value down to a steady-state value upon conversion of all or essentially all of the polymeric succinic diacid back into the desired polymeric succinic anhydride form.
- the amine may be selected from compounds such as described, e.g., in U.S. Pat. Nos. 4,863,623 , 5,075,383 , and 6,107,257 ,.
- the amine compound may be, an N-arylphenylenediamine represented by the general formula: in which R 1 is hydrogen, --NH-aryl, --NH-arylalkyl, --NH-alkyl, or a branched or straight chain radical having from 4 to 24 carbon atoms that can be alkyl, alkenyl, alkoxyl, aralkyl, alkaryl, hydroxyalkyl or aminoalkyl; R 2 is --NH 2 , CH 2 --(CH 2 ) n --NH 2 , CH 2 -aryl-NH 2 , in which n has a value from 1 to 10 and R.sup.3 is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, alkaryl having from 4 to 24 carbon atoms.
- R 1 is hydrogen, --NH-aryl, --NH-arylalkyl, --NH-alkyl, or a branched or straight chain radical having from 4 to 24 carbon atoms that can be alkyl,
- the amines in the present disclosure are N-arylphenylenediamines, more specifically the N-phenylphenylenediamines, for example, N-phenyl-1,4-phenylenediamine, N-phenyl-1,3-phenylendiamine, and N-phenyl-1,2-phenylenediamine.
- the amines contain only one primary amine group so as to avoid coupling and/or gelling of the olefin copolymers.
- the reaction between the copolymer having grafted thereon carboxylic acid acylating function and the prescribed amine compound may be conducted by heating a solution of the copolymer substrate under inert conditions and then adding the amine compound to the heated solution generally with mixing to effect the reaction. It is convenient to employ an oil solution of the copolymer substrate heated to 120° to 175° C., while maintaining the solution under a nitrogen blanket. The amine compound may be added to this solution and the reaction is effected under the noted conditions.
- the amine compound may be dissolved with a surfactant and added to a mineral or synthetic lubricating oil or solvent solution containing the acylated olefin copolymer.
- the solution of amine and olefin copolymer may be heated with agitation under an inert gas purge at a temperature in the range of 120° to 200° C. as described in U.S. Pat. No. 5,384,371 , the disclosure of which is herein incorporated by reference.
- the reactions may be carried out conveniently in a stirred reactor under nitrogen purge.
- a polymeric succinic anhydride oil solution is reacted with N-phenyl-1,4-phenylenediamines, along with ethoxylated lauryl alcohol in a reactor carried out at 165° C.
- Surfactants which may be used in carrying out the reaction of the acylated olefin copolymer with the polyamine(s) include but are not limited to those characterized as having (a) solubility characteristics compatible with mineral or synthetic lubricating oil, (b) boiling point and vapor pressure characteristics so as not to alter the flash point of the oil and (c) polarity suitable for solubilizing the polyamine(s).
- a suitable class of such surfactants includes the reaction products of aliphatic and aromatic hydroxy compounds with ethylene oxide, propylene oxide or mixtures thereof. Such surfactants are commonly known as aliphatic or phenolic alkoxylates. Useful surfactants can include those surfactants that contain a functional group, e.g., --OH, capable of reacting with the acylated olefin copolymer. Ethoxylated lauryl alcohol (C 12 H 25 (OCH 2 CH 2 ) n OH) is also useful herein. Ethoxylated lauryl alcohol is identified under CAS no. 9002-92-0 .
- the ethoxylated lauryl alcohol is a processing aid and viscosity stabilizer for the final multifunctional viscosity modifier product.
- the ethoxylated lauryl alcohol facilitates the amine charge into the reaction mixture. It is a reaction agent ensuring that no acylated functionality is left unreacted. Any unreacted acylated functionality may cause undesirable viscosity drift in finished lubrication formulations.
- the surfactant also modifies the viscoelastic response in the multifunctional viscosity modifier product allowing improved handling at low temperature (70 to 90° C.).
- the quantity of surfactant used depends in part on its ability to solubilize the amine. Typically, concentrations of 5 to 40 wt. % amine are employed. The surfactant may also be added separately, instead of or in addition to the concentrates discussed above, such that the total amount of surfactant in the finished additive is 10 wt. % or less.
- the highly grafted, multi-functional olefin copolymers of the present disclosure may be incorporated into lubricating oil in any convenient way.
- the highly grafted, multi-functional olefin copolymers may be added directly to the lubricating oil by dispersing or dissolving the same in the lubricating oil at the desired level of concentration. Such blending into the lubricating oil may occur at room temperature or elevated temperatures.
- the highly grafted, multi-functional olefin copolymers can be blended with a suitable oil-soluble solvent/diluent (such as benzene, xylene, toluene, lubricating base oils and petroleum distillates) to form a concentrate, and then blending the concentrate with a lubricating oil to obtain the final formulation.
- a suitable oil-soluble solvent/diluent such as benzene, xylene, toluene, lubricating base oils and petroleum distillates
- Such additive concentrates will typically contain (on an active ingredient (A.I.) basis) from about 3 to about 45 wt. %, and preferably from about 10 to about 35 wt. %, highly grafted, multi-functional olefin copolymer additive, and typically from about 20 to 90 wt %, preferably from about 40 to 60 wt %, base oil based on the concentrate weight.
- the acylated olefin copolymer also may be color stabilized after the amination reaction, such as by reacting the acylated olefin copolymer with a C 7 to C 12 alkyl aldehyde (e.g., nonyl aldehyde).
- the reaction may proceed when the alkyl aldehyde agent is added in an amount of about 0.2 to about 0.6 wt. % under similar temperature and pressure conditions as used in the amination reaction for about 2 to about 6 hours.
- color stabilized acylated olefin copolymer product it may be filtered by either bag or cartridge filtration or both in series.
- the copolymer intermediate may be prepared in the absence of solvent. Also, the copolymer intermediate may be received in pelletized or bale form as a starting material for performing the additional functionalization(s), viz. amination and color stabilization, on the grafted copolymer intermediate.
- the copolymer intermediate need not be received directly from the die face of an extruder or similar grafting reaction vessel, but instead the copolymer intermediate has been vacuum stripped of unreacted reactants and pelletized before these further functionalizations are performed on it.
- the pelletized copolymer intermediate contains less contaminants than a product that has been grafted in the presence of a solvent (which can lead to side reaction products) and/or aminated immediately after the grafting reaction as part of a continuous process flow arrangement (which leaves unreacted components as impurities in the reaction mass).
- graft monomer e.g., maleic anhydride
- graft monomer e.g., maleic anhydride
- amination proceeds more efficiently. That is, the presence of unreacted graft monomers are undesirable during the amination step as they may compete with the grafted copolymer (polymer intermediate) in reactions with the amine, reducing the level of functionalization achieved.
- the multi-functional reaction end product of embodiments of the present disclosure may contain fewer impurities (i.e., unreacted reactants, side reaction products and by-products) and may be more active for a given amount thereof.
- the additive reaction product may contain less than 0.1 wt. % total impurities comprising unreacted reactants, side reaction products and reaction by-products.
- the remainder may be composed of active grafted, multifunctionalized olefin copolymer either entirely, or substantially in combination with some minor amount of beneficial or inert additive introduced during processing, such as an antioxidant or colorant, which does not significantly reduce or impair the activity of the product compound.
- the highly grafted, multi-functional olefin copolymer product compounds of the present disclosure optionally may be post-treated so as to impart additional properties necessary or desired for a specific lubricant application.
- Post-treatment techniques are well known in the art and include boronation, phosphorylation, glycolation, ethylene-carbonation, and maleination.
- Suitable treat rates of the highly grafted, multi-functional olefin copolymer product compounds including process oil (i.e., not neat) would be from about 0.25 wt% to about 20 wt% in a finished lubricant. Further suitable treat rates may be from about 1 wt% to about 15 wt% or from about 1.5 wt% to about 10 wt% in a finished lubricant.
- Lubricating oil formulations for gasoline engines as described herein may conventionally contain additional additives that will supply the characteristics that are required in the formulations.
- additional viscosity index improvers include antioxidants, corrosion inhibitors, detergents, dispersants, pour point depressants, antiwear agents, antifoaming agents, demulsifiers and friction modifiers.
- DI dispersant/inhibitor
- the lubricating oil compositions herein also may optionally contain one or more antiwear agents.
- suitable antiwear agents include, but are not limited to, a metal thiophosphate; a metal dialkyldithiophosphate; a phosphoric acid ester or salt thereof; a phosphate ester(s); a phosphite; a phosphorus-containing carboxylic ester, ether, or amide; a sulfurized olefin; thiocarbamate-containing compounds including, thiocarbamate esters, alkylene-coupled thiocarbamates, and bis(S-alkyldithio-carbamyl)disulfides; and mixtures thereof.
- the phosphorus containing antiwear agents are more fully described in European Patent 612 839 .
- the metal in the dialkyl dithio phosphate salts may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc.
- a useful antiwear agent may be zinc dialkylthiophosphate.
- suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides.
- the tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups may be at least 8.
- the antiwear agent may in one embodiment include a citrate.
- the antiwear agent may be present in ranges including about 0 wt% to about 15 wt%, or about 0.01 wt% to about 10 wt%, or about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt% of the lubricating composition.
- the lubricating oil compositions herein may optionally contain one or more boron-containing compounds.
- boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Patent No. 5,883,057 .
- the boron-containing compound if present, can be used in an amount sufficient to provide up to about 8 wt%, about 0.01 wt% to about 7 wt%, about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt% of the lubricating composition.
- the lubricant composition may optionally further comprise one or more neutral, low based, or overbased detergents, and mixtures thereof.
- Suitable detergent substrates include phenates, sulfur containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphorus acids, mono- and/or di-thiophosphoric acids, alkyl phenols, sulfur coupled alkyl phenol compounds, or methylene bridged phenols.
- Suitable detergents and their methods of preparation are described in greater detail in numerous patent publications, including US 7,732,390 and references cited therein.
- the detergent substrate may be salted with an alkali or alkaline earth metal such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof.
- the detergent is free of barium.
- a suitable detergent may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylarylsulfonic acids with the aryl group being benzyl, tolyl, and xylyl.
- suitable detergents include, but are not limited to, calcium phenates, calcium sulfur containing phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylic acids, calcium phosphorus acids, calcium mono- and/or di-thiophosphoric acids, calcium alkyl phenols, calcium sulfur coupled alkyl phenol compounds, calcium methylene bridged phenols, magnesium phenates, magnesium sulfur containing phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylic acids, magnesium phosphorus acids, magnesium mono- and/or di-thiophosphoric acids, magnesium alkyl phenols, magnesium sulfur coupled alkyl phenol compounds, magnesium methylene bridged phenols, sodium phenates, sodium sulfur containing phenates, sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates, sodium carboxylic acids, sodium phosphorus acids,
- Overbased detergent additives are well known in the art and may be alkali or alkaline earth metal overbased detergent additives.
- Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas.
- the substrate is typically an acid, for example, an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.
- overbased relates to metal salts, such as metal salts of sulfonates, carboxylates, and phenates, wherein the amount of metal present exceeds the stoichiometric amount.
- Such salts may have a conversion level in excess of 100% (i.e., they may comprise more than 100% of the theoretical amount of metal needed to convert the acid to its "normal,” “neutral” salt).
- metal ratio often abbreviated as MR, is used to designate the ratio of total chemical equivalents of metal in the overbased salt to chemical equivalents of the metal in a neutral salt according to known chemical reactivity and stoichiometry.
- the metal ratio is one and in an overbased salt, MR, is greater than one.
- overbased salts are commonly referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.
- overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphorus acids, overbased calcium mono- and/or di-thiophosphoric acids, overbased calcium alkyl phenols, overbased calcium sulfur coupled alkyl phenol compounds, overbased calcium methylene bridged phenols, overbased magnesium phenates, overbased magnesium sulfur containing phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphorus acids, overbased magnesium mono- and/or di-thiophosphoric acids, overbased magnesium alkyl phenols, overbased magnesium sulfur coupled alkyl phenol compounds, or overbased magnesium methylene bridged phenols.
- the overbased detergent may have a metal to substrate ratio of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1.
- a detergent is effective at reducing or preventing rust in an engine.
- the detergent may be present at about 0 wt% to about 10 wt%, or about 0.1 wt% to about 8 wt%, or about 1 wt% to about 4 wt%, or greater than about 4 wt% to about 8 wt%.
- the lubricant composition may optionally further comprise one or more dispersants or mixtures thereof.
- Dispersants are often known as ashless-type dispersants because, prior to mixing in a lubricating oil composition, they do not contain ash-forming metals and they do not normally contribute any ash when added to a lubricant.
- Ashless type dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain.
- Typical ashless dispersants include N-substituted long chain alkenyl succinimides.
- N-substituted long chain alkenyl succinimides include polyisobutylene succinimide with number average molecular weight of the polyisobutylene substituent in the range about 350 to about 50,000, or to about 5,000, or to about 3,000.
- Succinimide dispersants and their preparation are disclosed, for instance in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435 .
- the polyolefin may be prepared from polymerizable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms.
- Succinimide dispersants are typically the imide formed from a polyamine, typically a poly(ethyleneamine).
- the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene with number average molecular weight in the range about 350 to about 50,000, or to about 5000, or to about 3000.
- the polyisobutylene succinimide may be used alone or in combination with other dispersants.
- polyisobutylene when included, may have greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol% content of terminal double bonds.
- PIB is also referred to as highly reactive PIB ("HR-PIB").
- HR-PIB having a number average molecular weight ranging from about 800 to about 5000 is suitable for use in embodiments of the present disclosure.
- Conventional PIB typically has less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol% content of terminal double bonds.
- An HR-PIB having a number average molecular weight ranging from about 900 to about 3000 may be suitable.
- Such HR-PIB is commercially available, or can be synthesized by the polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in US Patent No. 4,152,499 to Boerzel, et al. and U.S. Patent No. 5,739,355 to Gateau, et al.
- HR-PIB may lead to higher conversion rates in the reaction, as well as lower amounts of sediment formation, due to increased reactivity.
- a suitable method is described in U.S. Patent No. 7,897,696 .
- the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA").
- PIBSA polyisobutylene succinic anhydride
- the PIBSA may have an average of between about 1.0 and about 2.0 succinic acid moieties per polymer.
- the % actives of the alkenyl or alkyl succinic anhydride can be determined using a chromatographic technique. This method is described in column 5 and 6 in U.S. Pat. No. 5,334,321 .
- the percent conversion of the polyolefin is calculated from the % actives using the equation in column 5 and 6 in U.S. Pat. No. 5,334,321 .
- the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride.
- PAO polyalphaolefin
- the dispersant may be derived from olefin maleic anhydride copolymer.
- the dispersant may be described as a poly-PIBSA.
- the dispersant may be derived from an anhydride which is grafted to an ethylene-propylene copolymer.
- Mannich bases are materials that are formed by the condensation of a higher molecular weight, alkyl substituted phenol, a polyalkylene polyamine, and an aldehyde such as formaldehyde. Mannich bases are described in more detail in U.S. Patent No. 3,634,515 .
- a suitable class of dispersants may be high molecular weight esters or half ester amides.
- a suitable dispersant may also be post-treated by conventional methods by a reaction with any of a variety of agents.
- agents include boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds.
- US 7,645,726 ; US 7,214,649 ; and US 8,048,831 are incorporated herein by reference.
- both the compounds may be post-treated, or further post-treatment, with a variety of post-treatments designed to improve or impart different properties.
- post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003 , hereby incorporated by reference.
- Such treatments include, treatment with: Inorganic phosphorous acids or anhydrates (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980 ); Organic phosphorous compounds (e.g., U.S. Pat. No. 3,502,677 ); Phosphorous pentasulfides; Boron compounds as already noted above (e.g., U.S. Pat. Nos.
- Carboxylic acid, polycarboxylic acids, anhydrides and/or acid halides e.g., U.S. Pat. Nos. 3,708,522 and 4,948,386
- Epoxides polyepoxiates or thioexpoxides e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495
- Aldehyde or ketone e.g., U.S. Pat. No. 3,458,530
- Carbon disulfide e.g., U.S. Pat. No. 3,256,185
- Glycidol e.g., U.S. Pat. No.
- Urea, thiourea or guanidine e.g., U.S. Pat. Nos. 3,312,619 ; 3,865,813 ; and British Patent GB 1,065,595
- Organic sulfonic acid e.g., U.S. Pat. No. 3,189,544 and British Patent GB 2,140,811
- Alkenyl cyanide e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569
- Diketene e.g., U.S. Pat. No. 3,546,243
- a diisocyanate e.g., U.S. Pat. No.
- Alkane sulfone e.g., U.S. Pat. No. 3,749,695
- 1,3-Dicarbonyl Compound e.g., U.S. Pat. No. 4,579,675
- Sulfate of alkoxylated alcohol or phenol e.g., U.S. Pat. No. 3,954,639
- Cyclic lactone e.g., U.S. Pat. Nos.
- the TBN of a suitable dispersant may be from about 10 to about 65 on an oil-free basis, which is comparable to about 5 to about 30 TBN if measured on a dispersant sample containing about 50% diluent oil.
- the dispersant if present, can be used in an amount sufficient to provide up to about 20 wt%, based upon the final weight of the lubricating oil composition.
- Another amount of the dispersant that can be used may be about 0.1 wt% to about 15 wt%, or about 0.1 wt% to about 10 wt%, or about 3 wt% to about 10 wt%, or about 1 wt% to about 6 wt%, or about 7 wt% to about 12 wt%, based upon the final weight of the lubricating oil composition.
- the lubricating oil composition utilizes a mixed dispersant system.
- the lubricating oil compositions herein also may optionally contain one or more friction modifiers.
- Suitable friction modifiers may comprise metal containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, amino guanadine, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil other naturally occurring plant or animal oils, dicarboxylic acid esters, esters or partial esters of a polyol and one or more aliphatic or aromatic carboxylic acids, and the like.
- Suitable friction modifiers may contain hydrocarbyl groups that are selected from straight chain, branched chain, or aromatic hydrocarbyl groups or mixtures thereof, and may be saturated or unsaturated.
- the hydrocarbyl groups may be composed of carbon and hydrogen or hetero atoms such as sulfur or oxygen.
- the hydrocarbyl groups may range from about 12 to about 25 carbon atoms.
- the friction modifier may be a long chain fatty acid ester.
- the long chain fatty acid ester may be a mono-ester, or a di-ester, or a (tri)glyceride.
- the friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.
- suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers.
- Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols and generally include a polar terminal group (e.g. carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain.
- An example of an organic ashless nitrogen-free friction modifier is known generally as glycerol monooleate (GMO) which may contain mono-, di-, and triesters of oleic acid.
- GMO glycerol monooleate
- Other suitable friction modifiers are described in U.S. Pat. No. 6,723,685 .
- Aminic friction modifiers may include amines or polyamines. Such compounds can have hydrocarbyl groups that are linear, either saturated or unsaturated, or a mixture thereof and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are linear, either saturated, unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.
- the amines and amides may be used as such or in the form of an adduct or reaction product with a boron compound such as a boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.
- a boron compound such as a boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.
- boron compound such as a boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.
- a friction modifier may optionally be present in ranges such as about 0 wt% to about 10 wt%, or about 0.01 wt% to about 8 wt%, or about 0.1 wt% to about 4 wt%.
- the lubricating oil compositions herein also may optionally contain one or more molybdenum-containing compounds.
- An oil-soluble molybdenum compound may have the functional performance of an antiwear agent, an antioxidant, a friction modifier, or mixtures thereof.
- An oil-soluble molybdenum compound may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, a trinuclear organo-molybdenum compound, and/or mixtures thereof.
- the molybdenum sulfides include molybdenum disulfide.
- the molybdenum disulfide may be in the form of a stable dispersion.
- the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof.
- the oil-soluble molybdenum compound may be a molybdenum dithiocarbamate.
- Suitable examples of molybdenum compounds which may be used include commercial materials sold under the trade names such as Molyvan 822TM, MolyvanTM A, Molyvan 2000TM and Molyvan 855TM from R. T. Vanderbilt Co., Ltd., and Sakura-LubeTM S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof.
- Suitable molybdenum components are described in US 5,650,381 ; US RE 37,363 E1 ; US RE 38,929 E1 ; and US RE 40,595 E1 .
- the molybdenum compound may be an acidic molybdenum compound. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkaline metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOC14, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds.
- the compositions can be provided with molybdenum by molybdenum/sulfur complexes of basic nitrogen compounds as described, for example, in U.S. Pat. Nos.
- organo-molybdenum compounds are trinuclear molybdenum compounds, such as those of the formula Mo3SkLnQz and mixtures thereof, wherein S represents sulfur, L represents independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values.
- S sulfur
- L represents independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil
- n is from 1 to 4
- k varies from 4 through 7
- Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers
- At least 21 total carbon atoms may be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685 .
- the oil-soluble molybdenum compound may be present in an amount sufficient to provide about 0.5 ppm to about 2000 ppm, about 1 ppm to about 700 ppm, about 1 ppm to about 550 ppm, about 5 ppm to about 300 ppm, or about 20 ppm to about 250 ppm of molybdenum.
- the oil-soluble titanium compounds may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions.
- the oil soluble titanium compound may be a titanium (IV) alkoxide.
- the titanium alkoxide may be formed from a monohydric alcohol, a polyol, or mixtures thereof.
- the monohydric alkoxides may have 2 to 16, or 3 to 10 carbon atoms.
- the titanium alkoxide may be titanium (IV) isopropoxide.
- the titanium alkoxide may be titanium (IV) 2-ethylhexoxide.
- the titanium compound may be the alkoxide of a 1,2-diol or polyol.
- the 1,2-diol comprises a fatty acid mono-ester of glycerol, such as oleic acid.
- the oil soluble titanium compound may be a titanium carboxylate.
- the titanium (IV) carboxylate may be titanium neodecanoate.
- the oil soluble titanium compound may be present in the lubricating composition in an amount to provide from zero to about 1500 ppm titanium by weight or about 10 ppm to 500 ppm titanium by weight or about 25 ppm to about 150 ppm.
- the lubricating oil compositions herein also may optionally contain one or more viscosity index improvers.
- Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene/propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, styrene/maleic ester copolymers, hydrogenated styrene/butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof.
- Viscosity index improvers may include star polymers and suitable examples are described in US Publication No. 20120101017A1 .
- the total amount of viscosity index improver and/or dispersant viscosity index improver may be about 0 wt% to about 20 wt%, about 0.1 wt% to about 15 wt%, about 0.1 wt% to about 12 wt%, or about 0.5 wt% to about 10 wt%, of the lubricating composition.
- additives may be selected to perform one or more functions required of a lubricating fluid. Further, one or more of the mentioned additives may be multi-functional and provide functions in addition to or other than the function prescribed herein.
- a lubricating composition according to the present disclosure may optionally comprise other performance additives.
- the other performance additives may be in addition to specified additives of the present disclosure and/or may comprise one or more of metal deactivators, ashless TBN boosters, corrosion inhibitors, rust inhibitors, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swelling agents and mixtures thereof.
- fully-formulated lubricating oil will contain one or more of these performance additives.'
- Suitable metal deactivators may include derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.
- benzotriazoles typically tolyltriazole
- dimercaptothiadiazole derivatives 1,2,4-triazoles
- benzimidazoles 2-alkyldithiobenzimidazoles
- Suitable foam inhibitors include silicon-based compounds, such as siloxane.
- Suitable pour point depressants may include a polymethylmethacrylates or mixtures thereof. Pour point depressants may be present in an amount sufficient to provide from about 0 wt% to about 1 wt%, about 0.01 wt% to about 0.5 wt%, or about 0.02 wt% to about 0.04 wt% based upon the final weight of the lubricating oil composition.
- Suitable rust inhibitors may be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous metal surfaces.
- Nonlimiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids, such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimer and trimer acids, such as those produced from tall oil fatty acids, oleic acid, and linoleic acid.
- oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid
- oil-soluble polycarboxylic acids including dimer and trimer
- Suitable corrosion inhibitors include long-chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000 and alkenylsuccinic acids in which the alkenyl group contains about 10 or more carbon atoms such as, tetrapropenylsuccinic acid, tetradecenylsuccinic acid, and hexadecenylsuccinic acid.
- alkenylsuccinic acids include the half esters of alkenyl succinic acids having about 8 to about 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols. The corresponding half amides of such alkenyl succinic acids are also useful.
- a useful rust inhibitor is a high molecular weight organic acid.
- an engine oil is devoid of a rust inhibitor.
- the rust inhibitor if present, can be used in an amount sufficient to provide about 0 wt% to about 5 wt%, about 0.01 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, based upon the final weight of the lubricating oil composition.
- a suitable crankcase lubricant may include additive components in the ranges listed in the following table.
- Table 2 Component Wt. % (Suitable Embodiments) Wt. % (Suitable Embodiments) Dispersant(s) 0.1 - 10.0 1.0 - 5.0 Antioxidant(s) 0.1 - 5.0 0.01 - 3.0 Detergent(s) 0.1 - 15.0 0.2 - 8.0 Ashless TBN booster(s) 0.0 - 1.0 0.01 - 0.5 Corrosion inhibitor(s) 0.0 - 5.0 0.0 - 2.0 Metal dihydrocarbyldithiophosphate(s) 0.1 - 6.0 0.1 - 4.0 Ash-free phosphorus compound(s) 0.0 - 6.0 0.0 - 4.0 Antifoaming agent(s) 0.0 - 5.0 0.001 - 0.15 Antiwear agent(s) 0.0 - 1.0 0.0 - 0.8 Pour point depressant(s) 0.0 - 5.0 0.01
- the percentages of each component above represent the weight percent of each component, based upon the weight of the final lubricating oil composition.
- the remainder of the lubricating oil composition consists of one or more base oils.
- Additives used in formulating the compositions described herein may be blended into the base oil individually or in various sub-combinations. However, it may be suitable to blend all of the components concurrently using an additive concentrate (i.e., additives plus a diluent, such as a hydrocarbon solvent).
- an additive concentrate i.e., additives plus a diluent, such as a hydrocarbon solvent.
- used-oil data was collected from a field test that used a 2012 Ford Explorer having a 2.0L GDI/Turbo engine.
- the two lubricant compositions described below were each used in three different vehicles. Both lubricant compositions were GF-5 5W-30, whereas one of the compositions additionally contained 2 wt.% of the highly grafted, multi-functional olefin copolymer (DOCP) described herein. The results are shown in the following table. Table 3 Oil Name DOCP Conc., Wt % No. Vehicles Sample Size, n Average ODI, mi Average Soot, % Average Fe, ppmw GF-5 5W-30 0 3 17 9099 1.3 36.3 GF-5 5W-30 + DOCP 2 3 20 9039 1.3 24.8
- the lubricant composition containing 2 wt.% (12 wt.% active) of the highly grafted, multi-functional olefin copolymer (DOCP) exhibited significantly less iron pickup in the lubricant than the base oils devoid of the DOCP additive.
- a comparison of the cam chain stretch for each of the engines is shown in the following table.
- the cam chain was pre-measured before the start of the test and was re-measured after 120,000 miles.
- the difference in length (mm) for the cam chains in each of the vehicles is shown in the following table.
- Table 4 CAM CHAIN STRETCH, mm Vehicle 1 Vehicle 2 Vehicle 3 Average % Decrease from Baseline GF-5 5W-30 1.75 1.30 1.83 1.63 GF-5 5W-30 + DOCP 1.87 1.23 1.40 1.50 -7.75%
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Claims (11)
- Utilisation, dans un moteur à injection directe d'essence (GDI) turbocompressé d'une composition de lubrifiant pour réduire l'usure de chaîne de came, dans laquelle la composition de lubrifiant comprend une quantité majeure d'huile de viscosité lubrifiante, et de 0,25 % en poids à 10 % en poids, sur la base d'un poids total de la composition de lubrifiant, d'au moins un copolymère d'oléfine multifonctionnel hautement greffé préparé en faisant réagir un agent d'acylation avec un copolymère d'oléfine ayant une masse moléculaire moyenne en nombre supérieure à 1000 en présence d'un initiateur de radicaux libres pour fournir un copolymère d'oléfine acylé ayant un degré de greffage (DOG) de l'agent d'acylation sur le copolymère d'oléfine d'au moins 0,5 % en poids, et en faisant réagir le copolymère d'oléfine acylé avec une N-phénylphénylène-diamine pour fournir un copolymère d'oléfine multifonctionnel hautement greffé, dans laquelle le copolymère d'oléfine multifonctionnel hautement greffé est efficace pour réduire l'usure de moteur dans le moteur GDI turbocompressé en dessous de l'usure de moteur fournie par une composition de lubrifiant dépourvue du copolymère d'oléfine multifonctionnel hautement greffé.
- Utilisation selon la revendication 1, dans laquelle le copolymère d'oléfine comprend un copolymère d'éthylène et d'une ou plusieurs alpha-oléfines en C3 à C23.
- Utilisation selon la revendication 1 ou la revendication 2, dans laquelle la composition d'huile de lubrification comprend en outre un ensemble dispersant/inhibiteur.
- Utilisation selon la revendication 3, dans laquelle l'ensemble dispersant/inhibiteur comprend un dispersant, un détergent contenant du métal, un agent antiusure, un antioxydant et un modificateur de frottement.
- Utilisation selon la revendication 4, dans laquelle le détergent est choisi dans le groupe constitué de sulfonate de calcium neutre, sulfonate de calcium surbasique, sulfonate de magnésium neutre, sulfonate de magnésium surbasique, phénate de calcium neutre, phénate de calcium surbasique, salicylate de calcium neutre, salicylate de calcium surbasique, salicylate de magnésium neutre, salicylate de magnésium surbasique, phénate de magnésium neutre, phénate de magnésium surbasique, et des mélanges de ceux-ci.
- Utilisation selon la revendication 4, dans laquelle le dispersant comprend un ou plusieurs dispersants polyalcényl-succinimide.
- Utilisation selon la revendication 4, dans laquelle le modificateur de frottement est choisi dans le groupe constitué de modificateurs de frottement ne contenant pas de métal, modificateurs de frottement organométalliques, et des mélanges de ceux-ci.
- Utilisation selon la revendication 7, dans laquelle le modificateur de frottement organométallique est choisi dans le groupe constitué d'organo-titane soluble dans l'huile, composés d'organo-molybdène solubles dans l'huile, et composés d'organo-tungstène solubles dans l'huile.
- Utilisation selon la revendication 7, dans laquelle le modificateur de frottement ne contenant pas de métal est choisi dans le groupe constitué de mono-oléate de glycérol et de modificateurs de frottement contenant de l'azote.
- Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le copolymère d'oléfine acylé a un degré de greffage (DOG) allant de 1,5 à 2,5 % en poids.
- Utilisation selon l'une quelconque des revendications précédentes, dans laquelle l'usure de chaîne de came est présentée par un étirement de chaîne de came.
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US10323205B2 (en) * | 2016-05-05 | 2019-06-18 | Afton Chemical Corporation | Lubricant compositions for reducing timing chain stretch |
CN106701274B (zh) * | 2016-12-05 | 2019-12-17 | 浙江海洋大学 | 一种冲压油组合物 |
CN110869478A (zh) * | 2017-06-27 | 2020-03-06 | 路博润公司 | 内燃机的润滑组合物和润滑方法 |
US10513668B2 (en) | 2017-10-25 | 2019-12-24 | Afton Chemical Corporation | Dispersant viscosity index improvers to enhance wear protection in engine oils |
US20190127658A1 (en) * | 2017-10-30 | 2019-05-02 | Exxonmobil Research And Engineering Company | Lubricating oil compositions with engine wear protection |
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