EP1481040A1 - Friction modifier for hydrocarbon fuels - Google Patents
Friction modifier for hydrocarbon fuelsInfo
- Publication number
- EP1481040A1 EP1481040A1 EP03702764A EP03702764A EP1481040A1 EP 1481040 A1 EP1481040 A1 EP 1481040A1 EP 03702764 A EP03702764 A EP 03702764A EP 03702764 A EP03702764 A EP 03702764A EP 1481040 A1 EP1481040 A1 EP 1481040A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- friction
- friction modifier
- group
- fuel
- composition
- 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.)
- Withdrawn
Links
- 239000003607 modifier Substances 0.000 title claims abstract description 117
- 239000000446 fuel Substances 0.000 title claims description 73
- 229930195733 hydrocarbon Natural products 0.000 title claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 title description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 67
- 125000005647 linker group Chemical group 0.000 claims abstract description 12
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 126
- 239000002904 solvent Substances 0.000 claims description 38
- 239000002816 fuel additive Substances 0.000 claims description 29
- 238000002485 combustion reaction Methods 0.000 claims description 26
- 239000002199 base oil Substances 0.000 claims description 24
- 229920002367 Polyisobutene Polymers 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 230000001603 reducing effect Effects 0.000 claims description 17
- 239000003599 detergent Substances 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- 229920001451 polypropylene glycol Polymers 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 10
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 229960002317 succinimide Drugs 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000654 additive Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 150000001412 amines Chemical group 0.000 description 12
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- -1 nitro- Chemical class 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000010705 motor oil Substances 0.000 description 4
- 231100000241 scar Toxicity 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000002103 osmometry Methods 0.000 description 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- GHKSKVKCKMGRDU-UHFFFAOYSA-N 2-(3-aminopropylamino)ethanol Chemical compound NCCCNCCO GHKSKVKCKMGRDU-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000722921 Tulipa gesneriana Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CVHXKYDSSDLCSV-UHFFFAOYSA-N n'-(2-octoxyethyl)ethane-1,2-diamine Chemical compound CCCCCCCCOCCNCCN CVHXKYDSSDLCSV-UHFFFAOYSA-N 0.000 description 1
- WSEBQUMQLHKANI-UHFFFAOYSA-N n'-(3-decoxypropyl)-n'-methylpropane-1,3-diamine Chemical compound CCCCCCCCCCOCCCN(C)CCCN WSEBQUMQLHKANI-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid group Chemical group C(CCC(=O)O)(=O)O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
- C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
Definitions
- This invention relates to multi-functional friction modifiers and friction modifying compositions for hydrocarbon fuels, especially gasoline.
- the invention relates to alkenylsuccinimide-based friction modifiers and friction modifying compositions for hydrocarbon fuels and especially gasoline.
- Additive compositions for gasoline have to satisfy a large number of criteria, amongst the most important of which are: i) reduction of engine friction to increase fuel economy; ii) good lubrication to reduce wear; iii) elimination of carburettor and injector fouling; iv) good detergency in the intake port and intake valve regions of the engine; v) elimination of valve stick, a problem often associated with the use of high molecular weight detergents; vi) corrosion protection; vii) good demulsifying characteristics.
- WO-A-98/11175 discloses an additive package comprising an ashless friction modifier, a deposit inhibitor and a carrier fluid.
- current practice in the supply of gasoline is generally to pre-mix the fuel additives into a concentrate in a hydrocarbon solvent base, and then inject the concentrate into gasoline pipelines used to fill tankers prior to delivery to the customers.
- the maximum amount of concentrate that can be incorporated into a tanker of gasoline is typically about 2000ppm based on the weight of the gasoline.
- WO-A-93/20170 discloses a composition comprising succinimide detergents and mono end-capped polypropylene glycol. Each of the specifically disclosed detergents is derived from a polyalkylene polyamine comprising two primary amine groups. The resultant succinimide detergent comprises a terminal amine group.
- the present invention provides a friction modifier of the formula R 1 -L- N(R 2 )(R 3 ) wherein R 1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; L is an optional linker group; R 2 and R 3 are independently selected from H, a hydrocarbyl group and a bond to optional group L, wherein at least one of R 2 and R 3 is H or a hydrocarbyl group, with the proviso that if one of R 2 and R 3 is a hydrocarbyl group and the other of R 2 and R 3 is H, the hydrocarbyl group does not contain a terminal amine.
- the present invention provides a friction modifying composition
- a friction modifying composition comprising a friction modifier as herein defined and a carrier oil comprising an optionally esterified polyether.
- these new friction modifiers and friction modifying compositions are multi-functional and exhibit, in addition to their friction modifying characteristics, good intake valve detergency, good valve stick performance and good packagability.
- the multi-functional nature of the friction modifiers and friction modifying compositions according to the present invention enables them to be used in the substantial absence of any additional friction modifier or detergent. This is advantageous, for example, because of the need to conform to limits on the amount of fuel additive incorporated into fuel.
- the term “friction modifier” it is meant a substance capable of modifying friction.
- the term “friction modifier” it is meant a substance capable of reducing friction.
- the term “friction modifier” refers to a substance which is capable of reducing friction, when dosed into a fuel which is subsequently combusted in a combustion engine.
- the term "friction modifier” refers to a substance which, at a treat rate of 120mg/l in unleaded gasoline generates a Wear Scar Diameter in the High Frequency Reciprocating Rig test at 20°C of less than 500 microns, preferably less than 450 microns, more preferably less than 400 microns.
- hydrocarbyl group it is meant a group comprising at least C and H and may optionally comprise one or more other suitable substituents.
- substituents may include alkoxy-, nitro-, a hydrocarbon group, an N- acyl group, a cyclic group etc.
- a combination of substituents may form a cyclic group.
- the hydrocarbyl group comprises more than one C then those carbons need not necessarily be linked to each other. For example, at least two of the carbons may be linked via a suitable element or group.
- the hydrocarbyl group may contain hetero atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for instance, nitrogen and oxygen.
- R 1 is a hydrocarbon group.
- hydrocarbon group it is meant a group comprising only C and H.
- the hydrocarbon group may be saturated or unsaturated.
- the hydrocarbon group may be straight chained or branched.
- R 1 is a branched or straight chain alkyl group. More preferably R 1 is a branched alkyl group.
- R 1 is polyisobutene.
- High reactivity polyisobutenes are suitable for use in the invention.
- High reactivity is defined as a polyisobutene wherein at least 50%, preferably 70% or more of the terminal olefinic double bonds are of the vinylidene type.
- polyisobutenyl substituted succinic anhydrides PIBSA
- Suitable processes include thermally reacting polyisobutenes with maleic anhydride (see for example US-A-3,361,673 and US-A-3,018,250), and reacting a halogenated, in particular a chlorinated, polyisobutene (PIB) with maleic anhydride (see for example US-A-3, 172,892).
- PIB chlorinated, polyisobutene
- the polyisobutenyl succinic anhydride can be prepared by mixing the polyolefin with maleic anhydride and passing chlorine through the mixture (see for example GB-A-949,981 ).
- reaction product of these processes will be a complex mixture of unreacted polymer as well as the product polyisobutenyl succinic acid anhydride, the polyisobutenyl substituent being connected to either one or both of the alpha carbon atoms of the succinic acid group.
- R 1 may have a molecular weight selected to provide the required properties of the detergent compound.
- R 1 has a molecular weight of from 800 to 1300.
- R 1 is polyisobutene having a molecular weight of from 800 to 1300. The molecular weights are as determined by vapour phase osmometry or by gel permeation chromatography, on the originating polymer.
- R 1 may have from 10 to 200 carbons or from 10 to 100 carbons.
- the friction modifier of the formula R 1 -L-N(R 2 )(R 3 ) may or may not comprise optional linker L. If L is present it may be any suitable group. Suitable groups include • Ci- ⁇ hydrocarbyl groups optionally including one or more, preferably two, carbonyl groups, • C 1-6 hydrocarbon groups optionally including one or more, preferably two, carbonyl groups,
- e and f are independently an integer of from 0 to 6.
- the friction modifier of the present invention contains a nitrogen moiety N(R 2 )(R 3 ) attached to the hydrocarbyl group R 1 via optional linker L.
- the groups and R 2 and R 3 of the nitrogen moiety are independently H or a hydrocarbyl group.
- R 2 and R 3 may be H and the other of R 2 and R 3 may be hydrocarbyl
- R 2 and R 3 may be hydrocarbyl.
- R 2 and R 3 are independently selected from H, a hydrocarbyl group and a bond to optional group L, wherein at least one of R 2 and R 3 is H or a hydrocarbyl group.
- the nitrogen may contain either a double bond to a single atom of the group L or may be bonded to two different moieties of group L to form a cyclic group.
- optional group L is not present these explanations equally apply to the connection between R 1 and N(R 2 )(R 3 ).
- R 2 and R 3 is a hydrocarbyl group and the other of R 2 and R 3 is H
- the hydrocarbyl group does not contain a terminal amine.
- the hydrocarbyl group is an amine or polyamine the amine or amine units are selected from secondary and tertiary amines.
- Suitable derivatives include esters and ethers.
- the hydrocarbyl group R 2 and/or R 3 does not contain a terminal amine.
- R 2 and/or R 3 is a hydrocarbyl group selected from an amine or polyamine, the amine or amine units are selected from secondary and tertiary amines.
- a preferred hydrocarbyl group for each of R 2 and R 3 is a group of the formula
- a preferred hydrocarbyl group for each of R 2 and R 3 is a group of the formula
- X is -CH 3 , or -OH.
- the friction modifiers of the present invention may be derived from a wide range of precursors.
- Embodiments of the present invention include compounds derived from amines selected from ammonia, butylamine, aminoethylethanolamine, aminopropan-2-ol, 5-aminopentan-1-ol, 2-(2-aminoethoxy)ethanol, monoethanolamine, 3-aminopropan-1-ol, 2-((3-aminopropyl)amino)ethanol, dimethylaminopropylamine, and N-(alkoxyalkyl)- alkanediamines including N-(octyloxyethyl)-1,2-diaminoethane and N-(decyloxypropyl)- N-methyl-1,3-diaminopropane.
- R 2 and R 3 are groups of the formula -(CH 2 ) 3 CH 3 ; • one of R 2 and R 3 is a group of the formula -(CH 2 ) 3 CH 3l and the other of R 2 and R 3 is H;
- R 2 and R 3 are a group of the formula -(CH 2 ) 2 NH(CH 2 ) 2 OH;
- R 2 and R 3 are a group of the formula -(CH 2 ) 2 NH(CH 2 ) 2 OH, and the other of R 2 and R 3 is H; and • the friction modifier is a polyisobutenyl succinimide.
- the friction modifier of formula R 1 -L-N(R 2 )(R 3 ) comprises the optional linker L, and L, when bonded to N(R 2 )(R 3 ), provides a cyclic group of formula:
- R 3 is preferably a hydrocarbyl group.
- R 3 is a hydrocarbyl group of formula:
- R 1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; wherein L' is an optional linker group; wherein R ? is independently selected from H, a hydrocarbyl group and a bond to optional group L'; wherein R 4 is an alkylene group having from 1 to 10 carbons, preferably from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons; wherein R 5 is an alkylene group having from 1 to 10 carbons, preferably from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons; and wherein p is an integer from 0 to 10.
- R 3 is a hydrocarbyl group of formula:
- R 1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; wherein L' is an optional linker group; wherein R 2" is independently selected from H, a hydrocarbyl group and a bond to optional group L'; wherein p is an integer from 0 to 10, preferably 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2; wherein q is an integer from 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2; and wherein r is an integer from 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2.
- R 1 is a hydrocarbon group.
- R 1' is a branched or straight chain alkyl group. More preferably R 1' is a branched alkyl group. In a particulariy preferred embodiment R 1 is polyisobutene.
- R 1' may have a molecular weight selected to provide the required properties of the friction modifier.
- R 1 has a molecular weight of from 800 to 1300.
- R 1 is polyisobutene having a molecular weight of from 800 to 1300. The molecular weights are as determined by vapour phase osmometry or by gel permeation chromatography, on the originating polymer.
- R 1' may have from 10 to 200 carbons or from 10 to 100 carbons.
- L' is present it may be any suitable group. Suitable groups include
- the present invention provides a friction modifying composition
- a friction modifying composition comprising a friction modifier as herein defined and a carrier oil comprising an optionally esterified polyether.
- the carrier oil may have any suitable molecular weight.
- a preferred molecular weight is in the range 500 to 5000.
- the polyether carrier oil is a mono end-capped polypropylene glycol.
- the end cap is a group consisting of or containing a hydrocarbyl group having up to 30 carbon atoms. More preferably the end cap is or comprises an alkyl group having from 4 to 20 carbon atoms or from 12 to 18 carbon atoms.
- the alkyl group may be branched or straight chain. Preferably it is a straight chain group.
- hydrocarbyl end capping groups include alkyl-substituted phenyl, especially where the alkyl substituent(s) is or are alkyl groups of 4 to 20 carbon atoms, preferably 8 to 12, preferably straight chain.
- the hydrocarbyl end capping group may be attached to the polyether via a linker group.
- R ⁇ is straight chain CrC ⁇ alkyl, preferably C 4 -C 20 alkyl, preferably C 12 -C 18 alkyl; and n is an integer of from 10 to 50, preferably 10 to 30, more preferably 12 to 20.
- alkyl polypropyleneglycol monoethers are obtainable by the polymerisation of propylene oxide using an aliphatic alcohol, preferably a straight chain primary alcohol of to 20 carbon atoms, as an initiator. If desired a proportion of the propyleneoxy units may be replaced by units derived from other C ⁇ -Ce alkylene oxides, e.g. ethylene oxide or isobutylene oxide, and are to be included within the term "polypropyleneglycol".
- the initiator may also be a phenol or alkyl phenol of the formula R 7 OH, a hydrocarbyl amine or amide of the formula R 7 NH 2 or R 7 CONH, respectively, where R 7 is C Cr ⁇ hydrocarbyl group, preferably a saturated aliphatic or aromatic hydrocarbyl group such as alkyl, phenyl or phenalkyl etc.
- R 7 is C Cr ⁇ hydrocarbyl group, preferably a saturated aliphatic or aromatic hydrocarbyl group such as alkyl, phenyl or phenalkyl etc.
- Preferred initiators include long chain alkanols giving rise to the long chain polypropyleneglycol monoalkyl ethers.
- polypropyleneglycol may be an ester (R 6 COO) group where R ⁇ is defined above.
- the carrier oil may be a polypropyleneglycol monoester of the formula
- R ⁇ and n are as defined above and R8 is a C ⁇ Oso hydrocarbyl group, preferably an aliphatic hydrocarbyl group, and more preferably C do alkyl.
- the friction modifier may be present in the friction modifying composition in an amount to provide the necessary and/or required handling and/or functional properties.
- the friction modifier including solvent of production
- the friction modifier is present in an amount of from 10 to 60% by weight, preferably 30 to 60% by weight, based on the total composition.
- the friction modifier (excluding solvent of production) is present in an amount of from 6 to 36% by weight, preferably 18 to 36% by weight, based on the total composition.
- the carrier oil may be present in an amount of from 10 to 40% by weight, based on the total composition.
- the weight ratio of active friction modifier to carrier oil in the friction modifying composition may be from 0.2:1 to 5:1.
- the weight ratio of active friction modifier to carrier oil in the friction modifying composition will be in the range 0.2:1 to 5:1, or 0.6:1 to 5:1, typically about 5:1, 2:1, 1:1, 0.9:1, 0.8:1, or 0.6:1.
- the weight ratio of active friction modifier to carrier oil in the friction modifying composition will be in the range 1:0.2 to 1:1.8, or 1:0.3 to 1:1.7, or 1:0.4 to 1:1.6, or 1:0.5 to 1:1.5, or 1:0.6 to 1:1.4, or 1:0.7 to 1:1.3, or 1:0.8 to 1:1.2 or 1:0.9 to 1:1.1, typically approximately 1:0.2, 1:0.5, 1:0.7, 1:1, 1:1.1, 1:1.2 or 1:1.6, such as 1:1.
- the friction modifying composition of the present invention further comprises a solvent.
- the solvent may be a hydrocarbon solvent having a boiling point in the range 66 to 320°C.
- Suitable solvents include xylene, toluene, white spirit, mixtures of aromatic solvents boiling in the range 180°C to 270°C (including aromatic solvent mixtures sold under the trade marks Shellsol AB, Shellsol R, Solvesso 150, Aromatic 150), and environmentally friendly solvents such as the low aromatic content solvents of the FINALAN range.
- the amount of solvent to be incorporated will depend upon the desired final viscosity of the friction modifying composition. Typically the solvent will be present in an amount of from 20 to 70% of the final composition on a weight basis.
- the friction modifying composition of the present invention comprises a solvent and a co-solvent.
- the co-solvent may be typically present in an amount of 1-2 wt.%. Suitable co-solvents include aliphatic alcohols (such as CAS no 66455-17-2)
- the friction modifying compositions of the present invention may contain a number of minor ingredients, often added to meet specific customer requirements. Included amongst these are dehazers, usually an alkoxylated phenol formaldehyde resin, added to minimise water adso ⁇ tion and to prevent a hazy or cloudy appearance, and a corrosion inhibitor, usually of the type comprising a blend of one or more fatty acids and amines. Either or both may be present in the compositions of the present invention in amounts ranging from 1 to 5%, or 1 to 3% each, based on the total weight of the composition.
- dehazers usually an alkoxylated phenol formaldehyde resin, added to minimise water adso ⁇ tion and to prevent a hazy or cloudy appearance
- a corrosion inhibitor usually of the type comprising a blend of one or more fatty acids and amines. Either or both may be present in the compositions of the present invention in amounts ranging from 1 to 5%, or 1 to 3% each, based on the total weight of the composition.
- anti-oxidants include anti-oxidants, anti-icing agents, metal deactivators, dehazers, corrosion inhibitors, dyes, lubricity additives, additional friction modifiers, and the like. These may be added in amounts ranging from a few parts per million, up to 2 or 3% by weight, according to conventional practice.
- no lubricity additives or friction modifiers other than the friction modifier as herein defined are added to the friction modifying composition.
- the total amount of such minor functional ingredients in the friction modifying composition will not exceed about 10% by weight, more usually not exceeding about 5% by weight.
- the present invention provides a fuel additive composition
- a fuel additive composition comprising a friction modifier as herein defined and a carrier, diluent or solvent, wherein the fuel additive composition is substantially free of any detergent and/or friction modifier other than the friction modifier as herein defined.
- fuel additive composition refers to a composition which will undergo no modification before it is dosed into a fuel. In particular the term refers to a composition to which no further components are added before it is dosed into a fuel.
- substantially free of a given substance means that the substance is present in the fuel additive composition in an amount of less than 1% by weight of the composition, preferably less than 0.5%, preferably less than 0.1%, preferably less than 0.05%.
- the fuel additive composition is substantially free of any detergent other than the friction modifier as herein defined.
- the fuel additive composition is substantially free of any friction modifier other than the friction modifier as herein defined.
- the fuel additive composition is substantially free of any detergent and any friction modifier other than the friction modifier as herein defined.
- the carrier, diluent or solvent is a carrier oil comprising an optionally esterified polyether.
- the carrier, diluent or solvent is a polyether carrier oil as herein defined.
- the carrier, diluent or solvent of the fuel additive composition is a polypropyleneglycol monoether of the formula:
- R e is straight chain C12-C 18 alkyl; and n is an integer of from 10 to 30.
- the friction modifier of the present invention may be inco ⁇ orated in fuel to provide a fuel composition.
- the present invention provides a fuel composition comprising a fuel and a friction modifier as herein defined.
- the friction modifying composition of the present invention may be incorporated in fuel to provide a fuel composition.
- the present invention provides a fuel composition comprising a fuel and a friction modifying composition as herein defined.
- the fuel additive composition of the present invention may be incorporated in fuel to provide a fuel composition.
- the present invention provides a fuel composition comprising a fuel and a fuel additive composition as herein defined.
- the friction modifier is present in the fuel in an amount to provide on a weight basis, from 50 to 500 ppm.
- the friction modifying composition is present in the fuel in an amount to provide on a weight basis, from 50 to 500 ppm friction modifier and 30 to 500 ppm carrier oil.
- the fuel composition is substantially free of any detergent other than the friction modifier as herein defined.
- the fuel composition is substantially free of any friction modifier other than the friction modifier as herein defined.
- the fuel composition is substantially free of any detergent other than the friction modifier as herein defined and substantially free of any friction modifier other than the friction modifier as herein defined.
- substantially free of a given substance means that the substance is present in the fuel composition in an amount of less than 10 ppm, preferably less than 5 ppm, preferably less than 1 ppm.
- the fuel is a gasoline.
- gasoline it is meant a liquid fuel for use with spark ignition engines
- the term includes blends of distillate hydrocarbon fuels with oxygenated components such as ethanol, as well as the distillate fuels themselves.
- the fuels may contain, in addition to the additive composition of the invention, any of the other additives conventionally added to gasoline as, for example, antiknock additives, anti-icing additives, octane requirement additives, lubricity additives etc.”
- the present invention provides an oil composition comprising an engine oil and a friction modifier or friction modifying composition as herein defined.
- the present invention provides an oil composition
- an oil composition comprising (i) an oil, preferably an engine oil and (ii) a friction modifier of the formula R 1 -L-N(R 2 )(R 3 ) wherein R 1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; L is an optional linker group; R 2 and R 3 are independently selected from H, a hydrocarbyl group and a bond to optional group L, wherein at least one of R 2 and R 3 is H or a hydrocarbyl group, with the proviso that if one of R 2 and R 3 is a hydrocarbyl group and the other of R 2 and R 3 is H, the hydrocarbyl group does not contain a terminal amine.
- the present invention provides a process for the reduction of friction in a combustion engine comprising the steps of (i) dosing a fuel with a friction modifier as herein defined, or a friction modifying composition as herein defined, or a fuel additive composition as herein defined, to provide a fuel composition; (ii) combusting the fuel composition in a combustion engine.
- the present invention provides use of a friction modifier as herein defined for reducing friction and/or improving detergency in a combustion engine. In one preferred aspect the present invention provides use of a friction modifier as herein defined for reducing friction in a combustion engine. In one highly preferred aspect the present invention provides use of a friction modifier as herein defined for reducing friction and improving detergency in a combustion engine.
- the present invention provides use of a friction modifying composition as herein defined for reducing friction and/or improving detergency in a combustion engine. In one preferred aspect the present invention provides use of a friction modifying composition as herein defined for reducing friction in a combustion engine. In one highly preferred aspect the present invention provides use of a friction modifying composition as herein defined for reducing friction and improving detergency in a combustion engine.
- the present invention provides use of a fuel additive composition as herein defined for reducing friction and/or improving detergency in a combustion engine. In one preferred aspect the present invention provides use of a fuel additive composition as herein defined for reducing friction in a combustion engine. In one highly preferred aspect the present invention provides use of a fuel additive composition as herein defined for reducing friction and improving detergency in a combustion engine.
- the procedure was as follows. A steel ball was attached to an oscillating arm assembly and mated to a steel disk specimen in the HFRR sample cell.
- the fuel reservoir contained 6ml of the fuel composition being tested.
- a load of 200 grams was applied to the ball/disk interface by dead weights.
- the ball assembly was oscillated over a 1000 ⁇ path at a rate of 50 Hertz. After a prescribed period of time, the steel ball assembly was removed. Wear, and hence the lubricity of the fuel composition, was assessed by measuring the wear scar diameter on the ball resulting from oscillating contact with the disk. The lower the value of the wear scar diameter the better the performance of the additive in the fuel composition. A wear scar diameter of below 500 ⁇ is particularly desirable. The results are set out in the tables below.
- friction modifiers such as polyisobutenyl succinimide (PIBSI) and carrier fluids are incompatible without the addition of a suitable solvent. Many packages require additional solvent above the amount already present due to the manufacture of the friction modifier.
- PIBSI polyisobutenyl succinimide
- Carrier A is a C 13- ⁇ 5 initiated polyether having 12 propylene oxide units attached
- Carrier B is a C ⁇ s initiated polyether having 14 propylene oxide units attached
- Carrier C is a C 13-15 initiated polyether having 17 propylene oxide units attached
- Carrier D is a nonylphenol initiated polyether having 17 propylene oxide units attached
- the intake valve detergency properties exhibited by the friction modifier and carrier oil combinations listed below were measured using industry standard CEC-F-05-A93 test procedure on a bench engine.
- the test engine was a Mercedes-Benz M 102.982 four cylinder, four stroke 2.3 litre gasoline-injection engine with a standard KE-Jettonic injection system.
- the test carried out involved a cyclic procedure, each cycle including the following four operating states:
- each test was exactly 60 h with the cycle repeated 800 times.
- the engine was fitted with new inlet valves which were weighed before fitting.
- residues were cleaned carefully from the valve surface facing the combustion space.
- the valves were then immersed in n-heptane for 10 seconds and swung dry. After drying for 10 minutes, the valves were weighed and the increase in valve weight caused by deposits was measured in mg.
- the sticky or non-sticky appearance of the deposits formed on the valve tulip and valve stem was also evaluated. The tendency to form deposits of sticky appearance could indicate, ultimately, a tendency to the appearance of the valve stick phenomenon which is desirable to avoid.
- the fuel employed in the test procedure was an unleaded gasoline meeting EN228 specification.
- the test compositions were added to the fuel so as to obtain a concentration of active substance (friction modifier and carrier oil) in the fuel in the amounts indicated.
- Test running was carried out on a single roll distance accumulation dynamometer manufactured by Labeco.
- the test engine is a regular Volkswagen Transporter 1.9-liter, 44 kW water-cooled-boxer Otto engine type 2 series with hydraulic valve filter. It is a flat four cylinder engine mounted at the rear, with a three-speed automatic transmission.
- the valve guides and valve stems are measured before each test.
- the fuel used in these tests is an unleaded gasoline meeting EN228 specification.
- an engine compression test is carried out to highlight any valve which is not functioning correctly. If compression at one or more of the cylinders is less than 8 bar then the inlet valve is deemed to have been sticking in the valve guide. For the final result, with a pass at -18°C, the same cycle is used except the soak temperature is -18°C rather than 5°C.
- test compositions are added to the fuel so as to obtain a concentration of active substance in the fuel containing additives which is specified for each example in the Table below, which gives the results obtained.
- the intake valve detergency properties exhibited by the friction modifier and carrier oil combinations listed have been measured using the CEC F-20-A-98 test procedure on a bench engine.
- the test engine is a Mercedes Benz M111 four cylinder, four-stroke 2.0 litre gasoline-injection engine with four valves per cylinder and an electronically controlled ignition and fuel injection system.
- the test carried out involves a cyclic procedure, each cycle including the following four operating states:
- each test is 60 hours.
- the engine is fitted with new inlet valves, which are weighed before fitting.
- residues are cleaned carefully from the valve surface facing the combustion space.
- the valves are then immersed in n-heptane for 10 seconds and air dried for at least 10 minutes and a maximum of 2 hours.
- Each valve is then weighed on a precision scale to an accuracy of at least one milligram, to determine the total weight of the valve and all its deposits.
- the inlet valve deposit weight is determined by subtracting the weight of the clean intake valve that was determined before commencement of test and expressed in mg/valve.
- the fuel employed was an unleaded gasoline meeting EN228 specification.
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Abstract
There is provided a friction modifier of the formula R1-L-N(R2)(R3) wherein R1 is a hydrocarbyl group that has a number average molecular weight (Mn) of from 500 to 5000; L is an optional linker group; and R2 and R3 are independently selected from H, a hydrocarbyl group and a bond to optional group L, wherein at least one of R2 and R3 is H or a hydrocarbyl group, with the proviso that if one of R2 and R3 is a hydrocarbyl group and the other of R2 and R3 is H, the hydrocarbyl group does not contain a terminal amine.
Description
FRICTION MODIFIER FOR HYDROCARBON FUELS
This invention relates to multi-functional friction modifiers and friction modifying compositions for hydrocarbon fuels, especially gasoline. In particular, the invention relates to alkenylsuccinimide-based friction modifiers and friction modifying compositions for hydrocarbon fuels and especially gasoline.
It has been of major concern in this field to find methods of reducing engine friction and fuel consumption in internal combustion engines. It is believed that by reducing engine friction, increased power and fuel economy may be obtained. One method of reducing engine friction is to use fuel which has been dosed with an additive having friction reducing properties.
Additive compositions for gasoline have to satisfy a large number of criteria, amongst the most important of which are: i) reduction of engine friction to increase fuel economy; ii) good lubrication to reduce wear; iii) elimination of carburettor and injector fouling; iv) good detergency in the intake port and intake valve regions of the engine; v) elimination of valve stick, a problem often associated with the use of high molecular weight detergents; vi) corrosion protection; vii) good demulsifying characteristics.
In order to meet these criteria, it has been necessary until now to provide additive packages comprising a separate friction modifier and detergent/deposit inhibiting compound. For example, WO-A-98/11175 discloses an additive package comprising an ashless friction modifier, a deposit inhibitor and a carrier fluid. As discussed in WO-A- 98/11175, current practice in the supply of gasoline is generally to pre-mix the fuel additives into a concentrate in a hydrocarbon solvent base, and then inject the concentrate into gasoline pipelines used to fill tankers prior to delivery to the customers. Under present operating conditions, the maximum amount of concentrate that can be incorporated into a tanker of gasoline is typically about 2000ppm based on the weight of the gasoline. It would appear that in order to avoid exceeding this maximum amount of additive, the provision of multi-functional fuel additives would be advantageous.
WO-A-93/20170 discloses a composition comprising succinimide detergents and mono end-capped polypropylene glycol. Each of the specifically disclosed detergents is derived from a polyalkylene polyamine comprising two primary amine groups. The resultant succinimide detergent comprises a terminal amine group.
Some aspects of the present invention are defined in the appended claims.
In a first aspect the present invention provides a friction modifier of the formula R1-L- N(R2)(R3) wherein R1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; L is an optional linker group; R2 and R3 are independently selected from H, a hydrocarbyl group and a bond to optional group L, wherein at least one of R2 and R3 is H or a hydrocarbyl group, with the proviso that if one of R2 and R3 is a hydrocarbyl group and the other of R2 and R3 is H, the hydrocarbyl group does not contain a terminal amine.
In a second aspect the present invention provides a friction modifying composition comprising a friction modifier as herein defined and a carrier oil comprising an optionally esterified polyether.
It has surprisingly been found that these new friction modifiers and friction modifying compositions are multi-functional and exhibit, in addition to their friction modifying characteristics, good intake valve detergency, good valve stick performance and good packagability. The multi-functional nature of the friction modifiers and friction modifying compositions according to the present invention enables them to be used in the substantial absence of any additional friction modifier or detergent. This is advantageous, for example, because of the need to conform to limits on the amount of fuel additive incorporated into fuel.
Use of these new friction modifiers and friction modifying compositions in fuel in a combustion engine, may result in a considerable reduction in friction and wear, in particular a reduction in wear in the fuel pump and around the piston walls of the combustion engine. The reduction in friction should result in improved fuel economy. Wear of components of a combustion engine limits the useful life of these components and may be costly given that the engine components are expensive to produce. Additionally, wear of components of a combustion engine may result in down time for equipment, reduced safety and a decrease
in reliability. Use of the friction modifiers or friction modifying compositions according to the present invention may reduce wear increasing the lifetime of the combustion engine components and thus avoiding the problems associated with wear. These friction modifiers and friction modifying compositions may also be of benefit in gasoline direct injection engines (GDI).
In the present application by the term "friction modifier" it is meant a substance capable of modifying friction. In particular, by the term "friction modifier" it is meant a substance capable of reducing friction. In particular, the term "friction modifier" refers to a substance which is capable of reducing friction, when dosed into a fuel which is subsequently combusted in a combustion engine.
In one aspect, the term "friction modifier" refers to a substance which, at a treat rate of 120mg/l in unleaded gasoline generates a Wear Scar Diameter in the High Frequency Reciprocating Rig test at 20°C of less than 500 microns, preferably less than 450 microns, more preferably less than 400 microns.
In the present specification by the term "hydrocarbyl group" it is meant a group comprising at least C and H and may optionally comprise one or more other suitable substituents. Examples of such substituents may include alkoxy-, nitro-, a hydrocarbon group, an N- acyl group, a cyclic group etc. In addition to the possibility of the substituents being a cyclic group, a combination of substituents may form a cyclic group. If the hydrocarbyl group comprises more than one C then those carbons need not necessarily be linked to each other. For example, at least two of the carbons may be linked via a suitable element or group. Thus, the hydrocarbyl group may contain hetero atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for instance, nitrogen and oxygen.
FRICTION MODIFIER - R1
Preferably R1 is a hydrocarbon group. By the term "hydrocarbon group" it is meant a group comprising only C and H. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group may be straight chained or branched.
Preferably R1 is a branched or straight chain alkyl group. More preferably R1 is a
branched alkyl group.
In a particularly preferred embodiment R1 is polyisobutene.
Conventional and so called high reactivity polyisobutenes are suitable for use in the invention. High reactivity is defined as a polyisobutene wherein at least 50%, preferably 70% or more of the terminal olefinic double bonds are of the vinylidene type.
The preparation of polyisobutenyl substituted succinic anhydrides (PIBSA) is documented in the art. Suitable processes include thermally reacting polyisobutenes with maleic anhydride (see for example US-A-3,361,673 and US-A-3,018,250), and reacting a halogenated, in particular a chlorinated, polyisobutene (PIB) with maleic anhydride (see for example US-A-3, 172,892). Alternatively, the polyisobutenyl succinic anhydride can be prepared by mixing the polyolefin with maleic anhydride and passing chlorine through the mixture (see for example GB-A-949,981 ).
The reaction product of these processes will be a complex mixture of unreacted polymer as well as the product polyisobutenyl succinic acid anhydride, the polyisobutenyl substituent being connected to either one or both of the alpha carbon atoms of the succinic acid group.
R1 may have a molecular weight selected to provide the required properties of the detergent compound. In a preferred aspect R1 has a molecular weight of from 800 to 1300. In a particularly preferred aspect R1 is polyisobutene having a molecular weight of from 800 to 1300. The molecular weights are as determined by vapour phase osmometry or by gel permeation chromatography, on the originating polymer.
In one aspect R1 may have from 10 to 200 carbons or from 10 to 100 carbons.
FRICTION MODIFIER - LINKER
The friction modifier of the formula R1-L-N(R2)(R3) may or may not comprise optional linker L. If L is present it may be any suitable group. Suitable groups include • Ci-β hydrocarbyl groups optionally including one or more, preferably two, carbonyl groups,
• C1-6 hydrocarbon groups optionally including one or more, preferably two, carbonyl groups,
• C^diacyl groups which when bonded to N(R2)(R3) provides a cyclic group of formula:
wherein e and f are independently an integer of from 0 to 6.
• diacyl groups derived from succinic anhydride which when bonded to N(R2)(R3) provides a cyclic group of formula:
wherein e is 0 and f is 1.
FRICTION MODIFIER - N(R )(R3)
The friction modifier of the present invention contains a nitrogen moiety N(R2)(R3) attached to the hydrocarbyl group R1 via optional linker L. The groups and R2 and R3 of the nitrogen moiety are independently H or a hydrocarbyl group. Thus
• both R2 and R3 may be H
• one of R2 and R3 may be H and the other of R2 and R3 may be hydrocarbyl
• both of R2 and R3 may be hydrocarbyl.
R2 and R3 are independently selected from H, a hydrocarbyl group and a bond to optional group L, wherein at least one of R2 and R3 is H or a hydrocarbyl group. When one of R2 and R3 is a bond to optional group L, the nitrogen may contain either a double bond to a single atom of the group L or may be bonded to two different moieties of group L to form a cyclic group. Clearly if optional group L is not present these explanations equally apply to the connection between R1 and N(R2)(R3).
It is requirement that when one of R2 and R3 is a hydrocarbyl group and the other of R2
and R3 is H, the hydrocarbyl group does not contain a terminal amine. In other words when one of R2 and R3 is a hydrocarbyl group and the other of R2 and R3 is H, if the hydrocarbyl group is an amine or polyamine the amine or amine units are selected from secondary and tertiary amines.
Suitable terminal groups include -CH3, =CH2, -OH, -C(O)OH and derivatives thereof. Suitable derivatives include esters and ethers.
Preferably the hydrocarbyl group R2 and/or R3 does not contain a terminal amine. In other words if R2 and/or R3 is a hydrocarbyl group selected from an amine or polyamine, the amine or amine units are selected from secondary and tertiary amines.
A preferred hydrocarbyl group for each of R2 and R3 is a group of the formula
-[R4NH]PR5X wherein R4 is an alkylene group having from 1 to 10 carbons, preferably from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons; wherein R5 is an alkylene group having from 1 to 10 carbons, preferably from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons; wherein p is an integer from 0 to 10; wherein X is selected from -CH3, -CH2=CH2, -OH, and -C(O)OH.
A preferred hydrocarbyl group for each of R2 and R3 is a group of the formula
-[(CH2)qNH]p(CH2)rX wherein p is an integer from 0 to 10, preferably 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2; wherein q is an integer from 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2; wherein r is an integer from 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2; and wherein X is selected from -CH3, -CH =CH2, -OH, and -C(O)OH.
Preferably X is -CH3, or -OH.
The friction modifiers of the present invention may be derived from a wide range of precursors. Embodiments of the present invention include compounds derived from
amines selected from ammonia, butylamine, aminoethylethanolamine, aminopropan-2-ol, 5-aminopentan-1-ol, 2-(2-aminoethoxy)ethanol, monoethanolamine, 3-aminopropan-1-ol, 2-((3-aminopropyl)amino)ethanol, dimethylaminopropylamine, and N-(alkoxyalkyl)- alkanediamines including N-(octyloxyethyl)-1,2-diaminoethane and N-(decyloxypropyl)- N-methyl-1,3-diaminopropane.
The features described above may provide particularly preferred compounds in accordance with the present invention. These include compounds wherein
• at least one of R2 and R3 is a group of the formula -(CH2)3CH3; • one of R2 and R3 is a group of the formula -(CH2)3CH3l and the other of R2 and R3 is H;
• at least one of R2 and R3 is a group of the formula -(CH2)2NH(CH2)2OH;
• one of R2 and R3 is a group of the formula -(CH2)2NH(CH2)2OH, and the other of R2 and R3 is H; and • the friction modifier is a polyisobutenyl succinimide.
In one preferred aspect the friction modifier of formula R1-L-N(R2)(R3) comprises the optional linker L, and L, when bonded to N(R2)(R3), provides a cyclic group of formula:
wherein e and f are independently and integer from 0 to 6. In this aspect, R3 is preferably a hydrocarbyl group.
In one aspect R3 is a hydrocarbyl group of formula:
-[R4NH]pR5-N(R2')-L,-Rr wherein R1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; wherein L' is an optional linker group; wherein R? is independently selected from H, a hydrocarbyl group and a bond to optional group L'; wherein R4 is an alkylene group having from 1 to 10 carbons, preferably from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons;
wherein R5 is an alkylene group having from 1 to 10 carbons, preferably from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons; and wherein p is an integer from 0 to 10.
In a preferred aspect R3 is a hydrocarbyl group of formula:
-[(CH2)qNH]p(CH2)r-N(R2')-L,-R1' wherein R1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; wherein L' is an optional linker group; wherein R2" is independently selected from H, a hydrocarbyl group and a bond to optional group L'; wherein p is an integer from 0 to 10, preferably 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2; wherein q is an integer from 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2; and wherein r is an integer from 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2.
Preferably R1 is a hydrocarbon group. Preferably R1' is a branched or straight chain alkyl group. More preferably R1' is a branched alkyl group. In a particulariy preferred embodiment R1 is polyisobutene.
R1' may have a molecular weight selected to provide the required properties of the friction modifier. In a preferred aspect R1 has a molecular weight of from 800 to 1300. In a particularly preferred aspect R1 is polyisobutene having a molecular weight of from 800 to 1300. The molecular weights are as determined by vapour phase osmometry or by gel permeation chromatography, on the originating polymer.
In one aspect R1' may have from 10 to 200 carbons or from 10 to 100 carbons.
If L' is present it may be any suitable group. Suitable groups include
• C1-6 hydrocarbyl groups optionally including one or more, preferably two, carbonyl groups,
• C1-6 hydrocarbon groups optionally including one or more, preferably two, carbonyl groups,
• C3.12 diacyl groups which, when R2' is a bond to group L', provide a cyclic group of formula:
wherein e' and f are independently an integer of from 0 to 6. • diacyl groups derived from succinic anhydride which, when R2" is a bond to group L', provide a cyclic group of formula:
wherein e' is 0 and f is 1.
FRICTION MODIFYING COMPOSITION - CARRIER OIL
As previously mentioned, in one aspect the present invention provides a friction modifying composition comprising a friction modifier as herein defined and a carrier oil comprising an optionally esterified polyether.
The carrier oil may have any suitable molecular weight. A preferred molecular weight is in the range 500 to 5000.
In a preferred aspect the polyether carrier oil is a mono end-capped polypropylene glycol. Preferably the end cap is a group consisting of or containing a hydrocarbyl group having up to 30 carbon atoms. More preferably the end cap is or comprises an alkyl group having from 4 to 20 carbon atoms or from 12 to 18 carbon atoms.
The alkyl group may be branched or straight chain. Preferably it is a straight chain group.
Further hydrocarbyl end capping groups include alkyl-substituted phenyl, especially
where the alkyl substituent(s) is or are alkyl groups of 4 to 20 carbon atoms, preferably 8 to 12, preferably straight chain.
The hydrocarbyl end capping group may be attached to the polyether via a linker group. Suitable end cap linker groups include an ether oxygen atom (-O-), an amine group (- NH-), an amide group (-CONH-), or a carbonyl group -(C=O)-.
In a preferred embodiment the carrier oil is a polypropyleneglycol monoether of the formula:
where R ϊβ is straight chain CrC^ alkyl, preferably C4-C20 alkyl, preferably C12-C18 alkyl; and n is an integer of from 10 to 50, preferably 10 to 30, more preferably 12 to 20.
Such alkyl polypropyleneglycol monoethers are obtainable by the polymerisation of propylene oxide using an aliphatic alcohol, preferably a straight chain primary alcohol of to 20 carbon atoms, as an initiator. If desired a proportion of the propyleneoxy units may be replaced by units derived from other C^-Ce alkylene oxides, e.g. ethylene oxide or isobutylene oxide, and are to be included within the term "polypropyleneglycol". The initiator may also be a phenol or alkyl phenol of the formula R7OH, a hydrocarbyl amine or amide of the formula R7NH2 or R7CONH, respectively, where R7 is C Crø hydrocarbyl group, preferably a saturated aliphatic or aromatic hydrocarbyl group such as alkyl, phenyl or phenalkyl etc. Preferred initiators include long chain alkanols giving rise to the long chain polypropyleneglycol monoalkyl ethers.
In a further aspect the polypropyleneglycol may be an ester (R6COO) group where Rβ is defined above. In this aspect the carrier oil may be a polypropyleneglycol monoester of the formula
where Rβ and n are as defined above and R8 is a C^Oso hydrocarbyl group, preferably an aliphatic hydrocarbyl group, and more preferably C do alkyl.
FRICTION MODIFYING COMPOSITION - COMPOSITION
The friction modifier may be present in the friction modifying composition in an amount to provide the necessary and/or required handling and/or functional properties. Typically the friction modifier (including solvent of production) is present in an amount of from 10 to 60% by weight, preferably 30 to 60% by weight, based on the total composition. Typically the friction modifier (excluding solvent of production) is present in an amount of from 6 to 36% by weight, preferably 18 to 36% by weight, based on the total composition.
The carrier oil may be present in an amount of from 10 to 40% by weight, based on the total composition.
The weight ratio of active friction modifier to carrier oil in the friction modifying composition may be from 0.2:1 to 5:1.
Preferably the weight ratio of active friction modifier to carrier oil in the friction modifying composition will be in the range 0.2:1 to 5:1, or 0.6:1 to 5:1, typically about 5:1, 2:1, 1:1, 0.9:1, 0.8:1, or 0.6:1.
Preferably the weight ratio of active friction modifier to carrier oil in the friction modifying composition will be in the range 1:0.2 to 1:1.8, or 1:0.3 to 1:1.7, or 1:0.4 to 1:1.6, or 1:0.5 to 1:1.5, or 1:0.6 to 1:1.4, or 1:0.7 to 1:1.3, or 1:0.8 to 1:1.2 or 1:0.9 to 1:1.1, typically approximately 1:0.2, 1:0.5, 1:0.7, 1:1, 1:1.1, 1:1.2 or 1:1.6, such as 1:1.
In a preferred aspect the friction modifying composition of the present invention further comprises a solvent. The solvent may be a hydrocarbon solvent having a boiling point in the range 66 to 320°C. Suitable solvents include xylene, toluene, white spirit, mixtures of aromatic solvents boiling in the range 180°C to 270°C (including aromatic solvent mixtures sold under the trade marks Shellsol AB, Shellsol R, Solvesso 150, Aromatic 150), and environmentally friendly solvents such as the low aromatic content solvents of the FINALAN range.
If present the amount of solvent to be incorporated will depend upon the desired final viscosity of the friction modifying composition. Typically the solvent will be present in an amount of from 20 to 70% of the final composition on a weight basis.
In a preferred aspect the friction modifying composition of the present invention comprises a solvent and a co-solvent. The co-solvent may be typically present in an amount of 1-2 wt.%. Suitable co-solvents include aliphatic alcohols (such as CAS no 66455-17-2)
The friction modifying compositions of the present invention may contain a number of minor ingredients, often added to meet specific customer requirements. Included amongst these are dehazers, usually an alkoxylated phenol formaldehyde resin, added to minimise water adsoφtion and to prevent a hazy or cloudy appearance, and a corrosion inhibitor, usually of the type comprising a blend of one or more fatty acids and amines. Either or both may be present in the compositions of the present invention in amounts ranging from 1 to 5%, or 1 to 3% each, based on the total weight of the composition.
Other minor ingredients which may be added include anti-oxidants, anti-icing agents, metal deactivators, dehazers, corrosion inhibitors, dyes, lubricity additives, additional friction modifiers, and the like. These may be added in amounts ranging from a few parts per million, up to 2 or 3% by weight, according to conventional practice.
In one preferred aspect, no lubricity additives or friction modifiers other than the friction modifier as herein defined are added to the friction modifying composition.
In general terms the total amount of such minor functional ingredients in the friction modifying composition will not exceed about 10% by weight, more usually not exceeding about 5% by weight.
FUEL ADDITIVE COMPOSITION
In one aspect the present invention provides a fuel additive composition comprising a friction modifier as herein defined and a carrier, diluent or solvent, wherein the fuel additive composition is substantially free of any detergent and/or friction modifier other than the friction modifier as herein defined.
The term "fuel additive composition" as used herein refers to a composition which will undergo no modification before it is dosed into a fuel. In particular the term refers to a composition to which no further components are added before it is dosed into a fuel.
The term "substantially free" of a given substance, as used herein in relation to a fuel additive composition, means that the substance is present in the fuel additive composition in an amount of less than 1% by weight of the composition, preferably less than 0.5%, preferably less than 0.1%, preferably less than 0.05%.
Preferably the fuel additive composition is substantially free of any detergent other than the friction modifier as herein defined.
Preferably the fuel additive composition is substantially free of any friction modifier other than the friction modifier as herein defined.
Preferably the fuel additive composition is substantially free of any detergent and any friction modifier other than the friction modifier as herein defined.
In a preferred aspect, the carrier, diluent or solvent is a carrier oil comprising an optionally esterified polyether.
Preferably the carrier, diluent or solvent is a polyether carrier oil as herein defined.
Preferably the carrier, diluent or solvent of the fuel additive composition is a polypropyleneglycol monoether of the formula:
where Re is straight chain C12-C18 alkyl; and n is an integer of from 10 to 30.
FUEL COMPOSITIONS
The friction modifier of the present invention may be incoφorated in fuel to provide a fuel composition. Thus in a further aspect the present invention provides a fuel composition comprising a fuel and a friction modifier as herein defined.
The friction modifying composition of the present invention may be incorporated in fuel to provide a fuel composition. Thus in a further aspect the present invention provides a fuel composition comprising a fuel and a friction modifying composition as herein defined.
The fuel additive composition of the present invention may be incorporated in fuel to provide a fuel composition. Thus in a further aspect the present invention provides a fuel composition comprising a fuel and a fuel additive composition as herein defined.
Preferably the friction modifier is present in the fuel in an amount to provide on a weight basis, from 50 to 500 ppm.
Preferably the friction modifying composition is present in the fuel in an amount to provide on a weight basis, from 50 to 500 ppm friction modifier and 30 to 500 ppm carrier oil.
Preferably the fuel composition is substantially free of any detergent other than the friction modifier as herein defined.
Preferably the fuel composition is substantially free of any friction modifier other than the friction modifier as herein defined.
Preferably the fuel composition is substantially free of any detergent other than the friction modifier as herein defined and substantially free of any friction modifier other than the friction modifier as herein defined.
The term "substantially free" of a given substance, as used herein in relation to a fuel composition, means that the substance is present in the fuel composition in an amount of less than 10 ppm, preferably less than 5 ppm, preferably less than 1 ppm.
Preferably the fuel is a gasoline.
By the term "gasoline", it is meant a liquid fuel for use with spark ignition engines
(typically or preferably containing primarily or only C4-C12 hydrocarbons) and satisfying international gasoline specifications, such as ASTM D-439 and EN228. The term
includes blends of distillate hydrocarbon fuels with oxygenated components such as ethanol, as well as the distillate fuels themselves. The fuels may contain, in addition to the additive composition of the invention, any of the other additives conventionally added to gasoline as, for example, antiknock additives, anti-icing additives, octane requirement additives, lubricity additives etc."
It is known that prior to combustion certain fuel additives can reach the thin film of lubricant that coats the cylinder wall and can, over time, accumulate in engine oil. It is therefore envisaged that in one aspect the friction modifier or friction modifying composition accumulates in engine oil. In one embodiment, the present invention provides an oil composition comprising an engine oil and a friction modifier or friction modifying composition as herein defined. In one aspect the present invention provides an oil composition comprising (i) an oil, preferably an engine oil and (ii) a friction modifier of the formula R1-L-N(R2)(R3) wherein R1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; L is an optional linker group; R2 and R3 are independently selected from H, a hydrocarbyl group and a bond to optional group L, wherein at least one of R2 and R3 is H or a hydrocarbyl group, with the proviso that if one of R2 and R3 is a hydrocarbyl group and the other of R2 and R3 is H, the hydrocarbyl group does not contain a terminal amine.
PROCESS
In one aspect the present invention provides a process for the reduction of friction in a combustion engine comprising the steps of (i) dosing a fuel with a friction modifier as herein defined, or a friction modifying composition as herein defined, or a fuel additive composition as herein defined, to provide a fuel composition; (ii) combusting the fuel composition in a combustion engine.
USE
In one aspect the present invention provides use of a friction modifier as herein defined for reducing friction and/or improving detergency in a combustion engine. In one preferred aspect the present invention provides use of a friction modifier as herein defined for reducing friction in a combustion engine. In one highly preferred aspect the present invention provides use of a friction modifier as herein defined for reducing friction
and improving detergency in a combustion engine.
In one aspect the present invention provides use of a friction modifying composition as herein defined for reducing friction and/or improving detergency in a combustion engine. In one preferred aspect the present invention provides use of a friction modifying composition as herein defined for reducing friction in a combustion engine. In one highly preferred aspect the present invention provides use of a friction modifying composition as herein defined for reducing friction and improving detergency in a combustion engine.
In one aspect the present invention provides use of a fuel additive composition as herein defined for reducing friction and/or improving detergency in a combustion engine. In one preferred aspect the present invention provides use of a fuel additive composition as herein defined for reducing friction in a combustion engine. In one highly preferred aspect the present invention provides use of a fuel additive composition as herein defined for reducing friction and improving detergency in a combustion engine.
The present invention will now be described in further detail by way of Example only.
EXAMPLES
SYNTHESIS OF FRICTION MODIFIERS
Example 1 - 1000 mwt PIBSA & Butylamine
1000 mwt high reactive PIB derived PIBSA (467.6g) was stirred with Shellsol AB (311.8g) in a 11 oil jacketed reactor equipped with an overhead stirrer, thermometer and Dean & Stark trap. Whilst still at room temperature butylamine (31.5g) was added in one aliquot with continued stirring. An immediate exotherm was noted. The reaction mix was heated to ~150°C for three hours whilst removing water. 720g of product was isolated.
Analysis of the product showed it to contain 40%m/m solvent, 0.81 %m/m nitrogen.
Example 2 - 1000 mwt PIBSA & Aminoethylethanolamine
1000 mwt high reactive PIB derived PIBSA (633.2g) was stirred with Shellsol AB (421g) in a 11 oil jacketed reactor equipped with an overhead stirrer, thermometer and Dean & Stark trap. Whilst still at room temperature aminoethylethanolamine (60.6g) was added in one aliquot with continued stimng. An immediate exotherm was noted. The reaction mix was heated to 130-150°C for three hours whilst removing water. 1058g of product was isolated.
Analysis of the product showed it to contain 39%m/m solvent, 1.47%m/m nitrogen.
Example 3 - 550 mwt PIBSA & Aminoethylethanolamine
550 mwt high reactive PIB derived PIBSA in Shellsol AB (900g, 40% solvent) was stirred in a 11 oil jacketed reactor equipped with an overhead stirrer, thermometer and Dean & Stark trap. Aminoethylethanolamine (84.2g) was added at room temperature whilst stirring. An exotherm was noted. The reaction mix was heated to 140°C for four hours whilst removing water. 926g of product was isolated.
Analysis of the product showed it to contain 38.5 %m/m solvent, 2.33 %m/m nitrogen.
Example 4 - 2300 mwt PIBSA & Butylamine
2300 mwt high reactive PIB derived PIBSA in Shellsol (495g, 21.6% solvent) was stirred with extra Shellsol AB (110g) in a 11 oil jacketed reactor equipped with an overhead stirrer, thermometer and Dean & Stark trap. Butylamine (9.37g)was added at room temperature whilst stirring. The reaction mix was heated to 130°C for three hours whilst removing water. 645g of product was isolated.
Analysis of the product showed it to contain 38 %m/m solvent, 0.35 %m/m nitrogen.
Example 5 - 2300 mwt PIBSA & Aminoethylethanolamine
2300 mwt high reactive PIB derived PIBSA in Shellsol (508g, 21.6% solvent) was stirred with extra Shellsol AB (157g) in a 11 oil jacketed reactor equipped with an overhead stirrer, thermometer and Dean & Stark trap. Aminoethylethanolamine (17.65g) was added at room temperature whilst stirring. The reaction mix was heated to 140°C for 3.5 hours whilst removing water. 838g of product was isolated.
Analysis of the product showed it to contain 42 %m/m solvent, 0.65 %m/m nitrogen.
Example 6 - 1000 mwt PIBSA & Ammonia
1000 mwt high reactive PIB derived PIBSA (450.15g) was stirred with Shellsol AB (298.99g) in a 11 oil jacketed reactor equipped with an overhead stirrer, thermometer,
Dean & Stark trap and a dip tube through which to add ammonia. The temperature was taken up to 138°C and the ammonia gas (5.81g) was added over 3 hours, whilst collecting water in the trap. Heating was continued for a further 2 hours. 731 g of product was isolated.
Analysis of the product showed it to contain 40 %m/m solvent, 0.76 %m/m nitrogen.
TEST DATA
Example 7 - High Frequency Reciprocating Rig (HFRR) Test
The standard procedure for evaluating diesel fuel lubricity using the High Frequency Reciprocating Rig (HFRR) test was modified to evaluate gasoline lubricity. A temperature of 20°C, which is lower than the standard temperature, was selected due to the higher volatility of gasoline as compared with diesel.
The procedure was as follows. A steel ball was attached to an oscillating arm assembly and mated to a steel disk specimen in the HFRR sample cell. The fuel reservoir contained 6ml of the fuel composition being tested. A load of 200 grams was applied to the ball/disk interface by dead weights. The ball assembly was oscillated over a 1000μ path at a rate of 50 Hertz. After a prescribed period of time, the steel ball assembly was removed. Wear, and hence the lubricity of the fuel composition, was assessed by measuring the wear scar diameter on the ball resulting from oscillating contact with the disk. The lower the value of the wear scar diameter the better the performance of the additive in the fuel composition. A wear scar diameter of below 500μ is particularly desirable. The results are set out in the tables below.
The following table shows the results obtained for commercial gasoline additives and an example of the present invention in this test. The additives were tested at equivalent active treat rates.
Example 8 - Improved Packaqabilitv
Generally friction modifiers such as polyisobutenyl succinimide (PIBSI) and carrier fluids are incompatible without the addition of a suitable solvent. Many packages require additional solvent above the amount already present due to the manufacture of the friction modifier.
A series of packages were produced using a range of carriers and friction modifiers. The following table shows the total percentage of solvent required to keep a 1 :1 ratio of active friction modifier and carrier fluid package in one phase at ambient conditions. The lowest solvent content possible in this test is 25-26% due to the solvent associated with the friction modifier manufacture.
Carrier A is a C13-ι5 initiated polyether having 12 propylene oxide units attached
Carrier B is a C^s initiated polyether having 14 propylene oxide units attached Carrier C is a C13-15 initiated polyether having 17 propylene oxide units attached
Carrier D is a nonylphenol initiated polyether having 17 propylene oxide units attached
Further storage stability testing has been carried out at -10°C, ambient and +40°C over 5-7days. This showed that the amount of additional solvent required to keep a package, showing similar IVD performance, in one phase could be reduced by up to 60% by using the present invention.
Example 9 - Intake valve detergency
The intake valve detergency properties exhibited by the friction modifier and carrier oil combinations listed below were measured using industry standard CEC-F-05-A93 test procedure on a bench engine. The test engine was a Mercedes-Benz M 102.982 four cylinder, four stroke 2.3 litre gasoline-injection engine with a standard KE-Jettonic injection system. The test carried out involved a cyclic procedure, each cycle including the following four operating states:
The duration of each test was exactly 60 h with the cycle repeated 800 times. At the beginning of each test the engine was fitted with new inlet valves which were weighed before fitting. At the end of each test, and before the visual assessment and before weighing the used inlet valves, residues were cleaned carefully from the valve surface
facing the combustion space. The valves were then immersed in n-heptane for 10 seconds and swung dry. After drying for 10 minutes, the valves were weighed and the increase in valve weight caused by deposits was measured in mg. During the dismantling of the valves the sticky or non-sticky appearance of the deposits formed on the valve tulip and valve stem was also evaluated. The tendency to form deposits of sticky appearance could indicate, ultimately, a tendency to the appearance of the valve stick phenomenon which is desirable to avoid.
The fuel employed in the test procedure was an unleaded gasoline meeting EN228 specification. The test compositions were added to the fuel so as to obtain a concentration of active substance (friction modifier and carrier oil) in the fuel in the amounts indicated.
Using Carrier D as carrier, at 1:1.6 ratio of friction modifiercarrier
Using Carrier A as carrier, at 1:1 ratio of friction modrfieπcaπier
Using Carrier C at 1 :1 ratio of friction modifieπcaπier in a fuel of low sulphur content
Example 10 - Valve stick performance
A series of tests was also carried out to evaluate the actual valve stick properties of various formulations. Test running was carried out on a single roll distance accumulation dynamometer manufactured by Labeco. The test engine is a regular Volkswagen Transporter 1.9-liter, 44 kW water-cooled-boxer Otto engine type 2 series with hydraulic valve filter. It is a flat four cylinder engine mounted at the rear, with a three-speed automatic transmission. The cylinder heads are dismantled after each test (one test=3 runs on the same fuel) and are cleaned with a suitable cleansing agent until metallically clean. The valve guides and valve stems are measured before each test.
The fuel used in these tests is an unleaded gasoline meeting EN228 specification.
The procedure described by DKA (Deutscher Koordinierungs Ausschuess) CEC F-16-T- 96 was followed. Each cycle included the following operating states:
Drive 130 km at level road load as follows:
5 km at 50 km/h
5 km at 60 km/h
Stop engine - pause 10 minutes
Carry out a total of 13 times to occupy 4 hours 33 minutes
Switch off engine and soak to temperature for 15 h
Carry out three cycles with a soak temperature of +5°C
At the end of each engine soak phase, an engine compression test is carried out to highlight any valve which is not functioning correctly. If compression at one or more of the cylinders is less than 8 bar then the inlet valve is deemed to have been sticking in the valve guide. For the final result, with a pass at -18°C, the same cycle is used except the soak temperature is -18°C rather than 5°C.
The test compositions are added to the fuel so as to obtain a concentration of active substance in the fuel containing additives which is specified for each example in the Table below, which gives the results obtained.
Example 11 - Intake valve detergency
The intake valve detergency properties exhibited by the friction modifier and carrier oil combinations listed have been measured using the CEC F-20-A-98 test procedure on a bench engine. The test engine is a Mercedes Benz M111 four cylinder, four-stroke 2.0 litre gasoline-injection engine with four valves per cylinder and an electronically
controlled ignition and fuel injection system. The test carried out involves a cyclic procedure, each cycle including the following four operating states:
The duration of each test is 60 hours. At the beginning of each test, the engine is fitted with new inlet valves, which are weighed before fitting. At the end of each test, and before weighing of the used inlet valves, residues are cleaned carefully from the valve surface facing the combustion space. The valves are then immersed in n-heptane for 10 seconds and air dried for at least 10 minutes and a maximum of 2 hours. Each valve is then weighed on a precision scale to an accuracy of at least one milligram, to determine the total weight of the valve and all its deposits.
The inlet valve deposit weight is determined by subtracting the weight of the clean intake valve that was determined before commencement of test and expressed in mg/valve.
The fuel employed was an unleaded gasoline meeting EN228 specification.
Using Carrier C as carrier, at a 1:1 ratio of friction modifiercarrier:
All publications mentioned in the above specification are herein incoφorated by reference. Various modifications and variations of the described methods and system of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in chemistry or related fields are intended to be within the scope of the following claims.
Claims
1. A friction modifier of the formula R1-L-N(R2)(R3) wherein
R1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000;
L is an optional linker group; and
R2 and R3 are independently selected from H, a hydrocarbyl group and a bond to optional group L, wherein at least one of R2 and R3 is H or a hydrocarbyl group, with the proviso that if one of R2 and R3 is a hydrocarbyl group and the other of R2 and R3 is H, the hydrocarbyl group does not contain a terminal amine.
2. A friction modifier according to claim 1 wherein R1 is a hydrocarbon group.
3. A friction modifier according to claim 1 or 2 wherein R1 is a branched or straight chain alkyl group.
4. A friction modifier according to claim 3 wherein R1 is a branched alkyl group.
5. A friction modifier according to claim 2, 3 or 4 wherein R1 is polyisobutene.
6. A friction modifier according to any one of the preceding claims wherein R1 has a molecular weight of from 800 to 1300.
7. A friction modifier according to claim 5 wherein R1 is polyisobutene having a molecular weight of from 800 to 1300.
8. A friction modifier according to any one of the preceding claims wherein group R1 has from 10 to 200 carbons.
9. A friction modifier according to any one of the preceding claims wherein group R1 has from 10 to 100 carbons.
10. A friction modifier according to any one of the preceding claims which comprises
linker L.
11. A friction modifier according to any one of the preceding claims wherein L when bonded to N(R2)(R3) provides a cyclic group of formula:
wherein e and f are independently an integer of from 0 to 6.
12. A friction modifier according to any one of claims 1 to 10 wherein both R2 and R3 are H.
13. A friction modifier according to any one of claims 1 to 11 wherein at least one of R2 and R3 is a hydrocarbyl group.
14. A friction modifier according to claim 13 wherein at least one of R2 and R3 is a hydrocarbyl group terminated with a moiety selected from -CH3, =CH2, -OH, -C(O)OH, and derivatives thereof.
15. A friction modifier according to claim 13 or 14 wherein at least one of R2 and R3 is a hydrocarbyl group of the formula
-[R4NH]PR5X wherein R4 is an alkylene group having from 1 to 10 carbons wherein R5 is an alkylene group having from 1 to 10 carbons wherein p is an integer from 0 to 10; wherein X is selected from -CH3, -CH2=CH2, -OH, and -C(O)OH.
16. A friction modifier according to claim 15 wherein R4 is an alkylene group having from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons.
17. A friction modifier according to claim 15 or 16 wherein R5 is an alkylene group having from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons.
18. A friction modifier according to claim 15 wherein at least one of R2 and R3 is a hydrocarbyl group of the formula
-[(CH2)qNH]p(CH2)rX wherein p is an integer from 0 to 10; 5 wherein q is an integer from 1 to 10; wherein r is an integer from 1 to 10; and wherein X is selected from -CH3, -CH2=CH2, -OH, and -C(O)OH.
19. A friction modifier according to claim 18 wherein p is an integer from 1 to 10, 10 preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2.
20. A friction modifier according to claim 18 or 19 wherein q is an integer from 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2.
15 21. A friction modifier according to claim 18, 19 or 20 wherein r is an integer from 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2.
22. A friction modifier according to any one of claims 15 to 21 wherein X is selected from -CH3, and -OH. 0
23. A friction modifier according to any one of claims 15 to 22 wherein at least one of R2 and R3 is a group of the formula -(CH2)3CH3.
24. A friction modifier according to claim 23 wherein one of R2 and R3 is a group of 5 the formula -(CH2)3CH3, and the other of R2 and R3 is H.
25. A friction modifier according to any one of claims 15 to 22 wherein at least one of R2 and R3 is a group of the formula -(CH2)2NH(CH2)2OH.
0 26. A friction modifier according to claim 25 wherein one of R2 and R3 is a group of the formula -(CH2)2NH(CH2)2OH, and the other of R2 and R3 is H.
27. A friction modifier according to any one of the preceding claims which is a polyisobutenyl succinimide. 5
28. A friction modifying composition comprising:
(i) a friction modifier according to any one of claims 1 to 27;
(ii) a carrier oil comprising an optionally esterified polyether.
29. A friction modifying composition according to claim 28 wherein the polyether carrier oil has a molecular weight in the range 500 to 5000.
30. A friction modifying composition according to claim 28 or 29 wherein the polyether carrier oil is a mono end-capped polypropylene glycol.
31. A friction modifying composition according to claim 30 wherein the end cap is a group consisting of or containing a hydrocarbyl group having up to 30 carbon atoms.
32. A friction modifying composition according to claim 31 wherein the end cap is or comprises an alkyl group having from 4 to 20 carbon atoms.
33. A friction modifying composition according to claim 30 wherein the carrier oil is a polypropyleneglycol monoether of the formula:
where R6 is straight chain C12-Cι8 alkyl; and n is an integer of from 10 to 30.
34. A friction modifying composition according to any one of claims 28 to 33 wherein the friction modifier is present in an amount of from 10 to 60% by weight, preferably 30 to 60% by weight, based on the total composition.
35. A friction modifying composition according to any one of claims 28 to 34 wherein the carrier oil is present in an amount of from 10 to 40% by weight, based on the total composition.
36. A friction modifying composition according to any one of claims 28 to 35 wherein the weight ratio of friction modifier to carrier oil is from 0.2:1 to 5:1.
37. A friction modifying composition according to any one of claims 28 to 36 further
comprising a solvent.
38. A friction modifying composition according to claim 37 wherein the solvent is a hydrocarbon solvent having a boiling point in the range 66 to 320°C.
39. A fuel additive composition comprising:
(i) a friction modifier as defined in any one of claims 1 to 27; and (ii) a earner, diluent or solvent; which is substantially free of any detergent and/or friction modifier other than the friction modifier as defined in any one of claims 1 to 27.
40. A fuel additive composition according to claim 39 which is substantially free of any detergent and any friction modifier other than the friction modifier as defined in any one of claims 1 to 27.
41. A fuel additive composition according to claim 39 or 40 wherein the earner, diluent or solvent is a earner oil comprising an optionally esterified polyether.
42. A fuel additive composition according to any one of claims 39 to 41 wherein the carrier, diluent or solvent is a polyether carrier oil as defined in any one of claims 29 to
33.
43. A fuel composition comprising (i) a fuel; and (ii) a friction modifier according to any one of claims 1 to 27.
44. A fuel composition comprising (i) a fuel; and
(ii) a friction modifying composition according to any one of claims 28 to 38.
45. A fuel composition comprising (i) a fuel; and
(ii) a fuel additive composition according to any one of claims 39 to 42.
46. A fuel composition according to claim 43, 44 or 45 wherein the friction modifier is
present in an amount, on a weight basis, of 50 to 500ppm.
47. A fuel composition according to claim 44 wherein the friction modifying composition is present in an amount to provide on a weight basis, from 50 to 500 ppm
5 friction modifier and 30 to 500 ppm carrier oil.
48. A fuel composition according to any one of claims 43 to 47 wherein the fuel is a gasoline.
10 49. A process for the reduction of friction in a combustion engine comprising the steps of:
(i) dosing a fuel with a friction modifier as defined in any one of claims 1 to 27, or a friction modifying composition as defined in any one of claims 28 to 38, or a fuel additive composition as defined in any one of claims 39 to 42, to provide a fuel composition;
15 (ii)combusting the fuel composition in a combustion engine.
50. A process according to claim 49 wherein the fuel composition is substantially free of any detergent other than the friction modifier as defined in any one of claims 1 to 27.
0 51. A process according to claim 49 or 50 wherein the fuel composition is substantially free of any friction modifier other than the friction modifier as defined in any one of claims 1 to 27.
52. Use of a friction modifier as defined in any one of claims 1 to 27, or a friction 5 modifying composition as defined in any one of claims 28 to 38, or a fuel additive composition as defined in any one of claims 39 to 42, for reducing friction and/or improving detergency in a combustion engine.
53. Use of a friction modifier as defined in any one of claims 1 to 27, or a friction 0 modifying composition as defined in any one of claims 28 to 38, or a fuel additive composition as defined in any one of claims 39 to 42, for reducing friction and improving detergency in a combustion engine.
54. A friction modifier as substantially herein before described with reference to any 5 one of the Examples.
55. A friction modifying composition as substantially herein before described with reference to any one of the Examples.
56. A fuel additive composition as substantially herein before described with reference to any one of the Examples.
57. A fuel composition as substantially herein before described with reference to any one of the Examples.
58. A process for the reduction of friction in a combustion engine as substantially herein before described with reference to any one of the Examples.
59. A use as substantially herein before described with reference to any one of the Examples.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0204241.4A GB0204241D0 (en) | 2002-02-22 | 2002-02-22 | Compound |
GB0204241 | 2002-02-22 | ||
PCT/GB2003/000643 WO2003070860A1 (en) | 2002-02-22 | 2003-02-13 | Friction modifier for hydrocarbon fuels |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1481040A1 true EP1481040A1 (en) | 2004-12-01 |
Family
ID=9931605
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03702764A Withdrawn EP1481040A1 (en) | 2002-02-22 | 2003-02-13 | Friction modifier for hydrocarbon fuels |
Country Status (9)
Country | Link |
---|---|
US (1) | US20050223630A1 (en) |
EP (1) | EP1481040A1 (en) |
JP (1) | JP2005517797A (en) |
KR (1) | KR20040111359A (en) |
CN (1) | CN1643115A (en) |
AU (1) | AU2003205886A1 (en) |
CA (1) | CA2475601A1 (en) |
GB (1) | GB0204241D0 (en) |
WO (1) | WO2003070860A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8353740B2 (en) | 2005-09-09 | 2013-01-15 | Saint-Gobain Ceramics & Plastics, Inc. | Conductive hydrocarbon fluid |
US7708904B2 (en) | 2005-09-09 | 2010-05-04 | Saint-Gobain Ceramics & Plastics, Inc. | Conductive hydrocarbon fluid |
UY29994A1 (en) * | 2005-12-09 | 2007-07-31 | Envirofuels Llc | COMPOSITIONS AND METHODS TO IMPROVE LUBRICITY IN HYDROCARBON FUELS. |
JP4142060B2 (en) * | 2006-04-17 | 2008-08-27 | 新日本石油株式会社 | Lubricating oil composition for automatic transmission |
US9011556B2 (en) | 2007-03-09 | 2015-04-21 | Afton Chemical Corporation | Fuel composition containing a hydrocarbyl-substituted succinimide |
US8690968B2 (en) | 2008-04-04 | 2014-04-08 | Afton Chemical Corporation | Succinimide lubricity additive for diesel fuel and a method for reducing wear scarring in an engine |
GB0909351D0 (en) | 2009-06-01 | 2009-07-15 | Innospec Ltd | Improvements in efficiency |
BR112013012874B1 (en) | 2010-12-02 | 2019-09-03 | Basf Se | reaction product use, and fuel composition and additive concentrate preparation processes |
GB2486255A (en) | 2010-12-09 | 2012-06-13 | Innospec Ltd | Improvements in or relating to additives for fuels and lubricants |
US20150113867A1 (en) | 2013-10-24 | 2015-04-30 | Basf Se | Use of an alkoxylated polytetrahydrofuran to reduce fuel consumption |
US9321976B1 (en) * | 2015-09-16 | 2016-04-26 | Afton Chemical Corporation | Hydroxyalkyl substituted succinimides and fuels containing them |
Family Cites Families (15)
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US1151994A (en) * | 1912-12-02 | 1915-08-31 | Troy Laundry Machinery Co Ltd | Cylinder washing-machine. |
DE1248643B (en) * | 1959-03-30 | 1967-08-31 | The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) | Process for the preparation of oil-soluble aylated amines |
NL255194A (en) * | 1959-08-24 | |||
NL124842C (en) * | 1959-08-24 | |||
US4120887A (en) * | 1971-11-30 | 1978-10-17 | Toa Nenryo Kogyo Kabushiki Kaisha | Lubricating oil additive, process for the synthesis thereof and lubricating oil additive composition |
CA1139740A (en) * | 1979-05-18 | 1983-01-18 | Andrew G. Papay | Oil-soluble friction-reducing additive and lubricating oil composition |
US4325827A (en) * | 1981-01-26 | 1982-04-20 | Edwin Cooper, Inc. | Fuel and lubricating compositions containing N-hydroxymethyl succinimides |
US4704217A (en) * | 1986-08-20 | 1987-11-03 | Texaco Inc. | Gasoline crankcase lubricant |
GB9503104D0 (en) * | 1995-02-17 | 1995-04-05 | Bp Chemicals Additives | Diesel fuels |
EP0829527A1 (en) * | 1996-09-12 | 1998-03-18 | Exxon Research And Engineering Company | Additive concentrate for fuel compositions |
US6348075B1 (en) * | 1998-04-14 | 2002-02-19 | The Lubrizol Corporation | Compositions containing polyalkene-substituted amine and polyether alcohol |
DE19830818A1 (en) * | 1998-07-09 | 2000-01-13 | Basf Ag | Fuel compositions containing propoxylate |
US6051039A (en) * | 1998-09-14 | 2000-04-18 | The Lubrizol Corporation | Diesel fuel compositions |
EP1151994A1 (en) * | 2000-05-01 | 2001-11-07 | Ethyl Corporation | Succinimide-acid compounds and derivatives thereof |
GB0022473D0 (en) * | 2000-09-13 | 2000-11-01 | Ass Octel | Composition |
-
2002
- 2002-02-22 GB GBGB0204241.4A patent/GB0204241D0/en not_active Ceased
-
2003
- 2003-02-13 JP JP2003569757A patent/JP2005517797A/en not_active Withdrawn
- 2003-02-13 KR KR10-2004-7013027A patent/KR20040111359A/en not_active Application Discontinuation
- 2003-02-13 US US10/505,078 patent/US20050223630A1/en not_active Abandoned
- 2003-02-13 WO PCT/GB2003/000643 patent/WO2003070860A1/en not_active Application Discontinuation
- 2003-02-13 AU AU2003205886A patent/AU2003205886A1/en not_active Abandoned
- 2003-02-13 CN CNA038067137A patent/CN1643115A/en active Pending
- 2003-02-13 EP EP03702764A patent/EP1481040A1/en not_active Withdrawn
- 2003-02-13 CA CA002475601A patent/CA2475601A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO03070860A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU2003205886A1 (en) | 2003-09-09 |
CA2475601A1 (en) | 2003-08-28 |
CN1643115A (en) | 2005-07-20 |
WO2003070860A1 (en) | 2003-08-28 |
JP2005517797A (en) | 2005-06-16 |
GB0204241D0 (en) | 2002-04-10 |
US20050223630A1 (en) | 2005-10-13 |
KR20040111359A (en) | 2004-12-31 |
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