EP0353116A1 - Recipes of nitrogenous additives for engine fuels, and engine fuels containing them - Google Patents
Recipes of nitrogenous additives for engine fuels, and engine fuels containing them Download PDFInfo
- Publication number
- EP0353116A1 EP0353116A1 EP89401846A EP89401846A EP0353116A1 EP 0353116 A1 EP0353116 A1 EP 0353116A1 EP 89401846 A EP89401846 A EP 89401846A EP 89401846 A EP89401846 A EP 89401846A EP 0353116 A1 EP0353116 A1 EP 0353116A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- integer
- carbon atoms
- constituent
- polyamine
- formulation according
- 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.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 64
- 239000000654 additive Substances 0.000 title claims abstract description 38
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 80
- 238000009472 formulation Methods 0.000 claims abstract description 53
- 239000000470 constituent Substances 0.000 claims abstract description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229920000768 polyamine Polymers 0.000 claims abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 229920000151 polyglycol Polymers 0.000 claims abstract description 9
- 239000010695 polyglycol Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 150000008064 anhydrides Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- -1 nitrogenous compound Chemical class 0.000 claims description 11
- 150000007513 acids Chemical class 0.000 claims description 8
- BNGLZYYFFZFNDJ-UHFFFAOYSA-N 2-(2-heptadec-1-enyl-4,5-dihydroimidazol-1-yl)ethanol Chemical compound CCCCCCCCCCCCCCCC=CC1=NCCN1CCO BNGLZYYFFZFNDJ-UHFFFAOYSA-N 0.000 claims description 5
- CDUGROIHQRGVJS-UHFFFAOYSA-N 2-(2-methyl-4,5-dihydroimidazol-1-yl)ethanol Chemical compound CC1=NCCN1CCO CDUGROIHQRGVJS-UHFFFAOYSA-N 0.000 claims description 4
- GOHZKUSWWGUUNR-UHFFFAOYSA-N 2-(4,5-dihydroimidazol-1-yl)ethanol Chemical group OCCN1CCN=C1 GOHZKUSWWGUUNR-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 8
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 claims 1
- 150000002462 imidazolines Chemical class 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 abstract description 5
- 239000002816 fuel additive Substances 0.000 abstract description 3
- 125000002636 imidazolinyl group Chemical group 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 54
- 239000001294 propane Substances 0.000 description 27
- 239000008096 xylene Substances 0.000 description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- 239000011149 active material Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008030 elimination Effects 0.000 description 6
- 238000003379 elimination reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000009261 D 400 Substances 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 241000722921 Tulipa gesneriana Species 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 238000010533 azeotropic distillation Methods 0.000 description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid group Chemical group C(CCCCCCC\C=C/CCCCCC)(=O)O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N docos-13-enoic acid Chemical compound CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002466 imines Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- UWHZIFQPPBDJPM-BQYQJAHWSA-N vaccenic acid group Chemical group C(CCCCCCCCC\C=C\CCCCCC)(=O)O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- GWHCXVQVJPWHRF-KTKRTIGZSA-N (15Z)-tetracosenoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-KTKRTIGZSA-N 0.000 description 1
- GQSARBOWRIBUBV-UHFFFAOYSA-N 1-hydroxy-4,5-dihydroimidazole Chemical class ON1CCN=C1 GQSARBOWRIBUBV-UHFFFAOYSA-N 0.000 description 1
- OXEDXHIBHVMDST-UHFFFAOYSA-N 12Z-octadecenoic acid Natural products CCCCCC=CCCCCCCCCCCC(O)=O OXEDXHIBHVMDST-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- WECIKJKLCDCIMY-UHFFFAOYSA-N 2-chloro-n-(2-cyanoethyl)acetamide Chemical compound ClCC(=O)NCCC#N WECIKJKLCDCIMY-UHFFFAOYSA-N 0.000 description 1
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- KAYAKFYASWYOEB-ISLYRVAYSA-N 3-[(e)-octadec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCC\C=C\C1CC(=O)OC1=O KAYAKFYASWYOEB-ISLYRVAYSA-N 0.000 description 1
- 108010053481 Antifreeze Proteins Proteins 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000021322 Vaccenic acid Nutrition 0.000 description 1
- UWHZIFQPPBDJPM-FPLPWBNLSA-M Vaccenic acid Natural products CCCCCC\C=C/CCCCCCCCCC([O-])=O UWHZIFQPPBDJPM-FPLPWBNLSA-M 0.000 description 1
- QFHMNFAUXJAINK-UHFFFAOYSA-N [1-(carbamoylamino)-2-methylpropyl]urea Chemical group NC(=O)NC(C(C)C)NC(N)=O QFHMNFAUXJAINK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- OFHCOWSQAMBJIW-AVJTYSNKSA-N alfacalcidol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C OFHCOWSQAMBJIW-AVJTYSNKSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004534 cecum Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- CNVZJPUDSLNTQU-OUKQBFOZSA-N petroselaidic acid Chemical compound CCCCCCCCCCC\C=C\CCCCC(O)=O CNVZJPUDSLNTQU-OUKQBFOZSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000000007 visual effect Effects 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
- 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
-
- 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
- C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
-
- 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
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
-
- 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
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
-
- 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
- C10L1/22—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
- the present invention relates to additive formulations which, when added, for example, to engine fuels, significantly reduce their tendency to deposit and corrode various parts of the engine.
- the use of conventional fuels very often leads to fouling of the different parts of the engine as a result of the incomplete vaporization and combustion of the fuel in the intake system and / or in the combustion chamber and as a result of the presence traces of lubricants.
- the accumulation of these deposits can be done at the injectors, the carburetor and the intake valves.
- Such an accumulation has harmful consequences both in terms of driving pleasure, with the appearance of unstable idling and misfires in spark-ignition engines, and in terms of optimal engine operation by changing the richness as a result. fuel adsorption-desorption phenomena on the deposits formed.
- the accumulation of deposits in the engines and in particular on the intake valves can also be reduced by the use of fuels containing certain additives, for example detergent-type additives possibly combined for example with anticorrosion additives or anti-deposit for room combustion.
- fuels containing certain additives for example detergent-type additives possibly combined for example with anticorrosion additives or anti-deposit for room combustion.
- Additives well known in the trade, for example those of the polyisobutene-amine type, are usually associated with a mineral or synthetic oil and are capable of causing increased fouling of the combustion chambers and therefore an increase in the octane requirement of the motor with greater sensitivity to the rattling phenomenon.
- condensation products of polyalkenylsuccinic anhydrides on hydroxyimidazolines, and in particular on 1- (2-hydroxyethyl) imidazolines substituted in position 2 by an alkyl or alkenyl group such as those described in the patent application EP-A-74724.
- the products described in this application are good additives (for engine fuels and have a significant anticorrosion action but are not very effective in terms of the detergency of the carburetor.
- the invention provides formulations of additives, in particular for engine fuels, which make it possible to substantially reduce the abovementioned drawbacks.
- the additive formulations of the present invention can be used in particular as multifunctional fuel additives; in particular for fuels used in spark ignition engines.
- the additive formulations of the invention have excellent detergent properties at the intake valves and the carburetor and have very good anti-corrosion properties.
- the additive formulations of the invention used in particular in fuels for positive-ignition engines make it possible to greatly reduce the formation of deposits on the intake valves, and the fouling of carburetors or injectors.
- these additive formulations reduce the corrosion of the various mechanical parts with which the fuel comes into contact.
- These additive formulations can be used without the addition of mineral oil, which makes it possible to overcome the drawbacks mentioned above and related to the use of a mineral oil.
- these additive formulations include: a component (A) and a component (B) said component (A) consisting of at least one nitrogenous compound resulting from the reaction of at least one succinic derivative chosen from the group formed by alkenylsuccinic acids and anhydrides and acids and polyalkenylsuccinic anhydrides on at least one polyamine corresponding to the general formula in which R1 represents a hydrogen atom or a hydrocarbon group having from 1 to 60 carbon atoms, Z is chosen from the groups -O- and -NR3- in which R3 represents a hydrogen atom or a hydrocarbon group having 1 to 60 carbon atoms, R1 and R3 can form together with the nitrogen atom to which they are linked a heterocycle, each R2 independently represents a hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms, n is an integer from 2 to 6, m is an integer from 1 to 10 when Z is -NR3- and an integer from 2 to 10 when Z is
- the additive formulations according to the present invention further comprise at least one component (C) consisting of at least one polyglycol, soluble in said fuel, of molecular weight number 480 to 2100 and of general formula (III): (III) HO - R - (- O - R--) x -O - R - OH wherein each of the R groups independently represents a hydrocarbon group having 2 to 6 carbon atoms and x represents the average degree of polymerization.
- component (C) consisting of at least one polyglycol, soluble in said fuel, of molecular weight number 480 to 2100 and of general formula (III): (III) HO - R - (- O - R--) x -O - R - OH wherein each of the R groups independently represents a hydrocarbon group having 2 to 6 carbon atoms and x represents the average degree of polymerization.
- the constituent (C) is preferably a polyglycol of general formula (III) above in which each of the groups R independently represents an alkylene group, linear or branched, having from 2 to 4 atoms carbon and most often an ethylene or propylene group.
- each of the groups R independently represents an alkylene group, linear or branched, having from 2 to 4 atoms carbon and most often an ethylene or propylene group.
- the polyglycols, of general formula (III) which are particularly preferred, mention may be made of those in which each of the groups R represents a propylene group of formula: CH3-CH-CH2-
- Component (C) is preferably a polyglycol of number average molecular weight from 600 to 1800 and most often from 650 to 1250.
- the polydispersity index of the polyglycol, used as component (C), in the formulations according to the present invention, is usually about 1 to 1.25 and most often about 1 to 1.15.
- One of the characteristics of the invention relates to the synergistic effect observed when a constituent (A) and a constituent (B) are combined in a fuel.
- This synergistic effect is manifested in particular by a notable reduction in the tendency of the fuel to form deposits on the intake valves; one could not foresee such a significant reduction by considering the separate effects of constituents (A) and (B).
- This synergy is also manifested by a noticeable improvement in the cleanliness of the carburetor after a fixed operating time, an improvement which could not have been foreseen by considering the separate effects of the constituents (A) and (B).
- the molar ratio of the constituent (A) to the constituent ( B) or from 0.2: 1 to 5: 1, preferably from 0.2: 1 to 1: 1, most preferably from 0.3: 1 to 0.9: 1 and better still from 0, 4: 1 to 0.8: 1.
- the succinic acid and / or anhydride used to form component (A) and component (B) may be the same or different. It is possible to use a single succinic derivative or a mixture of several succinic derivatives.
- the succinic acid and / or anhydride used in the context of the present invention usually has a number average molecular weight of about 200 to 3000, preferably 500 to 2000 and most often 700 to 1500.
- These derivatives succinics are widely described in the prior art; they are for example obtained by the action of at least one alpha olefin or of a chlorinated hydrocarbon on maleic acid or anhydride.
- the alpha olefin or the chlorinated hydrocarbon used in this synthesis can be linear or branched, and usually contain from 10 to 150 carbon atoms, preferably from 15 to 80 carbon atoms and most often from 20 to 75 carbon atoms in their molecule.
- This olefin may also be an oligomer, for example a dimer, a trimer or a tetramer, or a polymer of a lower olefin, for example having 2 to 10 carbon atoms, such as ethylene, propylene, n -butene-1, isobutene, n-hexene-1, n-octene-1, methyl-2-heptene-1 or methyl-2-propyl-5-hexene-1. It is possible to use mixtures of olefins or mixtures of chlorinated hydrocarbons.
- succinic anhydrides mention may be made of n-octadecenylsuccinic anhydride, dodecenylsuccinic anhydride and polyisobutenyl succinic anhydrides, often called PIBSA, having a number-average molecular mass as defined above.
- the polyamines of formula (I) are preferably those in which R1 is a hydrogen atom or a hydrocarbon group having from 1 to 30 carbon atoms, Z is preferably a group -NR3- in which R3 preferably represents an atom of hydrogen or a hydrocarbon group having from 1 to 30 carbon atoms, each of the R2 independently represents preferably a hydrogen atom or a methyl group, n is an integer from 2 to 4 and when Z is a group -NR3- m is preferably an integer from 1 to 5.
- Z is -NR3-, R1, R2 and R3 each represent a hydrogen atom, n is equal to 2 and m is an integer from 1 to 5 or those in which R1 represents a hydrocarbon group preferably having from 5 to 24 carbon atoms, Z represents a group -NR3-in which R3 is a hydrogen atom, R2 represents a hydrogen atom, n is a number integer from 2 to 4, preferably 3, and m is an integer from 1 to 5, preferably 1.
- the hydrocarbon groups R1 and R3 are usually alkyl, alkenyl, linear or branched, aryl, aryl-alkyl (aralkyl), alkyl-aryl (alkaryl) or cycloaliphatic groups.
- the R1 and R3 groups are preferably alkyl or alkenyl groups, linear or branched.
- the hydrocarbon group R2 is usually an alkyl group, preferably linear, and for example methyl, ethyl, n-propyl or n-butyl.
- N-alkyl diamino-1,3 propane for example N-dodecyldiamino-1,3 propane, N-tetradecyldiamino-1,3 propane, N-hexadecyldiamino-1,3 propane, N-octadecyldiamino-1,3 propane, N-eicosyldiamino-1,3 propane and N-docosyldiamino-1,3 propane; mention may also be made of N-alkyldipropylene triamines, for example N-hexadecyldipropylene triamine, N-octadecyldipropylene triamine, N-eicosy
- N, N diamines examples include N, N-diethyl-1,2-diamino ethane, N, N-diisopropyl diamino-1,2 ethane, N, N-dibutyl diamino-1,2 ethane, N, N-diethyl diamino-1,4 butane, N, N-dimethyl diamino-1,3 propane, N, N 1,3-diethyl diamino-1,3 propane, N, N-dioctyl diamino-1,3 propane, N, N-didecyl diamino-1,3 propane, N, N-N-didodecyl diamino-1,3 propane, N , N-dissetradécyl diamino-1,3 propane, N, N-dihexadécyl diamino-1,3 propane, N, N-dioctadécyl di
- etheramines examples include N- (octyloxy-3-propyl) diamino-1,3 propane, N- (decyloxy-3 propyl) diamino-1,3 propane, N- (trimethyl- 2,4,6 decyl) oxy-3 propyl diamino-1,3 propane.
- the polyamines of formulas (II) are preferably those in which R1 and R3 each represent a hydrogen atom A, B, C and D identical or different each represent an alkylidene group having 2 to 4 carbon atoms, for example ethylidene , propylidene, isopropylidene, butylidene and isobutylidene, a is an integer from 1 to 60 and b and c are zero; or a is an integer from 1 to 59, c is zero or an integer such that the sum a + c is from 1 to 59 and b is an integer from 1 to 50; with in each case the sum a + b + c equal to an integer from 1 to 60.
- the reaction for the formation of component (A) is usually carried out by progressive addition of the polyamine to a solution or to a dispersion of the succinic derivative in an organic solvent, at ordinary temperature, then heating to a temperature usually between 65 and 250 ° C. and preferably between 80 and 200 ° C.
- the organic solvent used in this preparation has a boiling point of between 65 and 250 ° C. and is usually chosen so as to allow the elimination of the water formed during the condensation of the polyamine on the succinic derivative, preferably in the form of a water-organic solvent azeotrope.
- An organic solvent will usually be used such as for example benzene, toluene, xylenes, ethylbenzene or a hydrocarbon cut such as for example the commercial cut SOLVESSO 150 (190-209 ° C) containing 99% by weight of aromatic compounds.
- the duration of the heating after the end of the addition of the polyamine is usually 0.5 to 7 hours, preferably 1 to 5 hours.
- the heating is usually continued, at the chosen temperature, most often at reflux, until the end of the evolution of the water formed during the reaction.
- the product obtained is then optionally isolated by removing, for example by vacuum distillation, the solvent used in the preparation.
- the amount of water removed during the reaction is usually about 0.8 to 1.2 moles and most often about 1 mole of water per mole of succinic derivative.
- the polyamine is preferably diluted in an organic solvent, for example one of those mentioned above and preferably the same as that used to form the solution or dispersion of the succinic derivative; this dilution facilitates the gradual addition of the polyamine.
- the amount of polyamine employed is usually at least 0.5 mole per mole of succinic derivative, for example from 0.5: 1 to 2: 1 and preferably from 0.8: 1 to 1.2: 1. most often uses an amount of about 1 mole of polyamine per mole of succinic derivative.
- the constituent (A) used can be a commercial compound, for example the compound sold by the company OCTEL under the reference 0MA 41OG, which is based on a condensation product of tetraethylene pentamine on a PIBSA.
- the 1- (2-hydroxyethyl -) - imidazolines substituted in position 2 by an alkyl or alkenyl radical having from 1 to 25 carbon atoms used for the preparation of component (B) can be commercial compounds or can be synthesized for example by reaction of at least one organic acid with N- (2-hydroxyethyl) -ethylenediamine. The reaction proceeds by a first amidation step followed by cyclization.
- the organic acids used usually have from 2 to 26 carbon atoms; they are preferably aliphatic monocarboxylic acids.
- component (B) 1- (2-hydroxyethyl) -2 heptadecenylimidazoline is marketed by the company CIBA-GEIGY under the name "Amine-O" and by the company PROTEX under the name "Imidazoline-O".
- the preparation of component (B) is usually carried out by progressive addition of imidazoline, for example diluted in an organic solvent to a solution or to a dispersion of the succinic derivative in an organic solvent.
- the solvents used are preferably identical and they are, for example, chosen from those mentioned above in the description of the preparation of component (A).
- the addition of imidazoline to the succinic derivative is usually carried out at room temperature; after the end of the addition, the mixture is heated to a temperature usually around 65 to 250 ° C, preferably around 80 to 200 ° C.
- the duration of the heating, after the end of the addition of imidazoline is usually 0.5 to 7 hours, preferably 1 to 5 hours. Heating is usually continued, at the chosen temperature, most often at reflux, until the end of the evolution of the water formed during the reaction.
- the product obtained is then optionally isolated by removing, for example by vacuum distillation, the solvent used in the preparation.
- the amount of water removed during the reaction is usually about 0.2 to 0.8 moles and most often about 0.3 to 0.6 moles of water per mole of succinic derivative.
- the amount of imidazoline used in the reaction is usually at least 0.5 mole per mole of succinic derivative, for example from 0.5: 1 to 1.5: 1 and preferably from 0.9: 1 a 1.1: 1. Most of the time, approximately 1 mole of imidazoline is used per mole of succinic derivative.
- the formulations of the present invention can be used in the form of a solution in the reaction medium having served for the preparation of each of the constituents.
- the formulations can also be added directly to the fuel or be previously diluted in a solvent chosen, for example, from those mentioned above for the preparation of each of the constituents.
- the formulations of the present invention are mainly used as multifunctional additives for a fuel for engines, for example a fuel based on hydrocarbons or based on a mixture of hydrocarbons and at least one oxygenated compound chosen from the group formed. by alcohols and ethers, or a non-hydrocarbon fuel such as for example an alcohol or a mixture of alcohols.
- the formulations of the present invention are particularly well suited for use as additives for fuels used in spark ignition engines. Examples of fuels that may be mentioned include gasolines such as, for example, those defined by standard ASTM D-439, gas oils or diesel fuels, such as, for example, those defined by standard ASTM D-975.
- These fuels may also contain other additives as the formulations of the present invention for example anti-knock additives such as lead compounds (for example tetraethyl lead), methyltertiobutylether, methyl-tertioamylether or a mixture of methanol and tert-butyl alcohol, anti-freeze additives and octane reducers.
- anti-knock additives such as lead compounds (for example tetraethyl lead), methyltertiobutylether, methyl-tertioamylether or a mixture of methanol and tert-butyl alcohol, anti-freeze additives and octane reducers.
- the formulations of the present invention are used in an amount sufficient to obtain a significant reduction in deposits on the various components of the engine, in particular at the level of the intake valves and of the carburetor.
- amounts are used representing from 10 to 3000 ppm by weight of active material relative to the weight of the fuel, preferably from 10 to 1000 ppm and most often from 50 to 700 ppm.
- the amount of the constituent (C) is usually from 10 to 2000 ppm, most often from 10 to 900 ppm so preferred from 30 to 800 ppm.
- Examples 1 to 5 describe the preparation of constituents (A) and (B) used for the preparation of the formulations according to the invention.
- the progress of the reaction can also be followed by infrared spectrometry at the level of the absorption band of the imine function at 1660 cm ⁇ 1 which gradually disappears during the reaction, while two bands appear (1710 cm ⁇ 1 and 1770 cm ⁇ 1) characteristics of the succinimide function.
- a solution, at 50% by weight of active material, in xylene, of component 81 is thus obtained.
- the infrared spectrum shows an imine band at 1660 cm ⁇ 1 and in nuclear magnetic resonance spectrometry we detect the presence of the two methylene groups of the imidazoline cycle and the presence of the methyl group in position 2 on the imidazoline cycle. Elemental analysis provides a percentage of nitrogen of 22.1% by weight for a calculated percentage of 21.8%.
- the procedure described in Example 1 is repeated, replacing 1- (2-hydroxyethyl) -2-heptadecenylimidazoline with 1- (2-hydroxyethyl) -2-methylimidazoline prepared above.
- Example 1 The procedure described in Example 1 is repeated, replacing the imidazoline with a tallow diamine such as that sold under the brand Dinoram S by the company CECA and corresponding to cut E, the characteristics of which have been mentioned in table I below. -before. 306 g (0.3 mole) of PIBSA diluted in 306 g of xylene and 108 g (0.3 mole) of Dinoram S diluted in 108 g of xylene were used. The reflux is maintained for 5 hours. The reaction water is eliminated as it is formed; this elimination mainly occurs during the first 4 hours of reaction. A solution is thus obtained, adjusted to 50% by weight of active material, in xylene, of component A2.
- Example 3 The procedure of Example 3 is repeated, replacing Dinoram S with 0.3 mole of tetraetriylenepentamine (56 g) diluted in 56 g of xylene. The reflux is maintained for 5 hours. The reaction water is eliminated as it is formed; this elimination mainly occurs during the first 4 hours of reaction. A solution is thus obtained, at 50% by weight of active material, in xylene, of the constituent A3.
- Example 2 The procedure described in Example 1 is repeated, replacing the imidazoline with the polyoxyalkyleneamine sold by the company TEXACO under the name Jeffamine D-400 with a number average molecular mass of 400.
- the Jeffamine D-400 is added in the form of a solution in xylene containing 164 g (0.41 mole) of Jeffamine D-400.
- the reflux is maintained throughout the elimination of the reaction water by azeotropic distillation, then for an additional hour.
- a solution is thus obtained, adjusted to 50% by weight of active material, in the xylene of the constituent A4.
- the tests consist in determining the extent of the corrosion produced on samples of polished ordinary steel, in the presence of synthetic seawater, by following the modified ASTM D 665 standard (temperature 32.2 ° C, duration 20 hours) .
- the tests are carried out using some of the fuels described in Example 6.
- the results obtained are presented in Table IV below; they are expressed as percentages (%) of the surface of the corroded test piece after hours.
- Table IV Fuel % of corroded surface C1 100% C2 0% C8 0% C10 0%
- Formula F1 contains the component (A3) described in Example 4, component (B1) described in Example 1 and polypropylene glycol (component (C)) described above; the molar ratio of the number of moles of the constituent (A3) to the number of moles of the constituent (B1) is 0.7: 1; the quantity of polypropylene glycol contained in this formulation is such that the molar ratio of the sum of the number of moles of constituent (A3) and of constituent (B1) which it contains to the number of moles of polypropylene glycol which it contains ((A3) + (B1)) / (C) is 0.7: 1.
- the formulation F2 contains the constituent (A3) described in Example 4, the constituent (B1) described in Example 1 and the poylpropylene glycol (constituent ( C)) described above; the molar ratio of the number of moles of the constituent (A3) to the number of moles of the constituent (B1) is 2: 1; the quantity of polypropylene glycol contained in this formulation is such that the molar ratio of the sum of the number of moles of constituent (A3) and of constituent (B1) which it contains to the number of moles of polypropylene glycol which it contains ((A3) + (B1)) / (C) is 0.73: 1.
- Formulation F3 includes polypropylene glycol and contains neither component (A3) nor component (B1).
- the formulation F4 comprises each of the constituents (A3) and (B1) in a molar ratio of 2: 1 and does not contain polypropylene glycol.
- a series of tests is carried out in order to assess the detergency properties of valves of various formulations.
- the tests were carried out on a Mercédes M102E engine test bench, without additives in the case of examples 11 to 14 inclusive.
- the test procedure is a standard procedure comprising the use of an engine having 4 cylinders, of the Mercedes M102E type, having a displacement of 2299 cc and a compression ratio of 9/1.
- the test procedure is a cyclic procedure, each cycle comprising four successive periods of operation: - 30 s (seconds) at 800 rpm (revolutions per minute) under zero load, - 60 s at 1300 rpm under a load of 31 newtons (mxkgxs-2), - 120 s at 1850 rpm under a load of 34 newtons and - 60 s at 3000 rpm under a load of 37 newtons.
- the duration of each test is usually 40 to 150 hours; in examples 10 to 14 the duration of the test was fixed at 40 hours.
- the engine is conditioned with new valves that are weighed.
- the valves are dismantled, washed with hexane, dried, then weighed after physical removal (by scraping) of the deposits formed on the valve on the combustion chamber side.
- the results presented below give the average of deposits by weight relative to a valve, calculated from the weight of deposits measured, on the tulip of each intake valve, by difference between the weight of said new valve and the weight of said valve at the end of each test after removal of deposits on the combustion chamber side.
- each valve intake side: tulip
- CRC Coordinating Research Council
- the fuel used in these assessments is an unleaded premium fuel, comprising 2% by volume of a mixture of methanol and tert-butanol in a volume ratio of 1.5: 1.
- This premium fuel with an octane rating of 85 and octane distillation search of 227 ° C; it includes in volume: - 49% aromatics - 11% olefins - 40% of saturated compounds (paraffins + naphthenics)
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Exhaust Gas After Treatment (AREA)
- Control Of Vehicle Engines Or Engines For Specific Uses (AREA)
Abstract
Formulations d'additifs pour carburants comprenant au moins un constituant (A) et un constituant (B) résultant de la réaction d'au moins un dérivé alcényl ou polyacényl-succinique sur au moins une polyamine pour former le constituant (A) et sur au moins une 1- (2-hydroyéthyl) imidazoline substituée en position 2 par un radical alkyle ou alcényle ; linéaire ou ramifié, ayant de 1 à 25 atomes de carbone pour former le constituant (B). Les formulations préférées comprennent en outre un constituant (C) consistant en au moins un polyglycol, soluble dans ledit carburant, de masse moléculaire moyenne en nombre de 480 à 2100. Les rappports molaires (A)/(B) et ((A) + (B))/(C) sont de préférence respectivement de 0,05 : 1 à 20 : 1. Ces formulations sont utilisées comme additifs multifonctionnels pour les carburants à base d'hydrocarbures ou d'un mélange d'hydrocarbures et d'au moins un composé oxygéné. Elles sont particulièrement bien adaptées pour être utilisées comme additifs pour les carburants employés dans les moteurs à allumage commandé.Fuel additive formulations comprising at least one component (A) and one component (B) resulting from the reaction of at least one alkenyl or polyacenyl-succinic derivative on at least one polyamine to form component (A) and on at least one 1- (2-hydroyethyl) imidazoline substituted in position 2 by an alkyl or alkenyl radical; linear or branched, having from 1 to 25 carbon atoms to form component (B). The preferred formulations further comprise a constituent (C) consisting of at least one polyglycol, soluble in said fuel, of number average molecular weight from 480 to 2100. The molar ratios (A) / (B) and ((A) + (B)) / (C) are preferably respectively from 0.05: 1 to 20: 1. These formulations are used as multifunctional additives for fuels based on hydrocarbons or on a mixture of hydrocarbons and at least minus an oxygenated compound. They are particularly well suited for use as additives for fuels used in spark ignition engines.
Description
La présente invention concerne des formulations d'additifs qui, ajoutées par exemple aux carburants moteurs, réduisent sensiblement la tendance de ces derniers à former des dépôts et à corroder diverses parties du moteur.
L'utilisation de carburants conventionnels conduit très souvent à l'encrassement des différentes parties du moteur par suite de la vaporisation et de la combustion incomplètes du carburant dans le système d'admission et/ou dans la chambre de combustion et par suite de la présence de traces de lubrifiants.The present invention relates to additive formulations which, when added, for example, to engine fuels, significantly reduce their tendency to deposit and corrode various parts of the engine.
The use of conventional fuels very often leads to fouling of the different parts of the engine as a result of the incomplete vaporization and combustion of the fuel in the intake system and / or in the combustion chamber and as a result of the presence traces of lubricants.
Dans le système d'admission, l'accumulation de ces dépôts peut ainsi se faire au niveau des injecteurs, du carburateur et des soupapes d'admission.
Une telle accumulation a des conséquences néfastes tant au niveau de l'agrément de conduite, avec l'apparition de ralenti instable et de ratés dans les moteurs à allumage commandé, qu'au niveau du fonctionnement optimal du moteur par modification de la richesse comme suite aux phénomènes d'adsorption-désorption du carburant sur les dépôts formés.In the intake system, the accumulation of these deposits can be done at the injectors, the carburetor and the intake valves.
Such an accumulation has harmful consequences both in terms of driving pleasure, with the appearance of unstable idling and misfires in spark-ignition engines, and in terms of optimal engine operation by changing the richness as a result. fuel adsorption-desorption phenomena on the deposits formed.
Afin de remédier à l'encrassement il est possible de procéder à un nettoyage périodique, particulièrement onéreux, des organes concernés, en particulier des soupapes.In order to remedy the fouling, it is possible to carry out periodic, particularly expensive cleaning, of the organs concerned, in particular of the valves.
L'accumulation de dépôts dans les moteurs et en particulier sur les soupapes d'admission peut également être réduite par l'utilisation de carburants contenant certains additifs, par exemple des additifs du type détergent éventuellement combinés par exemple avec des additifs anticorrosion ou antidépôts pour chambre de combustion.The accumulation of deposits in the engines and in particular on the intake valves can also be reduced by the use of fuels containing certain additives, for example detergent-type additives possibly combined for example with anticorrosion additives or anti-deposit for room combustion.
Les additifs, bien connus dans le commerce, par exemple ceux du type polyisobutène-amine, sont habituellement associés a une huile minérale ou synthétique et sont susceptibles de provoquer un encrassement accru des chambres de combustion et donc une augmentation de l'exigence en octane du moteur avec une plus grande sensibilité au phénomène de cliquetis.Additives, well known in the trade, for example those of the polyisobutene-amine type, are usually associated with a mineral or synthetic oil and are capable of causing increased fouling of the combustion chambers and therefore an increase in the octane requirement of the motor with greater sensitivity to the rattling phenomenon.
Parmi les nombreux additifs décrits dans l'art antérieur on peut citer les produits de condensation des anhydrides polyalcénylsucciniques sur des polyamines, telles que, par exemple, la tétraéthylènepentamine, qui sont en particulier décrits dans le brevet US-A-3172892. Ces additifs donnent de bons résultats au niveau des propriétés anticorrosion, mais ne sont pas efficaces comme détergents de soupapes.Among the numerous additives described in the prior art, mention may be made of the condensation products of polyalkenylsuccinic anhydrides on polyamines, such as, for example, tetraethylenepentamine, which are in particular described in US-A-3172892. These additives give good results in terms of anti-corrosion properties, but are not effective as valve detergents.
On peut également citer les produits de condensation des anhydrides polyalcénylsucciniques sur des hydroxyimidazolines, et en particulier sur des 1-(2-hydroxyéthyl) imidazolines substituées en position 2 par un groupe alkyle ou alcényle, tels que ceux qui sont décrits dans la demande de brevet EP-A-74724. Les produits décrits dans cette demande sont de bons additifs (pour carburants moteurs et ont une action d'anticorrosion importante mais ne sont pas très efficaces au niveau de la détergence du carburateur.Mention may also be made of the condensation products of polyalkenylsuccinic anhydrides on hydroxyimidazolines, and in particular on 1- (2-hydroxyethyl) imidazolines substituted in position 2 by an alkyl or alkenyl group, such as those described in the patent application EP-A-74724. The products described in this application are good additives (for engine fuels and have a significant anticorrosion action but are not very effective in terms of the detergency of the carburetor.
La plupart des additifs commerciaux sont le plus souvent employés en association avec une huile minérale dont le rôle principal est d' augmenter ou d' obtenir la détergence "soupape" nécessaire.
L'utilisation d'une huile minérale provoque habituellement un encrassement relativement important de la chambre de combustion ce qui est préjudiciable au bon fonctionnement du moteur. La viscosité du concentré d'additif obtenu par addition de l'huile minérale est habituellement assez élevée ce qui peut entrainer des difficultés au niveau de la manutention et de l'additivation ( addition de l'additif au carburant ). Par ailleurs les concentrés d'additifs comprenant une huile minérale ont une mauvaise tenue au froid.Most commercial additives are most often used in combination with a mineral oil, the main role of which is to increase or obtain the necessary "valve" detergency.
The use of mineral oil usually causes a relatively large fouling of the combustion chamber which is detrimental to the proper functioning of the engine. The viscosity of the additive concentrate obtained by adding mineral oil is usually quite high which can cause difficulties in handling and additivation (addition of the additive to the fuel). Furthermore, the additive concentrates comprising a mineral oil have poor resistance to cold.
L'invention propose des formulations d'additifs, notamment pour carburants moteurs, qui permettent de réduire sensiblement les inconvénients précités. Les formulations d'additifs de la présente invention sont utilisables notamment comme additifs multifonctionnels pour carburants; en particulier pour les carburants utilisés dans les moteurs à allumage commandé.The invention provides formulations of additives, in particular for engine fuels, which make it possible to substantially reduce the abovementioned drawbacks. The additive formulations of the present invention can be used in particular as multifunctional fuel additives; in particular for fuels used in spark ignition engines.
Les formulations d'additifs de l'invention présentent d'excellentes propriétés détergentes au niveau des soupapes d'admission et du carburateur et ont de très bonnes propriétés d'anti-corrosion. Les formulations d'additifs de l'invention utilisées en particulier dans les carburants pour moteurs à allumage commandé permettent de réduire largement la formation de dépôts sur les soupapes d'admission, et l'encrassement des carburateurs ou des injecteurs.
De plus ces formulations d'additifs diminuent la corrosion des diverses pièces mécaniques avec lesquelles le carburant entre en contact.
Ces formulations d'additifs peuvent être utilisées sans addition d'huile minérale ce qui permet de s'affranchir des inconvénients mentionnés ci-avant et liés à l'emploi d'une huile minérale.
D'une manière générale, ces formulations d'additifs, notamment pour carburants moteurs, comprennent :
un constituant (A) et un constituant (B) ledit constituant (A) consistant en au moins un composé azoté résultant de la réaction d'au moins un dérivé succinique choisi dans le groupe formé par les acides et les anhydrides alcénylsucciniques et les acides et les anhydrides polyalcénylsucciniques sur au moins une polyamine répondant à la formule générale
Dans une forme préférée de réalisation les formulations d'additifs selon la présente invention comprennent en outre au moins un constituant (C) consistant en au moins un polyglycol, soluble dans ledit carburant, de masse moléculaire en nombre de 480 à 2100 et de formule générale (III) :
(III) HO--R--(-O--R--)x-O--R--OH
dans laquelle chacun des groupes R indépendamment représente un groupe hydrocarboné ayant de 2 à 6 atomes de carbone et x représente le degré moyen de polymérisation.The additive formulations of the invention have excellent detergent properties at the intake valves and the carburetor and have very good anti-corrosion properties. The additive formulations of the invention used in particular in fuels for positive-ignition engines make it possible to greatly reduce the formation of deposits on the intake valves, and the fouling of carburetors or injectors.
In addition, these additive formulations reduce the corrosion of the various mechanical parts with which the fuel comes into contact.
These additive formulations can be used without the addition of mineral oil, which makes it possible to overcome the drawbacks mentioned above and related to the use of a mineral oil.
In general, these additive formulations, in particular for engine fuels, include:
a component (A) and a component (B) said component (A) consisting of at least one nitrogenous compound resulting from the reaction of at least one succinic derivative chosen from the group formed by alkenylsuccinic acids and anhydrides and acids and polyalkenylsuccinic anhydrides on at least one polyamine corresponding to the general formula
In a preferred embodiment, the additive formulations according to the present invention further comprise at least one component (C) consisting of at least one polyglycol, soluble in said fuel, of molecular weight number 480 to 2100 and of general formula (III):
(III) HO - R - (- O - R--) x -O - R - OH
wherein each of the R groups independently represents a hydrocarbon group having 2 to 6 carbon atoms and x represents the average degree of polymerization.
Dans les formulations, selon la présente invention, le constituant (C) est de préférence un polyglycol de formule générale (III) ci-avant dans laquelle chacun des groupes R indépendamment représente un groupe alkylène, linéaire ou ramifié, ayant de 2 à 4 atomes de carbone et le plus souvent un groupe éthylène ou propylène. Parmi les polyglycols, de formule générale (III), particulièrement préférés on peut citer ceux dans lesquels chacun des groupes R représente un groupe propylène de formule :
CH₃-CH-CH₂-
In the formulations, according to the present invention, the constituent (C) is preferably a polyglycol of general formula (III) above in which each of the groups R independently represents an alkylene group, linear or branched, having from 2 to 4 atoms carbon and most often an ethylene or propylene group. Among the polyglycols, of general formula (III), which are particularly preferred, mention may be made of those in which each of the groups R represents a propylene group of formula:
CH₃-CH-CH₂-
Le constituant (C) est de préférence un polyglycol de masse moléculaire moyenne en nombre de 600 à 1800 et le plus souvent de 650 à 1250. L'indice de polydispersité du polyglycol, employé comme constituant (C), dans les formulations selon la présente invention, est habituellement d'environ 1 à 1,25 et le plus souvent d'environ 1 à 1,15.Component (C) is preferably a polyglycol of number average molecular weight from 600 to 1800 and most often from 650 to 1250. The polydispersity index of the polyglycol, used as component (C), in the formulations according to the present invention, is usually about 1 to 1.25 and most often about 1 to 1.15.
L'une des caractéristiques de l'invention concerne l'effet de synergie observé lorsque l'on associe dans un carburant le constituant (A) au constituant (B). Cet effet de synergie se manifeste notamment par une diminution notable de la tendance du carburant à former des dépôts sur les soupapes d'admission ; on ne pouvait pas prévoir une diminution aussi importante en considérant les effets séparés des constituants (A) et (B). Cette synergie se manifeste également par une amélioration notable de la propreté du carburateur après une durée de fonctionnement déterminée, amélioration qui ne pouvait pas être prévue en considérant les effets séparés des constituants (A) et (B).One of the characteristics of the invention relates to the synergistic effect observed when a constituent (A) and a constituent (B) are combined in a fuel. This synergistic effect is manifested in particular by a notable reduction in the tendency of the fuel to form deposits on the intake valves; one could not foresee such a significant reduction by considering the separate effects of constituents (A) and (B). This synergy is also manifested by a noticeable improvement in the cleanliness of the carburetor after a fixed operating time, an improvement which could not have been foreseen by considering the separate effects of the constituents (A) and (B).
Cet effet de synergie est également observé lors de l'association du constituant (C) aux constituants (A) et (B) précités.This synergistic effect is also observed when the constituent (C) is combined with the aforementioned constituents (A) and (B).
Dans les formulations de l'invention contenant les deux constituants (A) et (B) pour qu'un effet particulièrement accru de réduction de la formation de dépôts soit observé , il est avantageux que le rapport molaire du constituant (A) au constituant (B) soit de 0,2 : 1 à 5 : 1,de préférence de 0,2 : 1 a 1 : 1, de manière la plus préférée de 0,3 : 1 à 0,9 : 1 et mieux encore de 0,4 : 1 à 0,8 : 1.In the formulations of the invention containing the two constituents (A) and (B) so that a particularly increased effect of reducing the formation of deposits is observed, it is advantageous that the molar ratio of the constituent (A) to the constituent ( B) or from 0.2: 1 to 5: 1, preferably from 0.2: 1 to 1: 1, most preferably from 0.3: 1 to 0.9: 1 and better still from 0, 4: 1 to 0.8: 1.
Dans le cas de formulations selon la présente invention contenant les trois constituants (A), (B) et (C), il est avantageux, pour qu'un effet particulièrement accru de réduction de la formation de dépôts soit observé, que le rapport molaire de la somme des moles du constituant (A) et du constituant (B) au nombre de moles du constituant (C), ((A) + (B))/(C) soit d'environ 0,05 : 1 à 20 : 1 et de préférence d'environ 0,1 : 1 à 10 : 1 ; le rapport molaire du constituant (A) au constituant (B) restant dans les gammes précisées ci-avant.In the case of formulations according to the present invention containing the three constituents (A), (B) and (C), it is advantageous, for a particularly increased effect of reducing the formation of deposits to be observed, that the molar ratio of the sum of the moles of the constituent (A) and of the constituent (B) to the number of moles of the constituent (C), ((A) + (B)) / (C) or about 0.05: 1 to 20 : 1 and preferably from about 0.1: 1 to 10: 1; the molar ratio of component (A) to component (B) remaining in the ranges specified above.
L'acide et/ou l'anhydride succinique employés pour former le constituant (A) et le constituant (B) peuvent être identiques ou différents. Il est possible d'employer un seul dérivé succinique ou un mélange de plusieurs dérivés succiniques.
L'acide et/ou l'anhydride succinique utilisé dans le cadre de la présente invention a, habituellement, une masse moléculaire moyenne en nombre d'environ 200 à 3000, de préférence 500 à 2000 et le plus souvent 700 à 1500. Ces dérivés succiniques sont largement décrits dans l'art antérieur ; ils sont par exemple obtenus par l'action d'au moins une oléfine alpha ou d'un hydrocarbure chloré sur l'acide ou l'anhydride maléique. L'oléfine alpha ou l'hydrocarbure chloré utilisé dans cette synthèse peuvent être linéaires ou ramifiés, et comportent habituellement de 10 à 150 atomes de carbone, de préférence de 15 à 80 atomes de carbone et le plus souvent de 20 à 75 atomes de carbone dans leur molécule. Cette oléfine peut également être un oligomère, par exemple un dimère, un trimère ou un tétramère, ou un polymère d'une oléfine inférieure, ayant par exemple de 2 à 10 atomes de carbone, telle que l'éthylène, le propylène, le n-butène-1, l'isobutène, le n-hexène-1, le n-octène-1, le méthyl-2-heptène-1 ou le méthyl-2-propyl-5- hexène-1. Il est possible d'utiliser des mélanges d'oléfines ou des mélanges d'hydrocarbures chlorés.
A titre d'exemples d'anhydrides succiniques, on peut citer l'anhydride n-octadécénylsuccinique, l'anhydride dodécénylsuccinique et les anhydrides polyisobuténylsucciniques, souvent dénommés PIBSA, ayant une masse moléculaire moyenne en nombre telle que définie ci-avant. Les polyamines de formule (I) sont de préférence celles dans lesquelles R¹ est un atome d'hydrogène ou un groupe hydrocarboné ayant de 1 à 30 atomes de carbone, Z est de préférence un groupe -NR³- dans lequel R³ représente de préférence un atome d'hydrogène ou un groupe hydrocarboné ayant de 1 à 30 atomes de carbone, chacun des R² indépendamment représente de préférence un atome d'hydrogène ou un groupe méthyle, n est un nombre entier de 2 à 4 et lorsque Z est un groupe -NR³- m est de préférence un nombre entier de 1 à 5.
Parmi les composés de formules (I) ci-avant on emploie avantageusement ceux dans lesquels Z est -NR³-, R¹, R² et R³ représentent chacun un atome d'hydrogène, n est égal à 2 et m est un nombre entier de 1 à 5 ou ceux dans lesquels R¹ représente un groupe hydrocarboné ayant de préférence de 5 à 24 atomes de carbone, Z représente un groupe -NR³-dans lequel R³ est un atome d'hydrogène, R² représente un atome d'hydrogène, n est un nombre entier de 2 à 4, de préférence 3, et m est un nombre entier de 1 à 5, de préférence 1.The succinic acid and / or anhydride used to form component (A) and component (B) may be the same or different. It is possible to use a single succinic derivative or a mixture of several succinic derivatives.
The succinic acid and / or anhydride used in the context of the present invention usually has a number average molecular weight of about 200 to 3000, preferably 500 to 2000 and most often 700 to 1500. These derivatives succinics are widely described in the prior art; they are for example obtained by the action of at least one alpha olefin or of a chlorinated hydrocarbon on maleic acid or anhydride. The alpha olefin or the chlorinated hydrocarbon used in this synthesis can be linear or branched, and usually contain from 10 to 150 carbon atoms, preferably from 15 to 80 carbon atoms and most often from 20 to 75 carbon atoms in their molecule. This olefin may also be an oligomer, for example a dimer, a trimer or a tetramer, or a polymer of a lower olefin, for example having 2 to 10 carbon atoms, such as ethylene, propylene, n -butene-1, isobutene, n-hexene-1, n-octene-1, methyl-2-heptene-1 or methyl-2-propyl-5-hexene-1. It is possible to use mixtures of olefins or mixtures of chlorinated hydrocarbons.
As examples of succinic anhydrides, mention may be made of n-octadecenylsuccinic anhydride, dodecenylsuccinic anhydride and polyisobutenyl succinic anhydrides, often called PIBSA, having a number-average molecular mass as defined above. The polyamines of formula (I) are preferably those in which R¹ is a hydrogen atom or a hydrocarbon group having from 1 to 30 carbon atoms, Z is preferably a group -NR³- in which R³ preferably represents an atom of hydrogen or a hydrocarbon group having from 1 to 30 carbon atoms, each of the R² independently represents preferably a hydrogen atom or a methyl group, n is an integer from 2 to 4 and when Z is a group -NR³- m is preferably an integer from 1 to 5.
Among the compounds of formulas (I) above, advantageously those in which Z is -NR³-, R¹, R² and R³ each represent a hydrogen atom, n is equal to 2 and m is an integer from 1 to 5 or those in which R¹ represents a hydrocarbon group preferably having from 5 to 24 carbon atoms, Z represents a group -NR³-in which R³ is a hydrogen atom, R² represents a hydrogen atom, n is a number integer from 2 to 4, preferably 3, and m is an integer from 1 to 5, preferably 1.
Les groupes hydrocarbonés R¹ et R³ sont habituellement des groupes alkyles, alcényles, linéaires ou ramifiés, aryles, aryl-alkyles (aralkyles), alkyl-aryles (alkaryles) ou cycloaliphatiques. Les groupes R¹ et R³ sont de préférence des groupes alkyles ou alcényles, linéaires ou ramifiés. Le groupe hydrocarboné R² est habituellement un groupe alkyle, de préférence linéaire, et par exemple méthyle, éthyle, n-propyle ou n-butyle.The hydrocarbon groups R¹ and R³ are usually alkyl, alkenyl, linear or branched, aryl, aryl-alkyl (aralkyl), alkyl-aryl (alkaryl) or cycloaliphatic groups. The R¹ and R³ groups are preferably alkyl or alkenyl groups, linear or branched. The hydrocarbon group R² is usually an alkyl group, preferably linear, and for example methyl, ethyl, n-propyl or n-butyl.
Comme composés spécifiques on peut citer : l'éthylènediamine, la propylènediamine, la triéthylènetétramine, la tripropylènetétramine, la tétraéthylènepentamine, la triméthylènediamine, l'hexaméthylène diamine, la di(triméthylène)triamine, les N-alkyl diamino-1,3 propane par exemple le N-dodécyldiamino-1,3 propane, le N-tétradécyldiamino-1,3 propane, le N-hexadécyldiamino-1,3 propane, le N-octadécyldiamino-1,3 propane, le N-eicosyldiamino-1,3 propane et le N-docosyldiamino-1,3 propane ; on peut également citer les N-alkyldipropylène triamines par exemple la N-hexadécyldipropylène triamine, la N-octadécyldipropylène triamine, la N-eicosyldipropylène triamine et la N-docosyldipropylène triamine ; on peut également citer les N-alcényldiamino-1,3 propane et les N-alcényldipropylène triamines par exemple le N-octadécényldiamino-1,3 propane, le N-hexadécényldiamino-1,3 propane, le N-dodécylényldiamino-1,3 propane, le N-octadécadiényldiamino-1,3 propane et le N-docosényldiamino-1,3 propane. On peut citer à titre d'exemples de diamines N,N disubstituées le N,N-diéthyl diamino-1,2 éthane, le N,N-diisopropyl diamino-1,2 éthane, le N,N-dibutyl diamino-1,2 éthane, le N,N-diéthyl diamino-1,4 butane, le N,N-diméthyl diamino-1,3 propane, le N,N-diéthyl diamino-1,3 propane, le N,N-dioctyl diamino-1,3 propane, le N,N-didécyl diamino-1,3 propane, le N,N-didodécyl diamino-1,3 propane, le N,N-ditétradécyl diamino-1,3 propane, le N,N-dihexadécyl diamino-1,3 propane, le N,N-dioctadécyl diamino-1,3 propane, la N,N-didodécyldipropylène triamine, la N,N-ditétradécyldipropylène triamine, la N,N-dihexadécyldipropylène triamine, la N,N-dioctadécyldipropylène triamine, le N-méthyl, N-butyl diamino-1,2 éthane, le N-méthyl, N-octyl diamino-1,2 éthane, le N-éthyl,N-octyl diamino-1,2 éthane, le N-méthyl, N-décyl diamino-1,2 éthane, le N-méthyl, N-dodécyl diamino 1,3 propane, le N-méthyl, N-hexadécyl diamino-1,3 propane et le N-éthyl, N-octadécyl diamino-1,3 propane.As specific compounds, mention may be made of: ethylenediamine, propylenediamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, hexamethylene diamine, di (trimethylene) triamine, N-alkyl diamino-1,3 propane for example N-dodecyldiamino-1,3 propane, N-tetradecyldiamino-1,3 propane, N-hexadecyldiamino-1,3 propane, N-octadecyldiamino-1,3 propane, N-eicosyldiamino-1,3 propane and N-docosyldiamino-1,3 propane; mention may also be made of N-alkyldipropylene triamines, for example N-hexadecyldipropylene triamine, N-octadecyldipropylene triamine, N-eicosyldipropylene triamine and N-docosyldipropylene triamine; mention may also be made of N-alkenyldiamino-1,3 propane and N-alkenyldipropylene triamines, for example N-octadecenyldiamino-1,3 propane, N-hexadecenyldiamino-1,3 propane, N-dodecylenyldiamino-1,3 propane , N-octadecadienyldiamino-1,3 propane and N-docosényldiamino-1,3 propane. Examples of disubstituted N, N diamines that may be mentioned include N, N-diethyl-1,2-diamino ethane, N, N-diisopropyl diamino-1,2 ethane, N, N-dibutyl diamino-1,2 ethane, N, N-diethyl diamino-1,4 butane, N, N-dimethyl diamino-1,3 propane, N, N 1,3-diethyl diamino-1,3 propane, N, N-dioctyl diamino-1,3 propane, N, N-didecyl diamino-1,3 propane, N, N-N-didodecyl diamino-1,3 propane, N , N-ditétradécyl diamino-1,3 propane, N, N-dihexadécyl diamino-1,3 propane, N, N-dioctadécyl diamino-1,3 propane, N, N-didodécyldipropylène triamine, N, N- ditétradécyldipropylène triamine, N, N-dihexadécyldipropylène triamine, N, N-dioctadécyldipropylène triamine, N-methyl, N-butyl diamino-1,2 ethane, N-methyl, N-octyl diamino-1,2 ethane, N-ethyl, N-octyl diamino-1,2 ethane, N-methyl, N-decyl diamino-1,2 ethane, N-methyl, N-dodecyl diamino 1,3 propane, N-methyl, N- hexadecyl diamino-1,3 propane and N-ethyl, N-octadecyl diamino-1,3 propane.
A titre d'exemples d'étheramines on peut citer le N-(octyloxy-3-propyl)diamino-1,3 propane, le N-(décyloxy-3 propyl)diamino-1,3 propane, le N-(triméthyl-2,4,6 décyl)oxy-3 propyl diamino-1,3 propane.Examples of etheramines that may be mentioned include N- (octyloxy-3-propyl) diamino-1,3 propane, N- (decyloxy-3 propyl) diamino-1,3 propane, N- (trimethyl- 2,4,6 decyl) oxy-3 propyl diamino-1,3 propane.
Il doit être entendu qu'il est possible de mettre en jeu comme composé polyaminé un ou plusieurs composés répondant à la formule (I) et/ou (II). Comme exemples spécifiques de mélanges de composés répondant à la formule (I) on peut citer ;
les coupes de diamines grasses répondant à la formule R¹-NH-(CH₂-)₃NH₂ dont les groupes R¹ sont des radicaux hydrocarbonés aliphatiques en C₈, C₁₀, C₁₂, C₁₄, C₁₆, C₁₈, C₂₀ et C₂₂, en proportions molaires approximatives données dans le tableau I ci-après.
cuts of fatty diamines corresponding to the formula R¹-NH- (CH₂-) ₃NH₂ whose groups R¹ are aliphatic Cbon, C₁₀, C₁₂, C₁₄, C₁₆, C₁₈, C₂₀ and C₂₂ hydrocarbon radicals, in approximate molar proportions given in Table I below.
Les polyamines de formules (II) sont de préférence celles dans lesquelles R¹ et R³ représentent chacun un atome d' hydrogène A, B, C et D identiques ou différents représentent chacun un groupe alkylidène ayant de 2 à 4 atomes de carbone, par exemple éthylidène, propylidène, isopropylidène, butylidène et isobutylidène, a est un nombre entier de 1 à 60 et b et c sont égaux à zéro ; ou a est un nombre entier de 1 à 59, c est zéro ou un nombre entier tel que la somme a+c soit de 1 à 59 et b est un nombre entier de 1 à 50 ; avec dans chaque cas la somme a+b+c égale à un nombre entier de 1 à 60.
Comme composés spécifiques de fromule (II) on peut citer ceux répondant aux formules :
Ces produits sont en particulier commercialisés par la société TEXACO Chemical sous le nom Jeffamine EDR 148 pour le produit de formule (II₁) dans laquelle a = 2, Jeffamine D-230 pour un produit de formule (II₂) de masse moléculaire moyenne en nombre de 230, Jeffamine D-400 pour un produit de formule (II₂) de masse moléculaire moyenne en nombre de 400, Jeffamine D-2000 pour un produit de formule (II₂) de masse moléculaire moyenne en nombre de 2000, Jeffamine ED-600 pour un produit de formule (II₃) de masse moléculaire moyenne en nombre de 600, Jeffamine ED-900 pour un produit de formule (II₃) de masse moléculaire moyenne en nombre de 900 et Jeffamine ED-2001 pour un produit de formule (II₃) de masse moléculaire moyenne en nombre de 2000.The polyamines of formulas (II) are preferably those in which R¹ and R³ each represent a hydrogen atom A, B, C and D identical or different each represent an alkylidene group having 2 to 4 carbon atoms, for example ethylidene , propylidene, isopropylidene, butylidene and isobutylidene, a is an integer from 1 to 60 and b and c are zero; or a is an integer from 1 to 59, c is zero or an integer such that the sum a + c is from 1 to 59 and b is an integer from 1 to 50; with in each case the sum a + b + c equal to an integer from 1 to 60.
As specific compounds of cheese (II), mention may be made of those corresponding to the formulas:
These products are in particular marketed by the company TEXACO Chemical under the name Jeffamine EDR 148 for the product of formula (II₁) in which a = 2, Jeffamine D-230 for a product of formula (II₂) of average molecular mass in number of 230, Jeffamine D-400 for a product of formula (II₂) of number average molecular mass of 400, Jeffamine D-2000 for a product of formula (II₂) of number average molecular mass of 2000, Jeffamine ED-600 for a product of formula (II₃) of number average molecular mass of 600, Jeffamine ED-900 for a product of formula (II₃) of number average molecular mass of 900 and Jeffamine ED-2001 for a product of formula (II₃) of mass number average molecular of 2000.
La réaction de formation du constituant (A) est habituellement effectuée par addition progressive de la polyamine à une solution ou à une dispersion du dérivé succinique dans un solvant organique, à température ordinaire, puis chauffage à une température habituellement comprise entre 65 et 250 °C et de préférence entre 80 et 200 °C.
Le solvant organique utilisé dans cette préparation a un point d'ébullition compris entre 65 et 250 °C et est habituellement choisi de manière à pouvoir permettre l'élimination de l'eau formée au cours de la condensation de la polyamine sur le dérivé succinique, de préférence sous forme d'un azéotrope eau-solvant organique. On utilisera habituellement un solvant organique tel que par exemple le benzène, le toluène, les xylènes, l'éthylbenzène ou une coupe d'hydrocarbures telle que par exemple la coupe commerciale SOLVESSO 150 (190-209 °C) contenant 99 % en poids de composés aromatiques.The reaction for the formation of component (A) is usually carried out by progressive addition of the polyamine to a solution or to a dispersion of the succinic derivative in an organic solvent, at ordinary temperature, then heating to a temperature usually between 65 and 250 ° C. and preferably between 80 and 200 ° C.
The organic solvent used in this preparation has a boiling point of between 65 and 250 ° C. and is usually chosen so as to allow the elimination of the water formed during the condensation of the polyamine on the succinic derivative, preferably in the form of a water-organic solvent azeotrope. An organic solvent will usually be used such as for example benzene, toluene, xylenes, ethylbenzene or a hydrocarbon cut such as for example the commercial cut SOLVESSO 150 (190-209 ° C) containing 99% by weight of aromatic compounds.
Il est possible d'utiliser des mélanges de solvants, par exemple un mélange de xylènes. La durée du chauffage après la fin de l'addition de la polyamine est habituellement de 0,5 à 7 heures, de préférence de 1 à 5 heures.
Le chauffage est habituellement poursuivi, à la température choisie, le plus souvent au reflux , jusqu'à la fin du dégagement de l'eau formée au cours de la réaction. Le produit obtenu est ensuite éventuellement isolé en éliminant, par exemple par distillation sous vide, le solvant utilisé dans la préparation. La quantité d'eau éliminée au cours de la réaction est habituellement d'environ 0,8 à 1,2 mole et le plus souvent d'environ 1 mole d'eau par mole de dérivé succinique.
La polyamine est de préférence diluée dans un solvant organique par exemple l'un de ceux cités ci-avant et de préférence le même que celui employé pour former la solution ou la dispersion du dérivé succinique; cette dilution facilite l'addition progressive de la polyamine. La quantité de polyamine employée est habituellement d'au moins 0,5 mole par mole de dérivé succinique, par exemple de 0,5 : 1 à 2 : 1 et de préférence de 0,8 : 1 à 1,2 : 1. On utilise le plus souvent une quantité d'environ 1 mole de polyamine par mole de dérivé succinique. Le constituant (A) utilisé peut être un composé commercial, par exemple le composé vendu par la société OCTEL sous la référence 0MA 41OG, qui est à base d'un produit de condensation de la tétraéthylène pentamine sur un PIBSA.It is possible to use mixtures of solvents, for example a mixture of xylenes. The duration of the heating after the end of the addition of the polyamine is usually 0.5 to 7 hours, preferably 1 to 5 hours.
The heating is usually continued, at the chosen temperature, most often at reflux, until the end of the evolution of the water formed during the reaction. The product obtained is then optionally isolated by removing, for example by vacuum distillation, the solvent used in the preparation. The amount of water removed during the reaction is usually about 0.8 to 1.2 moles and most often about 1 mole of water per mole of succinic derivative.
The polyamine is preferably diluted in an organic solvent, for example one of those mentioned above and preferably the same as that used to form the solution or dispersion of the succinic derivative; this dilution facilitates the gradual addition of the polyamine. The amount of polyamine employed is usually at least 0.5 mole per mole of succinic derivative, for example from 0.5: 1 to 2: 1 and preferably from 0.8: 1 to 1.2: 1. most often uses an amount of about 1 mole of polyamine per mole of succinic derivative. The constituent (A) used can be a commercial compound, for example the compound sold by the company OCTEL under the reference 0MA 41OG, which is based on a condensation product of tetraethylene pentamine on a PIBSA.
Les 1-(2-hydroxyéthyl-)-imidazolines substituées en position 2 par un radical alkyle ou alcényle ayant de 1 à 25 atomes de carbone employées pour la préparation du constituant (B) peuvent être des composés commerciaux ou peuvent être synthétisées par exemple par réaction d'au moins un acide organique avec la N-(2-hydroxyéthyl)-éthylènediamine. La réaction procède par une première étape d'amidification suivie d'une cyclisation. Les acides organiques utilisés ont habituellement de 2 à 26 atomes de carbone ; ce sont de préférence des acides aliphatiques monocarboxyliques. A titre d'exemples on peut citer l'acide acétique, l'acide propanoïque, l'acide butanoïque, l'acide caproïque, l'acide caprique, l'acide laurique, l'acide myristique, l'acide palmitique, l'acide stéarique, l'acide béhénique, l'acide cérotique et les acides gras insaturés suivants :
On utilisera par exemple la 1-(2-hydroxyéthyl)-2-heptadécényl imidazoline, préparée par exemple à partir de l'acide oléique et de la N-(2-hydroxyéthyl)-éthylènediamine. Cette préparation est par exemple décrite dans le brevet US-A-2987515.
On peut également citer à titre d'exemple la 1-(2-hydroxyéthyl)-2-méthyl imidazoline préparée par exemple à partir de l'acide acétique et de la N-(2-hydroxyéthyl-)éthylènediamine.
La 1-(2-hydroxyéthyl)-2 heptadécénylimidazoline est commercialisée par la société CIBA-GEIGY sous le nom "Amine-O" et par la société PROTEX sous le nom "Imidazoline-O".
La préparation du constituant (B) est habituellement effectuée par addition progressive de l'imidazoline par exemple diluée dans un solvant organique à une solution ou à une dispersion du dérivé succinique dans un solvant organique. Les solvants utilisés sont de préférence identiques et ils sont par exemple choisis parmi ceux cités ci-avant dans la description de la préparation du constituant (A).
L'addition de l'imidazoline au dérivé succinique est habituellement effectuée à température ambiante ; après la fin de l'addition on chauffe à une température habituellement d'environ 65 à 250 °C, de préférence d'environ 80 à 200°C. La durée du chauffage,après la fin de l'addition de l'imidazoline, est habituellement de 0,5 à 7 heures, de préférence de 1 a 5 heures. Le chauffage est habituellement poursuivi, à la température choisie, le plus souvent au reflux, jusqu'a la fin du dégagement de l'eau formée au cours de la réaction.
Le produit obtenu est ensuite éventuellement isolé en éliminant, par exemple par distillation sous vide, le solvant utilisé dans la préparation. La quantité d'eau éliminée au cours de la réaction est habiuellement d'environ 0,2 à 0,8 mole et le plus souvent d'environ 0,3 à 0,6 mole d'eau par mole de dérivé succinique. La quantité d'imidazoline mise en oeuvre dans la réaction est habituellement d'au moins 0,5 mole par mole de dérivé succinique, par exemple de 0,5 : 1 à 1,5 : 1 et de préférence de 0,9 : 1 a 1,1 : 1. On utilise le plus souvent une quantité d'environ 1 mole d'imidazoline par mole de dérivé succinique. Les formulations de la présente invention peuvent être utilisées sous forme de solution dans le milieu réactionnel ayant servi à la préparation de chacun des constituants.
Les formulations peuvent également être ajoutées directement dans le carburant ou être préalablement diluées dans un solvant choisi par exemple parmi ceux mentionnés ci-avant pour la préparation de chacun des constituants.For example, use 1- (2-hydroxyethyl) -2-heptadecenyl imidazoline, prepared for example from oleic acid and N- (2-hydroxyethyl) -ethylenediamine. This preparation is for example described in patent US-A-2987515.
Mention may also be made, by way of example, of 1- (2-hydroxyethyl) -2-methyl imidazoline, prepared for example from acetic acid and N- (2-hydroxyethyl-) ethylenediamine.
1- (2-hydroxyethyl) -2 heptadecenylimidazoline is marketed by the company CIBA-GEIGY under the name "Amine-O" and by the company PROTEX under the name "Imidazoline-O".
The preparation of component (B) is usually carried out by progressive addition of imidazoline, for example diluted in an organic solvent to a solution or to a dispersion of the succinic derivative in an organic solvent. The solvents used are preferably identical and they are, for example, chosen from those mentioned above in the description of the preparation of component (A).
The addition of imidazoline to the succinic derivative is usually carried out at room temperature; after the end of the addition, the mixture is heated to a temperature usually around 65 to 250 ° C, preferably around 80 to 200 ° C. The duration of the heating, after the end of the addition of imidazoline is usually 0.5 to 7 hours, preferably 1 to 5 hours. Heating is usually continued, at the chosen temperature, most often at reflux, until the end of the evolution of the water formed during the reaction.
The product obtained is then optionally isolated by removing, for example by vacuum distillation, the solvent used in the preparation. The amount of water removed during the reaction is usually about 0.2 to 0.8 moles and most often about 0.3 to 0.6 moles of water per mole of succinic derivative. The amount of imidazoline used in the reaction is usually at least 0.5 mole per mole of succinic derivative, for example from 0.5: 1 to 1.5: 1 and preferably from 0.9: 1 a 1.1: 1. Most of the time, approximately 1 mole of imidazoline is used per mole of succinic derivative. The formulations of the present invention can be used in the form of a solution in the reaction medium having served for the preparation of each of the constituents.
The formulations can also be added directly to the fuel or be previously diluted in a solvent chosen, for example, from those mentioned above for the preparation of each of the constituents.
Les formulations de la présente invention sont principalement utilisées comme additifs multifonctionnels pour un carburant pour moteurs, par exemple un carburant à base d'hydrocarbures ou à base d'un mélange d'hydrocarbures et d'au moins un composé oxygéné choisi dans le groupe formé par les alcools et les éthers, ou d'un carburant non hydrocarboné tel que par exemple un alcool ou un mélange d'alcools.
Les formulations de la présente invention sont particulièrement bien adaptées pour être utilisées comme additifs pour les carburants employés dans les moteurs à allumage commandé.
A titre d'exemples de carburants on peut citer les essences telles que par exemple celles définies par la norme ASTM D-439, les gas-oils ou carburants Diesel tels que, par exemple, ceux définis par la norme ASTM D-975. Ces carburants peuvent également contenir d'autres additifs que les formulations de la présente invention par exemple des additifs antidétonants tels que des composés de plomb (par exemple le plomb tétraéthyle), du méthyltertiobutyléther, du méthyl-tertioamyléther ou un mélange de méthanol et d'alcool tertiobutylique, des additifs antigels et des réducteurs d'exigence en octane.The formulations of the present invention are mainly used as multifunctional additives for a fuel for engines, for example a fuel based on hydrocarbons or based on a mixture of hydrocarbons and at least one oxygenated compound chosen from the group formed. by alcohols and ethers, or a non-hydrocarbon fuel such as for example an alcohol or a mixture of alcohols.
The formulations of the present invention are particularly well suited for use as additives for fuels used in spark ignition engines.
Examples of fuels that may be mentioned include gasolines such as, for example, those defined by standard ASTM D-439, gas oils or diesel fuels, such as, for example, those defined by standard ASTM D-975. These fuels may also contain other additives as the formulations of the present invention for example anti-knock additives such as lead compounds (for example tetraethyl lead), methyltertiobutylether, methyl-tertioamylether or a mixture of methanol and tert-butyl alcohol, anti-freeze additives and octane reducers.
Les formulations de la présente invention sont utilisées en quantité suffisante pour obtenir une diminution importante des dépôts sur les divers organes du moteur en particulier au niveau des soupapes d'admission et du carburateur. Habituellement on emploie des quantités représentant de 10 à 3000 ppm en poids de matière active par rapport au poids du carburant, de préférence de 10 à 1000 ppm et le plus souvent de 50 à 700 ppm. Dans les formulations selon la présente invention contenant l'ensemble des trois constituants (A), (B) et (C) la quantité du constituant (C) est habituellement de 10 à 2000 ppm, le plus souvent de 10 à 900 ppm de façon préférée de 30 à 800 ppm.
Les exemples suivants illustrent l'invention sans en limiter la portée.
Les exemples 1 à 5 décrivent la préparation des constituants (A) et (B) utilisés pour la préparation des formulations selon l'invention.The formulations of the present invention are used in an amount sufficient to obtain a significant reduction in deposits on the various components of the engine, in particular at the level of the intake valves and of the carburetor. Usually amounts are used representing from 10 to 3000 ppm by weight of active material relative to the weight of the fuel, preferably from 10 to 1000 ppm and most often from 50 to 700 ppm. In the formulations according to the present invention containing all of the three constituents (A), (B) and (C) the amount of the constituent (C) is usually from 10 to 2000 ppm, most often from 10 to 900 ppm so preferred from 30 to 800 ppm.
The following examples illustrate the invention without limiting its scope.
Examples 1 to 5 describe the preparation of constituents (A) and (B) used for the preparation of the formulations according to the invention.
Dans un réacteur de 2 litres muni d'une agitation mécanique, d'un Dean-Stark et d'un système de régulation de température on charge 408 g(0,40 mole) d'anhydride polyisobuténylsuccinique (PIBSA), résultant de la condensation de polyisobutène (polyisobutène de masse moléculaire moyenne en nombre de 920) sur l'anhydride maléique (le dosage des fonctions anhydride de ce produit montre que l'on a 0,7 fonction anhydride par mole théorique de PIBSA) et 408 g de xylène. On procède ensuite, à température ambiante et sous agitation, à l'addition goutte à goutte de 145 g (0,41 mole) de 1-(2-hydroxyéthyl)-2-heptadécényl imidazoline diluée dans 143 g de xylène. L'addition est effectuée en 30 minutes et accompagnée d'une augmentation rapide de température du mélange réactionnel d'environ 5 °C. Le mélange est ensuite porté à reflux pendant 3 heures avec élimination d'eau réactionnelle par distillation azéotropique. La quantité d'eau recueillie est de 2,3 ml. L'état d'avancement de la réaction peut également être suivi par spectrométrie infrarouge au niveau de la bande d'absorption de la fonction imine à 1660 cm⁻¹ qui disparait progressivement au cours de la réaction, tandis qu'apparaîssent deux bandes (1710 cm⁻¹ et 1770 cm⁻¹ )caractéristiques de la fonction succinimide.
On obtient ainsi une solution, à 50 % en poids de matière active, dans le xylène, du constituant 81.408 g (0.40 mole) of polyisobutenyl succinic anhydride (PIBSA), resulting from condensation, are charged to a 2-liter reactor fitted with mechanical agitation, a Dean-Stark and a temperature control system. of polyisobutene (polyisobutene of number average molecular mass of 920) on maleic anhydride (the assay of the anhydride functions of this product shows that there is 0.7 anhydride function per theoretical mole of PIBSA) and 408 g of xylene. Then, at room temperature and with stirring, the dropwise addition of 145 g (0.41 mole) of 1- (2-hydroxyethyl) -2-heptadecenyl imidazoline diluted in 143 g of xylene. The addition is carried out in 30 minutes and accompanied by a rapid increase in temperature of the reaction mixture of approximately 5 ° C. The mixture is then brought to reflux for 3 hours with elimination of reaction water by azeotropic distillation. The amount of water collected is 2.3 ml. The progress of the reaction can also be followed by infrared spectrometry at the level of the absorption band of the imine function at 1660 cm⁻¹ which gradually disappears during the reaction, while two bands appear (1710 cm⁻¹ and 1770 cm⁻¹) characteristics of the succinimide function.
A solution, at 50% by weight of active material, in xylene, of component 81 is thus obtained.
Dans un réacteur de 2 litres muni d'une agitation mécanique, d'un Dean-Stark et d'un système de régulation de température on introduit 15,6 g (0,15 mole) de N-hydroxyéthyléthylènediamine diluée dans 15,6 g de toluène. On ajoute ensuite progressivement (goutte à goutte) 9 g (0,15 mole) d'acide acétique glacial dilué dans 9 g de toluène. Le mélange est ensuite porté au reflux pendant 16 heures au cours desquelles on élimine 4,8 ml d'eau par distillation azéotropique. Le produit de la réaction est isolé après évaporation sous vide du toluène. On obtient ainsi un produit huileux jaune pale qui a été caractérisé par les moyens classiques d'analyses comme étant la 1-(2-hydroxyéthyl)-2-méthyl imidazoline.15.6 g (0.15 mole) of N-hydroxyethylethylenediamine diluted in 15.6 g are introduced into a 2 liter reactor fitted with mechanical stirring, a Dean-Stark and a temperature control system toluene. 9 g (0.15 mol) of glacial acetic acid diluted in 9 g of toluene are then added gradually (dropwise). The mixture is then brought to reflux for 16 hours during which 4.8 ml of water are removed by azeotropic distillation. The reaction product is isolated after evaporation of the toluene under vacuum. A pale yellow oily product is thus obtained which has been characterized by conventional means of analysis as being 1- (2-hydroxyethyl) -2-methyl imidazoline.
Le spectre infrarouge fait apparaître une bande imine à 1660 cm⁻¹ et en spectrométrie de résonance magnétique nucléaire on détecte la présence des deux groupes méthylène du cycle imidazoline et la présence du groupe méthyle en position 2 sur le cycle imidazoline. L'analyse élémentaire fournit un pourcentage d'azote de 22,1 % en poids pour un pourcentage calculé de 21,8 %.
La procédure décrite dans l'exemple 1 est répétée en remplaçant la 1-(2-hydroxyéthyl)-2-heptadécénylimidazoline par la 1-(2-hydroxyéthyl)-2-méthylimidazoline préparée ci-avant. On a utilisé 122,4 g (0,12 mole) de PIBSA dilué dans 122,4 g de xylène et 6,1 g (0,048 mole) d'imidazoline préparée comme ci-avant diluée dans 5 g de xylène. Le reflux est maintenu pendant 3 heures et on élimine 0,9 ml d'eau. On obtient ainsi une solution, à 50% en poids de matière active, dans le xylène, du constituant B2.The infrared spectrum shows an imine band at 1660 cm⁻¹ and in nuclear magnetic resonance spectrometry we detect the presence of the two methylene groups of the imidazoline cycle and the presence of the methyl group in position 2 on the imidazoline cycle. Elemental analysis provides a percentage of nitrogen of 22.1% by weight for a calculated percentage of 21.8%.
The procedure described in Example 1 is repeated, replacing 1- (2-hydroxyethyl) -2-heptadecenylimidazoline with 1- (2-hydroxyethyl) -2-methylimidazoline prepared above. 122.4 g (0.12 mole) of PIBSA diluted in 122.4 g of xylene and 6.1 g (0.048 mole) of imidazoline prepared as above diluted in 5 g of xylene were used. The reflux is maintained for 3 hours and 0.9 ml of water is removed. A solution is thus obtained, at 50% by weight of active material, in xylene, of component B2.
La procédure décrite dans l'exemple 1 est répétée en remplaçant l'imidazoline par une diamine de suif telle que celle commercialisée sous la marque Dinoram S par la société CECA et correspondant à la coupe E dont les caractéristiques ont été mentionnées dans le tableau I ci-avant.
On a utilisé 306 g (0,3 mole) de PIBSA dilué dans 306 g de xylène et 108 g (0,3 mole) de Dinoram S diluée dans 108 g de xylène. Le reflux est maintenu pendant 5 heures. L'eau de réaction est éliminée au fur et à mesure de sa formation ; cette élimination se produit essentiellement pendant les 4 premières heures de réaction. On obtient ainsi une solution, ajustée à 50% en poids de matière active, dans le xylène, du constituant A2.The procedure described in Example 1 is repeated, replacing the imidazoline with a tallow diamine such as that sold under the brand Dinoram S by the company CECA and corresponding to cut E, the characteristics of which have been mentioned in table I below. -before.
306 g (0.3 mole) of PIBSA diluted in 306 g of xylene and 108 g (0.3 mole) of Dinoram S diluted in 108 g of xylene were used. The reflux is maintained for 5 hours. The reaction water is eliminated as it is formed; this elimination mainly occurs during the first 4 hours of reaction. A solution is thus obtained, adjusted to 50% by weight of active material, in xylene, of component A2.
La procédure de l'exemple 3 est répétée en remplaçant la Dinoram S par 0,3 mole de tétraétriylènepentamine (56 g) diluée dans 56 g de xylène. Le reflux est maintenu pendant 5 heures. L'eau de réaction est éliminée au fur et à mesure de sa formation; cette élimination se produit essentiellement pendant les 4 premières heures de réaction. On obtient ainsi une solution, à 50 % en poids de matière active, dans le xylène, du constituant A3.The procedure of Example 3 is repeated, replacing Dinoram S with 0.3 mole of tetraetriylenepentamine (56 g) diluted in 56 g of xylene. The reflux is maintained for 5 hours. The reaction water is eliminated as it is formed; this elimination mainly occurs during the first 4 hours of reaction. A solution is thus obtained, at 50% by weight of active material, in xylene, of the constituent A3.
La procédure décrite dans l'exemple 1 est répétée en remplaçant l'imidazoline par la polyoxyalkylèneamine commercialisée par la société TEXACO sous le nom Jeffamine D-400 de masse moléculaire moyenne en nombre de 400. La Jeffamine D-400 est ajoutée sous forme d'une solution dans le xylène contenant 164 g (0,41 mole) de Jeffamine D-400. Le reflux est maintenu pendant toute la durée de l'élimination de l'eau de réaction par distillation azéotropique, puis pendant une heure supplémentaire. On obtient ainsi une solution, ajustée à 50% en poids de matière active, dans le xylène du constituant A4.The procedure described in Example 1 is repeated, replacing the imidazoline with the polyoxyalkyleneamine sold by the company TEXACO under the name Jeffamine D-400 with a number average molecular mass of 400. The Jeffamine D-400 is added in the form of a solution in xylene containing 164 g (0.41 mole) of Jeffamine D-400. The reflux is maintained throughout the elimination of the reaction water by azeotropic distillation, then for an additional hour. A solution is thus obtained, adjusted to 50% by weight of active material, in the xylene of the constituent A4.
Pour montrer l'effet de formulations selon l'invention sur la tendance des carburants à former des dépôts sur les soupapes d'admission on utilise un véhicule Renault 11 GTL. Les essais sont réalisés par traitements de type préventif sur un parcours de 5000 km. Le carburant utilisé est un supercarburant classique additivé en alkyles de plomb à 0,4 g de plomb par litre (carburant de base).
Ce supercarburant comprend en volume : 48,1 % de paraffines
15,4 % d'oléfines
29,2 % d'aromatiques
et 4,3 % de naphténiques
Au départ de chaque test le moteur est conditionné avec des soupapes neuves que l'on pèse. En fin d'essai, les soupapes sont démontées, lavées à l'hexane, séchées, puis pesées après élimination physique (par grattage) des dépôts formés sur la soupape côté chambre de combustion.
Les résultats présentés ci-après donnent le poids de dépôts mesuré, sur la tulipe de chaque soupape d'admission, par différence entre le poids de la soupape neuve et le poids de la soupape à la fin de chaque essai après élimination des dépôts côté chambre de combustion.
Onze essais sont effectués à partir des carburants suivants.
- C1 : Carburant de base seul
- C2 : Carburant de base contenant 306 ppm en masse de matière active du constituant B1
- C3 : Carburant de base contenant 306 ppm en masse de matière active du constituant A2
- C4 : Carburant de base contenant 306 ppm en masse de matière active du constituant B2
- C5 : Carburant de base contenant 306 ppm en masse de matière active du constituant A3
- C6 : Carburant de base contenant 306 ppm en masse de matière active d'un mélange du constituant A3 et du constituant B1 dans un rapport de molaire 0,7 : 1
- C7 : Carburant de base contenant 306 ppm en masse de matière active d'un mélange du constituant A3 et du constituant B1 dans un rapport molaire de 0,4 : 1
- C8 : Carburant de base contenant 306 ppm en masse de matière active d'un mélange du constituant A3 et du constituant B2 dans un rapport molaire de 2 : 1
- C9 : Carburant de base contenant 306 ppm en masse de matière active du mélange du constituant A2 et du Constituant B1 dans un rapport molaire de 0,7 : 1
- C10 : Carburant de base contenant 306 ppm en masse de matière active d'un mélange du constituant A2 et du constituant B2 dans rapport molaire de 0,7 : 1.
- C11 : Carburant de base contenant 306 ppm en masse de matière active d'un mélange du constituant A4 et du constituant B1 dans un rapport molaire de 0,7 : 1.
This premium fuel comprises by volume: 48.1% paraffins
15.4% olefins
29.2% aromatics
and 4.3% naphthenics
At the start of each test, the engine is conditioned with new valves that are weighed. At the end of the test, the valves are dismantled, washed with hexane, dried, then weighed after physical removal (by scraping) of the deposits formed on the valve on the combustion chamber side.
The results presented below give the weight of deposits measured, on the tulip of each intake valve, by difference between the weight of the new valve and the weight of the valve at the end of each test after elimination of deposits on the chamber side. combustion.
Eleven tests are carried out using the following fuels.
- C1: Basic fuel only
- C2: Base fuel containing 306 ppm by mass of active ingredient of component B1
- C3: Base fuel containing 306 ppm by mass of active ingredient of component A2
- C4: Base fuel containing 306 ppm by mass of active ingredient of component B2
- C5: Base fuel containing 306 ppm by mass of active ingredient of component A3
- C6: Base fuel containing 306 ppm by mass of active material of a mixture of component A3 and component B1 in a molar ratio 0.7: 1
- C7: Base fuel containing 306 ppm by mass of active material of a mixture of component A3 and component B1 in a molar ratio of 0.4: 1
- C8: Base fuel containing 306 ppm by mass of active material of a mixture of component A3 and component B2 in a molar ratio of 2: 1
- C9: Base fuel containing 306 ppm by mass of active material of the mixture of component A2 and component B1 in a molar ratio of 0.7: 1
- C10: Base fuel containing 306 ppm by mass of active material of a mixture of component A2 and component B2 in molar ratio of 0.7: 1.
- C11: Base fuel containing 306 ppm by mass of active material of a mixture of component A4 and component B1 in a molar ratio of 0.7: 1.
Les résultats obtenus sont présentés dans le tableau II ci-après
On constate que l'utilisation des carburants C6 à C11 comprenant des formulations selon l'invention entraine un dépôt sur les soupapes nettement inférieur à celui obtenu lors de l'utilisation du carburant de base C1 et inférieur à celui obtenu avec les carburants C2 à C5 contenant les additifs séparés (comparer, par exemple, le cas du carburant C6 au cas des carburants C2 et C5)It is noted that the use of fuels C6 to C11 comprising formulations according to the invention leads to a deposition on the valves significantly lower than that obtained during the use of the base fuel C1 and lower than that obtained with the fuels C2 to C5 containing the separate additives (compare, for example, the case of fuel C6 with the case of fuels C2 and C5)
On procède à l'évaluation des propriétés de détergence "carburateur" des formulations selon l'invention et des additifs séparés à titre de comparaison.The “carburetor” detergency properties of the formulations according to the invention and of the separate additives are evaluated for comparison.
La procédure d'essai sur moteur est effectuée en suivant la norme européenne R5-CEC-FO3-T-81. Les résultats sont exprimés en terme de mérite de zéro à dix. Un mérite 10 correspond à un carburateur propre et un mérite 0 à un carburateur très encrassé. Les essais sont effectués à partir des carburants C1 à C10 décrits dans l'exemple 6. Les résultats obtenus sont présentés dans le tableau III ci-après.
On procède à l'évaluation des propriétés d'anti-corrosion des formulations selon l'invention.The anti-corrosion properties of the formulations according to the invention are evaluated.
Les essais consistent à déterminer l'étendue de la corrosion produite sur des échantillons d'acier ordinaire poli, en présence d'eau de mer synthétique, en suivant la norme ASTM D 665 modifiée (température 32,2 °C, durée 20 heures). Les essais sont effectués à partir de certains des carburants décrits dans l'exemple 6. Les résultats obtenus sont présentés dans le tableau IV ci-après ; ils sont exprimés en pourcentages (%) de la surface de l'éprouvette corrodée au bout de heures.
On prépare des solutions, à 40% en poids de matière active, dans le xylène, de formulations F1 à F4 comprenant diverses quantités pondérales du polypropylèneglycol (constituant (C)) de formule :
Une série d'essais est effectuée de manière à évaluer les propriétés de détergence soupapes de diverses formulations. Les essais ont été réalisés sur banc moteur Mercédes M102E, sans additif dans le cas des exemples 11 à 14 inclus. La procédure d'essai est une procédure clasique comprenant l'utilisation d'un moteur ayant 4 cylindres, de type Mercédes M102E, ayant une cylindrée de 2299 cm³ et un taux de compression de 9/1. La procédure de test est une procédure cyclique, chaque cycle comprenant quatre périodes succesives de fonctionnement :
- 30 s (secondes) à 800 t/min (tours par minute) sous une charge nulle,
- 60 s à 1300 t/min sous une charge de 31 newtons (mxkgxs-2),
- 120 s à 1850 t/min sous une charge de 34 newtons et
- 60 s à 3000 t/min sous une charge de 37 newtons.
A series of tests is carried out in order to assess the detergency properties of valves of various formulations. The tests were carried out on a Mercédes M102E engine test bench, without additives in the case of examples 11 to 14 inclusive. The test procedure is a standard procedure comprising the use of an engine having 4 cylinders, of the Mercedes M102E type, having a displacement of 2299 cc and a compression ratio of 9/1. The test procedure is a cyclic procedure, each cycle comprising four successive periods of operation:
- 30 s (seconds) at 800 rpm (revolutions per minute) under zero load,
- 60 s at 1300 rpm under a load of 31 newtons (mxkgxs-2),
- 120 s at 1850 rpm under a load of 34 newtons and
- 60 s at 3000 rpm under a load of 37 newtons.
La durée de chaque test est habituellement de 40 à 150 heures; dans les exemples 10 à 14 la durée de l'essai a été fixée à 40 heures. Au départ de chaque test le moteur est conditionné avec des soupapes neuves que l'on pèse. En fin d'essai, les soupapes sont démontées, lavées à l'hexane, séchées, puis pesées après élimination physique (par grattage) des dépôts formés sur la soupape côté chambre de combustion. Les résultats présentés ci-après donnent la moyenne de dépôts en poids rapportée à une soupape, calculée à partir du poids de dépôts mesuré, sur la tulipe de chaque soupape d'admission, par différence entre le poids de ladite soupape neuve et le poids de ladite soupape à la fin de chaque essai après élimination des dépôts côté chambre de combustion. On évalue également par cotation visuelle l'état de chaque soupape (côté admission : tulipe) en terme de mérite de 1 à 10 selon la procédure habituellement dénommée CRC (initiales anglaises de Coordinating Research Council) par les hommes du métier; les résultats sont exprimés ci-après sous forme de moyenne par soupape, un mérite de 10 correspond à une soupape propre et un mérite de 1 à une soupape très encrassée. On évalue également, au cours du démontage des soupapes, l'aspect collant ou non collant des dépôts formés sur les soupapes d'admission côté admission. La tendance à former des dépôts d'aspect collant pourrait indiquer, à terme, une tendance à l'apparition future du phénomène dit de collage des soupapes, phénomène qu'il est souhaitable d'éviter.
Le carburant utilisé dans ces évaluations est un supercarburant, sans plomb, comprenant 2% en volume d'un mélange de méthanol et de tertiobutanol dans un rapport volumique de 1,5 : 1. Ce supercarburant, d'indice d'octane moteur de 85 et d'indice d'octane recherche de distillation de 227°C; il comprend en volume :
- 49% d'aromatiques
- 11% d'oléfines
- 40% de composés saturés (paraffines + naphténiques)The duration of each test is usually 40 to 150 hours; in examples 10 to 14 the duration of the test was fixed at 40 hours. At the start of each test, the engine is conditioned with new valves that are weighed. At the end of the test, the valves are dismantled, washed with hexane, dried, then weighed after physical removal (by scraping) of the deposits formed on the valve on the combustion chamber side. The results presented below give the average of deposits by weight relative to a valve, calculated from the weight of deposits measured, on the tulip of each intake valve, by difference between the weight of said new valve and the weight of said valve at the end of each test after removal of deposits on the combustion chamber side. The state of each valve (intake side: tulip) is also evaluated by visual rating in terms of merit from 1 to 10 according to the procedure usually called CRC (English initials of Coordinating Research Council) by those skilled in the art; the results are expressed below as an average per valve, a merit of 10 corresponds to a clean valve and a merit of 1 to a very dirty valve. During the disassembly of the valves, the tacky or non-sticky appearance of deposits formed on the intake side intake valves is also evaluated. The tendency to form deposits of sticky appearance could indicate, in the long term, a tendency to the future appearance of the phenomenon known as of sticking of the valves, phenomenon which it is desirable to avoid.
The fuel used in these assessments is an unleaded premium fuel, comprising 2% by volume of a mixture of methanol and tert-butanol in a volume ratio of 1.5: 1. This premium fuel, with an octane rating of 85 and octane distillation search of 227 ° C; it includes in volume:
- 49% aromatics
- 11% olefins
- 40% of saturated compounds (paraffins + naphthenics)
Les formulations sont ajoutées au carburant de manière à obtenir une concentration, en poids de matière active dans le carburant additivé, précisé pour chaque exemple dans le tableau V ci-après donnant les résultats obtenus.
L'analyse des résultats obtenus dans les exemples 10 à 14 montre que les formulations selon la présente invention comprenant les trois constituants (A), (B) et (C) permettent de réduire très largement les quantités de dépôts formés sur les soupapes d'admission et également de changer l'aspect de ces dépôts par rapport à celui qu'ils ont en présence d'une formulation ne contenant pas le constituant (C).Analysis of the results obtained in Examples 10 to 14 shows that the formulations according to the present invention comprising the three constituents (A), (B) and (C) make it possible to greatly reduce the amounts of deposits formed on the pressure valves. admission and also to change the appearance of these deposits compared to that which they have in the presence of a formulation not containing the constituent (C).
Claims (15)
(III) HO--R--(-O--R--)x-O--R--OH
dans laquelle chacun des groupes R indépendamment représente un groupe hydrocarboné ayant de 2 à 6 atomes de carbone et x représente le degré moyen de polymérisation.10. Formulation according to one of claims 1 to 9 characterized in that it further comprises at least one component (C) consisting of at least one polyglycol, soluble in said fuel, of number average molecular weight from 480 to 2100 and of general formula (III):
(III) HO - R - (- O - R--) x -O - R - OH
wherein each of the R groups independently represents a hydrocarbon group having 2 to 6 carbon atoms and x represents the average degree of polymerization.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT89401846T ATE74950T1 (en) | 1988-06-29 | 1989-06-28 | RECIPES OF NITROGEN CONTAINING ADDITIVES FOR ENGINE FUEL AND CONTAINING ENGINE FUEL. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8808900 | 1988-06-29 | ||
FR8808900A FR2633638B1 (en) | 1988-06-29 | 1988-06-29 | FORMULATIONS OF NITROGEN ADDITIVES FOR ENGINE FUELS AND THE ENGINE FUELS CONTAINING THE SAME |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0353116A1 true EP0353116A1 (en) | 1990-01-31 |
EP0353116B1 EP0353116B1 (en) | 1992-04-15 |
Family
ID=9367960
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89401846A Expired - Lifetime EP0353116B1 (en) | 1988-06-29 | 1989-06-28 | Recipes of nitrogenous additives for engine fuels, and engine fuels containing them |
Country Status (13)
Country | Link |
---|---|
US (1) | US4976746A (en) |
EP (1) | EP0353116B1 (en) |
JP (1) | JP2645893B2 (en) |
AT (1) | ATE74950T1 (en) |
BR (1) | BR8903221A (en) |
CA (1) | CA1340495C (en) |
DE (1) | DE68901226D1 (en) |
DK (1) | DK174037B1 (en) |
ES (1) | ES2032666T3 (en) |
FR (1) | FR2633638B1 (en) |
MY (1) | MY106959A (en) |
NO (1) | NO173554C (en) |
ZA (1) | ZA894901B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0411811A1 (en) * | 1989-08-03 | 1991-02-06 | Texaco Development Corporation | Process for producing ORI control additives |
WO1994013758A1 (en) * | 1992-12-17 | 1994-06-23 | Institut Francais Du Petrole | Middle petroleum distillate composition containing a paraffin settling speed limiter |
WO1995009220A1 (en) * | 1993-09-30 | 1995-04-06 | Elf Antar France | Low temperature operability additive compositions of average distillates |
FR2839315A1 (en) * | 2002-05-03 | 2003-11-07 | Totalfinaelf France | ADDITIVE FOR IMPROVING THERMAL STABILITY OF HYDROCARBON COMPOSITIONS |
US6860908B2 (en) | 1992-12-17 | 2005-03-01 | Institut Francais du Pétrole | Petroleum middle distillate composition containing a substance for limiting the paraffin sedimentation rate |
US20110296746A1 (en) * | 2010-06-03 | 2011-12-08 | Instituto Mexicano Del Petroleo | Amino and imino propionic acids, process of preparation and use |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2680796B1 (en) * | 1991-08-30 | 1994-10-21 | Inst Francais Du Petrole | FORMULATION OF FUEL ADDITIVES COMPRISING PRODUCTS WITH ESTER FUNCTION AND A DETERGENT - DISPERSANT. |
US5348674A (en) * | 1993-04-12 | 1994-09-20 | Mobil Oil Corporation | Amide/ester heterocyclic derivatives of hydrocarbylsuccinic anhydrides as rust/corrosion inhibiting additives for lubricants |
US5601624A (en) * | 1995-04-10 | 1997-02-11 | Mobil Oil Corporation | Fuel composition with reaction product of oxygenated amine, dicarbonyl linking agent, and hydrocarbyl(ene) amine |
FR2749756B1 (en) * | 1996-06-14 | 1998-09-11 | Bioland | PROCESS FOR THE PREPARATION OF AN IMPLANTABLE COMPOSITE MATERIAL, MATERIAL OBTAINED, IMPLANT COMPRISING SUCH MATERIAL, AND IMPLEMENTATION KIT |
FR2792646B1 (en) * | 1999-04-26 | 2001-07-27 | Elf Antar France | COMPOSITION OF MULTI-FUNCTIONAL COLD OPERABILITY ADDITIVES FOR MEDIUM DISTILLATES |
US20030056431A1 (en) * | 2001-09-14 | 2003-03-27 | Schwab Scott D. | Deposit control additives for direct injection gasoline engines |
JP2008509236A (en) * | 2004-08-06 | 2008-03-27 | ビーエーエスエフ ソシエタス・ヨーロピア | Polyamine additives for fuels and lubricants |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB708193A (en) * | 1951-05-08 | 1954-04-28 | Thompson Prod Inc | Improvements in or relating to fuel charges for internal combustion engines |
FR2096298A5 (en) * | 1970-06-16 | 1972-02-11 | Shell Int Research | |
FR2133072A5 (en) * | 1971-04-07 | 1972-11-24 | Lubrizol Corp | Hydrocarbon fuel additive compsn - for cleaning fuel systems in engines, furnaces etc |
US4151173A (en) * | 1971-05-17 | 1979-04-24 | The Lubrizol Corporation | Acylated polyoxyalkylene polyamines |
EP0071513A2 (en) * | 1981-07-30 | 1983-02-09 | Institut Français du Pétrole | Additives for use as pour point dispersants for middle distillate hydrocarbons, and compositions of middle distillate hydrocarbons containing said additives |
EP0074724A2 (en) * | 1981-09-03 | 1983-03-23 | The Lubrizol Corporation | Acylated imidazolines and fuel and lubricant compositions thereof |
EP0144922A2 (en) * | 1983-12-03 | 1985-06-19 | Mineralölwerke Wenzel und Weidmann Zweigniederlassung der Fuchs Mineralölwerke GmbH, Mannheim | Lubricant |
US4531948A (en) * | 1984-06-13 | 1985-07-30 | Ethyl Corporation | Alcohol and gasohol fuels having corrosion inhibiting properties |
USRE32174E (en) * | 1981-12-14 | 1986-06-10 | The Lubrizol Corporation | Combination of hydroxy amines and carboxylic dispersants as fuel additives |
US4659336A (en) * | 1986-03-28 | 1987-04-21 | Texaco Inc. | Motor fuel composition |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2568876A (en) * | 1949-11-14 | 1951-09-25 | Socony Vacuum Oil Co Inc | Reaction products of n-acylated polyalkylene-polyamines with alkenyl succinic acid anhydrides |
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 |
US3138610A (en) * | 1961-03-10 | 1964-06-23 | Gen Aniline & Film Corp | Substituted imidazolines |
US3458530A (en) * | 1962-11-21 | 1969-07-29 | Exxon Research Engineering Co | Multi-purpose polyalkenyl succinic acid derivative |
US3312619A (en) * | 1963-10-14 | 1967-04-04 | Monsanto Co | 2-substituted imidazolidines and their lubricant compositions |
FR2414542A1 (en) * | 1978-01-11 | 1979-08-10 | Orogil | NEW COMPOSITIONS BASED ON ALCENYLSUCCINIMIDES, DERIVED FROM TRIS (5-AMINO-THIA-3 PENTYL) AMINE, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS ADDITIVES FOR LUBRICANTS |
US4247300A (en) * | 1978-04-27 | 1981-01-27 | Phillips Petroleum Company | Imidazoline fuel detergents |
FR2476119B1 (en) * | 1980-02-15 | 1985-07-26 | Inst Francais Du Petrole | N-SUBSTITUTED SUCCINIMIDE ETHERS, THEIR PREPARATION AND THEIR USE AS FUEL ADDITIVES |
-
1988
- 1988-06-29 FR FR8808900A patent/FR2633638B1/en not_active Expired - Lifetime
-
1989
- 1989-06-27 MY MYPI89000870A patent/MY106959A/en unknown
- 1989-06-27 DK DK198903194A patent/DK174037B1/en not_active IP Right Cessation
- 1989-06-27 NO NO892658A patent/NO173554C/en not_active IP Right Cessation
- 1989-06-28 ES ES198989401846T patent/ES2032666T3/en not_active Expired - Lifetime
- 1989-06-28 ZA ZA894901A patent/ZA894901B/en unknown
- 1989-06-28 EP EP89401846A patent/EP0353116B1/en not_active Expired - Lifetime
- 1989-06-28 AT AT89401846T patent/ATE74950T1/en not_active IP Right Cessation
- 1989-06-28 DE DE8989401846T patent/DE68901226D1/en not_active Expired - Fee Related
- 1989-06-28 US US07/372,598 patent/US4976746A/en not_active Expired - Lifetime
- 1989-06-29 BR BR898903221A patent/BR8903221A/en not_active IP Right Cessation
- 1989-06-29 JP JP1168292A patent/JP2645893B2/en not_active Expired - Fee Related
- 1989-06-29 CA CA000604407A patent/CA1340495C/en not_active Expired - Fee Related
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB708193A (en) * | 1951-05-08 | 1954-04-28 | Thompson Prod Inc | Improvements in or relating to fuel charges for internal combustion engines |
FR2096298A5 (en) * | 1970-06-16 | 1972-02-11 | Shell Int Research | |
FR2133072A5 (en) * | 1971-04-07 | 1972-11-24 | Lubrizol Corp | Hydrocarbon fuel additive compsn - for cleaning fuel systems in engines, furnaces etc |
US4151173A (en) * | 1971-05-17 | 1979-04-24 | The Lubrizol Corporation | Acylated polyoxyalkylene polyamines |
EP0071513A2 (en) * | 1981-07-30 | 1983-02-09 | Institut Français du Pétrole | Additives for use as pour point dispersants for middle distillate hydrocarbons, and compositions of middle distillate hydrocarbons containing said additives |
EP0074724A2 (en) * | 1981-09-03 | 1983-03-23 | The Lubrizol Corporation | Acylated imidazolines and fuel and lubricant compositions thereof |
USRE32174E (en) * | 1981-12-14 | 1986-06-10 | The Lubrizol Corporation | Combination of hydroxy amines and carboxylic dispersants as fuel additives |
EP0144922A2 (en) * | 1983-12-03 | 1985-06-19 | Mineralölwerke Wenzel und Weidmann Zweigniederlassung der Fuchs Mineralölwerke GmbH, Mannheim | Lubricant |
US4531948A (en) * | 1984-06-13 | 1985-07-30 | Ethyl Corporation | Alcohol and gasohol fuels having corrosion inhibiting properties |
US4659336A (en) * | 1986-03-28 | 1987-04-21 | Texaco Inc. | Motor fuel composition |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0411811A1 (en) * | 1989-08-03 | 1991-02-06 | Texaco Development Corporation | Process for producing ORI control additives |
WO1994013758A1 (en) * | 1992-12-17 | 1994-06-23 | Institut Francais Du Petrole | Middle petroleum distillate composition containing a paraffin settling speed limiter |
FR2699550A1 (en) * | 1992-12-17 | 1994-06-24 | Inst Francais Du Petrole | Medium petroleum distillate composition containing nitrogen additives which can be used as agents for limiting the sedimentation rate of paraffins. |
US6860908B2 (en) | 1992-12-17 | 2005-03-01 | Institut Francais du Pétrole | Petroleum middle distillate composition containing a substance for limiting the paraffin sedimentation rate |
WO1995009220A1 (en) * | 1993-09-30 | 1995-04-06 | Elf Antar France | Low temperature operability additive compositions of average distillates |
FR2710652A1 (en) * | 1993-09-30 | 1995-04-07 | Elf Antar France | Cold operability additive composition of middle distillates. |
FR2839315A1 (en) * | 2002-05-03 | 2003-11-07 | Totalfinaelf France | ADDITIVE FOR IMPROVING THERMAL STABILITY OF HYDROCARBON COMPOSITIONS |
WO2003095593A1 (en) * | 2002-05-03 | 2003-11-20 | Total France | Additive for improving the thermal stability of hydrocarbon compositions |
US20110296746A1 (en) * | 2010-06-03 | 2011-12-08 | Instituto Mexicano Del Petroleo | Amino and imino propionic acids, process of preparation and use |
US10167249B2 (en) | 2010-06-03 | 2019-01-01 | Instituto Mexicano Del Petroleo | Amino and imino propionic acids, process of preparation and use |
US10207983B2 (en) | 2010-06-03 | 2019-02-19 | Instituto Mexicano Del Petroleo | Amino and imino propionic acids, process of preparation and use |
Also Published As
Publication number | Publication date |
---|---|
DE68901226D1 (en) | 1992-05-21 |
FR2633638B1 (en) | 1991-04-19 |
DK319489D0 (en) | 1989-06-27 |
BR8903221A (en) | 1990-02-13 |
CA1340495C (en) | 1999-04-13 |
NO892658L (en) | 1990-01-02 |
DK319489A (en) | 1990-02-14 |
JP2645893B2 (en) | 1997-08-25 |
NO892658D0 (en) | 1989-06-27 |
FR2633638A1 (en) | 1990-01-05 |
NO173554C (en) | 1993-12-29 |
US4976746A (en) | 1990-12-11 |
DK174037B1 (en) | 2002-05-06 |
ZA894901B (en) | 1990-03-28 |
EP0353116B1 (en) | 1992-04-15 |
NO173554B (en) | 1993-09-20 |
JPH02196889A (en) | 1990-08-03 |
ATE74950T1 (en) | 1992-05-15 |
ES2032666T3 (en) | 1993-02-16 |
MY106959A (en) | 1995-08-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2266522C (en) | Detergent and anti-corrosive additive for fuels and fuel composition | |
EP0271385B1 (en) | Polymers having nitrogen functions derived from unsaturated polyesters, and their use as additives for lowering the flow point of middle distillate hydrocarbons | |
CA1201722A (en) | Nitrogen containing copolymers especially useful as additives for the lowering of hydrocarbons middle distillates turbidity point; hydrocarbons middle distillates compositions containing said copolymers | |
EP0353116B1 (en) | Recipes of nitrogenous additives for engine fuels, and engine fuels containing them | |
FR2528423A1 (en) | Nitrogen contg. additives reducing cloud pt. of middle distillates - obtd. by reacting aliphatic di:carboxylic cpd., of e.g. (alkyl)maleic anhydride, with amide cpds. | |
BE1020410A3 (en) | FUEL ADDITIVES TO MAINTAIN THE PERFORMANCE OF THE OPTIMAL INJECTOR. | |
EP0071513A2 (en) | Additives for use as pour point dispersants for middle distillate hydrocarbons, and compositions of middle distillate hydrocarbons containing said additives | |
EP0327423A1 (en) | Polymers derived from unsaturated polyesters by addition of compounds having an amine function, and their use as additives to modify the properties in the cold state of middle distillates of petroleum | |
BE1019145A5 (en) | ADDITIVES IMPROVING CONDUCTIVITY FOR FUELS. | |
FR2699550A1 (en) | Medium petroleum distillate composition containing nitrogen additives which can be used as agents for limiting the sedimentation rate of paraffins. | |
EP0349369B1 (en) | Composition obtained from hydroxy-imidazolines and polyamines, and their use as fuel additives | |
EP4157971B1 (en) | Additive composition for motor fuel | |
EP0530094B1 (en) | Motor fuel additive formulation comprising ester products and a detergent-dispersant agent | |
EP0627483B1 (en) | Additives formulated for motor-fuels containing at least one alkoxylated imidazo-oxazole compound | |
EP4157972A1 (en) | Use of a fuel composition comprising three additives for cleaning the internal parts of petrol engines | |
FR2679902A1 (en) | POLYAZOT COMPOUNDS COMPRISING TWO IMIDE TYPE TERMINAL CYCLES, THEIR PREPARATIONS AND THEIR USES. | |
EP0596769A1 (en) | Motor fuel additives compositions comprising nitrogenated products having two imide rings and motor fuels containing them | |
FR2633637A1 (en) | Compositions obtained from hydroxyimidazolines and polyamines and their use as fuel additives | |
BE1017295A3 (en) | DETERGENT FOR DIESEL. | |
FR2617861A1 (en) | Heterocyclic compounds capable of being employed as additives to motor vehicle fuels and compositions containing the said compounds | |
WO2002048212A1 (en) | Guanidinoalkylated compounds, preparation thereof and use as fuel and lubricant additives | |
FR2705964A1 (en) | Polyalkoxylated imidazooxazoles, their preparations and their uses | |
FR2649118A2 (en) | Improved additives formulation for engine fuels and engine fuels containing them | |
FR2743811A1 (en) | PROCESS FOR PRODUCING ALKENYL SUCCINIMIDES OR POLYALKENYL SUCCINIMIDES | |
FR2648472A2 (en) | Improved formulation containing nitrogenous additives for engine fuels and the engine fuels containing them |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19900217 |
|
17Q | First examination report despatched |
Effective date: 19910426 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
ITF | It: translation for a ep patent filed | ||
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 74950 Country of ref document: AT Date of ref document: 19920515 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 68901226 Country of ref document: DE Date of ref document: 19920521 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2032666 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
EAL | Se: european patent in force in sweden |
Ref document number: 89401846.4 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20070618 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20070620 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20070626 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20070627 Year of fee payment: 19 Ref country code: NL Payment date: 20070627 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20070629 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20070625 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20070622 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20080617 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20080410 Year of fee payment: 20 |
|
BERE | Be: lapsed |
Owner name: INSTITUT FRANCAIS DU *PETROLE Effective date: 20080630 Owner name: *ELF FRANCE Effective date: 20080630 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
EUG | Se: european patent has lapsed | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20080628 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20090101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080630 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20090228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090101 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080628 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080628 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080630 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080630 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20090629 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080628 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20090629 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080629 |