EP3940043B1 - Corrosion inhibitors for fuels and lubricants - Google Patents
Corrosion inhibitors for fuels and lubricants Download PDFInfo
- Publication number
- EP3940043B1 EP3940043B1 EP21177666.1A EP21177666A EP3940043B1 EP 3940043 B1 EP3940043 B1 EP 3940043B1 EP 21177666 A EP21177666 A EP 21177666A EP 3940043 B1 EP3940043 B1 EP 3940043B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fuels
- use according
- olefin
- carbon atoms
- isomers
- 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.)
- Active
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- 239000000446 fuel Substances 0.000 title claims description 70
- 238000005260 corrosion Methods 0.000 title claims description 32
- 230000007797 corrosion Effects 0.000 title claims description 31
- 239000003112 inhibitor Substances 0.000 title claims description 21
- 239000000314 lubricant Substances 0.000 title claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 83
- -1 acrylic ester Chemical class 0.000 claims description 67
- 239000000203 mixture Substances 0.000 claims description 64
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical class CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- 150000001336 alkenes Chemical class 0.000 claims description 47
- 239000000654 additive Substances 0.000 claims description 45
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 37
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 31
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000004711 α-olefin Substances 0.000 claims description 26
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 24
- 150000008064 anhydrides Chemical group 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
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- 239000002283 diesel fuel Substances 0.000 claims description 16
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- 230000000996 additive effect Effects 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Chemical class CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 8
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 8
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- 229920001155 polypropylene Polymers 0.000 claims description 4
- ZDLBWMYNYNATIW-UHFFFAOYSA-N tetracos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCCCCC=C ZDLBWMYNYNATIW-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
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- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Chemical class CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 2
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 claims 2
- 239000000047 product Substances 0.000 description 34
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- 239000002808 molecular sieve Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 description 1
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- QUISWUAUMRRNFA-UHFFFAOYSA-N n-docosyldocosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCCCCCC QUISWUAUMRRNFA-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical group C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 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
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229940058287 salicylic acid derivative anticestodals Drugs 0.000 description 1
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ASLXNOZOXWPTNG-UHFFFAOYSA-N tricosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCCN ASLXNOZOXWPTNG-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- 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
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- 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
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
- C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
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- 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
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
- C10L2200/0415—Light distillates, e.g. LPG, naphtha
- C10L2200/0423—Gasoline
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- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
- C10L2200/043—Kerosene, jet fuel
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- 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
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
- C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
- C10L2200/0446—Diesel
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- 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
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0461—Fractions defined by their origin
- C10L2200/0469—Renewables or materials of biological origin
- C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
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- 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
- C10L2270/00—Specifically adapted fuels
- C10L2270/02—Specifically adapted fuels for internal combustion engines
- C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
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- 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
- C10L2270/00—Specifically adapted fuels
- C10L2270/02—Specifically adapted fuels for internal combustion engines
- C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- C—CHEMISTRY; METALLURGY
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/70—Soluble oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- the present invention relates to new uses of corrosion inhibitors in fuels and lubricants.
- Corrosion inhibitors are common additives in fuels and lubricants, which are often based on structures containing acid groups, e.g. dimeric fatty acids.
- a disadvantage of these corrosion inhibitors is that they tend to precipitate, particularly in the presence of metal ions, especially calcium ions, and their corrosion-inhibiting effect is reduced as a result.
- the deposits formed by these precipitations can also impair the functioning of engines, engine components or parts of the fuel system, in particular the injection system, specifically the injection pumps or injectors.
- injection system is understood to mean the part of the fuel system in motor vehicles from the fuel pump up to and including the injector outlet.
- fuel system is understood to mean the components of motor vehicles that are in contact with the respective fuel, preferably the area from the tank up to and including the injector outlet.
- the compounds according to the invention act against corrosion not only in the injection system but also in the rest of the fuel system, here in particular against corrosion in fuel filters and fuel pumps.
- WO 2015/113681 describes copolymers of ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof and ⁇ -olefins having from at least 12 up to and including 30 carbon atoms as additives in fuels or lubricants.
- WO 2015/114029 describes copolymers of ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof and ⁇ -olefins having from at least 12 up to and including 30 carbon atoms, and optionally other monomers, as corrosion inhibitors in fuels or lubricants.
- WO 2018/007375 describes the use of terpolymers of C20-C24 olefin, maleic anhydride and lauryl acrylate in fuels to remove and/or prevent deposits in the fuel system and/or injection system of direct injection diesel and/or gasoline engines.
- the object was therefore to provide corrosion inhibitors which show increased compatibility with calcium ions and good compatibility and formulatability in fuel additive packages while retaining their effect as corrosion inhibitors.
- the polymers described show a particular advantage in fuels or lubricants, especially in fuels containing alkali and/or alkaline earth metals and/or zinc of at least 0.1 ppm by weight, particularly preferably at least 0.2 ppm by weight, very particularly preferably at least 0.3 ppm by weight and in particular at least 0.5 ppm by weight. It is an advantage of the polymers described that they also show their corrosion-inhibiting effect in the presence of alkali metals and/or alkaline earth metals and/or zinc, preferably also in the presence of alkaline earth metals.
- alkali metals and/or alkaline earth metals in fuels are due, for example, to mixing with lubricants containing alkali metals and/or alkaline earth metals, for example in the fuel pump.
- alkali metals and/or alkaline earth metals can come from fuel additives that have not been desalinated or have been insufficiently desalinated, for example carrier oils.
- the disadvantages mentioned above can be caused by the entrainment of alkali metals and/or alkaline earth metals in the fuels.
- One source of zinc is, for example, anti-wear additives.
- Alkali metals which should be mentioned are, in particular, sodium and potassium, in particular sodium.
- alkaline earth metals especially magnesium and calcium, especially calcium.
- the polymers described are still active even in the presence of calcium and show no precipitation.
- alkali and/or alkaline earth metals and/or zinc relate in each case to individual metal species.
- the monomer (A) is maleic anhydride.
- the monomer (B) is at least one, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular precisely one ⁇ -olefin having from at least 12 up to and including 30 carbon atoms.
- the ⁇ -olefins (B) preferably have at least 14, particularly preferably at least 16 and very particularly preferably at least 18 carbon atoms.
- the ⁇ -olefins (B) preferably have up to and including 28, particularly preferably up to and including 26 and very particularly preferably up to and including 24 carbon atoms.
- the ⁇ -olefins can preferably be linear or branched, preferably linear, 1-alkenes.
- Examples thereof are 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonodecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene , and mixtures thereof are preferred.
- ⁇ -olefin (B) are those olefins which are oligomers or polymers of C 2 - to C 12 -olefins, preferably of C 3 - to C 10 -olefins, particularly preferably of C 4 - to C 6 olefins.
- olefins which are oligomers or polymers of C 2 - to C 12 -olefins, preferably of C 3 - to C 10 -olefins, particularly preferably of C 4 - to C 6 olefins.
- Examples thereof are ethene, propene, 1-butene, 2-butene, isobutene, pentene isomers and hexene isomers, preference being given to ethene, propene, 1-butene, 2-butene and isobutene.
- ⁇ -olefins Mentioned specifically as ⁇ -olefins (B) are oligomers and polymers of propene, 1-butene, 2-butene, isobutene and mixtures thereof, especially oligomers and polymers of propene or isobutene or of mixtures of 1-butene and 2-butene.
- the oligomers the trimers, tetramers, pentamers and hexamers and mixtures thereof are preferred.
- the olefins (C) can be olefins with a terminal ( ⁇ ) double bond or those with a non-terminal double bond, preferably with an ⁇ double bond.
- the olefin (C) is preferably an olefin having from 4 to less than 12 or more than 30 carbon atoms. If the olefin (C) is an olefin having 12 to 30 carbon atoms, this olefin (C) has no double bond in the ⁇ position.
- Examples of aliphatic olefins (C) are 1-butene, 2-butene, isobutene, pentene isomers, hexene isomers, heptene isomers, octene isomers, nonene isomers, decene isomers, undecene isomers and mixtures thereof .
- cycloaliphatic olefins are cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, ⁇ - or ⁇ -pinene and mixtures thereof, limonene and norbornene.
- olefins (C) are polymers of propene, 1-butene, 2-butene or isobutene containing more than 30 carbon atoms or olefin mixtures containing such, preferably isobutene or olefin mixtures containing such, particularly preferably having an average molecular weight M w in the range from 500 to 5000 g/mol, preferably 650 to 3000, particularly preferably 800 to 1500 g/mol.
- the oligomers or polymers containing isobutene in copolymerized form preferably have a high content of terminal ethylenic double bonds ( ⁇ -double bonds), for example at least 50 mol %, preferably at least 60 mol %, particularly preferably at least 70 mol % and most preferably at least 80 mole percent.
- ⁇ -double bonds terminal ethylenic double bonds
- Suitable isobutene sources for the preparation of such isobutene-containing oligomers or polymers are both pure isobutene and isobutene-containing C4 hydrocarbon streams, for example C4 raffinates, in particular "raffinate 1", C4 cuts from isobutane -Dehydrogenation, C4 cuts from steam crackers and from FCC crackers (fluid catalysed cracking), provided they are largely freed from the 1,3-butadiene contained therein.
- a C4 hydrocarbon stream from an FCC refinery unit is also known as a "b/b" stream.
- Suitable isobutenic C4 hydrocarbon streams are, for example, the product stream of a propylene-isobutane co-oxidation or the product stream from a metathesis unit, which are generally used after customary purification and/or concentration.
- Suitable C4 hydrocarbon streams typically contain less than 500 ppm, preferably less than 200 ppm, butadiene.
- the presence of 1-butene and of cis- and trans-2-butene is largely uncritical.
- the isobutene concentration in the C4 hydrocarbon streams mentioned is in the range from 40 to 60% by weight.
- raffinate 1 generally consists essentially of 30 to 50% by weight isobutene, 10 to 50% by weight 1-butene, 10 to 40% by weight cis- and trans-2-butene and 2 to 35% by weight butanes;
- the unbranched butenes in raffinate 1 are generally practically inert and only the isobutene is polymerized.
- Said isobutenic monomer mixture can contain small amounts of contaminants, such as water, carboxylic acids or mineral acids, without critical losses in yield or selectivity occurring. It is expedient to avoid accumulation of these impurities by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
- the monomer mixture preferably contains at least 5% by weight, more preferably at least 10% by weight and in particular at least 20% by weight isobutene, and preferably at most 95% by weight, especially preferably at most 90% by weight and in particular at most 80% by weight of comonomers.
- the substance mixture of the olefins (B) and optionally (C), averaged for their amounts has at least 12 carbon atoms, preferably at least 14, particularly preferably at least 16 and very particularly preferably at least 17 carbon atoms.
- the upper limit is less relevant and is usually no more than 60 carbon atoms, preferably no more than 55, more preferably no more than 50, most preferably no more than 45 and especially no more than 40 carbon atoms.
- the monomer (D) is at least one, preferably one to three, particularly preferably one or two and very particularly preferably precisely one (meth)acrylic ester of alcohols which have at least 5 carbon atoms.
- Preferred (meth)acrylic esters (D) are (meth)acrylic esters of C 5 - to C 18 -alkanols, preferably of n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol ), tridecanol isomer mixtures, n-tetradecanol, n-hexadecanol, heptadecanol isomer mixtures, n-octadecanol, 2-ethylhexanol or 2-propylheptanol.
- the acrylic esters are preferred over the methacrylic esters. Dodecyl acrylate, 2-ethylhexyl acrylate and 2-propylheptyl acrylate are particularly preferred.
- the alcohol is a mixture of alcohols containing 13 carbon atoms, particularly preferably obtainable by oligomerization of C 2 -C 2 -olefins, in particular C 3 - or C 4 -olefins, and subsequent hydroformylation.
- the alcohol is a mixture of alcohols having 17 carbon atoms, particularly preferably one that can be obtained by hydroformylation from a C 16 olefin mixture, which in turn can be obtained by oligomerization of an olefin mixture that contains predominantly four Contains hydrocarbons containing carbon atoms.
- this olefin mixture has from 15 to 17 carbon atoms, preferably from 15.1 to 16.9, more preferably from 15.2 to 16.8, very preferably from 15.5 to 16.5 and in particular from 15.8 to 16.2 .
- this alcohol has an average degree of branching, measured as the ISO index, of 2.8 to 3.7.
- this alcohol is obtained by a process as described in WO 2009/124979 A1 , there in particular page 5, line 4 to page 16, line 29, and the examples from page 19, line 19 to page 21, line 25, which is hereby incorporated by reference into the present disclosure.
- a C 17 -alcohol mixture having particularly advantageous performance properties can be prepared as the product of the transition metal-catalyzed oligomerization of olefins having 2 to 6 carbon atoms.
- a C 16 -olefin mixture is first isolated from the product of the olefin oligomerization by distillation and only then is this C 16 -olefin mixture subjected to hydroformylation. It is thus possible to provide a more highly branched C 17 -alcohol mixture with particularly advantageous performance properties.
- the incorporation ratio of the monomers (A) and (B) and (D) and optionally (C) in the copolymer obtained from reaction step (I) is generally as follows:
- the molar ratio of (A)/((B) and (C)) (total) is generally from 10:1 to 1:10, preferably from 8:1 to 1:8, particularly preferably from 5:1 to 1 :5, very particularly preferably 3:1 to 1:3, in particular 2:1 to 1:2 and especially 1.5:1 to 1:1.5.
- the molar incorporation ratio of maleic anhydride to monomers ((B) and (C)) (total) is about 1:1.
- maleic anhydride in a slight excess over the ⁇ -olefin, for example 1.01-1.5:1, preferably 1.02-1.4 :1, particularly preferably 1.05-1.3:1, very particularly preferably 1.07-1.2:1 and in particular 1.1-1.15:1.
- the molar ratio of the obligatory monomer (B) to the optional monomer (C), if present, is generally from 1:0.05 to 10, preferably from 1:0.1 to 6, particularly preferably from 1:0 .2 to 4, very particularly preferably from 1:0.3 to 2.5 and especially 1:0.5 to 1.5.
- no optional monomer (C) is present in addition to monomer (B).
- the proportion of one or more of the (meth)acrylic esters (D) based on the amount of the monomers (A), (B) and optionally (C) (in total) is generally 5 to 200 mol%, preferably 10 to 150 mol%, particularly preferably 15 to 100 mol%, very particularly preferably 20 to 50 mol% and in particular more than 20 to 33 mol%.
- the copolymer consists of the monomers (A) and (B) and (D).
- the anhydride or carboxylic acid ester functionalities present in the copolymer obtained from (I) can be partially or completely hydrolyzed and/or hydrolyzed.
- anhydride functionalities are hydrolyzed and carboxylic acid ester functionalities are left substantially intact.
- Reaction step (II) is carried out and at least 10% of the anhydride and carboxylic acid ester functionalities present are to be hydrolyzed or saponified. Particularly preferably at least 25%, very particularly preferably at least 50%, in particular at least 75%, especially at least 85% and even at least 90% of the anhydride and carboxylic acid ester functionalities present are hydrolyzed or hydrolyzed. Anhydride functionalities are preferred in reaction step (II). hydrolyzed leaving carboxylic acid ester functionalities essentially intact.
- anhydride functionalities are fully hydrolyzed, more preferably up to 99.9%, most preferably up to 99.5%, especially up to 99% and especially up to 95%.
- the amount of water corresponding to the desired degree of hydrolysis, based on the anhydride functionalities present, is added and the copolymer obtained from (I) is heated in the presence of the added water.
- more than the required equimolar amount of water can also be added, for example at least 1.05 times, preferably at least 1.1 times, particularly preferably at least 1.2 times and very particularly preferably at least 1.25 times the molar amount of water.
- the reaction can be carried out under pressure to prevent water from escaping. Under these reaction conditions, the anhydride functionalities in the copolymer are generally reacted selectively, whereas any carboxylic acid ester functionalities present in the copolymer do not react, or at least react only to a minor extent.
- the copolymer is reacted with an amount of strong base in the presence of water equal to the degree of saponification desired.
- Hydroxides, oxides, carbonates or bicarbonates of alkali metals or alkaline earth metals can preferably be used as strong bases.
- the copolymer obtained from (I) is then heated in the presence of the added water and the strong base.
- the acids used are preferably mineral, carboxylic, sulfonic or phosphorus-containing acids with a pKa value of not more than 5, particularly preferably not more than 4.
- acetic acid formic acid, oxalic acid, salicylic acid, substituted succinic acids, benzenesulfonic acids substituted or unsubstituted on the aromatic compound, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid; the use of acidic ion exchange resins is also conceivable.
- the copolymer obtained from (I) is then heated in the presence of the added water and acid.
- the copolymers obtained from step (II) still contain residues of acid anions, it may be preferable to remove these acid anions from the copolymer using an ion exchanger and preferably to exchange them for hydroxide ions or carboxylate ions, particularly preferably hydroxide ions. This is particularly the case when the acid anions contained in the copolymer are halides, contain sulfur or contain nitrogen.
- the copolymer obtained from reaction step (II) generally has a weight-average molecular weight Mw of 0.5 to 20 kDa, preferably 0.6 to 15, particularly preferably 0.7 to 7, very particularly preferably 1 to 7 and in particular 1, 5 to 54 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standards).
- the number-average molecular weight Mn is usually from 0.5 to 10 kDa, preferably from 0.6 to 5, particularly preferably from 0.7 to 4, very particularly preferably from 0.8 to 3 and in particular from 1 to 2 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
- the polydispersity is generally from 1 to 10, preferably from 1.1 to 8, particularly preferably from 1.2 to 7, very particularly preferably from 1.3 to 5 and in particular from 1.5 to 3.
- the acid numbers according to DIN EN ISO 2114 (titration with KOH, potentiometric) of the copolymers after going through the reaction step (II) (based on the solids in the absence of solvent) are preferably from 5 to 100 mg KOH/g of copolymer, particularly preferably from 7 to 90 mg KOH/g and most preferably from 10 to 80 mg/g copolymer.
- the copolymers contain a high proportion of adjacent carboxylic acid groups, as determined by measuring adjacency. For this purpose, a sample of the copolymer for a period of 30 minutes at a Tempered at a temperature of 290 °C between two Teflon foils and an FTIR spectrum recorded at a bubble-free point. The IR spectrum of Teflon is subtracted from the spectra obtained, the layer thickness is determined and the content of cyclic anhydride is determined.
- the adjacency is at least 10%, preferably at least 15%, particularly preferably at least 20%, very particularly preferably at least 25% and in particular at least 30%.
- the use according to the invention relates to the inhibition of the corrosion of iron, steel, magnesium, aluminum and/or non-ferrous metal surfaces and their alloys.
- non-ferrous metals preference is given to copper, zinc and their alloys, as well as brass and bronze.
- the corrosion of steel surfaces is particularly preferably inhibited.
- the polymers described are added to fuels, which can optionally have the above-specified content of alkali metals and/or alkaline earth metals and/or zinc, generally in amounts of from 1 to 60 ppm by weight, preferably from 5 to 40 ppm by weight.
- the polymers described are often used in the form of fuel additive mixtures, together with the usual additives: In the case of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators , dyes and/or solvents.
- additives In the case of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators , dyes and/or solvents.
- lubricity improvers In the case of petrol, these are primarily lubricity improvers (friction modifiers), corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and/or solvents.
- detergent additives Da), (Dh) and (Di)
- detergent additives Da and (Di)
- more preferred are detergent additives (Da) and (Di)
- most preferred are (Da).
- the hydrophobic hydrocarbon residue in the above detergent additives which provides sufficient solubility in fuel, has a number average molecular weight ( Mn ) of from 85 to 20,000, preferably from 113 to 10,000, more preferably from 300 to 5,000, more preferably from 300 to 3,000, even more preferably from 500 to 2,500 and in particular from 700 to 2,500, especially from 800 to 1500.
- Mn number average molecular weight
- a typical hydrophobic hydrocarbon radical, in particular in connection with the polar groups is in particular polypropenyl, polybutenyl and polyisobutenyl radicals with a number-average molecular weight Mn of preferably 300 to 5000, particularly preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and in particular 800 to 1500.
- Such additives based on highly reactive polyisobutene which are obtained from the polyisobutene, which can contain up to 20% by weight of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethyl -aminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be prepared, in particular from the EP-A 244 616 known.
- the production route offers itself by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to the carbonyl or Carboxyl compound and subsequent amination under reductive (hydrogenating) conditions.
- Amines such as e.g. B. ammonia, monoamines or the above polyamines can be used.
- Corresponding additives based on polypropylene are in particular in the WO-A 94/24231 described.
- Da-containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as they are in particular in DE-A 196 20 262 are described.
- Additives containing carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copolymers of C 2 - to C 40 -olefins with maleic anhydride having a total molecular weight of 500 to 20,000, all or part of the carboxyl groups to the alkali metal or alkaline earth metal salts and one remaining Rest of the carboxyl groups are reacted with alcohols or amines.
- Such additives are in particular from EP-A 307 815 known.
- Such additives are mainly used to prevent valve seat wear and, as in the WO-A 87/01126 described, are used with advantage in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.
- Additives containing sulfonic acid groups or their alkali metal or alkaline earth metal salts are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as is found in particular in EP-A 639 632 is described.
- Such additives serve mainly to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly(iso)buteneamines or polyetheramines.
- Additives containing polyoxy-C 2 -C 4 -alkylene groups are preferably polyethers or polyetheramines, which are obtained by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkylcyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, are obtainable by subsequent reductive amination with ammonia, monoamines or polyamines.
- Such products are particularly in the EP-A 310 875 , EP-A 356 725 , EP-A 700 985 and US-A 4,877,416 described.
- polyethers such products also have carrier oil properties. Typical examples of these are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
- Carboxylic acid ester groups (Dg) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those with a minimum viscosity of 2 mm 2 / s at 100 ° C, as in particular in the DE-A 38 38 918 are described.
- Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives having, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or ester polyols.
- esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol. Such products also fulfill carrier oil properties.
- the groups with hydroxyl and/or amino and/or amido and/or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with a acid and an amide function, carboxylic acid imides with monoamines, carboxylic acid imides with di- or polyamines which, in addition to the imide function, also have free amine groups, or diimides which are formed by reacting di- or polyamines with two succinic acid derivatives.
- Such fuel additives are generally known and are described, for example, in documents (1) and (2).
- reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines are preferably the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines.
- reaction products with aliphatic polyamines such as in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.
- detergent additives which contain a hydrophobic hydrocarbon radical having a number average molecular weight (Mn) of 85 to 20,000 and at least one mono- or polyamino group having up to 6 nitrogen atoms have, wherein at least one nitrogen atom has basic properties.
- Mn number average molecular weight
- the compounds according to the invention can be combined with quaternized compounds, as described in WO 2012/004300 , there preferably page 5, line 18 to page 33, line 5, particularly preferably of preparation example 1.
- the compounds according to the invention can be combined with quaternized compounds, as described in WO 2014/195464 , there preferably page 5, line 21 to page 47, line 34, particularly preferably of preparation examples 1 to 17.
- the compounds according to the invention can be combined with quaternized compounds, as described in WO 11/95819 A1 , there preferably page 4, line 5 to page 13, line 26, particularly preferably preparation example 2.
- the compounds according to the invention can be combined with quaternized compounds, as described in WO 11/110860 A1 , there preferably page 4, line 7 to page 16, line 26, particularly preferably of preparation examples 8, 9, 11 and 13.
- the compounds according to the invention can be combined with quaternized compounds, as described in WO 06/135881 A2 , there preferably page 5, line 14 to page 12, line 14, particularly preferably examples 1 to 4.
- the compounds according to the invention can be combined with quaternized compounds, as described in WO 10/132259 A1 , there preferably page 3, line 29 to page 10, line 21, particularly preferably example 3.
- the compounds according to the invention can be combined with quaternized compounds, as described in WO 08/060888 A2 , there preferably page 6, line 15 to page 14, line 29, particularly preferably examples 1 to 4.
- the compounds according to the invention can be combined with quaternized compounds, as described in GB 2496514A , there preferably paragraphs [00012] to [00039], particularly preferably examples 1 to 3.
- the compounds according to the invention can be combined with quaternized compounds, as described in WO 2013 070503 A1 , there preferably paragraphs [00011] to [00039], particularly preferably examples 1 to 5.
- Additives containing groups (Di) produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
- One or more of the detergent additives mentioned can be added to the fuel in such an amount that the dosing rate of these detergent additives is preferably 25 to 2500 ppm by weight, in particular 75 to 1500 ppm by weight, especially 150 to 1000 ppm by weight .-ppm, is.
- Carrier oils used can be mineral or synthetic. Suitable mineral carrier oils are fractions obtained during petroleum processing, such as bright stock or base oils with viscosities such as those from the SN class 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. A fraction known as "hydrocrack oil” and obtained in the refining of mineral oil (vacuum distillate cut with a boiling range of about 360 to 500° C., obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized and dewaxed under high pressure) can also be used. Mixtures of the mineral carrier oils mentioned above are also suitable.
- suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternal olefins), (poly)esters, poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic acid esters of long-chain alkanols.
- suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 - to C 4 -alkylene groups, which are obtained by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkyl-cyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, if the polyetheramines, are obtainable by subsequent reductive amination with ammonia, monoamines or polyamines.
- Such products are particularly in the EP-A 310 875 , EP-A 356 725 , EP-A 700 985 and the US-A 4,877,416 described.
- polyetheramines poly-C 2 - to C 6 -alkylene oxide amines or functional derivatives thereof can be used. Typical examples of these are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
- carboxylic acid esters of long-chain alkanols are, in particular, esters of mono-, di-, or tricarboxylic acids with long-chain alkanols or polyols, such as those in particular DE-A 38 38 918 are described.
- Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives having, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or ester polyols.
- esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, e.g. B. di-(n- or isotridecyl)phthalate.
- Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C 3 - to C 6 -alkylene oxide units, z. B. propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule.
- suitable starter alcohols are long-chain alkanols or phenols substituted with long-chain alkyl, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 - to C 18 -alkyl radical.
- Particular examples include tridecanol and nonylphenol.
- Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric aliphatic C 6 - to C 18 -alcohols with C 3 - to C 6 -alkylene oxides.
- monohydric aliphatic C 6 -C 18 alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitutional and positional isomers.
- the alcohols can be used either in the form of the pure isomers or in the form of technical mixtures.
- a particularly preferred alcohol is tridecanol.
- C 3 - to C 6 -alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide.
- propylene oxide such as 1,2-propylene oxide
- butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran
- pentylene oxide and hexylene oxide particular preference is given to C 3 - to C 4 -alkylene oxides, ie propylene oxide such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide.
- Suitable synthetic carrier oils are alkoxylated alkyl phenols, as in the DE-A 10 102 913 are described.
- Particular carrier oils are synthetic carrier oils, with the alcohol-started polyethers described above being particularly preferred.
- the carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably 1 to 1000 ppm by weight, particularly preferably 10 to 500 ppm by weight and in particular 20 to 100 ppm by weight.
- suitable cold flow improvers are all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Appropriately, they must have sufficient oil solubility.
- the cold flow improvers (middle distillate flow improvers", "MDFI") usually used with middle distillates of fossil origin, ie with conventional mineral diesel fuels, come into consideration for this.
- MDFI middle distillate flow improvers
- WASA wax anti-settling additive
- Suitable C 2 - to C 40 -olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10, carbon atoms and having 1 to 3, preferably with 1 or 2, in particular with a carbon-carbon double bond.
- the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and internally.
- ⁇ -olefins particularly preferably ⁇ -olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and especially ethylene.
- the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic acid alkenyl esters, (meth)acrylic acid esters and other olefins.
- olefins are also polymerized, these are preferably higher molecular weight than the abovementioned C 2 - to C 40 -olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, C 10 - to C 40 - ⁇ -olefins are particularly suitable as further olefins. In most cases, further olefins are only polymerized in if monomers with carboxylic acid ester functions are also used.
- Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic acid with C 1 - to C 20 -alkanols, in particular C 1 - to Cw-alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec. Butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof.
- Suitable carboxylic acid alkenyl esters are, for example, C 2 - to C 14 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, the hydrocarbon radical of which can be linear or branched.
- carboxylic acids with a branched hydrocarbon radical preference is given to those whose branching is in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom particularly preferably being tertiary, ie the carboxylic acid being a so-called neocarboxylic acid.
- the hydrocarbyl radical of the carboxylic acid is preferably linear.
- carboxylic acid alkenyl esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, preference being given to the vinyl esters.
- a particularly preferred carboxylic acid alkenyl ester is vinyl acetate;
- Typical group (K1) copolymers resulting therefrom are the ethylene-vinyl acetate copolymers ("EVA”) used most frequently.
- class (K1) copolymers are those which contain two or more different carboxylic acid alkenyl esters as copolymerized units, these differing in the alkenyl function and/or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenyl carboxylic ester(s), contain at least one olefin and/or at least one (meth)acrylic ester as copolymerized units.
- terpolymers of a C 2 - to C 40 - ⁇ -olefin, a C 1 - to C 20 -alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C 2 - to C 14 -alkenyl ester of a saturated monocarboxylic acid having 2 to 21 Carbon atoms are suitable as class (K1) copolymers.
- Such terpolymers are in the WO 2005/054314 described.
- a typical terpolymer of this type is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.
- the at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably 1 to 50% by weight, in particular 10 to 45% by weight and above all 20 to 40% by weight. %, based on the total copolymer, polymerized.
- the majority by weight of the monomer units in the copolymers of class (K1) thus generally comes from the C 2 - to C 40 -base olefins.
- the class (K1) copolymers preferably have a number-average molecular weight M n of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.
- Typical comb polymers of component (K2) are, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol with at least 10 carbon atoms available.
- Other suitable comb polymers are copolymers of ⁇ -olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid.
- Suitable comb polymers can also be polyfumarates or polymaleates.
- homo- and copolymers of vinyl ethers are suitable comb polymers.
- suitable comb polymers are, for example, those in the WO 2004/035715 and in " Comb-Like Polymers. Structure and Properties", NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pp. 117-253 (1974 )" are described. Mixtures of comb polymers are also suitable.
- Polyoxyalkylenes suitable as a component of class (K3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof. These polyoxyalkylene compounds preferably contain at least one, preferably at least two, linear alkyl groups each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number-average molecular weight of up to 5000. Such polyoxyalkylene compounds are, for example, in EP-A 061 895 as well as in the U.S. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number-average molecular weight of 100 to 5000. Polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid, are also suitable.
- Polar nitrogen compounds suitable as a component of class (K4) can be both ionic and nonionic in nature and preferably have at least one, in particular at least two, substituents in the form of a tertiary nitrogen atom of the general formula >NR 7 , where R 7 is a C 8 - bis C 40 hydrocarbon residue.
- the nitrogen substituents can also be quaternized, ie in cationic form. Examples of such nitrogen compounds are ammonium salts and/or amides which can be obtained by reacting at least one amine substituted by at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
- the amines preferably contain at least one linear C 8 - to C 40 -alkyl radical.
- Examples of primary amines suitable for preparing the polar nitrogen compounds mentioned are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues; examples of secondary amines suitable for this purpose are dioctadecylamine and methylbehenylamine.
- Amine mixtures are also suitable for this purpose, in particular amine mixtures that are available on an industrial scale, such as fatty amines or hydrogenated tall amines, such as those used in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic" to be discribed.
- acids suitable for the reaction are cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted with long-chain hydrocarbon radicals.
- the component of class (K4) is an oil-soluble reaction product of poly(C 2 - to C 20 -carboxylic acids) having at least one tertiary amino group with primary or secondary amines.
- the poly(C 2 -C 20 -carboxylic acids) containing at least one tertiary amino group and on which this reaction product is based preferably contain at least 3 carboxyl groups, in particular 3 to 12, in particular 3 to 5 carboxyl groups.
- the carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms on, in particular there are acetic acid units.
- the carboxylic acid units are linked in a suitable manner to form the polycarboxylic acids, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in the case of several nitrogen atoms, are connected via hydrocarbon chains.
- the component of class (K4) is preferably an oil-soluble reaction product based on poly(C 2 - to C 20 -carboxylic acids) having at least one tertiary amino group and having the general formula Ila or IIb in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III and the variable B denotes a C 1 to C 19 alkylene group.
- the compounds of the general formulas Ila and IIb have, in particular, the properties of a WASA.
- the preferred oil-soluble reaction product of component (K4) in particular that of the general formula Ila or IIb, is an amide, an amide-ammonium salt or an ammonium salt in which none, one or more carboxylic acid groups have been converted into amide groups.
- Straight-chain or branched C 2 - to C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and especially 1,2-ethylene.
- the variable A preferably comprises 2 to 4, in particular 2 or 3, carbon atoms.
- C 1 - to C 19 -Alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and especially methylene .
- the variable B preferably comprises 1 to 10, in particular 1 to 4, carbon atoms.
- the primary and secondary amines as reaction partners for the polycarboxylic acids to form component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines can be selected from a large number of amines which carry hydrocarbon radicals, which may be bonded to one another.
- These amines on which the oil-soluble reaction products of component (K4) are based are usually secondary amines and have the general formula HN(R 8 ) 2 , in which the two variables R 8 are each, independently of one another, straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C 24 -alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
- the secondary amines mentioned are derived, with regard to their relatively long-chain alkyl radicals, from naturally occurring fatty acids or from their derivatives.
- the two radicals R 8 are preferably the same.
- the secondary amines mentioned can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts; it is also possible for only a part to be present as amide structures and another part as ammonium salts. Preferably there are few or no free acid groups present.
- the oil-soluble reaction products of component (K4) are preferably present entirely in the form of the amide structures.
- Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group , dioleylamine, dipalmitinamine, dicoco fatty amine, distearylamine, dibehenylamine or especially ditallow fatty amine.
- a particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.
- component (K4) are the N,N-dialkylammonium salts of 2-N',N'-dialkylamidobenzoates, for example the reaction product of 1 mole of phthalic anhydride and 2 moles of ditallow fatty amine, the latter being hydrogenated or non-hydrogenated , and the reaction product of 1 mole of an alkenylspirobislactone with 2 moles of a dialkylamine, for example ditallow fatty amine and/or tallow fatty amine, the latter two being hydrogenated or non-hydrogenated.
- component of class (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as in the WO 93/18115 are described.
- Sulfocarboxylic acids, sulfonic acids or derivatives thereof suitable as cold flow improvers for the component of class (K5) are, for example, the oil-soluble carboxamides and carboxylic acid esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as in EP-A 261 957 to be discribed.
- Poly(meth)acrylic acid esters suitable as cold flow improvers of the component of class (K6) are both homo- and copolymers of acrylic and methacrylic acid esters. Copolymers of at least two different (meth)acrylic acid esters, which differ in terms of the alcohol condensed in, are preferred. If appropriate, the copolymer also contains another, different, olefinically unsaturated monomer as copolymerized units. The weight average molecular weight of the polymer is preferably 50,000 to 500,000.
- a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C14 and C15 alcohols, the acid groups being neutralized with hydrogenated tallamine. Suitable poly (meth) acrylic acid esters are for example in WO 00/44857 described.
- the cold flow improver or the mixture of different cold flow improvers is added to the middle distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by weight, particularly preferably 20 to 2000 ppm by weight, more preferably 50 to 1000 ppm by weight and especially from 100 to 700 wppm, for example from 200 to 500 wppm.
- Suitable lubricity improvers are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, such as in WO 98/004656 described, and glycerol monooleate. Also the one in the U.S. 6,743 266 B2 reaction products described from natural or synthetic oils, for example triglycerides, and alkanolamines are suitable as such lubricity improvers.
- Suitable corrosion inhibitors are, for example, succinic esters, especially with polyols, fatty acid derivatives, e.g (Ethyl Corporation).
- demulsifiers are the alkali metal or alkaline earth metal salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali metal or alkaline earth metal salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, Alkyl phenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO/PO block copolymers, polyethylene imines or polysiloxanes.
- EO ethylene oxide
- PO propylene oxide
- Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, such as the products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).
- Suitable antifoams are, for example, polyether-modified polysiloxanes, such as the products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).
- Suitable cetane improvers include aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide.
- antioxidants examples include substituted phenols such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol and phenylenediamines such as N,N'-di-sec-butyl-p-phenylenediamine.
- Suitable metal deactivators include salicylic acid derivatives such as N,N'-disalicylidene-1,2-propanediamine.
- Suitable are, for example, non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit” and products sold under the trade names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents -for example alcohols such as 2-ethylhexanol, decanol and isotridecanol.
- solvents usually get into the diesel fuel together with the aforementioned additives and co-additives, which they are supposed to dissolve or dilute for better handling.
- the additive according to the invention is outstandingly suitable as a fuel additive and can in principle be used in any fuel. It brings about a whole range of beneficial effects when operating internal combustion engines with fuels.
- the quaternized additive according to the invention is preferably used in middle distillate fuels, in particular diesel fuels.
- the present invention therefore also relates to fuels, in particular middle distillate fuels, with an effective content as an additive to achieve advantageous effects when operating internal combustion engines, for example diesel engines, in particular direct-injection diesel engines, especially diesel engines with common-rail injection systems on the quaternized additive according to the invention.
- This effective content (dosage rate) is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, in particular from 30 to 750 ppm by weight. in each case based on the total amount of fuel.
- the use according to the invention relates to any fuel, preferably diesel and Otto fuels.
- Middle distillate fuels such as diesel fuels or heating oils are preferably petroleum raffinates which usually have a boiling range of 100 to 400.degree. These are mostly distillates with a 95% point up to 360°C or even higher. However, this can also be so-called “ultra low sulfur diesel” or "city diesel", characterized by a 95% point of, for example, a maximum of 345° C. and a maximum sulfur content of 0.005% by weight or by a 95% point of for example 285°C and a maximum sulfur content of 0.001% by weight.
- middle distillate fuels of fossil, vegetable or animal origin which are essentially hydrocarbon mixtures
- biofuel oils biodiesel
- middle distillate fuel Such mixtures are encompassed by the term "middle distillate fuel”. They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30% by weight, in particular 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil.
- Biofuel oils are typically based on fatty acid esters, preferably essentially on alkyl esters, of fatty acids derived from vegetable and/or animal oils and/or fats.
- Alkyl esters are usually understood to mean lower alkyl esters, in particular C 1 - to C 4 -alkyl esters, which are obtained by transesterification of the glycerides occurring in vegetable and/or animal oils and/or fats, in particular triglycerides, using lower alcohols, for example ethanol or, above all, methanol (“FAME”), are available.
- Typical lower alkyl esters based on vegetable and/or animal oils and/or fats that are used as biofuel oil or components thereof are, for example, sunflower methyl ester, palm oil methyl ester (“PME”), soybean oil methyl ester (“SME”), animal fat methyl ester (“FME”), tallow methyl ester (“TME”), methyl esters of recovered vegetable oils, recycled used cooking oils and frying fats, used vegetable oil (“UVO”), waste vegetable oil (“WVE”), used cooking oil methyl ester (“UCOME”), tall oil methyl ester and rapeseed oil methyl ester (“RME”).
- sunflower methyl ester palm oil methyl ester
- SME soybean oil methyl ester
- FME animal fat methyl ester
- TME tallow methyl ester
- UVO used vegetable oil
- WVE waste vegetable oil
- UCOME used cooking oil methyl ester
- RME tall oil methyl ester and rapeseed oil methyl ester
- the middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight and especially less than 0.001% by weight sulphur.
- petrol compositions can be used as petrol.
- the standard Eurosuper base fuel according to EN 228 should be mentioned here as a typical representative.
- gasoline compositions are also in accordance with the specification WO 00/47698 possible areas of application for the present invention.
- test methods mentioned below are part of the general disclosure of the application and are not limited to the specific exemplary embodiments.
- the mass average Mw and number average molecular weight Mn of the copolymers were measured by gel permeation chromatography (GPC). GPC separation was performed using two PLge Mixed B columns (Agilent) in tetrahydrofuran at 35 °C. The calibration was carried out using a narrow-distribution polystyrene standard (PSS, Germany) with a molecular weight of 162-50400 Da. Hexylbenzene was used as a low molecular weight marker.
- the product has a solids content of 54.3% (measured after 2 hours under vacuum at 100°C).
- the solids content of the hydrolyzed product is 62.7% (measured after 2 hours under vacuum at 100°C).
- a copolymer of C 20 -C 24 olefin, maleic anhydride and lauryl acrylate in a molar ratio of 0.43:0.43:0.14 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride).
- the solids content of the hydrolyzed product is 57.7% (measured after 2 hours under vacuum at 100°C).
- a copolymer of C 20 -C 24 olefin, maleic anhydride and lauryl acrylate in a molar ratio of 0.35:0.35:0.3 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride).
- the solids content of the hydrolyzed product is 64.4% (measured after 2 hours under vacuum at 100°C).
- a copolymer of C 20 -C 24 olefin, maleic anhydride and lauryl acrylate in a molar ratio of 0.4:0.4:0.2 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol of maleic anhydride).
- the solids content of the hydrolyzed product is 58.8% (measured after 2 hours under vacuum at 100°C).
- a copolymer was prepared from C 20 -C 24 olefin, maleic anhydride and 2-ethylhexyl acrylate in a molar ratio of 0.35:0.35:0.3 and treated with 1.1 equivalents of deionized water (based on mol maleic anhydride) hydrolyzed.
- the solids content of the hydrolyzed product is 61.2% (measured after 2 hours under vacuum at 100°C).
- a copolymer of C 20 -C 24 olefin, maleic anhydride and 2-ethylhexyl acrylate in a molar ratio of 0.4:0.4:0.2 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride). .
- the solids content of the hydrolyzed product is 58.3% (measured after 2 hours under vacuum at 100°C).
- a copolymer of C 20 -C 24 olefin, maleic anhydride and 2-ethylhexyl acrylate in a molar ratio of 0.45:0.45:0.1 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride). .
- the solids content of the hydrolyzed product is 58.3% (measured after 2 hours under vacuum at 100°C).
- the solids content of the hydrolyzed product is 55% (measured after 2 hours under vacuum at 100°C).
- Table 1 Polyisobutenamine* + carrier oil** [mg/kg] Solvent/ Dehazer*** [mg/kg] anti-corrosion component Rating according to NACE Formulation 1 443 47 4 mg/kg dimer fatty acid**** B/A Formulation 2 443 47 4 mg/kg Synthesis Example 1 B+ Formulation 3 443 47 4 mg/kg Synthesis Example 2 B Formulation 4 443 47 4 mg/kg Synthesis Example 3 B Formulation 5 443 47 4 mg/kg Synthesis Example 4 B+ Formulation 6 443 47 4 mg/kg reference product 1 B++ Formulation 7 443 47 4 mg/kg Synthesis Example 7 A Formulation 8 443 47 4 mg/kg Synthesis Example 6 B Formulation 9 443 47 4 mg/kg Synthesis Example 5 A * Polyisobuteneamine: commercially available polyisobuteneamine obtainable from polyisobutene having a number-average molar mass of 1000 g/mol by hydroformylation
- 100 ml engine oil (Shell Helix ® , figure 1 and 2 , each beaker on the far left, with a Ca content of 1500 ppm, Mg content 1100 ppm and Zn content 1300 ppm) were heated to 70° C. in the beaker and then 1 ml of corrosion inhibitor was added. If the solution is still clear, add another 1 ml of inhibitor. If the solution becomes cloudy, the test is failed (e.g figure 1 and 2 , right beaker with dimer fatty acid as comparison).
- figure 1 shows the oil, which remains clear, as the second beaker from the left, to which 2 ml of synthesis example 1 has been added.
- 2 ml of Synthesis Example 4 was added to the oil. The oil always remains clear.
- figure 2 shows the oil, which remains clear, as the second beaker from the left, to which 2 ml of synthesis example 2 have been added.
- 2 ml of Synthesis Example 3 was added to the oil. The oil always remains clear.
- Solution experiment 1 To test the solution properties, 1.600 g of the product from synthesis example 6 were placed in a 100 ml laboratory bottle at room temperature and mixed with 39.68 g of polyisobuteneamine (see Table 1), 31.2 g of a carrier oil analogous to entry 2 of Table 1 in WO 00/02978 and 7.52 g of kerosene are added.
- Solution experiment 2 For comparison, 1.696 g of comparative product 1 were presented and 39.648 g of polyisobuteneamine (see Table 1), 31.168 g of KC 3489 and 7.488 g of kerosene were added as in solution experiment 1.
Description
Die vorliegende Erfindung betrifft neue Verwendungen von Korrosionsinhibitoren in Kraft- und Schmierstoffen.The present invention relates to new uses of corrosion inhibitors in fuels and lubricants.
Korrosionsinhibitoren sind gängige Additive in Kraft- und Schmierstoffen, die oftmals auf säuregruppenhaltigen Strukturen beruhen, z.B. Dimerfettsäuren.Corrosion inhibitors are common additives in fuels and lubricants, which are often based on structures containing acid groups, e.g. dimeric fatty acids.
Nachteilig an diesen Korrosionsinhibitoren ist, daß sie insbesondere in Gegenwart von Metall-, insbesondere Calcium-Ionen zu Ausfällungen neigen und dadurch ihre korrosionsinhibierende Wirkung vermindert wird. Die durch diese Ausfällungen gebildeten Ablagerungen können darüber hinaus die Funktionsweise von Motoren, Motorbestandteilen oder Teilen des Kraftstoffsystems, insbesondere dem Einspritzsystem, speziell den Einspritzpumpen oder -düsen, beeinträchtigen.A disadvantage of these corrosion inhibitors is that they tend to precipitate, particularly in the presence of metal ions, especially calcium ions, and their corrosion-inhibiting effect is reduced as a result. The deposits formed by these precipitations can also impair the functioning of engines, engine components or parts of the fuel system, in particular the injection system, specifically the injection pumps or injectors.
Unter dem "Einspritzsystem" wird dabei der Teil des Kraftstoffsystems in Kraftfahrzeugen von Kraftstoffpumpe bis einschließlich Injektorauslass verstanden. Als "Kraftstoffsystem" werden dabei die Bauteile von Kraftfahrzeugen verstanden, die mit dem jeweiligen Kraftstoff in Kontakt stehen, bevorzugt der Bereich von Tank bis einschließlich Injektorauslass.The “injection system” is understood to mean the part of the fuel system in motor vehicles from the fuel pump up to and including the injector outlet. The “fuel system” is understood to mean the components of motor vehicles that are in contact with the respective fuel, preferably the area from the tank up to and including the injector outlet.
Es stelle eine Ausführungsform der vorliegenden Erfindung dar, daß die erfindungsgemäßen Verbindungen gegen Korrosion nicht nur im Einspritzsystem wirken, sondern auch im übrigen Kraftstoffsystem, hier insbesondere gegen Korrosion in Kraftstofffiltern und -pumpen.It represents an embodiment of the present invention that the compounds according to the invention act against corrosion not only in the injection system but also in the rest of the fuel system, here in particular against corrosion in fuel filters and fuel pumps.
Nachteilig ist, daß diese Produkte eine hohe Viskosität aufweisen und in Kraftstoffen und Lösungsmitteln nur schwer aufzulösen sind.The disadvantage is that these products have a high viscosity and are difficult to dissolve in fuels and solvents.
Es bestand daher die Aufgabe, Korrosionsinhibitoren zur Verfügung zu stellen, die eine erhöhte Verträglichkeit gegen Calcium-Ionen und eine gute Verträglichkeit und Formulierbarkeit in Kaftstoffadditivpaketen zeigen und dabei ihre Wirkung als Korrosionsinhibitor behalten.The object was therefore to provide corrosion inhibitors which show increased compatibility with calcium ions and good compatibility and formulatability in fuel additive packages while retaining their effect as corrosion inhibitors.
Die Aufgabe wird gelöst durch
die Verwendung von Copolymeren, erhältlich durch
- in einem ersten Reaktionsschritt (I) Copolymerisation von
- (A) Maleinsäureanhydrid,
- (B) mindestens einem α-Olefin mit von mindestens 12 bis zu einschließlich 30 Kohlenstoffatomen,
- (C) optional mindestens einem weiteren, mindestens 4 Kohlenstoffatome aufweisenden, aliphatischen oder cycloaliphatischen Olefin, das ein anderes als (B) ist und
- (D) mindestens einem (Meth)acrylsäureester von Alkoholen, die mindestens 5 Kohlenstoffatome aufweisen,
gefolgt von
- in einem zweiten Reaktionsschritt (II) teilweise oder vollständige Hydrolyse der im aus (I) erhaltenen Copolymer enthaltenen Anhydridfunktionalitäten und/oder teilweise Verseifung von im aus (I) erhaltenen Copolymer enthaltenen Carbonsäureesterfunktionalitäten, als Korrosionsinhibitoren in Kraft- oder Schmierstoffen, bevorzugt in Kraftstoffen, besonders bevorzugt in Kraftstoffen, die einen Gehalt an Alkali- und/oder Erdalkalimetallen und/oder Zink von mindestens 0,1 Gew.ppm aufweisen.
the use of copolymers available from
- in a first reaction step (I) copolymerization of
- (A) maleic anhydride,
- (B) at least one α-olefin having from at least 12 up to and including 30 carbon atoms,
- (C) optionally at least one further aliphatic or cycloaliphatic olefin having at least 4 carbon atoms, which is other than (B) and
- (D) at least one (meth)acrylic acid ester of alcohols having at least 5 carbon atoms,
followed by
- in a second reaction step (II) partial or complete hydrolysis of the anhydride functionalities contained in the copolymer obtained from (I) and/or partial saponification of carboxylic acid ester functionalities contained in the copolymer obtained from (I), as corrosion inhibitors in fuels or lubricants, preferably in fuels, especially preferably in fuels which have a content of alkali and/or alkaline earth metals and/or zinc of at least 0.1 ppm by weight.
Die beschriebenen Polymere zeigen einen besonderen Vorteil in Kraft- oder Schmierstoffen, besonders in Kraftstoffen, die einen Gehalt an Alkali- und/oder Erdalkalimetallen und/oder Zink von mindestens 0,1 Gew.ppm aufweisen, besonders bevorzugt mindestens 0,2 Gew.ppm, ganz besonders bevorzugt mindestens 0,3 Gew.ppm und insbesondere mindestens 0,5 Gew.ppm. Es stellt einen Vorteil der beschriebenen Polymere dar, daß sie ihre korrosionsinhibierende Wirkung auch in Gegenwart von Alkali- und/oder Erdalkalimetallen und/oder Zink zeigen, bevorzugt auch in Gegenwart von Erdalkalimetallen. Der Gehalt an Alkali- und/oder Erdalkalimetallen in Kraftstoffen rührt beispielsweise her durch Vermischung mit Alkali- und/oder Erdalkalimetallenhaltigen Schmierstoffen, beispielsweise in der Kraftstoffpumpe. Ferner können Alkali- und/oder Erdalkalimetalle aus nicht oder unzureichend entsalzten Kraftstoffadditiven stammen, beispielsweise Trägerölen. Durch das Einschleppen von Alkali- und/oder Erdalkalimetallen in die Kraftstoffe können die oben genannten Nachteile hervorgerufen werden. Eine Quelle für Zink sind beispielsweise anti-wear Additive.The polymers described show a particular advantage in fuels or lubricants, especially in fuels containing alkali and/or alkaline earth metals and/or zinc of at least 0.1 ppm by weight, particularly preferably at least 0.2 ppm by weight, very particularly preferably at least 0.3 ppm by weight and in particular at least 0.5 ppm by weight. It is an advantage of the polymers described that they also show their corrosion-inhibiting effect in the presence of alkali metals and/or alkaline earth metals and/or zinc, preferably also in the presence of alkaline earth metals. The content of alkali metals and/or alkaline earth metals in fuels is due, for example, to mixing with lubricants containing alkali metals and/or alkaline earth metals, for example in the fuel pump. Furthermore, alkali metals and/or alkaline earth metals can come from fuel additives that have not been desalinated or have been insufficiently desalinated, for example carrier oils. The disadvantages mentioned above can be caused by the entrainment of alkali metals and/or alkaline earth metals in the fuels. One source of zinc is, for example, anti-wear additives.
Als Alkalimetalle zu nennen sind besonders Natrium und Kalium, insbesondere Natrium.Alkali metals which should be mentioned are, in particular, sodium and potassium, in particular sodium.
Als Erdalkalimetalle zu nennen sind besonders Magnesium und Calcium, insbesondere Calcium.Mention should be made as alkaline earth metals especially magnesium and calcium, especially calcium.
Ferner ist Zink hervorzuhebenZinc should also be highlighted
Mit besonderem Vorteil sind die beschriebenen Polymere auch in Gegenwart von Calcium noch aktiv und zeigen keine Ausfällungen.With particular advantage, the polymers described are still active even in the presence of calcium and show no precipitation.
Die angegebenen Mengen an Alkali- und/oder Erdalkalimetallen und/oder Zink beziehen sich dabei jeweils auf einzelne Metallspezies.The stated amounts of alkali and/or alkaline earth metals and/or zinc relate in each case to individual metal species.
Spezielle Ausführungsformen der Erfindung sind:
- 1. Verwendung von Copolymeren, erhältlich durch
- in einem ersten Reaktionsschritt (I) Copolymerisation von
- (A) Maleinsäureanhydrid,
- (B) mindestens einem α-Olefin mit von mindestens 12 bis zu einschließlich 30 Kohlenstoffatomen,
- (C) optional mindestens einem weiteren, mindestens 4 Kohlenstoffatome aufweisenden, aliphatischen oder cycloaliphatischen Olefin, das ein anderes als (B) ist und
- (D) mindestens einem (Meth)acrylsäureester von Alkoholen, die mindestens 5 Kohlenstoffatome aufweisen,
gefolgt von
- in einem zweiten Reaktionsschritt (II) teilweise oder vollständige Hydrolyse der im aus (I) erhaltenen Copolymer enthaltenen Anhydridfunktionalitäten und/oder teilweise Verseifung von im aus (I) erhaltenen Copolymer enthaltenen Carbonsäureesterfunktionalitäten, als Korrosionsinhibitoren in Kraft- oder Schmierstoffen.
- in einem ersten Reaktionsschritt (I) Copolymerisation von
- 2. Verwendung nach der
Ausführungsform 1 als Korrosionsinhibitoren in Kraftstoffen. - 3. Verwendung nach einer der vorstehenden Ausführungsformen als Korrosionsinhibitoren in Kraftstoffen, die einen Gehalt an Alkali- und/oder Erdalkalimetallen und/oder Zink von mindestens 0,1 Gew.ppm aufweisen.
- 4. Verwendung nach einer der vorhergehenden Ausführungsformen, wobei der Kraftstoff ausgewählt unter Dieselkraftstoffen, Biodieselkraftstoffen, Ottokraftstoffen, und Alkanol-haltigen Ottokraftstoffen.
- 5. Verwendung nach einer der Ausführungsformen, wobei der Kraftstoff ein Ottokraftstoff ist.
- 6. Verwendung nach einer der
Ausführungsformen 1 bis 3, wobei der Kraftstoff ein Dieselkraftstoff ist.
- 1. Use of copolymers available from
- in a first reaction step (I) copolymerization of
- (A) maleic anhydride,
- (B) at least one α-olefin having from at least 12 up to and including 30 carbon atoms,
- (C) optionally at least one further aliphatic or cycloaliphatic olefin having at least 4 carbon atoms, which is other than (B) and
- (D) at least one (meth)acrylic acid ester of alcohols having at least 5 carbon atoms,
followed by
- in a second reaction step (II) partial or complete hydrolysis of the anhydride functionalities present in the copolymer obtained from (I) and/or partial hydrolysis of carboxylic acid ester functionalities present in the copolymer obtained from (I), as corrosion inhibitors in fuels or lubricants.
- in a first reaction step (I) copolymerization of
- 2. Use according to
embodiment 1 as corrosion inhibitors in fuels. - 3. Use according to one of the above embodiments as corrosion inhibitors in fuels which have a content of alkali and/or alkaline earth metals and/or zinc of at least 0.1 ppm by weight.
- 4. Use according to one of the preceding embodiments, wherein the fuel is selected from among diesel fuels, biodiesel fuels, petrol fuels and petrol fuels containing alkanol.
- 5. Use according to any one of the embodiments, wherein the fuel is a gasoline.
- 6. Use according to any one of
embodiments 1 to 3, wherein the fuel is a diesel fuel.
Bei dem Monomer (A) handelt es sich um Maleinsäureanhydrid. Bei dem Monomer (B) handelt es sich um mindestens ein, bevorzugt ein bis vier, besonders bevorzugt ein bis drei, ganz besonders bevorzugt ein oder zwei und insbesondere genau ein α-Olefin mit von mindestens 12 bis zu einschließlich 30 Kohlenstoffatomen. Die α-Olefine (B) weisen bevorzugt mindestens 14, besonders bevorzugt mindestens 16 und ganz besonders bevorzugt mindestens 18 Kohlenstoffatome auf. Bevorzugt weisen die α-Olefine (B) bis einschließlich 28, besonders bevorzugt bis einschließlich 26 und ganz besonders bevorzugt bis einschließlich 24 Kohlenstoffatome auf.The monomer (A) is maleic anhydride. The monomer (B) is at least one, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular precisely one α-olefin having from at least 12 up to and including 30 carbon atoms. The α-olefins (B) preferably have at least 14, particularly preferably at least 16 and very particularly preferably at least 18 carbon atoms. The α-olefins (B) preferably have up to and including 28, particularly preferably up to and including 26 and very particularly preferably up to and including 24 carbon atoms.
Bevorzugt kann es sich bei den α-Olefinen um lineare oder verzweigte, bevorzugt lineare 1-Alkene handeln.The α-olefins can preferably be linear or branched, preferably linear, 1-alkenes.
Beispiele dafür sind 1-Dodecen, 1-Tridecen, 1-Tetradecen, 1-Pentadecen, 1-Hexadecen, 1-Heptadecen, 1- Octadecen, 1-Nonodecen, 1-Eicosen, 1-Docosen, 1-Tetracosen, 1-Hexacosen, sowie deren Gemische bevorzugt werden.Examples thereof are 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonodecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene , and mixtures thereof are preferred.
Weitere Beispiele für α-Olefin (B) sind solche Olefine, bei denen es sich um Oligomere oder Polymere von C2- bis C12-Olefinen handelt, bevorzugt von C3- bis C10-Olefinen, besonders bevorzugt von C4- bis C6-Olefinen. Beispiele dafür sind Ethen, Propen, 1-Buten, 2-Buten, iso-Buten, Penten-Isomere sowie Hexen-Isomere, bevorzugt sind Ethen, Propen, 1-Buten, 2-Buten und iso-Buten.Further examples of α-olefin (B) are those olefins which are oligomers or polymers of C 2 - to C 12 -olefins, preferably of C 3 - to C 10 -olefins, particularly preferably of C 4 - to C 6 olefins. Examples thereof are ethene, propene, 1-butene, 2-butene, isobutene, pentene isomers and hexene isomers, preference being given to ethene, propene, 1-butene, 2-butene and isobutene.
Namentlich als α-Olefine (B) genannt seien Oligomere und Polymere von Propen, 1-Buten, 2-Buten, iso-Buten, sowie deren Mischungen, besonders Oligomere und Polymere von Propen oder iso-Buten oder von Mischungen aus 1-Buten und 2-Buten. Unter den Oligomeren sind die Trimere, Tetramere, Pentamere und Hexamere sowie deren Gemische bevorzugt.Mentioned specifically as α-olefins (B) are oligomers and polymers of propene, 1-butene, 2-butene, isobutene and mixtures thereof, especially oligomers and polymers of propene or isobutene or of mixtures of 1-butene and 2-butene. Among the oligomers, the trimers, tetramers, pentamers and hexamers and mixtures thereof are preferred.
Zusätzlich zu dem Olefin (B) kann optional mindestens ein, bevorzugt ein bis vier, besonders bevorzugt ein bis drei, ganz besonders bevorzugt ein oder zwei und insbesondere genau ein weiteres, mindestens 4 Kohlenstoffatome aufweisendes, aliphatisches oder cycloaliphatisches Olefin (C), das ein anderes als (B) ist, in das erfindungsgemäße Copolymer einpolymerisiert werden.In addition to the olefin (B), optionally at least one, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one further, at least 4 carbon atoms, aliphatic or cycloaliphatic olefin (C), the one is other than (B), are polymerized into the copolymer of the invention.
Bei den Olefinen (C) kann es sich um Olefine mit endständiger (α-) Doppelbindung handeln oder solche mit nicht-endständiger Doppelbindung, bevorzugt mit α-Doppelbindung. Bevorzugt handelt es sich bei dem Olefin (C) um Olefine mit 4 bis weniger als 12 oder mehr als 30 Kohlenstoffatomen. Sofern es sich bei dem Olefin (C) um ein Olefin mit 12 bis 30 Kohlenstoffatomen handelt, so weist dieses Olefin (C) keine α-ständige Doppelbindung auf.The olefins (C) can be olefins with a terminal (α) double bond or those with a non-terminal double bond, preferably with an α double bond. The olefin (C) is preferably an olefin having from 4 to less than 12 or more than 30 carbon atoms. If the olefin (C) is an olefin having 12 to 30 carbon atoms, this olefin (C) has no double bond in the α position.
Beispiele für aliphatische Olefine (C) sind 1-Buten, 2-Buten, iso-Buten, Penten-Isomere, Hexen-Isomere, Hepten-Isomere, Octen-Isomere, Nonen-Isomere, Decen-Isomere, Undecen-Isomere sowie deren Gemische.Examples of aliphatic olefins (C) are 1-butene, 2-butene, isobutene, pentene isomers, hexene isomers, heptene isomers, octene isomers, nonene isomers, decene isomers, undecene isomers and mixtures thereof .
Beispiele für cycloaliphatische Olefine (C) sind Cyclopenten, Cyclohexen, Cycloocten, Cyclodecen, Cyclododecen, α- oder β-Pinen und deren Gemische, Limonen und Norbornen.Examples of cycloaliphatic olefins (C) are cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, α- or β-pinene and mixtures thereof, limonene and norbornene.
Weitere Beispiele für Olefine (C) sind mehr als 30 Kohlenstoffatome aufweisende Polymere von Propen, 1-Buten, 2-Buten oder iso-Buten oder solche enthaltende Olefingemische, bevorzugt von iso-Buten oder solches enthaltende Olefingemische, besonders bevorzugt mit einem mittleren Molekulargewicht Mw im Bereich von 500 bis 5000 g/mol, bevorzugt 650 bis 3000, besonders bevorzugt 800 bis 1500 g/mol.Further examples of olefins (C) are polymers of propene, 1-butene, 2-butene or isobutene containing more than 30 carbon atoms or olefin mixtures containing such, preferably isobutene or olefin mixtures containing such, particularly preferably having an average molecular weight M w in the range from 500 to 5000 g/mol, preferably 650 to 3000, particularly preferably 800 to 1500 g/mol.
Bevorzugt weisen die iso-Buten in einpolymerisierter Form enthaltenden Oligomere oder Polymere einen hohen Gehalt an terminal angeordneten ethylenischen Doppelbindungen (α-Doppelbindungen) auf, beispielsweise wenigstens 50 Mol-%, bevorzugt wenigstens 60 Mol-%, besonders bevorzugt wenigstens 70 Mol-% und ganz besonders bevorzugt wenigstens 80 Mol-%.The oligomers or polymers containing isobutene in copolymerized form preferably have a high content of terminal ethylenic double bonds (α-double bonds), for example at least 50 mol %, preferably at least 60 mol %, particularly preferably at least 70 mol % and most preferably at least 80 mole percent.
Für die Herstellung solcher iso-Buten in einpolymerisierter Form enthaltender Oligomere oder Polymere eignen sich als Isobuten-Quelle sowohl Rein-Isobuten als auch Isobuten-haltige C4-Kohlenwasserstoffströme, beispielsweise C4-Raffinate, insbesondere "Raffinat 1", C4-Schnitte aus der Isobutan-Dehydrierung, C4-Schnitte aus Steamcrackern und aus FCC-Crackern (fluid catalysed cracking), sofern sie weitgehend von darin enthaltenem 1,3-Butadien befreit sind. Ein C4-Kohlenwasserstoffstrom aus einer FCC-Raffinerieeinheit ist auch als "b/b"-Strom bekannt. Weitere geeignete Isobuten-haltige C4-Kohlenwasserstoffströme sind beispielsweise der Produktstrom einer Propylen-Isobutan-Cooxidation oder der Produktstrom aus einer Metathese-Einheit, welche in der Regel nach üblicher Aufreinigung und/oder Aufkonzentrierung eingesetzt werden. Geeignete C4-Kohlenwasserstoffströme enthalten in der Regel weniger als 500 ppm, vorzugsweise weniger als 200 ppm, Butadien. Die Anwesenheit von 1-Buten sowie von cis- und trans-2-Buten ist weitgehend unkritisch. Typischerweise liegt die Isobutenkonzentration in den genannten C4-Kohlenwasserstoffströmen im Bereich von 40 bis 60 Gew.-%. So besteht Raffinat 1 in der Regel im wesentlichen aus 30 bis 50 Gew.-% Isobuten, 10 bis 50 Gew.-% 1-Buten, 10 bis 40 Gew.-% cis- und trans-2-Buten sowie 2 bis 35 Gew.-% Butanen; beim erfindungsgemäßen Polymerisationsverfahren verhalten sich die unverzeigten Butene im Raffinat 1 in der Regel praktisch inert und nur das Isobuten wird polymerisierteiner bevorzugten Ausführungsform setzt man als Monomerquelle für die Polymerisation einen technischen C4-Kohlenwasserstoffstrom mit einem Isobuten-Gehalt von 1 bis 100 Gew.-%, insbesondere von 1 bis 99 Gew.-%, vor allem von 1 bis 90 Gew.-%, besonders bevorzugt von 30 bis 60 Gew.-%, insbesondere einen Raffinat 1-Strom, einen b/b-Strom aus einer FCC-Raffinerieeinheit, einen Produktstrom einer Propylen-Isobutan-Cooxidation oder einen Produktstrom aus einer Metathese-Einheit ein.Suitable isobutene sources for the preparation of such isobutene-containing oligomers or polymers are both pure isobutene and isobutene-containing C4 hydrocarbon streams, for example C4 raffinates, in particular "
Insbesondere bei Verwendung eines Raffinat 1-Stromes als Isobutenquelle hat sich die Verwendung von Wasser als alleinigem oder als weiterem Initiator bewährt, vor allem wenn man bei Temperaturen von -20°C bis +30°C, insbesondere von 0°C bis +20°C, polymerisiert. Bei Temperaturen von -20°C bis +30°C, insbesondere von 0°C bis +20°C, kann man bei Verwendung eines Raffinat 1-Stromes als Isobutenquelle jedoch auch auf den Einsatz eines Initiators verzichten.In particular when using a
Das genannte Isobuten-haltige Monomerengemisch kann geringe Mengen an Kontaminanten wie Wasser, Carbonsäuren oder Mineralsäuren enthalten, ohne dass es zu kritischen Ausbeute- oder Selektivitätseinbußen kommt. Es ist zweckdienlich, eine Anreicherung dieser Verunreinigungen zu vermeiden, indem man solche Schadstoffe beispielsweise durch Adsorption an feste Adsorbentien wie Aktivkohle, Molekularsiebe oder Ionenaustauscher, aus dem Isobuten-haltigen Monomerengemisch entfernt.Said isobutenic monomer mixture can contain small amounts of contaminants, such as water, carboxylic acids or mineral acids, without critical losses in yield or selectivity occurring. It is expedient to avoid accumulation of these impurities by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
Es können, wenn auch weniger bevorzugt, auch Monomermischungen von Isobuten beziehungsweise des Isobuten-haltigen Kohlenwasserstoffgemischs mit olefinisch ungesättigten Monomeren, welche mit Isobuten copolymerisierbar sind, umgesetzt werden. Sofern Monomermischungen des Isobutens mit geeigneten Comonomeren copolymerisiert werden sollen, enthält die Monomermischung vorzugsweise wenigstens 5 Gew.-%, besonders bevorzugt wenigstens 10 Gew.-% und insbesondere wenigstens 20 Gew.-% Isobuten, und vorzugsweise höchstens 95 Gew.-%, besonders bevorzugt höchstens 90 Gew.-% und insbesondere höchstens 80 Gew.-% Comonomere.Although less preferred, it is also possible to react monomer mixtures of isobutene or the isobutene-containing hydrocarbon mixture with olefinically unsaturated monomers which are copolymerizable with isobutene. If monomer mixtures of isobutene are to be copolymerized with suitable comonomers, the monomer mixture preferably contains at least 5% by weight, more preferably at least 10% by weight and in particular at least 20% by weight isobutene, and preferably at most 95% by weight, especially preferably at most 90% by weight and in particular at most 80% by weight of comonomers.
In einer bevorzugten Ausführungsform weist das Stoffgemisch der Olefine (B) und optional (C) gemittelt auf ihre Stoffmengen mindestens 12 Kohlenstoffatome auf, bevorzugt mindestens 14, besonders bevorzugt mindestens 16 und ganz besonders bevorzugt mindestens 17 Kohlenstoffatome auf.In a preferred embodiment, the substance mixture of the olefins (B) and optionally (C), averaged for their amounts, has at least 12 carbon atoms, preferably at least 14, particularly preferably at least 16 and very particularly preferably at least 17 carbon atoms.
So weist beispielsweise ein 2:3-Gemisch aus Docosen und Tetradecen einen gemittelten Wert für die Kohlenstoffatome von 0,4 × 22 + 0,6 × 14 = 17,2 auf.For example, a 2:3 mixture of docosene and tetradecene has an average carbon atom value of 0.4 × 22 + 0.6 × 14 = 17.2.
Die Obergrenze ist weniger relevant und beträgt in der Regel nicht mehr als 60 Kohlenstoffatome, bevorzugt nicht mehr als 55, besonders bevorzugt nicht mehr als 50, ganz besonders bevorzugt nicht mehr als 45 und insbesondere nicht mehr als 40 Kohlenstoffatome.The upper limit is less relevant and is usually no more than 60 carbon atoms, preferably no more than 55, more preferably no more than 50, most preferably no more than 45 and especially no more than 40 carbon atoms.
Das Monomer (D) ist mindestens ein, bevorzugt ein bis drei, besonders bevorzugt ein oder zwei und ganz besonders bevorzugt genau ein (Meth)acrylsäureester von Alkoholen, die mindestens 5 Kohlenstoffatome aufweisen.The monomer (D) is at least one, preferably one to three, particularly preferably one or two and very particularly preferably precisely one (meth)acrylic ester of alcohols which have at least 5 carbon atoms.
Bevorzugte (Meth)acrylsäureester (D) sind (Meth)acrylsäureester von C5- bis C18-Alkanolen, bevorzugt von n-Pentanol, n-Hexanol, n-Heptanol, n-Octanol, n-Decanol, n-Dodecanol (Laurylalkohol), Tridecanol Isomerengemischen, n-Tetradecanol, n-Hexadecanol, Heptadecanol Isomerengemischen, n-Octadecanol, 2-Ethylhexanol oder 2-Propylheptanol. Dabei sind die Acrylester gegenüber den Methacrylestern bevorzugt. Besonders bevorzugt sind Acrylsäuredodecylester, Acrylsäure-2-ethylhexylester und Acrylsäure-2-propylheptylester.Preferred (meth)acrylic esters (D) are (meth)acrylic esters of C 5 - to C 18 -alkanols, preferably of n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol ), tridecanol isomer mixtures, n-tetradecanol, n-hexadecanol, heptadecanol isomer mixtures, n-octadecanol, 2-ethylhexanol or 2-propylheptanol. The acrylic esters are preferred over the methacrylic esters. Dodecyl acrylate, 2-ethylhexyl acrylate and 2-propylheptyl acrylate are particularly preferred.
In einer besonderen Ausführungsform handelt es sich bei dem Alkohol um ein Gemisch aus 13 Kohlenstoffatome aufweisenden Alkoholen, besonders bevorzugt erhältlich durch Oligomerisierung von C2-C2-Olefinen, insbesondere C3- oder C4-Olefinen, und anschließender Hydroformylierung.In a particular embodiment, the alcohol is a mixture of alcohols containing 13 carbon atoms, particularly preferably obtainable by oligomerization of C 2 -C 2 -olefins, in particular C 3 - or C 4 -olefins, and subsequent hydroformylation.
In einer weiteren besonderen Ausführungsform handelt es sich bei dem Alkohol um ein Gemisch aus 17 Kohlenstoffatome aufweisenden Alkoholen, besonders bevorzugt um ein solches, das durch Hydroformylierung aus einem C16-Olefingemisch erhältlich ist, das seinerseits durch Oligomerisierung eines Olefingemisches erhältlich ist, das überwiegend vier Kohlenstoffatome aufweisende Kohlenwasserstoffe enthält.In a further particular embodiment, the alcohol is a mixture of alcohols having 17 carbon atoms, particularly preferably one that can be obtained by hydroformylation from a C 16 olefin mixture, which in turn can be obtained by oligomerization of an olefin mixture that contains predominantly four Contains hydrocarbons containing carbon atoms.
Im statistischen Mittel weist dieses Olefingemisch 15 bis 17 Kohlenstoffatome auf, bevorzugt 15,1 bis 16,9, besonders bevorzugt 15,2 bis 16,8, ganz besonders bevorzugt 15,5 bis 16,5 und insbesondere 15,8 bis 16,2.On average, this olefin mixture has from 15 to 17 carbon atoms, preferably from 15.1 to 16.9, more preferably from 15.2 to 16.8, very preferably from 15.5 to 16.5 and in particular from 15.8 to 16.2 .
In einer ganz besonders bevorzugten Ausführungsform weist dieser Alkohol einen mittleren Verzweigungsgrad, gemessen als ISO-Index, von 2,8 bis 3,7 auf.In a very particularly preferred embodiment, this alcohol has an average degree of branching, measured as the ISO index, of 2.8 to 3.7.
Insbesondere wird dieser Alkohol erhalten nach einem Verfahren wie beschrieben in
Nach diesem bevorzugten Verfahren läßt sich als Produkt der Übergangsmetall-katalysierten Oligomerisierung von Olefinen mit 2 bis 6 Kohlenstoffatomen ein C17-Alkoholgemisch mit besonders vorteilhaften anwendungstechnischen Eigenschaften herstellen. Dabei wird zunächst aus dem Produkt der Olefinoligomerisierung ein C16-Olefingemisch destillativ isoliert und erst anschließend dieses C16-Olefingemisch einer Hydroformylierung unterzogen. Somit gelingt es, ein höher verzweigtes C17-Alkoholgemisch mit besonders vorteilhaften anwendungstechnischen Eigenschaften bereitzustellen.According to this preferred process, a C 17 -alcohol mixture having particularly advantageous performance properties can be prepared as the product of the transition metal-catalyzed oligomerization of olefins having 2 to 6 carbon atoms. In this process, a C 16 -olefin mixture is first isolated from the product of the olefin oligomerization by distillation and only then is this C 16 -olefin mixture subjected to hydroformylation. It is thus possible to provide a more highly branched C 17 -alcohol mixture with particularly advantageous performance properties.
Das Einbauverhältnis der Monomere (A) und (B) und (D) sowie optional (C) im aus dem Reaktionsschritt (I) erhaltenen Copolymer ist in der Regel wie folgt:
Das molare Verhältnis von (A) / ((B) und (C)) (in Summe) beträgt in der Regel von 10:1 bis 1:10, bevorzugt 8:1 bis 1:8, besonders bevorzugt 5:1 bis 1:5, ganz besonders bevorzugt 3:1 bis 1:3, insbesondere 2:1 bis 1:2 und speziell 1,5:1 bis 1:1,5. Für den besonderen Fall von Maleinsäureanhydrid als Monomer (A) beträgt das molare Einbauverhältnis von Maleinsäureanhydrid zu Monomeren ((B) und (C)) (in Summe) etwa 1:1. Um einen vollständigen Umsatz des α-Olefins (B) zu erzielen kann es dennoch sinnvoll sein, Maleinsäureanhydrid in einem leichten Überschuß gegenüber dem α-Olefin einzusetzen, beispielsweise 1,01 - 1,5:1, bevorzugt 1,02 - 1,4:1, besonders bevorzugt 1,05 - 1,3:1, ganz besonders bevorzugt 1,07 - 1,2:1 und insbesondere 1,1 - 1,15:1.The incorporation ratio of the monomers (A) and (B) and (D) and optionally (C) in the copolymer obtained from reaction step (I) is generally as follows:
The molar ratio of (A)/((B) and (C)) (total) is generally from 10:1 to 1:10, preferably from 8:1 to 1:8, particularly preferably from 5:1 to 1 :5, very particularly preferably 3:1 to 1:3, in particular 2:1 to 1:2 and especially 1.5:1 to 1:1.5. For the special case of maleic anhydride as monomer (A), the molar incorporation ratio of maleic anhydride to monomers ((B) and (C)) (total) is about 1:1. In order to achieve complete conversion of the α-olefin (B), it can nevertheless be useful to use maleic anhydride in a slight excess over the α-olefin, for example 1.01-1.5:1, preferably 1.02-1.4 :1, particularly preferably 1.05-1.3:1, very particularly preferably 1.07-1.2:1 and in particular 1.1-1.15:1.
Das molare Verhältnis vom obligaten Monomer (B) zum optionalen Monomer (C), soweit es anwesend ist, beträgt in der Regel von 1 : 0,05 bis 10, bevorzugt von 1 : 0,1 bis 6, besonders bevorzugt von 1 : 0,2 bis 4, ganz besonders bevorzugt von 1 : 0,3 bis 2,5 und speziell 1 : 0,5 bis 1,5.The molar ratio of the obligatory monomer (B) to the optional monomer (C), if present, is generally from 1:0.05 to 10, preferably from 1:0.1 to 6, particularly preferably from 1:0 .2 to 4, very particularly preferably from 1:0.3 to 2.5 and especially 1:0.5 to 1.5.
In einer bevorzugten Ausführungsform ist zusätzlich zu Monomer (B) kein optionales Monomer (C) anwesend.In a preferred embodiment, no optional monomer (C) is present in addition to monomer (B).
Der Anteil an einem oder mehreren der (Meth)acrylsäureester (D) bezogen auf die Menge der Monomere (A), (B) sowie optional (C) (in Summe) beträgt in der Regel 5 bis 200 mol%, bevorzugt 10 bis 150 mol%, besonders bevorzugt 15 bis 100 mol%, ganz besonders bevorzugt 20 bis 50 mol% und insbesondere mehr als 20 bis 33 mol%.The proportion of one or more of the (meth)acrylic esters (D) based on the amount of the monomers (A), (B) and optionally (C) (in total) is generally 5 to 200 mol%, preferably 10 to 150 mol%, particularly preferably 15 to 100 mol%, very particularly preferably 20 to 50 mol% and in particular more than 20 to 33 mol%.
In einer besonders bevorzugten Ausführungsform besteht das Copolymer aus den Monomeren (A) und (B) und (D).In a particularly preferred embodiment, the copolymer consists of the monomers (A) and (B) and (D).
In einem zweiten Reaktionsschritt (II) können die im aus (I) erhaltenen Copolymer enthaltenen Anhydrid- oder Carbonsäureesterfunktionalitäten teilweise oder vollständig hydrolysiert und/oder verseift werden. Bevorzugt werden im Reaktionsschritt (II) Anhydridfunktionalitäten hydrolysiert und Carbonsäureesterfunktionalitäten im wesentlichen intakt gelassen.In a second reaction step (II), the anhydride or carboxylic acid ester functionalities present in the copolymer obtained from (I) can be partially or completely hydrolyzed and/or hydrolyzed. Preferably, in reaction step (II), anhydride functionalities are hydrolyzed and carboxylic acid ester functionalities are left substantially intact.
Der Reaktionsschritt (II) wird durchlaufen und mindestens 10% der enthaltenen Anhydrid- und Carbonsäureesterfunktionalitäten sind zu hydrolysieren bzw. zu verseifen. Besonders bevorzugt werden mindestens 25% ganz besonders bevorzugt mindestens 50%, insbesondere mindestens 75%, speziell mindestens 85% und sogar mindestens 90% der enthaltenen Anhydrid- und Carbonsäureesterfunktionalitäten hydrolysiert bzw. verseift. Bevorzugt werden im Reaktionsschritt (II) Anhydridfunktionalitäten hydrolysiert und Carbonsäureesterfunktionalitäten im wesentlichen intakt gelassen.Reaction step (II) is carried out and at least 10% of the anhydride and carboxylic acid ester functionalities present are to be hydrolyzed or saponified. Particularly preferably at least 25%, very particularly preferably at least 50%, in particular at least 75%, especially at least 85% and even at least 90% of the anhydride and carboxylic acid ester functionalities present are hydrolyzed or hydrolyzed. Anhydride functionalities are preferred in reaction step (II). hydrolyzed leaving carboxylic acid ester functionalities essentially intact.
Bevorzugt werden die Anhydridfunktionalitäten vollständig hydrolysiert, besonders bevorzugt bis zu 99,9%, ganz besonders bevorzugt bis zu 99,5%, insbesondere bis zu 99% und speziell bis zu 95%.Preferably the anhydride functionalities are fully hydrolyzed, more preferably up to 99.9%, most preferably up to 99.5%, especially up to 99% and especially up to 95%.
Für eine Hydrolyse wird bezogen auf die enthaltenen Anhydridfunktionalitäten die Menge Wasser hinzugegeben, die dem gewünschten Hydrolysegrad entspricht und das aus (I) erhaltene Copolymer in Gegenwart des zugegebenen Wassers erwärmt. Im Fall einer bevorzugten vollständigen Hydrolyse von Anhydridgruppen kann auch mehr als die erforderliche äquimolare Menge Wasser zugegeben werden, beispielsweise die mindestens 1,05-fache, bevorzugt die mindestens 1,1-fache, besonders bevorzugt die mindestens 1,2-fache und ganz besonders bevorzugt die mindestens 1,25-fache molare Menge Wasser. In der Regel ist dafür eine Temperatur von vorzugsweise 20 bis 150°C ausreichend, bevorzugt 60 bis 100°C. Falls erforderlich kann die Reaktion unter Druck durchgeführt werden, um das Entweichen von Wasser zu verhindern. Unter diesen Reaktionsbedingungen werden in der Regel selektiv die Anhydridfunktionalitäten im Copolymer umgesetzt, wohingegen etwaige im Copolymer enthaltene Carbonsäureesterfunktionalitäten nicht oder zumindest nur untergeordnet reagieren.For hydrolysis, the amount of water corresponding to the desired degree of hydrolysis, based on the anhydride functionalities present, is added and the copolymer obtained from (I) is heated in the presence of the added water. In the case of preferred complete hydrolysis of anhydride groups, more than the required equimolar amount of water can also be added, for example at least 1.05 times, preferably at least 1.1 times, particularly preferably at least 1.2 times and very particularly preferably at least 1.25 times the molar amount of water. A temperature of preferably 20 to 150° C., preferably 60 to 100° C., is generally sufficient for this. If necessary, the reaction can be carried out under pressure to prevent water from escaping. Under these reaction conditions, the anhydride functionalities in the copolymer are generally reacted selectively, whereas any carboxylic acid ester functionalities present in the copolymer do not react, or at least react only to a minor extent.
Für eine Verseifung wird das Copolymer mit einer Menge einer starken Base in Gegenwart von Wasser umgesetzt, die dem gewünschten Verseifungsgrad entspricht.For saponification, the copolymer is reacted with an amount of strong base in the presence of water equal to the degree of saponification desired.
Als starke Basen können bevorzugt Hydroxide, Oxide, Carbonate oder Hydrogencarbonate von Alkali- oder Erdalkalimetallen eingesetzt werden.Hydroxides, oxides, carbonates or bicarbonates of alkali metals or alkaline earth metals can preferably be used as strong bases.
Das aus (I) erhaltene Copolymer wird dann in Gegenwart des zugegebenen Wassers und der starken Base erwärmt. In der Regel ist dafür eine Temperatur von vorzugsweise 20 bis 130°C ausreichend, bevorzugt 50 bis 110°C. Falls erforderlich kann die Reaktion unter Druck durchgeführt werden.The copolymer obtained from (I) is then heated in the presence of the added water and the strong base. A temperature of preferably 20 to 130° C., preferably 50 to 110° C., is generally sufficient for this. If necessary, the reaction can be carried out under pressure.
Es ist auch möglich, die Carbonsäureesterfunktionalitäten mit Wasser in Gegenwart einer Säure zu hydrolysieren. Als Säuren werden dabei bevorzugt Mineral-, Carbon-, Sulfon- oder phosphorhaltige Säuren mit einem pKs-Wert von nicht mehr als 5, besonders bevorzugt nicht mehr als 4 eingesetzt.It is also possible to hydrolyze the carboxylic acid ester functionalities with water in the presence of an acid. The acids used are preferably mineral, carboxylic, sulfonic or phosphorus-containing acids with a pKa value of not more than 5, particularly preferably not more than 4.
Beispiele sind Essigsäure, Ameisensäure, Oxalsäure, Salicylsäure, substituierte Bernsteinsäuren, am Aromaten substituierte oder unsubstituierte Benzolsulfonsäuren, Schwefelsäure, Salpetersäure, Salzsäure oder Phosphorsäure, denkbar ist auch der Einsatz von sauren lonentauscherharzen.Examples are acetic acid, formic acid, oxalic acid, salicylic acid, substituted succinic acids, benzenesulfonic acids substituted or unsubstituted on the aromatic compound, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid; the use of acidic ion exchange resins is also conceivable.
Das aus (I) erhaltene Copolymer wird dann in Gegenwart des zugegebenen Wassers und der Säure erwärmt. In der Regel ist dafür eine Temperatur von vorzugsweise 40 bis 200°C ausreichend, bevorzugt 80 bis 150°C. Falls erforderlich kann die Reaktion unter Druck durchgeführt werden.The copolymer obtained from (I) is then heated in the presence of the added water and acid. As a rule, a temperature of preferably 40 to 200° C., preferably 80 to 150° C., is sufficient for this. If necessary, the reaction can be carried out under pressure.
Sollten die aus Schritt (II) erhaltenen Copolymere noch Reste von Säureanionen enthalten, so kann es bevorzugt sein, diese Säureanionen mit Hilfe eines lonentauschers aus dem Copolymer zu entfernen und bevorzugt gegen Hydroxidionen oder Carboxylationen, besonders bevorzugt Hydroxidionen auszutauschen. Dies ist insbesondere dann der Fall, wenn die im Copolymer enthaltenen Säureanionen Halogenide, schwefelhaltig oder stickstoffhaltig sind.If the copolymers obtained from step (II) still contain residues of acid anions, it may be preferable to remove these acid anions from the copolymer using an ion exchanger and preferably to exchange them for hydroxide ions or carboxylate ions, particularly preferably hydroxide ions. This is particularly the case when the acid anions contained in the copolymer are halides, contain sulfur or contain nitrogen.
Das aus Reaktionsschritt (II) erhaltene Copolymer weist in der Regel ein gewichtsmittleres Molekulargewicht Mw von 0,5 bis 20 kDa auf, bevorzugt 0,6 bis 15, besonders bevorzugt 0,7 bis 7, ganz besonders bevorzugt 1 bis 7 und insbesondere 1,5 bis 54 kDa auf (bestimmt durch Gelpermeationschromatographie mit Tetrahydrofuran und Polystyrol als Standard).The copolymer obtained from reaction step (II) generally has a weight-average molecular weight Mw of 0.5 to 20 kDa, preferably 0.6 to 15, particularly preferably 0.7 to 7, very particularly preferably 1 to 7 and in particular 1, 5 to 54 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standards).
Das zahlenmittlere Molekulargewicht Mn beträgt zumeist von 0,5 bis 10 kDa, bevorzugt 0,6 bis 5, besonders bevorzugt 0,7 bis 4, ganz besonders bevorzugt 0,8 bis 3 und insbesondere 1 bis 2 kDa auf (bestimmt durch Gelpermeationschromatographie mit Tetrahydrofuran und Polystyrol als Standard).The number-average molecular weight Mn is usually from 0.5 to 10 kDa, preferably from 0.6 to 5, particularly preferably from 0.7 to 4, very particularly preferably from 0.8 to 3 and in particular from 1 to 2 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
Die Polydispersität beträgt in der Regel von 1 bis 10, bevorzugt von 1,1 bis 8, besonders bevorzugt von 1,2 bis 7, ganz besonders bevorzugt von 1,3 bis 5 und insbesondere von 1,5 bis 3.The polydispersity is generally from 1 to 10, preferably from 1.1 to 8, particularly preferably from 1.2 to 7, very particularly preferably from 1.3 to 5 and in particular from 1.5 to 3.
Die Säurezahlen gemäß DIN EN ISO 2114 (Titration mit KOH, potentiometrisch) der Copolymere nach Durchlaufen des Reaktionsschrittes (II) (bezogen auf den Festkörper in Abwesenheit von Lösungsmittel) liegen bevorzugt von 5 bis 100 mg KOH/g Copolymer, besonders bevorzugt von 7 bis 90 mg KOH/g und ganz besonders bevorzugt von 10 bis 80 mg/g Copolymer.The acid numbers according to DIN EN ISO 2114 (titration with KOH, potentiometric) of the copolymers after going through the reaction step (II) (based on the solids in the absence of solvent) are preferably from 5 to 100 mg KOH/g of copolymer, particularly preferably from 7 to 90 mg KOH/g and most preferably from 10 to 80 mg/g copolymer.
In einer bevorzugten Ausführungsform enthalten die Copolymere einen hohen Anteil an benachbarten Carbonsäuregruppen, was durch eine Messung der Adjazenz (engl. Adjacency) bestimmt wird. Dazu wird eine Probe des Copolymers für eine Dauer von 30 Minuten bei einer Temperatur von 290 °C zwischen zwei Teflonfolien getempert und an einer blasenfreien Stelle ein FTIR Spektrum aufgenommen. Von den erhaltenen Spektren wird das IR-Spektrum von Teflon subtrahiert, die Schichtdicke bestimmt und der Gehalt an cyclischem Anhydrid bestimmt.In a preferred embodiment, the copolymers contain a high proportion of adjacent carboxylic acid groups, as determined by measuring adjacency. For this purpose, a sample of the copolymer for a period of 30 minutes at a Tempered at a temperature of 290 °C between two Teflon foils and an FTIR spectrum recorded at a bubble-free point. The IR spectrum of Teflon is subtracted from the spectra obtained, the layer thickness is determined and the content of cyclic anhydride is determined.
In einer bevorzugten Ausführungsform beträgt die Adjazenz mindestens 10 %, bevorzugt mindestens 15%, besonders bevorzugt mindestens 20%, ganz besonders bevorzugt mindestens 25% und insbesondere mindestens 30%.In a preferred embodiment, the adjacency is at least 10%, preferably at least 15%, particularly preferably at least 20%, very particularly preferably at least 25% and in particular at least 30%.
Die erfindungsgemäße Verwendung betrifft die Inhibierung der Korrosion von Eisen-, Stahl-, Magnesium-, Aluminium- und/oder Buntmetalloberflächen, sowie deren Legierungen.The use according to the invention relates to the inhibition of the corrosion of iron, steel, magnesium, aluminum and/or non-ferrous metal surfaces and their alloys.
Unter den Buntmetallen sind dabei Kupfer, Zink und deren Legierungen bevorzugt, sowie Messing und Bronze.Among the non-ferrous metals, preference is given to copper, zinc and their alloys, as well as brass and bronze.
Besonders bevorzugt wird die Korrosion von Stahloberflächen inhibiert.The corrosion of steel surfaces is particularly preferably inhibited.
Die beschriebenen Polymere werden Kraftstoffen, die optional den oben spezifizierten Gehalt an Alkali- und/oder Erdalkalimetallen und/oder Zink aufweisen können, in der Regel in Mengen von 1 bis 60, bevorzugt 5 bis 40 Gew. ppm zugesetzt.The polymers described are added to fuels, which can optionally have the above-specified content of alkali metals and/or alkaline earth metals and/or zinc, generally in amounts of from 1 to 60 ppm by weight, preferably from 5 to 40 ppm by weight.
Häufig werden die beschriebenen Polymere in Form von Kraftstoffadditivgemischen eingesetzt, zusammen mit üblichen Additiven:
Im Falle von Dieselkraftstoffen sind dies in erster Linie übliche Detergenz-Additive, Trägeröle, Kaltfließverbesserer, Schmierfähigkeitsverbesserer (Lubricity Improver), andere Korrosionsinhibitoren als die beschriebenen Polymere, Demulgatoren, Dehazer, Antischaummittel, Cetanzahlverbesserer, Verbrennungsverbesserer, Antioxidantien oder Stabilisatoren, Antistatika, Metallocene, Metalldeaktivatoren, Farbstoffe und/oder Lösungsmittel.The polymers described are often used in the form of fuel additive mixtures, together with the usual additives:
In the case of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators , dyes and/or solvents.
Demgemäß offenbart wird die Verwendung von Copolymeren, erhältlich durch
- in einem ersten Reaktionsschritt (I) Copolymerisation von
- (A) mindestens einer ethylenisch ungesättigten Mono- oder Dicarbonsäure oder deren Derivate, bevorzugt einer Dicarbonsäure oder deren Derivate, besonders bevorzugt dem Anhydrid einer Dicarbonsäure,
- (B) mindestens einem α-Olefin mit von mindestens 12 bis zu einschließlich 30 Kohlenstoffatomen,
- (C) optional mindestens einem weiteren, mindestens 4 Kohlenstoffatome aufweisenden, aliphatischen oder cycloaliphatischen Olefin, das ein anderes als (B) ist und
- (D) mindestens einem (Meth)acrylsäureester von Alkoholen, die mindestens 5 Kohlenstoffatome aufweisen,
gefolgt von
- in einem zweiten optionalen Reaktionsschritt (II) teilweise oder vollständige Hydrolyse der im aus (I) erhaltenen Copolymer enthaltenen Anhydridfunktionalitäten und/oder teilweise Verseifung von im aus (I) erhaltenen Copolymer enthaltenen Carbonsäureesterfunktionalitäten, in Additivpaketen, enthaltend mindestens ein Additiv ausgewählt aus der Gruppe bestehend aus Detergenz-Additiven, Trägerölen, Kaltfließverbesserern, Schmierfähigkeitsverbesserern (Lubricity Improver), andere Korrosionsinhibitoren als die beschriebenen Polymere, Demulgatoren, Dehazern, Antischaummitteln, Cetanzahlverbesserern, Verbrennungsverbesserern, Antioxidantien, Stabilisatoren, Antistatika, Metallocenen, Metalldeaktivatoren, Farbstoffen und Lösungsmitteln, zur Verminderung der Korrosion in Dieselkraftstoffen, die optional einen Gehalt an Alkali- und/oder Erdalkalimetallen und/oder
Zink von mindestens 0,1 Gew.ppm aufweisen können.
- in a first reaction step (I) copolymerization of
- (A) at least one ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof, preferably a dicarboxylic acid or derivatives thereof, particularly preferably the anhydride a dicarboxylic acid,
- (B) at least one α-olefin having from at least 12 up to and including 30 carbon atoms,
- (C) optionally at least one further aliphatic or cycloaliphatic olefin having at least 4 carbon atoms, which is other than (B) and
- (D) at least one (meth)acrylic acid ester of alcohols having at least 5 carbon atoms,
followed by
- in a second optional reaction step (II) partial or complete hydrolysis of the anhydride functionalities contained in the copolymer obtained from (I) and/or partial saponification of carboxylic acid ester functionalities contained in the copolymer obtained from (I), in additive packages containing at least one additive selected from the group consisting from detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants, stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and solvents, to reduce corrosion in diesel fuels, which can optionally have a content of alkali and/or alkaline earth metals and/or zinc of at least 0.1 ppm by weight.
Im Falle von Ottokraftstoffen sind dies vor allem Schmierfähigkeitsverbesserer (Friction Modifier), andere Korrosionsinhibitoren als die beschriebenen Polymere, Demulgatoren, Dehazer, Antischaummittel, Verbrennungsverbesserer, Antioxidantien oder Stabilisatoren, Antistatika, Metallocene, Metalldeaktivatoren, Farbstoffe und/oder Lösungsmittel.In the case of petrol, these are primarily lubricity improvers (friction modifiers), corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and/or solvents.
Demgemäß offenbart wird die Verwendung von Copolymeren, erhältlich durch
- in einem ersten Reaktionsschritt (I) Copolymerisation von
- (A) mindestens einer ethylenisch ungesättigten Mono- oder Dicarbonsäure oder deren Derivate, bevorzugt einer Dicarbonsäure oder deren Derivate, besonders bevorzugt dem Anhydrid einer Dicarbonsäure,
- (B) mindestens einem α-Olefin mit von mindestens 12 bis zu einschließlich 30 Kohlenstoffatomen,
- (C) optional mindestens einem weiteren, mindestens 4 Kohlenstoffatome aufweisenden, aliphatischen oder cycloaliphatischen Olefin, das ein anderes als (B) ist und
- (D) mindestens einem (Meth)acrylsäureester von Alkoholen, die mindestens 5 Kohlenstoffatome aufweisen,
gefolgt von
- in einem zweiten optionalen Reaktionsschritt (II) teilweise oder vollständige Hydrolyse der im aus (I) erhaltenen Copolymer enthaltenen Anhydridfunktionalitäten und/oder teilweise Verseifung von im aus (I) erhaltenen Copolymer enthaltenen Carbonsäureesterfunktionalitäten,
in Additivpaketen, enthaltend mindestens ein Additiv ausgewählt aus der Gruppe bestehend aus Schmierfähigkeitsverbesserern (Friction Modifier), andere Korrosionsinhibitoren als die beschriebenen Polymere, Demulgatoren, Dehazern, Antischaummitteln, Verbrennungsverbesserern, Antioxidantien, Stabilisatoren, Antistatika, Metallocenen, Metalldeaktivatoren, Farbstoffen und Lösungsmitteln, zur Verminderung der Korrosion in Ottokraftstoffen, die optional einen Gehalt an Alkali- und/oder Erdalkalimetallen und/oderZink von mindestens 0,1 Gew.ppm aufweisen können.
- in a first reaction step (I) copolymerization of
- (A) at least one ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof, preferably a dicarboxylic acid or derivatives thereof, particularly preferably the anhydride of a dicarboxylic acid,
- (B) at least one α-olefin having from at least 12 up to and including 30 carbon atoms,
- (C) optionally at least one further aliphatic or cycloaliphatic olefin having at least 4 carbon atoms, which is other than (B) and
- (D) at least one (meth)acrylic acid ester of alcohols having at least 5 carbon atoms,
followed by
- in a second optional reaction step (II) partial or complete hydrolysis of the anhydride functionalities contained in the copolymer obtained from (I) and/or partial hydrolysis of carboxylic acid ester functionalities contained in the copolymer obtained from (I),
in additive packages containing at least one additive selected from the group consisting of lubricity improvers (friction modifiers), corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants, stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and solvents, for reduction of corrosion in petrol, which can optionally have a content of alkali and/or alkaline earth metals and/or zinc of at least 0.1 ppm by weight.
Typische Beispiele geeigneter Co-Additive sind im folgenden Abschnitt aufgeführt:Typical examples of suitable co-additives are listed in the following section:
Vorzugsweise handelt es sich bei den üblichen Detergenz-Additiven um amphiphile Substanzen, die mindestens einen hydrophoben Kohlenwasserstoffrest mit einem zahlengemittelten Molekulargewicht (Mn) von 85 bis 20.000 und mindestens eine polare Gruppierung besitzen, die ausgewählt ist unter:
- (Da) Mono- oder Polyaminogruppen mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
- (Db) Nitrogruppen, gegebenenfalls in Kombination mit Hydroxylgruppen;
- (Dc) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
- (Dd) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
- (De) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
- (Df) Polyoxy-C2- bis C4-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind;
- (Dg) Carbonsäureestergruppen;
- (Dh) aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen; und/oder
- (Di) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Monooder Polyaminen erzeugten Gruppierungen.
- (Da) mono- or polyamino groups with up to 6 nitrogen atoms, where at least one nitrogen atom has basic properties;
- (Db) nitro groups, optionally in combination with hydroxyl groups;
- (Dc) hydroxyl groups in combination with mono- or polyamino groups, where at least one nitrogen atom has basic properties;
- (Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;
- (De) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
- (Df) polyoxy-C 2 - to C 4 -alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, where at least one nitrogen atom has basic properties, or by carbamate groups;
- (Dg) carboxylic acid ester groups;
- (Dh) succinic anhydride derived moieties having hydroxy and/or amino and/or amido and/or imido groups; and or
- (Di) moieties generated by Mannich reaction of substituted phenols with aldehydes and mono or polyamines.
Unter diesen sind die Detergens-Additive (Da), (Dh) und (Di) bevorzugt, besonders bevorzugt sind die Detergens-Additive (Da) und (Di) und ganz besonders bevorzugt (Da).Among these, preferred are detergent additives (Da), (Dh) and (Di), more preferred are detergent additives (Da) and (Di), and most preferred are (Da).
Der hydrophobe Kohlenwasserstoffrest in den obigen Detergenz-Additiven, welcher für die ausreichende Löslichkeit im Kraftstoff sorgt, hat ein zahlengemitteltes Molekulargewicht (Mn) von 85 bis 20.000, vorzugsweise von 113 bis 10.000, besonders bevorzugt von 300 bis 5.000, stärker bevorzugt von 300 bis 3.000, noch stärker bevorzugt von 500 bis 2.500 und insbesondere von 700 bis 2.500, vor allem von 800 bis 1500. Als typischer hydrophober Kohlenwasserstoffrest, insbesondere in Verbindung mit den polaren Gruppierungen, kommt insbesondere Polypropenyl, Polybutenyl- und Polyisobutenylreste mit einem zahlenmittleren Molekulargewicht Mn von vorzugsweise jeweils 300 bis 5.000, besonders bevorzugt 300 bis 3.000, stärker bevorzugt 500 bis 2.500 noch stärker bevorzugt 700 bis 2.500 und insbesondere 800 bis 1.500 in Betracht.The hydrophobic hydrocarbon residue in the above detergent additives, which provides sufficient solubility in fuel, has a number average molecular weight ( Mn ) of from 85 to 20,000, preferably from 113 to 10,000, more preferably from 300 to 5,000, more preferably from 300 to 3,000, even more preferably from 500 to 2,500 and in particular from 700 to 2,500, especially from 800 to 1500. A typical hydrophobic hydrocarbon radical, in particular in connection with the polar groups, is in particular polypropenyl, polybutenyl and polyisobutenyl radicals with a number-average molecular weight Mn of preferably 300 to 5000, particularly preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and in particular 800 to 1500.
Als Beispiele für obige Gruppen von Detergenz-Additiven seien die folgenden genannt:
Mono- oder Polyaminogruppen (Da) enthaltende Additive sind vorzugsweise Polyalkenmono- oder Polyalkenpolyamine auf Basis von Polypropen oder von hochreaktivem (d.h. mit überwiegend endständigen Doppelbindungen) oder konventionellem (d.h. mit überwiegend mittenständigen Doppelbindungen) Polybuten oder Polyisobuten mit Mn = 300 bis 5000, besonders bevorzugt 500 bis 2500 und insbesondere 700 bis 2500. Derartige Additive auf Basis von hochreaktivem Polyisobuten, welche aus dem Polyisobuten, das bis zu 20 Gew.-% n-Buten-Einheiten enthalten kann, durch Hydroformylierung und reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen wie Dimethyl-aminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin hergestellt werden können, sind insbesondere aus der
Additives containing mono- or polyamino groups (Da) are preferably polyalkenemono- or polyalkenepolyamines based on polypropene or highly reactive (ie with predominantly terminal double bonds) or conventional (ie with predominantly central double bonds) polybutene or polyisobutene with M n =300 to 5000, especially preferably 500 to 2500 and in particular 700 to 2500. Such additives based on highly reactive polyisobutene, which are obtained from the polyisobutene, which can contain up to 20% by weight of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethyl -aminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be prepared, in particular from the
Weitere besondere Monoaminogruppen (Da) enthaltende Additive sind die Hydrierungsprodukte der Umsetzungsprodukte aus Polyisobutenen mit einem mittleren Polymerisationsgrad P = 5 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in der
Weitere besondere Monoaminogruppen (Da) enthaltende Additive sind die aus Poly-isobutenepoxiden durch Umsetzung mit Aminen und nachfolgender Dehydratisierung und Reduktion der Aminoalkohole erhältlichen Verbindungen, wie sie insbesondere in der
Nitrogruppen (Db), gegebenenfalls in Kombination mit Hydroxylgruppen, enthaltende Additive sind vorzugsweise Umsetzungsprodukte aus Polyisobutenen des mittleren Polymerisationsgrades P = 5 bis 100 oder 10 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in der
Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen (Dc) enthaltende Additive sind insbesondere Umsetzungsprodukte von Polyisobutenepoxiden, erhältlich aus vorzugsweise überwiegend endständige Doppelbindungen aufweisendem Polyisobuten mit Mn = 300 bis 5000 mit Ammoniak, Mono- oder Polyaminen, wie sie insbeson-dere in der
Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (Dd) enthaltende Additive sind vorzugsweise Copolymere von C2- bis C40-Olefinen mit Maleinsäureanhydrid mit einer Gesamt-Molmasse von 500 bis 20.000, deren Carboxylgruppen ganz oder teilweise zu den Alkalimetall- oder Erdalkalimetallsalzen und ein verbleibender Rest der Carboxylgruppen mit Alkoholen oder Aminen umgesetzt sind. Solche Additive sind insbesondere aus der
Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (De) enthaltende Additive sind vorzugsweise Alkalimetall- oder Erdalkalimetallsalze eines Sulfobern-steinsäurealkylesters, wie er insbesondere in der
Polyoxy-C2-C4-alkylengruppierungen (Df) enthaltende Additive sind vorzugsweise Polyether oder Polyetheramine, welche durch Umsetzung von C2- bis C60-Alkanolen, C6- bis C30-Alkandiolen, Mono- oder Di-C2- bis C30-alkylaminen, C1- bis C30-Alkylcyclo-hexanolen oder C1- bis C30-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/oder Propylenoxid und/oder Butylenoxid pro Hydroxylgruppe oder Aminogruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in der
Carbonsäureestergruppen (Dg) enthaltende Additive sind vorzugsweise Ester aus Mono-, Di- oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, insbesondere solche mit einer Mindestviskosität von 2 mm2/s bei 100 °C, wie sie insbesondere in der
Aus Bernsteinsäureanhydrid abgeleitete Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder insbesondere Imidogruppen (Dh) enthaltende Additive sind vorzugsweise entsprechende Derivate von Alkyl- oder Alkenyl-substituiertem Bernsteinsäureanhydrid und insbesondere die entsprechenden Derivate von Polyisobutenylbernsteinsäureanhydrid, welche durch Umsetzung von konventionellem oder hochreaktivem Polyisobuten mit Mn = vorzugsweise 300 bis 5000, besonders bevorzugt 300 bis 3000, stärker bevorzugt 500 bis 2500, noch stärker bevorzugt 700 bis 2500 und insbesondere 800 bis 1500, mit Maleinsäureanhydrid auf thermischem Weg in einer En-Reaktion oder über das chlorierte Polyisobuten erhältlich sind. Bei den Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen handelt es sich beispielsweise um Carbonsäuregruppen, Säureamide von Monoaminen, Säure-amide von Dioder Polyaminen, die neben der Amidfunktion noch freie Amingruppen aufweisen, Bernsteinsäurederivate mit einer Säure- und einer Amidfunktion, Carbonsäureimide mit Monoaminen, Carbonsäureimide mit Di- oder Polyaminen, die neben der Imidfunktion noch freie Amingruppen aufweisen, oder Diimide, die durch die Umsetzung von Di- oder Polyaminen mit zwei Bernsteinsäurederivaten gebildet werden. Derartige Kraftstoffadditive sind allgemein bekannt und beispielsweise in den Dokumenten (1) und (2) beschrieben. Bevorzugt handelt es sich um die Umsetzungsprodukte von Alkyl- oder Alkenyl-substituierten Bernsteinsäuren oder Derivaten davon mit Aminen und besonders bevorzugt um die Umsetzungsprodukte von Polyisobutenyl-substituierten Bernsteinsäuren oder Derivaten davon mit Aminen. Von besonderem Interesse sind hierbei Umsetzungsprodukte mit aliphatischen Polyaminen (Polyalkylenimine) wie insbesondere Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin, Pentaethylenhexamin und Hexaethylenheptamin, welche eine Imidstruktur aufweisen.Additives containing groups containing hydroxyl and/or amino and/or amido and/or in particular imido groups (Dh) derived from succinic anhydride are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and in particular the corresponding derivatives of polyisobutenylsuccinic anhydride, which are obtained by reaction of conventional or highly reactive polyisobutene with M n = preferably 300 to 5000, more preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride thermally in an ene reaction or via the chlorinated polyisobutene are available. The groups with hydroxyl and/or amino and/or amido and/or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with a acid and an amide function, carboxylic acid imides with monoamines, carboxylic acid imides with di- or polyamines which, in addition to the imide function, also have free amine groups, or diimides which are formed by reacting di- or polyamines with two succinic acid derivatives. Such fuel additives are generally known and are described, for example, in documents (1) and (2). They are preferably the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and particularly preferably the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines. Of particular interest here are reaction products with aliphatic polyamines (polyalkyleneimines), such as in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.
Es stellt eine bevorzugte Ausführungsform der vorliegenden Erfindung dar, die erfindungsgemäßen Verbindungen zusammen mit Detergenz-Additiven (Da) einzusetzen, die einen hydrophoben Kohlenwasserstoffrest mit einem zahlengemittelten Molekulargewicht (Mn) von 85 bis 20.000 und mindestens eine Mono- oder Polyaminogruppe mit bis zu 6 Stickstoffatomen aufweisen, wobei mindestens ein Stick-stoffatom basische Eigenschaften hat. Besonders bevorzugt sind Polyalkenmono- oder Polyalkenpolyamine als Detergenz-Additive (Da), die auf Basis von Polypropen, Polybuten oder Polyisobuten mit Mn = 500 bis 2500 durch Hydroformylierung und reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind.It is a preferred embodiment of the present invention to use the compounds of the invention together with detergent additives (Da) which contain a hydrophobic hydrocarbon radical having a number average molecular weight (Mn) of 85 to 20,000 and at least one mono- or polyamino group having up to 6 nitrogen atoms have, wherein at least one nitrogen atom has basic properties. Polyalkene monoamines or polyalkene polyamines are particularly preferred as detergent additives (Da) which are obtainable based on polypropene, polybutene or polyisobutene with Mn=500 to 2500 by hydroformylation and reductive amination with ammonia, monoamines or polyamines.
In einer bevorzugten Ausführungsform können die erfindungsgemäßen Verbindungen kombiniert werden mit quaternisierten Verbindungen, wie beschrieben in
In einer weiteren bevorzugten Ausführungsform können die erfindungsgemäßen Verbindungen kombiniert werden mit quaternisierten Verbindungen, wie beschrieben in
In einer weiteren bevorzugten Ausführungsform können die erfindungsgemäßen Verbindungen kombiniert werden mit quaternisierten Verbindungen, wie beschrieben in
In einer weiteren bevorzugten Ausführungsform können die erfindungsgemäßen Verbindungen kombiniert werden mit quaternisierten Verbindungen, wie beschrieben in
In einer weiteren bevorzugten Ausführungsform können die erfindungsgemäßen Verbindungen kombiniert werden mit quaternisierten Verbindungen, wie beschrieben in
In einer weiteren bevorzugten Ausführungsform können die erfindungsgemäßen Verbindungen kombiniert werden mit quaternisierten Verbindungen, wie beschrieben in
In einer weiteren bevorzugten Ausführungsform können die erfindungsgemäßen Verbindungen kombiniert werden mit quaternisierten Verbindungen, wie beschrieben in
In einer weiteren bevorzugten Ausführungsform können die erfindungsgemäßen Verbindungen kombiniert werden mit quaternisierten Verbindungen, wie beschrieben in
In einer weiteren bevorzugten Ausführungsform können die erfindungsgemäßen Verbindungen kombiniert werden mit quaternisierten Verbindungen, wie beschrieben in
Durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugte Gruppierungen (Di) enthaltende Additive sind vorzugsweise Umsetzungsprodukte von Polyisobuten-substituierten Phenolen mit Formaldehyd und Mono- oder Polyaminen wie Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetra-ethylenpentamin oder Dimethylaminopropylamin. Die Polyisobutenyl-substituierten Phenole können aus konventionellem oder hochreaktivem Polyisobuten mit Mn = 300 bis 5000 stammen. Derartige "Polyisobuten-Mannichbasen" sind insbesondere in der
Dem Kraftstoff können ein oder mehrere der genannten Detergenz-Additive in solch einer Menge zugegeben werden, dass die Dosierrate an diesen Detergenz-Additiven vozugsweise 25 bis 2500 Gew.-ppm, insbesondere 75 bis 1500 Gew.-ppm, vor allem 150 bis 1000 Gew.-ppm, beträgt.One or more of the detergent additives mentioned can be added to the fuel in such an amount that the dosing rate of these detergent additives is preferably 25 to 2500 ppm by weight, in particular 75 to 1500 ppm by weight, especially 150 to 1000 ppm by weight .-ppm, is.
Mitverwendete Trägeröle können mineralischer oder synthetischer Natur sein. Geeignete mineralische Trägeröle sind bei der Erdölverarbeitung anfallende Fraktionen, wie Brightstock oder Grundöle mit Viskositäten wie beispielsweise aus der Klasse SN 500 bis 2000, aber auch aromatische Kohlenwasserstoffe, paraffinische Kohlenwasserstoffe und Alkoxyalkanole. Brauchbar ist ebenfalls eine als "hydrocrack oil" bekannte und bei der Raffination von Mineralöl anfallende Fraktion (Vakuumdestillatschnitt mit einem Siedebereich von etwa 360 bis 500 °C, erhältlich aus unter Hochdruck katalytisch hydriertem und isomerisiertem sowie entparaffiniertem natürlichen Mineralöl). Ebenfalls geeignet sind Mischungen oben genannter mineralischer Trägeröle.Carrier oils used can be mineral or synthetic. Suitable mineral carrier oils are fractions obtained during petroleum processing, such as bright stock or base oils with viscosities such as those from the SN class 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. A fraction known as "hydrocrack oil" and obtained in the refining of mineral oil (vacuum distillate cut with a boiling range of about 360 to 500° C., obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized and dewaxed under high pressure) can also be used. Mixtures of the mineral carrier oils mentioned above are also suitable.
Beispiele für geeignete synthetische Trägeröle sind Polyolefine (Polyalphaolefine oder Polyinternalolefine), (Poly)ester, Poly)alkoxylate, Polyether, aliphatische Polyetheramine, alkylphenolgestartete Polyether, alkylphenolgestartete Polyetheramine und Carbonsäureester langkettiger Alkanole.Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternal olefins), (poly)esters, poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic acid esters of long-chain alkanols.
Beispiele für geeignete Polyolefine sind Olefinpolymerisate mit Mn = 400 bis 1800, vor allem auf Polybuten- oder Polyisobuten-Basis (hydriert oder nicht hydriert).Examples of suitable polyolefins are olefin polymers with M n =400 to 1800, primarily based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).
Beispiele für geeignete Polyether oder Polyetheramine sind vorzugsweise Polyoxy-C2- bis C4-alkylengruppierungen enthaltende Verbindungen, welche durch Umsetzung von C2- bis C60-Alkanolen, C6- bis C30-Alkandiolen, Mono- oder Di-C2- bis C30-alkylaminen, C1- bis C30-Alkyl-cyclohexanolen oder C1- bis C30-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/ oder Propylenoxid und/oder Butylenoxid pro Hydroxylgruppe oder Amino-gruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in der
Beispiele für Carbonsäureester langkettiger Alkanole sind insbesondere Ester aus Mono-, Di-oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, wie sie insbesondere in der
Weitere geeignete Trägerölsysteme sind beispielsweise in der
Beispiele für besonders geeignete synthetische Trägeröle sind alkoholgestartete Polyether mit etwa 5 bis 35, vorzugsweise etwa 5 bis 30, besonders bevorzugt 10 bis 30 und insbesondere 15 bis 30 C3- bis C6-Alkylenoxideinheiten, z. B. Propylenoxid-, n-Butylenoxid- und Isobutylenoxid-Einheiten oder Gemischen davon, pro Alkoholmolekül. Nichtlimitierende Beispiele für geeignete Starteralkohole sind langkettige Alkanole oder mit langkettigem Alkyl-substituierte Phenole, wobei der langkettige Alkylrest insbesondere für einen geradkettigen oder verzweigten C6- bis C18-Alkylrest steht. Als besondere Beispiele sind zu nennen Tridecanol und Nonylphenol. Besonders bevorzugte alkoholgestartete Polyether sind die Umsetzungsprodukte (Polyveretherungsprodukte) von einwertigen aliphatischen C6- bis C18-Alkoholen mit C3- bis C6-Alkylenoxiden. Beispiele für einwertige aliphatische C6-C18-Alkohole sind Hexanol, Heptanol, Octanol, 2-Ethyl-hexanol, Nonylalkohol, Decanol, 3-Propylheptanol, Undecanol, Dodecanol, Tridecanol, Tetradecanol, Pentadecanol, Hexadecanol, Octadecanol und deren Konstitutions- und Stellungsisomere. Die Alkohole können sowohl in Form der reinen Isomere als auch in Form technischer Gemische eingesetzt werden. Ein besonders bevorzugter Alkohol ist Tridecanol. Beispiele für C3- bis C6-Alkylenoxide sind Propylenoxid, wie 1,2-Propylen-oxid, Butylenoxid, wie 1,2-Butylenoxid, 2,3-Butylenoxid, Isobutylenoxid oder Tetrahydrofuran, Pentylenoxid und Hexylenoxid. Besonders bevorzugt sind hierunter C3- bis C4-Alkylenoxide, d.h. Propylenoxid wie 1,2-Propylenoxid und Butylenoxid wie 1,2-Buty-lenoxid, 2,3-Butylenoxid und Isobutylenoxid. Speziell verwendet man Butylenoxid.Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C 3 - to C 6 -alkylene oxide units, z. B. propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule. Non-limiting examples of suitable starter alcohols are long-chain alkanols or phenols substituted with long-chain alkyl, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 - to C 18 -alkyl radical. Particular examples include tridecanol and nonylphenol. Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric aliphatic C 6 - to C 18 -alcohols with C 3 - to C 6 -alkylene oxides. Examples of monohydric aliphatic C 6 -C 18 alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitutional and positional isomers. The alcohols can be used either in the form of the pure isomers or in the form of technical mixtures. A particularly preferred alcohol is tridecanol. Examples of C 3 - to C 6 -alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide. Among these, particular preference is given to C 3 - to C 4 -alkylene oxides, ie propylene oxide such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Specifically, butylene oxide is used.
Weitere geeignete synthetische Trägeröle sind alkoxylierte Alkylphenole, wie sie in der
Besondere Trägeröle sind synthetische Trägeröle, wobei die zuvor beschriebenen al-koholgestarteten Polyether besonders bevorzugt sind.Particular carrier oils are synthetic carrier oils, with the alcohol-started polyethers described above being particularly preferred.
Das Trägeröl bzw. das Gemisch verschiedener Trägeröle wird dem Kraftstoff in einer Menge von vorzugsweise 1 bis 1000 Gew.-ppm, besonders bevorzugt von 10 bis 500 Gew.-ppm und insbesondere von 20 bis 100 Gew.-ppm zugesetzt.The carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably 1 to 1000 ppm by weight, particularly preferably 10 to 500 ppm by weight and in particular 20 to 100 ppm by weight.
Geeignete Kaltfließverbesserer sind im Prinzip alle organischen Verbindungen, welche in der Lage sind, das Fließverhalten von Mitteldestillat-Kraftstoffen bzw. Dieselkraftstoffen in der Kälte zu verbessern. Zweckmäßigerweise müssen sie eine ausreichende Öllöslichkeit aufweisen. Insbesondere kommen hierfür die üblicherweise bei Mitteldestillaten aus fossilem Ursprung, also bei üblichen mineralischen Dieselkraftstoffen, eingesetzten Kaltfließverbesserer ("middle distillate flow improvers", "MDFI") in Betracht. Jedoch können auch organische Verbindungen verwendet werden, die beim Einsatz in üblichen Dieselkraftstoffen zum Teil oder überwiegend die Eigenschaften eines Wax Anti-Settling Additivs ("WASA") aufweisen. Auch können sie zum Teil oder überwiegend als Nukleatoren wirken. Es können aber auch Mischungen aus als MDFI wirksamen und/oder als WASA wirksamen und/oder als Nukleatoren wirksamen organischen Verbindungen eingesetzt werden.In principle, suitable cold flow improvers are all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Appropriately, they must have sufficient oil solubility. In particular, the cold flow improvers ("middle distillate flow improvers", "MDFI") usually used with middle distillates of fossil origin, ie with conventional mineral diesel fuels, come into consideration for this. However, it is also possible to use organic compounds which, when used in conventional diesel fuels, partially or predominantly have the properties of a wax anti-settling additive ("WASA"). They can also act partly or mainly as nucleators. However, it is also possible to use mixtures of organic compounds which are active as MDFIs and/or active as WASAs and/or active as nucleators.
Typischerweise wird der Kaltfließverbesserer ausgewählt aus:
- (K1) Copolymeren eines C2- bis C40-Olefins mit wenigstens einem weiteren ethylenisch ungesättigten Monomer;
- (K2) Kammpolymeren;
- (K3) Polyoxyalkylenen;
- (K4) polaren Stickstoffverbindungen;
- (K5) Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivaten; und
- (K6) Poly(meth)acrylsäureestern.
- (K1) Copolymers of a C 2 - to C 40 -olefin with at least one further ethylenically unsaturated monomer;
- (K2) comb polymers;
- (K3) polyoxyalkylenes;
- (K4) polar nitrogen compounds;
- (K5) sulfocarboxylic acids or sulfonic acids or their derivatives; and
- (K6) Poly(meth)acrylic acid esters.
Es können sowohl Mischungen verschiedener Vertreter aus einer der jeweiligen Klassen (K1) bis (K6) als auch Mischungen von Vertretern aus verschiedenen Klassen (K1) bis (K6) eingesetzt werden.Both mixtures of different representatives from one of the respective classes (K1) to (K6) and mixtures of representatives from different classes (K1) to (K6) can be used.
Geeignete C2- bis C40-Olefin-Monomere für die Copolymeren der Klasse (K1) sind beispielsweise solche mit 2 bis 20, insbesondere 2 bis10 Kohlenstoffatomen sowie mit 1 bis 3, vorzugsweise mit 1 oder 2, insbesondere mit einer Kohlenstoff-Kohlenstoff-Dop-pelbindung. Im zuletzt genannten Fall kann die Kohlenstoff-Kohlenstoff-Doppelbindung sowohl terminal (α-Olefine) als auch intern angeordnet sein kann. Bevorzugt sind jedoch α-Olefine, besonders bevorzugt α-Olefine mit 2 bis 6 Kohlenstoffatomen, beispielsweise Propen, 1-Buten, 1-Penten, 1-Hexen und vor allem Ethylen.Suitable C 2 - to C 40 -olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10, carbon atoms and having 1 to 3, preferably with 1 or 2, in particular with a carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally (α-olefins) and internally. However, preference is given to α-olefins, particularly preferably α-olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and especially ethylene.
Bei den Copolymeren der Klasse (K1) ist das wenigstens eine weitere ethylenisch ungesättigte Monomer vorzugsweise ausgewählt unter Carbonsäurealkenylestern, (Meth)Acrylsäureestern und weiteren Olefinen.In the case of the copolymers of class (K1), the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic acid alkenyl esters, (meth)acrylic acid esters and other olefins.
Werden weitere Olefine mit einpolymerisiert, sind dies vorzugsweise höhermolekulare als das oben genannte C2- bis C40-Olefin-Basismonomere. Setzt man beispielsweise als Olefin-Basismonomer Ethylen oder Propen ein, eignen sich als weitere Olefine insbesondere C10- bis C40-α-Olefine. Weitere Olefine werden in den meisten Fällen nur dann mit einpolymerisiert, wenn auch Monomere mit Carbonsäureester-Funktionen eingesetzt werden.If other olefins are also polymerized, these are preferably higher molecular weight than the abovementioned C 2 - to C 40 -olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, C 10 - to C 40 -α-olefins are particularly suitable as further olefins. In most cases, further olefins are only polymerized in if monomers with carboxylic acid ester functions are also used.
Geeignete (Meth)Acrylsäureester sind beispielsweise Ester der (Meth)Acrylsäure mit C1- bis C20-Alkanolen, insbesondere C1- bis Cw-Alkanolen, vor allem mit Methanol, Ethanol, Propanol, Isopropanol, n-Butanol, sec.-Butanol, Isobutanol, tert.-Butanol, Pentanol, Hexanol, Heptanol, Octanol, 2-Ethylhexanol, Nonanol und Decanol sowie Strukturisomeren hiervon.Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic acid with C 1 - to C 20 -alkanols, in particular C 1 - to Cw-alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec. Butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof.
Geeignete Carbonsäurealkenylester sind beispielsweise C2- bis C14-Alkenylester, z.B. die Vinylund Propenylester, von Carbonsäuren mit 2 bis 21 Kohlenstoffatomen, deren Kohlenwasserstoffrest linear oder verzweigt sein kann. Bevorzugt sind hierunter die Vinylester. Unter den Carbonsäuren mit verzweigtem Kohlenwasserstoffrest sind solche bevorzugt, deren Verzweigung sich in der α-Position zur Carboxylgruppe befindet, wobei das α-Kohlenstoffatom besonders bevorzugt tertiär ist, d. h. die Carbonsäure eine sogenannte Neocarbonsäure ist. Vorzugsweise ist der Kohlenwasserstoffrest der Carbonsäure jedoch linear.Suitable carboxylic acid alkenyl esters are, for example, C 2 - to C 14 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, the hydrocarbon radical of which can be linear or branched. Among these, preference is given to the vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical, preference is given to those whose branching is in the α-position to the carboxyl group, the α-carbon atom particularly preferably being tertiary, ie the carboxylic acid being a so-called neocarboxylic acid. However, the hydrocarbyl radical of the carboxylic acid is preferably linear.
Beispiele für geeignete Carbonsäurealkenylester sind Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinyl-2-ethylhexanoat, Neopentansäurevinylester, Hexansäurevinylester, Neononansäurevinylester, Neodecansäurevinylester und die entsprechenden Propenylester, wobei die Vinylester bevorzugt sind. Ein besonders bevorzugter Carbonsäurealkenylester ist Vinylacetat; typische hieraus resultierende Copolymere der Gruppe (K1) sind die mit am häufigsten eingesetzten Ethylen-Vinylacetat-Copolymere ("EVA").Examples of suitable carboxylic acid alkenyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, preference being given to the vinyl esters. A particularly preferred carboxylic acid alkenyl ester is vinyl acetate; Typical group (K1) copolymers resulting therefrom are the ethylene-vinyl acetate copolymers ("EVA") used most frequently.
Besonders vorteilhaft einsetzbare Ethylen-Vinylacetat-Copolymere und ihre Herstellung sind in der
Als Copolymere der Klasse (K1) sind auch solche geeignet, die zwei oder mehrere voneinander verschiedene Carbonsäurealkenylester einpolymerisiert enthalten, wobei diese sich in der Alkenylfunktion und/oder in der Carbonsäuregruppe unterscheiden. Ebenfalls geeignet sind Copolymere, die neben dem/den Carbonsäurealkenylester(n) wenigstens ein Olefin und/oder wenigstens ein (Meth)Acrylsäureester einpolymerisiert enthalten.Also suitable as class (K1) copolymers are those which contain two or more different carboxylic acid alkenyl esters as copolymerized units, these differing in the alkenyl function and/or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenyl carboxylic ester(s), contain at least one olefin and/or at least one (meth)acrylic ester as copolymerized units.
Auch Terpolymere aus einem C2- bis C40-α-Olefin, einem C1- bis C20-Alkylester einer ethylenisch ungesättigten Monocarbonsäure mit 3 bis 15 Kohlenstoffatomen und einem C2- bis C14-Alkenylester einer gesättigten Monocarbonsäure mit 2 bis 21 Kohlenstoffatomen sind als Copolymere der Klasse (K1) geeignet. Derartige Terpolymere sind in der
Das wenigstens eine oder die weiteren ethylenisch ungesättigten Monomeren sind in den Copolymeren der Klasse (K1) in einer Menge von vorzugsweise 1 bis 50 Gew.-%, insbesondere von 10 bis 45 Gew.-% und vor allem von 20 bis 40 Gew.-%, bezogen auf das Gesamtcopolymer, einpolymerisiert. Der gewichtsmäßige Hauptanteil der Monomereinheiten in den Copolymeren der Klasse (K1) stammt somit in der Regel aus den C2- bis C40-Basis-Olefinen.The at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably 1 to 50% by weight, in particular 10 to 45% by weight and above all 20 to 40% by weight. %, based on the total copolymer, polymerized. The majority by weight of the monomer units in the copolymers of class (K1) thus generally comes from the C 2 - to C 40 -base olefins.
Die Copolymere der Klasse (K1) weisen vorzugsweise ein zahlenmittleres Molekulargewicht Mn von 1000 bis 20.000, besonders bevorzugt von 1000 bis 10.000 und insbesondere von 1000 bis 8000 auf.The class (K1) copolymers preferably have a number-average molecular weight M n of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.
Typische Kammpolymere der Komponente (K2) sind beispielsweise durch die Copolymerisation von Maleinsäureanhydrid oder Fumarsäure mit einem anderen ethylenisch ungesättigten Monomer, beispielsweise mit einem α-Olefin oder einem ungesättigten Ester wie Vinylacetat, und anschließende Veresterung der Anhydrid- bzw. Säurefunktion mit einem Alkohol mit wenigstens 10 Kohlenstoffatomen erhältlich. Weitere geeignete Kammpolymere sind Copolymere von α-Olefinen und veresterten Comonomeren, beispielsweise veresterte Copolymere von Styrol und Maleinsäureanhydrid oder veresterte Copolymere von Styrol und Fumarsäure. Geeignete Kammpolymere können auch Polyfumarate oder Polymaleinate sein. Außerdem sind Homo- und Copolymere von Vinylethern geeignete Kammpolymere. Als Komponente der Klasse (K2) geeignete Kammpolymere sind beispielsweise auch solche, die in der
Als Komponente der Klasse (K3) geeignete Polyoxyalkylene sind beispielsweise Poly-oxyalkylenester, Polyoxyalkylenether, gemischte Polyoxyalkylenesterether und Gemische davon. Bevorzugt enthalten diese Polyoxyalkylenverbindungen wenigstens eine, vorzugsweise wenigstens zwei lineare Alkylgruppen mit jeweils 10 bis 30 Kohlenstoffatomen und eine Polyoxyalkylengruppe mit einem zahlenmittleren Molekulargewicht von bis zu 5000. Derartige Polyoxyalkylenverbindungen sind beispielsweise in der
Als Komponente der Klasse (K4) geeignete polare Stickstoffverbindungen können sowohl ionischer als auch nicht ionischer Natur sein und besitzen vorzugsweise wenigstens einen, insbesondere wenigstens zwei Substituenten in Form eines tertiären Stickstoffatoms der allgemeinen Formel >NR7, worin R7 für einen C8- bis C40-Kohlenwas-serstoffrest steht. Die Stickstoffsubstituenten können auch quaternisiert, das heißt in kationischer Form, vorliegen. Beispiele für solche Stickstoffverbindungen sind Ammoniumsalze und/oder Amide, die durch die Umsetzung wenigstens eines mit wenigstens einem Kohlenwasserstoffrest substituierten Amins mit einer Carbonsäure mit 1 bis 4 Carboxylgruppen bzw. mit einem geeignetem Derivat davon erhältlich sind. Vorzugsweise enthalten die Amine wenigstens einen linearen C8- bis C40-Alkylrest. Zur Herstellung der genannten polaren Stickstoffverbindungen geeignete primäre Amine sind beispielsweise Octylamin, Nonylamin, Decylamin, Undecylamin, Dodecylamin, Tetradecylamin und die höheren linearen Homologen, hierzu geeignete sekundäre Amine sind beispielsweise Dioctadecylamin und Methylbehenylamin. Geeignet sind hierzu auch Amingemische, insbesondere großtechnisch zugängliche Amingemische wie Fettamine oder hydrierte Tallamine, wie sie beispielsweise in
Insbesondere ist die Komponente der Klasse (K4) ein öllösliches Umsetzungsprodukt aus mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) mit primären oder sekundären Aminen. Die diesem Umsetzungsprodukt zugrundeliegenden mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) enthalten vorzugsweise mindestens 3 Carboxylgruppen, insbesondere 3 bis 12, vor allem 3 bis 5 Carboxylgruppen. Die Carbonsäure-Einheiten in den Polycarbonsäuren weisen vorzugsweise 2 bis 10 Kohlenstoffatome auf, insbesondere sind es Essigsäure-Einheiten. Die Carbonsäure-Einheiten sind in geeigneter Weise zu den Polycarbonsäuren verknüpft, meist über ein oder mehrere Kohlenstoff- und/oder Stickstoffatome. Vorzugsweise sind sie an tertiäre Stickstoffatome angebunden, die im Falle mehrerer Stickstoffatome über Kohlenwasserstoffketten verbunden sind.In particular, the component of class (K4) is an oil-soluble reaction product of poly(C 2 - to C 20 -carboxylic acids) having at least one tertiary amino group with primary or secondary amines. The poly(C 2 -C 20 -carboxylic acids) containing at least one tertiary amino group and on which this reaction product is based preferably contain at least 3 carboxyl groups, in particular 3 to 12, in particular 3 to 5 carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms on, in particular there are acetic acid units. The carboxylic acid units are linked in a suitable manner to form the polycarboxylic acids, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in the case of several nitrogen atoms, are connected via hydrocarbon chains.
Vorzugsweise ist die Komponente der Klasse (K4) ein öllösliches Umsetzungsprodukt auf Basis von mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) der allgemeinen Formel Ila oder Ilb
Weiterhin ist das bevorzugte öllösliche Umsetzungsprodukt der Komponente (K4), insbesondere das der allgemeinen Formel Ila oder Ilb, ein Amid, ein Amidammoniumsalz oder ein Ammoniumsalz, in dem keine, eine oder mehrere Carbonsäuregruppen in Amidgruppen übergeführt sind.Furthermore, the preferred oil-soluble reaction product of component (K4), in particular that of the general formula Ila or IIb, is an amide, an amide-ammonium salt or an ammonium salt in which none, one or more carboxylic acid groups have been converted into amide groups.
Geradkettige oder verzweigte C2- bis C6-Alkylengruppen der Variablen A sind beispielsweise 1,1-Ethylen, 1,2-Propylen, 1,3-Propylen, 1,2-Butylen, 1,3-Butylen, 1,4-Butylen, 2-Methyl-1,3-propylen, 1,5-Pentylen, 2-Methyl-1,4-butylen, 2,2-Dimethyl-1,3-pro-pylen, 1,6-Hexylen (Hexamethylen) und insbesondere 1,2-Ethylen. Vorzugsweise umfasst die Variable A 2 bis 4, insbesondere 2 oder 3 Kohlenstoffatome.Straight-chain or branched C 2 - to C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and especially 1,2-ethylene. The variable A preferably comprises 2 to 4, in particular 2 or 3, carbon atoms.
C1- bis C19-Alkylengruppen der Variablen B sind vor beispielsweise 1,2-Ethylen, 1,3-Propylen, 1,4-Butylen, Hexamethylen, Octamethylen, Decamethylen, Dodecamethylen, Tetradecamethylen, Hexadecamethylen, Octadecamethylen, Nonadecamethylen und insbesondere Methylen. Vorzugsweise umfasst die Variable B 1 bis 10, insbesondere 1 bis 4 Kohlenstoffatome.C 1 - to C 19 -Alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and especially methylene . The variable B preferably comprises 1 to 10, in particular 1 to 4, carbon atoms.
Die primären und sekundären Amine als Umsetzungspartner für die Polycarbonsäuren zur Bildung der Komponente (K4) sind üblicherweise Monoamine, insbesondere aliphatische Monoamine. Diese primären und sekundären Amine können aus einer Vielzahl von Aminen ausgewählt sein, die - gegebenenfalls miteinander verbundene - Kohlenwasserstoffreste tragen.The primary and secondary amines as reaction partners for the polycarboxylic acids to form component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines can be selected from a large number of amines which carry hydrocarbon radicals, which may be bonded to one another.
Meist sind diese den öllöslichen Umsetzungsprodukten der Komponente (K4) zugrundeliegenden Amine sekundären Amine und weisen die allgemeine Formel HN(R8)2 auf, in der die beiden Variablen R8 unabhängig voneinander jeweils geradkettige oder verzweigte C10- bis C30-Alkylreste, insbesondere C14- bis C24-Alkylreste bedeuten. Diese längerkettigen Alkylreste sind vorzugsweise geradkettig oder nur in geringem Grade verzweigt. In der Regel leiten sich die genannten sekundären Amine hinsichtlich ihrer längerkettigen Alkylreste von natürlich vorkommenden Fettsäuren bzw. von deren Derivaten ab. Vorzugsweise sind die beiden Reste R8 gleich.These amines on which the oil-soluble reaction products of component (K4) are based are usually secondary amines and have the general formula HN(R 8 ) 2 , in which the two variables R 8 are each, independently of one another, straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C 24 -alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched. As a rule, the secondary amines mentioned are derived, with regard to their relatively long-chain alkyl radicals, from naturally occurring fatty acids or from their derivatives. The two radicals R 8 are preferably the same.
Die genannten sekundären Amine können mittels Amidstrukturen oder in Form der Ammoniumsalze an die Polycarbonsäuren gebunden sein, auch kann nur ein Teil als Amidstrukturen und ein anderer Teil als Ammoniumsalze vorliegen. Vorzugsweise liegen nur wenige oder keine freien Säuregruppen vor. Vorzugsweise liegen die öllöslichen Umsetzungsprodukte der Komponente (K4) vollständig in Form der Amidstrukturen vor.The secondary amines mentioned can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts; it is also possible for only a part to be present as amide structures and another part as ammonium salts. Preferably there are few or no free acid groups present. The oil-soluble reaction products of component (K4) are preferably present entirely in the form of the amide structures.
Typische Beispiele für derartige Komponenten (K4) sind Umsetzungsprodukte der Nitrilotriessigsäure, der Ethylendiamintetraessigsäure oder der Propylen-1,2-diamintetra-essigsäure mit jeweils 0,5 bis 1,5 Mol pro Carboxylgruppe, insbesondere 0,8 bis 1,2 Mol pro Carboxylgruppe, Dioleylamin, Dipalmitinamin, Dikokosfettamin, Distearylamin, Dibehenylamin oder insbesondere Ditalgfettamin. Eine besonders bevorzugte Komponente (K4) ist das Umsetzungsprodukt aus 1 Mol Ethylendiamintetraessigsäure und 4 Mol hydriertem Ditalgfettamin.Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group , dioleylamine, dipalmitinamine, dicoco fatty amine, distearylamine, dibehenylamine or especially ditallow fatty amine. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.
Als weitere typische Beispiele für die Komponente (K4) seien die N,N-Dialkylammoni-umsalze von 2-N',N'-Dialkylamidobenzoaten, beispielsweise das Reaktionsprodukt aus 1 Mol Phthalsäureanhydrid und 2 Mol Ditalgfettamin, wobei letzteres hydriert oder nicht hydriert sein kann, und das Reaktionsprodukt von 1 Mol eines Alkenylspirobislactons mit 2 Mol eines Dialkylamins, beispielsweise Ditalgfettamin und/oder Talgfettamin, wobei die beiden letzteren hydriert oder nicht hydriert sein können, genannt.Other typical examples of component (K4) are the N,N-dialkylammonium salts of 2-N',N'-dialkylamidobenzoates, for example the reaction product of 1 mole of phthalic anhydride and 2 moles of ditallow fatty amine, the latter being hydrogenated or non-hydrogenated , and the reaction product of 1 mole of an alkenylspirobislactone with 2 moles of a dialkylamine, for example ditallow fatty amine and/or tallow fatty amine, the latter two being hydrogenated or non-hydrogenated.
Weitere typische Strukturtypen für die Komponente der Klasse (K4) sind cyclische Verbindungen mit tertiären Aminogruppen oder Kondensate langkettiger primärer oder sekundärer Amine mit carbonsäurehaltigen Polymeren, wie sie in der
Als Kaltfließverbesserer der Komponente der Klasse (K5) geeignete Sulfocarbonsäuren, Sulfonsäuren oder deren Derivate sind beispielsweise die öllöslichen Carbonsäureamide und Carbonsäureester von ortho-Sulfobenzoesäure, in denen die Sulfonsäurefunktion als Sulfonat mit alkylsubstituierten Ammoniumkationen vorliegt, wie sie in der
Als Kaltfließverbesserer der Komponente der Klasse (K6) geeignete Poly(meth)acryl-säureester sind sowohl Homo- als auch Copolymere von Acryl- und Methacrylsäure-estern. Bevorzugt sind Copolymere von wenigstens zwei voneinander verschiedenen (Meth)Acrylsäureestern, die sich bezüglich des einkondensierten Alkohols unterscheiden. Gegebenenfalls enthält das Copolymer noch ein weiteres, davon verschiedenes olefinisch ungesättigtes Monomer einpolymerisiert. Das gewichtsmittlere Molekulargewicht des Polymers beträgt vorzugsweise 50.000 bis 500.000. Ein besonders bevorzugtes Polymer ist ein Copolymer von Methacrylsäure und Methacrylsäureestern von gesättigten C14- und C15-Alkoholen, wobei die Säuregruppen mit hydriertem Tallamin neutralisiert sind. Geeignete Poly(meth)acrylsäureester sind beispielsweise in der
Dem Mitteldestillat-Kraftstoff bzw. Dieselkraftstoff wird der Kaltfließverbesserer bzw. das Gemisch verschiedener Kaltfließverbesserer in einer Gesamtmenge von vorzugsweise 10 bis 5000 Gew.-ppm, besonders bevorzugt von 20 bis 2000 Gew.-ppm, stärker bevorzugt von 50 bis 1000 Gew.-ppm und insbesondere von 100 bis 700 Gew.-ppm, z.B. von 200 bis 500 Gew.-ppm, zugegeben.The cold flow improver or the mixture of different cold flow improvers is added to the middle distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by weight, particularly preferably 20 to 2000 ppm by weight, more preferably 50 to 1000 ppm by weight and especially from 100 to 700 wppm, for example from 200 to 500 wppm.
Geeignete Schmierfähigkeitsverbesserer (Lubricity Improver bzw. Friction Modifier) basieren üblicherweise auf Fettsäuren oder Fettsäureestern. Typische Beispiele sind Tallölfettsäure, wie beispielsweise in der
Geeignete Korrosionsinhibitoren sind z.B. Bernsteinsäureester, vor allem mit Polyolen, Fettsäurederivate, z.B. Ölsäureester, oligomerisierte Fettsäuren, substituierte Ethanol-amine und Produkte, die unter dem Handelsnamen RC 4801 (Rhein Chemie Mannheim, Deutschland), Irgacor® L12 (BASF SE) oder HiTEC 536 (Ethyl Corporation) vertrieben werden.Suitable corrosion inhibitors are, for example, succinic esters, especially with polyols, fatty acid derivatives, e.g (Ethyl Corporation).
Geeignete Demulgatoren sind z.B. die Alkali- oder Erdalkalisalze von Alkyl-substituier-ten Phenol- und Naphthalinsulfonaten und die Alkali- oder Erdalkalisalze von Fettsäuren, außerdem neutrale Verbindungen wie Alkoholalkoxylate, z.B. Alkoholethoxylate, Phenolalkoxylate, z.B. tert-Butylphenolethoxylat oder tert-Pentylphenolethoxylat, Fettsäuren, Alkylphenole, Kondensationsprodunkte von Ethylenoxid (EO) und Propylenoxid (PO), z.B. auch in Form von EO/PO-Blockcopolymeren, Polyethylenimine oder auch Polysiloxane.Examples of suitable demulsifiers are the alkali metal or alkaline earth metal salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali metal or alkaline earth metal salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, Alkyl phenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO/PO block copolymers, polyethylene imines or polysiloxanes.
Geeignete Dehazer sind z.B. alkoxylierte Phenol-Formaldehyd-Kondensate, wie beispielsweise die unter dem Handelsnamen erhältlichen Produkte NALCO 7D07 (Nalco) und TOLAD 2683 (Petrolite).Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, such as the products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).
Geeignete Antischaummittel sind z.B. Polyether-modifizierte Polysiloxane, wie beispielsweise die unter dem Handelsnamen erhältlichen Produkte TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) und RHODOSIL (Rhone Poulenc).Suitable antifoams are, for example, polyether-modified polysiloxanes, such as the products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).
Geeignete Cetanzahlverbesserer sind z.B. aliphatische Nitrate wie 2-Ethylhexylnitrat und Cyclohexylnitrat sowie Peroxide wie Di-tert-butylperoxid.Suitable cetane improvers include aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide.
Geeignete Antioxidantien sind z.B. substituierte Phenole, wie 2,6-Di-tert.-butylphenol und 6-Di-tert.-butyl-3-methylphenol sowie Phenylendiamine wie N,N'-Di-sec.-butyl-p-phenylendiamin.Examples of suitable antioxidants are substituted phenols such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol and phenylenediamines such as N,N'-di-sec-butyl-p-phenylenediamine.
Geeignete Metalldeaktivatoren sind z.B. Salicylsäurederivate wie N,N'-Disalicyliden-1,2-propandiamin.Suitable metal deactivators include salicylic acid derivatives such as N,N'-disalicylidene-1,2-propanediamine.
Geeignete sind z.B. unpolare organische Lösungsmittel wie aromatische und aliphatische Kohlenwasserstoffe, beispielsweise Toluol, Xylole, "white spirit" und Produkte, die unter dem Handelsnamen SHELLSOL (Royal Dutch/Shell Group) und EXXSOL (ExxonMobil) vertrieben werden, sowie polare organische Lösungsmittel, bei-spielsweise Alkohole wie 2-Ethylhexanol, Decanol und Isotridecanol. Derartige Lösungsmittel gelangen meist zusammen mit den vorgenannten Additiven und Co-Additiven, die sie zur besseren Handhabung lösen oder verdünnen sollen, in den Dieselkraftstoff.Suitable are, for example, non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit" and products sold under the trade names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents -for example alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents usually get into the diesel fuel together with the aforementioned additives and co-additives, which they are supposed to dissolve or dilute for better handling.
Das erfindungsgemäße Additiv eignet sich in hervorragender Weise als Kraftstoffzusatz und kann im Prinzip in jeglichen Kraftstoffen eingesetzt werden. Es bewirkt eine ganze Reihe von vorteilhaften Effekten beim Betrieb von Verbrennungsmotoren mit Kraftstoffen. Bevorzugt wird das erfindungsgemäße quaternisierte Additiv in Mitteldestillat-Kraftstoffen, insbesondere Dieselkraftstoffen, eingesetzt.The additive according to the invention is outstandingly suitable as a fuel additive and can in principle be used in any fuel. It brings about a whole range of beneficial effects when operating internal combustion engines with fuels. The quaternized additive according to the invention is preferably used in middle distillate fuels, in particular diesel fuels.
Gegenstand der vorliegenden Erfindung sind daher auch Kraftstoffe, insbesondere Mitteldestillat-Kraftstoffe, mit einem als Zusatzstoff zur Erzielung von vorteilhaften Effekten beim Betrieb von Verbrennungsmotoren, beispielsweise von Dieselmotoren, insbesondere von direkteinspritzenden Dieselmotoren, vor allem von Dieselmotoren mit Common-Rail-Einspritzsystemen, wirksamen Gehalt an dem erfindungsgemäßen quaternisierten Additiv. Dieser wirksame Gehalt (Dosierrate) liegt in der Regel bei 10 bis 5000 Gew.-ppm, vorzugsweise bei 20 bis 1500 Gew.-ppm, insbesondere bei 25 bis 1000 Gew.-ppm, vor allem bei 30 bis 750 Gew.-ppm, jeweils bezogen auf die Gesamtmenge an Kraftstoff.The present invention therefore also relates to fuels, in particular middle distillate fuels, with an effective content as an additive to achieve advantageous effects when operating internal combustion engines, for example diesel engines, in particular direct-injection diesel engines, especially diesel engines with common-rail injection systems on the quaternized additive according to the invention. This effective content (dosage rate) is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, in particular from 30 to 750 ppm by weight. in each case based on the total amount of fuel.
Die erfindungsgemäße Verwendung betrifft im Prinzip jegliche Kraftstoffe, bevorzugt Diesel- und Ottokraftstoffe.In principle, the use according to the invention relates to any fuel, preferably diesel and Otto fuels.
Bei Mitteldestillat-Kraftstoffen wie Dieselkraftstoffen oder Heizölen handelt es sich vorzugsweise um Erdölraffinate, die üblicherweise einen Siedebereich von 100 bis 400°C haben. Dies sind meist Destillate mit einem 95%-Punkt bis zu 360°C oder auch darüber hinaus. Dies können aber auch so genannte "Ultra Low Sulfur Diesel" oder "City Diesel" sein, gekennzeichnet durch einen 95%-Punkt von beispielsweise maximal 345°C und einem Schwefelgehalt von maximal 0,005 Gew.-% oder durch einen 95%-Punkt von beispielsweise 285°C und einem Schwefelgehalt von maximal 0,001 Gew.-%. Neben den durch Raffination erhältlichen mineralischen Mitteldestillat-Kraftstoffen bzw. Dieselkraftstoffen sind auch solche, die durch Kohlevergasung oder Gasverflüssigung ["gas to liquid" (GTL)-Kraftstoffe] oder durch Biomasse-Verflüssigung ["biomass to liquid" (BTL)-Kraftstoffe] erhältlich sind, geeignet. Geeignet sind auch Mischungen der vorstehend genannten Mitteldestillat-Kraftstoffe bzw. Dieselkraftstoffe mit regenerativen Kraftstoffen, wie Biodiesel oder Bioethanol.Middle distillate fuels such as diesel fuels or heating oils are preferably petroleum raffinates which usually have a boiling range of 100 to 400.degree. These are mostly distillates with a 95% point up to 360°C or even higher. However, this can also be so-called "ultra low sulfur diesel" or "city diesel", characterized by a 95% point of, for example, a maximum of 345° C. and a maximum sulfur content of 0.005% by weight or by a 95% point of for example 285°C and a maximum sulfur content of 0.001% by weight. In addition to the mineral middle distillate fuels or diesel fuels that can be obtained through refining, there are also those that have been produced through coal gasification or gas liquefaction ["gas to liquid" (GTL) fuels] or through biomass liquefaction ["biomass to liquid" (BTL) fuels]. are available. Mixtures of the aforementioned middle distillate fuels or diesel fuels with regenerative fuels such as biodiesel or bioethanol are also suitable.
Die Qualitäten der Heizöle und Dieselkraftstoffe sind beispielsweise in DIN 51603 und EN 590 näher festgelegt (vgl. auch
Die erfindungsgemäße Verwendung in Mitteldestillat-Kraftstoffen aus fossilem, pflanzlichem oder tierischem Ursprung, die im wesentlichen Kohlenwasserstoffmischungen darstellen, betrifft auch Mischungen aus solchen Mitteldestillaten mit Biobrennstoffölen (Biodiesel). Derartige Mischungen werden von dem Begriff "Mitteldestillat-Kraftstoff" umfasst. Sie sind handelsüblich und enthalten meist die Biobrennstofföle in untergeordneten Mengen, typischerweise in Mengen von 1 bis 30 Gew.-% insbesondere von 3 bis 10 Gew.-%, bezogen auf die Gesamtmenge aus Mitteldestillat fossilen, pflanzlichem oder tierischen Ursprungs und Biobrennstofföl.The use according to the invention in middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, also relates to mixtures of such middle distillates with biofuel oils (biodiesel). Such mixtures are encompassed by the term "middle distillate fuel". They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30% by weight, in particular 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil.
Biobrennstofföle basieren in der Regel auf Fettsäureestern, vorzugsweise im wesentlichen auf Alkylester von Fettsäuren, die sich von pflanzlichen und/oder tierischen Ölen und/oder Fetten ableiten. Unter Alkylestern werden üblicherweise Niedrigalkylester, insbesondere C1- bis C4-Alkylester, verstanden, die durch Umesterung der in pflanzlichen und/oder tierischen Ölen und/oder Fetten vorkommenden Glyceride, insbesondere Triglyceride, mittels Niedrigalkoholen, beispielsweise Ethanol oder vor allem Methanol ("FAME"), erhältlich sind. Typische Niedrigalkylester auf Basis von pflanzlichen und/oder tierischen Ölen und/oder Fetten, die als Biobrennstofföl oder Komponenten hierfür Verwendung finden, sind beispielsweise Sonnenblumenmethylester, Palmölmethylester ("PME"), Sojaölmethylester ("SME"), Tierfettmethylester ("FME"), Talgmethylester ("TME"), Methylester von wiedergewonnenen Pflanzenölen, aufbereiteten Altspeiseölen und -frittierfetten, used vegetable oil ("UVO"), waste vegetable oil ("WVE"), used cooking oil methyl ester ("UCOME"), Tallöl methylester und Rapsölmethylester ("RME").Biofuel oils are typically based on fatty acid esters, preferably essentially on alkyl esters, of fatty acids derived from vegetable and/or animal oils and/or fats. Alkyl esters are usually understood to mean lower alkyl esters, in particular C 1 - to C 4 -alkyl esters, which are obtained by transesterification of the glycerides occurring in vegetable and/or animal oils and/or fats, in particular triglycerides, using lower alcohols, for example ethanol or, above all, methanol ("FAME"), are available. Typical lower alkyl esters based on vegetable and/or animal oils and/or fats that are used as biofuel oil or components thereof are, for example, sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME"), animal fat methyl ester ("FME"), tallow methyl ester ("TME"), methyl esters of recovered vegetable oils, recycled used cooking oils and frying fats, used vegetable oil ("UVO"), waste vegetable oil ("WVE"), used cooking oil methyl ester ("UCOME"), tall oil methyl ester and rapeseed oil methyl ester ("RME").
Besonders bevorzugt handelt es sich bei den Mitteldestillat-Kraftstoffen bzw. Dieselkraftstoffen um solche mit niedrigem Schwefelgehalt, das heißt mit einem Schwefelgehalt von weniger als 0,05 Gew.-%, vorzugsweise von weniger als 0,02 Gew.-%, insbesondere von weniger als 0,005 Gew.-% und speziell von weniger als 0,001 Gew.-% Schwefel.The middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight and especially less than 0.001% by weight sulphur.
Als Ottokraftstoffe kommen alle handelsüblichen Ottokraftstoffzusammensetzungen in Betracht. Als typischer Vertreter soll hier der marktübliche Eurosuper Grundkraftstoff gemäß EN 228 genannt werden. Weiterhin sind auch Ottokraftstoffzusammensetzungen der Spezifikation gemäß
Die Erfindung wird nun anhand der folgenden Ausführungsbeispiele näher beschrieben. Insbesondere die im Folgenden genannten Testmethoden sind Teil der allgemeinen Offenbarung der Anmeldung und nicht auf die konkreten Ausführungsbeispiele beschränkt.The invention will now be described in more detail using the following exemplary embodiments. In particular, the test methods mentioned below are part of the general disclosure of the application and are not limited to the specific exemplary embodiments.
Wenn nicht anders angegeben wurde das massenmittlere Mw und zahlenmittlere Molekulargewicht Mn der Copolymere mittels Gel-Permeations-Chromatographie gemessen (GPC). GPC-Trennung erfolgte über zwei PLge Mixed B-Säulen (Agilent) in Tetrahydrofuran bei 35 °C. Die Kalibrierung erfolgte mittels eines engverteilten Polystyrolstandards (Firma PSS, Deutschland) mit Molekulargewicht 162-50400 Da. Hexylbenzol wurde als Marker für niedriges Molekulargewicht verwendet.Unless otherwise stated, the mass average Mw and number average molecular weight Mn of the copolymers were measured by gel permeation chromatography (GPC). GPC separation was performed using two PLge Mixed B columns (Agilent) in tetrahydrofuran at 35 °C. The calibration was carried out using a narrow-distribution polystyrene standard (PSS, Germany) with a molecular weight of 162-50400 Da. Hexylbenzene was used as a low molecular weight marker.
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Vorlage: 131,43 g C20-C24 Olefin und 154,29 g Solvesso® 150Initial charge: 131.43 g C 20 -C 24 olefin and 154.29
g Solvesso ® 150 - Zulauf 1: 43,50 Maleinsäureanhydrid (beheizt bei 80°C)Feed 1: 43.50 maleic anhydride (heated at 80° C.)
- Zulauf 2: 25,08 g LaurylacrylatFeed 2: 25.08 g lauryl acrylate
-
Zulauf 3: 2,31 g Di- tert. Butylperoxid gelöst in 13,07 g von Solvesso® 150Feed 3: 2.31 g of ditert. Butyl peroxide dissolved in 13.07 g of
Solvesso ® 150 - In einem 1 Liter Pilotwerkrührer wurde die Vorlage aufgeheizt bis 150°C.The receiver was heated to 150° C. in a 1 liter pilot plant stirrer.
-
Zulauf 1, 2 und 3 (Molverhältnis der Monomere zueinander 0,45 : 0,45 : 0,1) wurden innerhalb von 3 Stunden zudosiert und anschließend wurde 1 Stunde nachpolymerisiert.
Feeds 1, 2 and 3 (molar ratio of the monomers to one another 0.45:0.45:0.1) were metered in over the course of 3 hours and polymerization was then continued for 1 hour.
In einem Reaktor (1 Liter Pilotwerkrührer) wurden 131,43 g C20-C24 Olefin und 154,29 g Solvesso® 150 vorgelegt. Die Mischung wurde unter einem Stickstoffstrom und unter Rühren auf 150°C erhitzt. Hierzu gab man innerhalb von 3 Stunden 2,31 g Di- tert. Butylperoxid gelöst in 13,07 g von Solvesso® 150, geschmolzenes Maleinsäureanhydrid (43,50 g Maleinsäureanhydrid, beheizt bei 80°C) sowie 25,08 g Laurylacrylat. Der Reaktionsansatz wurde bei 150°C für eine weitere Stunde gerührt und dann abgekühlt.131.43 g of C 20 -C 24 olefin and 154.29 g of Solvesso® 150 were placed in a reactor (1 liter pilot plant stirrer). The mixture was heated to 150°C under a stream of nitrogen and with stirring. 2.31 g of di-tert were added to this over the course of 3 hours. Butyl peroxide dissolved in 13.07 g of Solvesso® 150, molten maleic anhydride (43.50 g maleic anhydride, heated at 80°C) and 25.08 g lauryl acrylate. The reaction mixture was stirred at 150°C for an additional hour and then cooled.
Das Produkt weist einen Feststoffgehalt von 54,3 % auf (gemessen nach 2 Stunden unter Vakuum bei 100°C).The product has a solids content of 54.3% (measured after 2 hours under vacuum at 100°C).
110,50 g des so hergestellten Produktes wurden zusammen mit 2,63 g Wasser (1,1 Äquivalente bezogen auf mol Maleinsäureanhydrid) vermischt und bei 95°C über 3 Stunden gerührt. Anschließend wurde das nicht umgesetzte Wasser abdestilliert.110.50 g of the product prepared in this way were mixed with 2.63 g of water (1.1 equivalents based on mole of maleic anhydride) and stirred at 95° C. for 3 hours. Then the unreacted water was distilled off.
Der Feststoffgehalt des hydrolysierten Produktes beträgt 62,7% (gemessen nach 2 Stunden unter Vakuum bei 100°C).The solids content of the hydrolyzed product is 62.7% (measured after 2 hours under vacuum at 100°C).
Das GPC (in THF) ergab für das Copolymer ein Mn = 1400 g/mol, Mw = 2920 g/mol, was einer Polydispersität von 2,1 entspricht.GPC (in THF) gave the copolymer Mn = 1400 g/mol, Mw = 2920 g/mol, corresponding to a polydispersity of 2.1.
Wie in Synthesebeispiel 1 beschrieben wurde ein Copolymer aus C20-C24 Olefin, Maleinsäureanhydrid und Laurylacrylat im Molverhältnis 0,43 : 0,43 : 0,14 hergestellt und mit 1,1 Äquivalenten vollentsalztem Wasser (bezogen auf mol Maleinsäureanhydrid) hydrolysiert.A copolymer of C 20 -C 24 olefin, maleic anhydride and lauryl acrylate in a molar ratio of 0.43:0.43:0.14 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride).
Der Feststoffgehalt des hydrolysierten Produktes beträgt 57,7% (gemessen nach 2 Stunden unter Vakuum bei 100°C).The solids content of the hydrolyzed product is 57.7% (measured after 2 hours under vacuum at 100°C).
Das GPC (in THF) ergab für das Copolymer ein Mn = 1450 g/mol, Mw = 2970 g/mol, was einer Polydispersität von 2,1 entspricht.GPC (in THF) gave the copolymer Mn = 1450 g/mol, Mw = 2970 g/mol, corresponding to a polydispersity of 2.1.
Wie in Synthesebeispiel 1 beschrieben wurde ein Copolymer aus C20-C24 Olefin, Maleinsäureanhydrid und Laurylacrylat im Molverhältnis 0,35 : 0,35 : 0,3 hergestellt und mit 1,1 Äquivalenten vollentsalztem Wasser (bezogen auf mol Maleinsäureanhydrid) hydrolysiert.A copolymer of C 20 -C 24 olefin, maleic anhydride and lauryl acrylate in a molar ratio of 0.35:0.35:0.3 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride).
Der Feststoffgehalt des hydrolysierten Produktes beträgt 64,4% (gemessen nach 2 Stunden unter Vakuum bei 100 °C).The solids content of the hydrolyzed product is 64.4% (measured after 2 hours under vacuum at 100°C).
Das GPC (in THF) ergab für das Copolymer ein Mn = 1880 g/mol, Mw = 4330 g/mol, was einer Polydispersität von 2,3 entspricht.GPC (in THF) gave the copolymer Mn = 1880 g/mol, Mw = 4330 g/mol, corresponding to a polydispersity of 2.3.
Wie in Synthesebeispiel 1 beschrieben wurde ein Copolymer aus C20-C24 Olefin, Maleinsäureanhydrid und Laurylacrylat im Molverhältnis 0,4 : 0,4 : 0,2 hergestellt und mit 1,1 Äquivalenten vollentsalztem Wasser (bezogen auf mol Maleinsäureanhydrid) hydrolysiert.A copolymer of C 20 -C 24 olefin, maleic anhydride and lauryl acrylate in a molar ratio of 0.4:0.4:0.2 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol of maleic anhydride).
Der Feststoffgehalt des hydrolysierten Produktes beträgt 58,8% (gemessen nach 2 Stunden unter Vakuum bei 100 °C).The solids content of the hydrolyzed product is 58.8% (measured after 2 hours under vacuum at 100°C).
Das GPC (in THF) ergab für das Copolymer ein Mn = 1690 g/mol, Mw = 4070 g/mol, was einer Polydispersität von 2,4 entspricht.GPC (in THF) gave the copolymer Mn = 1690 g/mol, Mw = 4070 g/mol, corresponding to a polydispersity of 2.4.
Wie in Synthesebeispiel 1 beschrieben, wurde ein Copolymer aus C20-C24 Olefin, Maleinsäureanhydrid und 2-Ethylhexylacrylat im Molverhältnis 0,35 : 0,35 : 0,3 hergestellt und mit 1,1 Äquivalenten vollentsalztem Wasser (bezogen auf mol Maleinsäureanhydrid) hydrolysiert.As described in Synthesis Example 1, a copolymer was prepared from C 20 -C 24 olefin, maleic anhydride and 2-ethylhexyl acrylate in a molar ratio of 0.35:0.35:0.3 and treated with 1.1 equivalents of deionized water (based on mol maleic anhydride) hydrolyzed.
Der Feststoffgehalt des hydrolysierten Produktes beträgt 61,2% (gemessen nach 2 Stunden unter Vakuum bei 100 °C).The solids content of the hydrolyzed product is 61.2% (measured after 2 hours under vacuum at 100°C).
Das GPC (in THF) ergab für das Copolymer ein Mn = 1540 g/mol, Mw = 3080 g/mol, was einer Polydispersität von 2 entspricht.GPC (in THF) gave the copolymer Mn = 1540 g/mol, Mw = 3080 g/mol, which corresponds to a polydispersity of 2.
Wie in Synthesebeispiel 1 beschrieben wurde ein Copolymer aus C20-C24 Olefin, Maleinsäureanhydrid und 2-Ethylhexylacrylat im Molverhältnis 0,4 : 0,4 : 0,2 hergestellt und mit 1,1 Äquivalenten vollentsalztem Wasser (bezogen auf mol Maleinsäureanhydrid) hydrolysiert.A copolymer of C 20 -C 24 olefin, maleic anhydride and 2-ethylhexyl acrylate in a molar ratio of 0.4:0.4:0.2 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride). .
Der Feststoffgehalt des hydrolysierten Produktes beträgt 58,3% (gemessen nach 2 Stunden unter Vakuum bei 100 °C).The solids content of the hydrolyzed product is 58.3% (measured after 2 hours under vacuum at 100°C).
Das GPC (in THF) ergab für das Copolymer ein Mn = 1500 g/mol, Mw = 3030 g/mol, was einer Polydispersität von 2 entspricht.GPC (in THF) gave the copolymer Mn = 1500 g/mol, Mw = 3030 g/mol, which corresponds to a polydispersity of 2.
Wie in Synthesebeispiel 1 beschrieben wurde ein Copolymer aus C20-C24 Olefin, Maleinsäureanhydrid und 2-Ethylhexylacrylat im Molverhältnis 0,45 : 0,45 : 0,1 hergestellt und mit 1,1 Äquivalenten vollentsalztem Wasser (bezogen auf mol Maleinsäureanhydrid) hydrolysiert.A copolymer of C 20 -C 24 olefin, maleic anhydride and 2-ethylhexyl acrylate in a molar ratio of 0.45:0.45:0.1 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride). .
Der Feststoffgehalt des hydrolysierten Produktes beträgt 58,3% (gemessen nach 2 Stunden unter Vakuum bei 100 °C).The solids content of the hydrolyzed product is 58.3% (measured after 2 hours under vacuum at 100°C).
Das GPC (in THF) ergab für das Copolymer ein Mn = 1440 g/mol, Mw = 2970 g/mol, was einer Polydispersität von 2,1 entspricht.GPC (in THF) gave the copolymer Mn = 1440 g/mol, Mw = 2970 g/mol, corresponding to a polydispersity of 2.1.
Wie in Synthesebeispiel 1 beschrieben wurde ein Copolymer aus C20-C24 Olefin, Maleinsäureanhydrid, jedoch ohne Acrylat im Molverhältnis 1:1 hergestellt und mit 1,1 Äquivalenten vollentsalztem Wasser (bezogen auf mol Maleinsäureanhydrid) hydrolysiert.A copolymer of C 20 -C 24 olefin, maleic anhydride, but without acrylate in a molar ratio of 1:1, was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride).
Der Feststoffgehalt des hydrolysierten Produktes beträgt 55% (gemessen nach 2 Stunden unter Vakuum bei 100°C).The solids content of the hydrolyzed product is 55% (measured after 2 hours under vacuum at 100°C).
Das GPC (in THF) ergab für das Copolymer ein Mn = 1210 g/mol, Mw = 2330 g/mol, was einer Polydispersität von 1,9 entspricht.GPC (in THF) gave the copolymer Mn = 1210 g/mol, Mw = 2330 g/mol, corresponding to a polydispersity of 1.9.
Mit den Copolymeren aus den obigen Synthesebeispielen wurden in Tabelle 1 angegebenen Formulierungen hergestellt:
** Trägeröl: Polypropylenglykol der Molmasse 1000 g/mol
*** kommerziell verfügbarer Dehazer Kerocom® 3655 der BASF, Ludwigshafen
**** Dimerfettsäure: dimere Ölsäure; CAS: 61788-89-4 als Korrosionsinhibitor, 20%ig in Solvent Naphtha
** Carrier oil: polypropylene glycol with a molecular weight of 1000 g/mol
*** commercially available dehazer Kerocom® 3655 from BASF, Ludwigshafen
****Dimer fatty acid: dimeric oleic acid; CAS: 61788-89-4 as a corrosion inhibitor, 20% in Solvent Naphtha
Als Kraftstoff wurde ein E0 Referenzkraftstoff gemäß CEC RF-12-09 eingesetzt. Die in Tabelle 1 angegebenen Formulierungen wurden einem Korrosionstest nach ASTM D 665 A unterworfen und lieferten die in Tabelle 1 angegebenen Ergebnisse.An E0 reference fuel according to CEC RF-12-09 was used as the fuel. The formulations given in Table 1 were subjected to a corrosion test according to ASTM D 665 A and gave the results given in Table 1.
Die Bewertung erfolgte folgendermaßen:
100 ml Motorenöl (Shell Helix®,
Lösungsversuch 1: Zur Prüfung der Lösungseigenschaften wurden 1,600 g des Produktes aus Synthesebeispiel 6 in einer 100 ml Laborflasche bei Raumtemperatur vorgelegt und mit 39,68 g Polyisobutenamin (siehe Tabelle 1), 31,2 g eines Trägeröls analog Eintrag 2 der Tabelle 1 in
Lösungsversuch 2: Zum Vergleich wurden 1,696 g Vergleichsprodukt 1 vorgelegt und mit 39,648 g Polyisobutenamin (siehe Tabelle 1), 31,168g KC 3489 und 7,488g Kerosin versetzt wie bei Lösungsversuch 1.Solution experiment 2: For comparison, 1.696 g of
Beide Proben wurden jeweils mit den gleichen Rührstäbchen versehen und 5 Minuten bei Raumtemperatur auf einem Magnetrührer gerührt.Both samples were each fitted with the same stir bar and stirred on a magnetic stirrer at room temperature for 5 minutes.
In Lösungsversuch 1 sind nach 5 Minuten Rühren lediglich leichte Schlieren zu erkennen, das Produkt blieb jedoch in der flüssigen Phase verteilt und setzte sich nicht ab.In
In Lösungsversuch 2 war auch nach 5 Minuten Rühren am Boden der Laborflasche noch deutlich eine nicht aufgelöste Phase des Produktes zu erkennen.In solution experiment 2, an undissolved phase of the product was still clearly visible at the bottom of the laboratory bottle even after stirring for 5 minutes.
Man erkennt also, daß die erfindungsgemäßen Produkte in Lösungsmitteln besser auflösbar sind als die Produkte gemäß der
Claims (12)
- The use of copolymers obtainable by- in a first reaction step (I) copolymerizing(A) maleic anhydride,(B) at least one α-olefin having from at least 12 up to and including 30 carbon atoms,(C) optionally at least one further aliphatic or cycloaliphatic olefin which has at least 4 carbon atoms and is different than (B) and(D) at least one (meth)acrylic ester of alcohols having at least 5 carbon atoms,
followed by- in a second reaction step (II) partly or fully hydrolyzing the anhydride functionalities present in the copolymer obtained from (I) and/or partly hydrolyzing carboxylic ester functionalities present in the copolymer obtained from (I),
as corrosion inhibitors in fuels or lubricants, preferably in fuels, more preferably in fuels having a content of alkali metals and/or alkaline earth metals and/or zinc of at least 0.1 ppm by weight, where at least 10% of the anhydride functionalities are hydrolyzed in reaction step (II). - The use according to claim 1, wherein the alkali metals are selected from the group consisting of sodium and potassium.
- The use according to either of the preceding claims, wherein the alkaline earth metals are selected from the group consisting of magnesium and calcium.
- The use according to any of the preceding claims, wherein component (B) is selected from the group consisting of 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene and mixtures thereof.
- The use according to any of the preceding claims, wherein no component (C) is present.
- The use according to any of claims 1 to 4, wherein component (C) is selected from the group consisting of 1-butene, 2-butene, isobutene, pentene isomers, hexene isomers, heptene isomers, octene isomers, nonene isomers, decene isomers, undecene isomers and mixtures thereof.
- The use according to any of claims 1 to 4, wherein component (C) is at least one polymer having more than 30 carbon atoms of propene, 1-butene, 2-butene or isobutene or olefin mixtures comprising the latter, having an average molecular weight Mw in the range from 500 to 5000 g/mol.
- The use according to any of the preceding claims, wherein component (D) is at least one (meth)acrylic ester of C5- to C18-alkanols.
- The use according to any of claims 1 to 7, wherein component (D) is selected from the group consisting of dodecyl acrylate, 2-ethylhexyl acrylate and 2-propylheptyl acrylate.
- The use according to any of the preceding claims, wherein the fuel is selected from diesel fuels, biodiesel fuels, gasoline fuels, and alkanolcontaining gasoline fuels.
- The use according to any of the preceding claims, wherein, in reaction step (II), the anhydride functionalities present in the copolymer are essentially fully hydrolyzed.
- The use according to any of the preceding claims, wherein the fuel additionally comprises at least one detergent additive (Da) having a hydrophobic hydrocarbyl radical having a number-average molecular weight (Mn) of 85 to 20 000 and at least one monoor polyamino group having up to 6 nitrogen atoms, where at least one nitrogen atom has basic properties, preferably at least one polyalkenemonoor polyalkenepolyamine which is obtainable based on polypropene, polybutene or polyisobutene with Mn = 500 to 2500 by hydroformylation and reductive amination with ammonia, monoamines of the polyamines.
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-
2021
- 2021-06-04 EP EP21177666.1A patent/EP3940043B1/en active Active
- 2021-06-04 ES ES21177666T patent/ES2964845T3/en active Active
- 2021-06-04 PL PL21177666.1T patent/PL3940043T3/en unknown
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EP3940043A1 (en) | 2022-01-19 |
PL3940043T3 (en) | 2024-02-19 |
ES2964845T3 (en) | 2024-04-09 |
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