US3573010A - Acid salts of polyisobutenyl alkylene polyamines as fuel detergents - Google Patents
Acid salts of polyisobutenyl alkylene polyamines as fuel detergents Download PDFInfo
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- US3573010A US3573010A US756249A US3573010DA US3573010A US 3573010 A US3573010 A US 3573010A US 756249 A US756249 A US 756249A US 3573010D A US3573010D A US 3573010DA US 3573010 A US3573010 A US 3573010A
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- polyisobutenyl
- fuel
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- alkylene
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- 239000000446 fuel Substances 0.000 title abstract description 45
- 239000003599 detergent Substances 0.000 title abstract description 23
- 229920000768 polyamine Polymers 0.000 title abstract description 23
- 239000002253 acid Substances 0.000 title abstract description 17
- 125000002947 alkylene group Chemical group 0.000 title description 20
- 150000003839 salts Chemical class 0.000 title description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 10
- 239000011707 mineral Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 26
- 125000004432 carbon atom Chemical group C* 0.000 description 23
- 150000001412 amines Chemical class 0.000 description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 13
- -1 amine salts Chemical class 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229960001124 trientine Drugs 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229920005603 alternating copolymer Polymers 0.000 description 3
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 3
- 239000003849 aromatic solvent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 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 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- RVRHBLSINNOLPI-UHFFFAOYSA-N Lythridin Natural products COc1ccc(cc1OC)C2CC(CC3CCCCN23)OC(=O)CC(O)c4ccc(O)cc4 RVRHBLSINNOLPI-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- LTNZEXKYNRNOGT-UHFFFAOYSA-N dequalinium chloride Chemical compound [Cl-].[Cl-].C1=CC=C2[N+](CCCCCCCCCC[N+]3=C4C=CC=CC4=C(N)C=C3C)=C(C)C=C(N)C2=C1 LTNZEXKYNRNOGT-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 239000006080 lead scavenger Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XOOGZRUBTYCLHG-UHFFFAOYSA-N tetramethyllead Chemical compound C[Pb](C)(C)C XOOGZRUBTYCLHG-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
Definitions
- hydrocarbyl polyamines are reported as detergents in fuels. It is found, however, that when the fuels are shaken with water, the separation of the fuel from the water and the clarity of the fuel phase are not as good as is desired. This phenomenon referred to as water tolerance varies, depending on the composition of the hydrocarbyl polyamine.
- transferring by means of a centrifugal pump can result in homogenization of water and fuel, if a water phase is present in the holding tank. Rapid separation of the water from the fuel is essential, if the fuel is to be in condition for use.
- Mineral acid salts of high molecular weight branched chain aliphatic hydrocarbon N-substituted alkylene polylCC amines are provided as detergents and dispersants having good Water tolerance. These salts are particularly useful for extended detergent action in hydrocarbouaceous liquid fuels for internal combustion engines.
- the hydrocarbon substituted amine portion of the molecule has average molecular weights in the range of about 460 to 10,000, more usually in the range of about 600 to 5,000.
- FIG. 1 is a graph of haze rating versus time for water tolerance determinations according to a modified version of ASTM D 109457, wherein polyisobutenyl tetraethylene pentarnine is neutralized to varying degress with phosphoric acid.
- FIG. 2 is a graph of the emulsion volume versus time for the same compositions employed for FIG. 1 and under the same test conditions.
- compositions which find use in this invention will, for the most part, have the following formula:
- U is alkylene of from 2 to 6 carbon atoms, more usually of from 2 to 3 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms.
- R is an aliphatic hydrocarbon radical of from about 420 to 5,000 average molecular weight.
- the alkylene polyamine is titrated to determine the amount of titratable base.
- the method of titration will be described in the experimental section. From 10 up to about percent, usually 15 to 60 percent, of the titrat able base is neutralized with the mineral acid.
- the acid will be titrated to determine the available acidity and the amine and acid combined in the proportion according to the titrimetric determination.
- compositions will have the following formula:
- R is an oil soluble branched chain aliphatic hydrocarbon radical of from about 450 to 5,000 average molecular weight, usually polypropylene or polyisobutylene; U is alkylene of from 2 to 3 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms; Y is phosphoric acid or sulfuric acid; a is an integrer of from 1 to 5; c is an integer of from 1 to 5; x is in the range from 0.1 to a and, n is the number of titratable protons of the mineral acid Y
- the compositions of this invention are readily prepared by combining in a suitable medium or neat, the acid and the amine. Cooling may be desirable or slow addition of the acid to the amine to avoid undue exothermicity.
- the alkylene radical indicated as U will have from 2 to 6 carbon atoms and more usually, from 2 to 3 carbon atoms, the nitrogen atoms connected by U being separated by at least 2 carbon atoms.
- the alkylene group may be straight or branched chain and is preferably polymethylene of from 2 to 3 carbon atoms.
- Illustrative alkylene groups are ethylene, 1,2-propylene, 2,2-dimethyl propylene-1,3, trimethylene, hexamethylene, 2-methyl-l,3-pr0pylene, etc.
- alkylene polyamines which are substituted with the hydrocarbon radical may be derived from such alkylene polyamines as ethylene diamine, diethylene triamine, tetraethylene pentamine, nonaethylene decamine, Z-aminoethyl piperazine, 1,3-propylene diamine, 1,2-propylene diamine, tetramethylene diamine, etc.
- a single compound will not be used as a reactant in the preparation of the compositions of this invention. That is, mixtures will be used in which one or two compounds will predominate and the average composition or molecular Weight is indicated.
- tetraethylene pentamine prepared by the polymerization of aziridine or reaction of dichloroethylene and ammonia will have both lower and higher members, e.g., triethylene tetramine and pentaethylene hexamine, but the composition will be mainly tetraethylene pentamine and the em pirical formula of the total composition will closely ap proximate that of tetraethylene pentamine.
- the molecular weight reported for the branched chain aliphatic hydrocarbon group is an average for a mixture which is sharply peaked when graphing the number average molecular weight distribution. Also, when the nitrogens of the alkylene polyamines are not equivalent, substitution on different nitrogens will afford different compounds.
- the alkylene polyamines may have only one hydrocarbon substituent or may be polysubstituted with hydrocarbon radicals.
- the monosubstituted alkylene polyamine compositions will have the following formula:
- a an integer of from 0 to 5, preferably of from 0 to 4 b --an integer of from 0 to 1, preferably 0 when a is greater than 0 a +2b an integer of from 1 to 5 d-an integer of from 2 to 3 R -a branched chain aliphatic hydrocarbon radical derived from polymerizing olefins of from 2 to 6 carbon atoms, preferably of from 3 to 4 carbon atoms, and particularly preferred of propylene and isobutylene and having an average molecular weight in the range of 400 to 3,000, preferably 400 to 2,5 00
- N-polyisobutenyl ethylene diamine N-polypropenyl ethylene diamine, N-poly(1-butenyl) ethylene diamine, N-(alternating copolymer of ethylene and isobutylene) ethylene diamine (alternating copolymers of ethylene and isobutylene may be achieved by the cationic polymerization of 4-methylpentene-1), N-polypropenyl 2- aminoethylpiperazine, N polyisobutenyl 2 aminoethylpiperazine, N-polypropenyl diethylene triamine, N-polyisobutenyl diethylene triamine, N-po1y(1-pentenyl) diethylene triamine, N-polypropenyl trimethylene diamine, N-
- polyisobutenyl trimethylene diamine N-polypropenyl di(trimethylene) triamine, N-polyisobutenyl di(trimethyl ene) triamine, N-polyisobutenyl 1,2-propylene diamine,
- N-polyisobutenyl di(1,2-propylene) triamine N-polypropenyl triethylene tetramine, N-polyisobutenyl triethylene tetramine, N-(alternating copolymer of ethylene and isobutylene) triethylene tetramine, N-polypropenyl tetraethylene pentamiue, N-polyisobutenyl tetraethylene pentamine, N-polyisobutenyl pentaethylene hexamine, etc.
- the polyhydrocarbon radical substituted alkylene polyamine compositions have the following formula:
- a an integer of from 0 to 5, preferably an integer of from 1 to 4 b an integer of from 0 to 1, preferably 0 when a is greater than 0 a +2b -an integer of from 1 to 5 c an integer in the range of 1 to 3, on the average there being fewer R groups than nitrogen atoms d an integer of from 2 to 3 R a branched chain aliphatic hydrocarbon radical either free of or having aliphatic unsaturation, e.g., olefinic and of from 400 to 3,000 average molecular weight, preferably of from 400 to about 2,500 average molecular weight (As indicated by the above formula, the number of hydrocarbon substituents need not be a whole number when averaged over a total composition; generally, a mixture will be obtained containing mono-, diand trior higher substituted molecules averaging out to a fractional or whole number.)
- Illustrative compounds coming within the above formula are as follows: N,N-di(polypropenyl) diethylene triamine, N,N'-di(polyisobutenyl) diethylene triamine, N, N-di(polyisobutenyl) triethylene tetramine, N,N'-di(polypropenyl) tetraethylene pentamine, N,N'-di(polyisobutenyl) tetraethylene pentamine, N,N,N"-tri(polyisobutenyl) tetraethylene pentamine, N,N' di(polyisobutenyl) 2 aminoethylpiperazine, N,N' di(poly 1- butenyl) triethylene tetramine, N,N'-di(polyisobutenyl) di-(trimethylene) triamine, etc.
- compositions are those having the straight chain alkylene polyamines, particularly ethylene diamine and polyethylene polyamines. These compositions have the following formula:
- the preparation of the polyamines is usually carried out by combining a halogenated aliphatic hydrocarbon of the appropriate molecular weight with the desired amine. An extensive discussion of the method of preparation is foud in copending application Ser. No. 647,611, filed on June 21, 1967, and now US. 3,438,757.
- the detergent will generally be employed in a hydrocarbon base liquid fuel.
- the detergent additive may be formulated as a concentrate, using a suitable hydrocarbon alcohol solvent boiling in the range of about to 400 F.
- a suitable hydrocarbon alcohol solvent such as benzene, toluene, xylene or higher boiling aromatics or aromatic thinners.
- Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol and the like, in combination with hydrocarbon solvents are also suitable for use with the detergent additive.
- the amount of the additive will be ordinarily at least 10 percent by Weight and generally not exceed 70 percent by weight.
- the amount of the detergent used in the fuel will generally be from about 50 to 1,000 ppm.
- antiknock agents e.g., tetramethyl lead or tetraethyl lead.
- lead scavengers such as aryl halides, e.g., dichlorobenzene or alkyl halides, e.g., ethylene dibromide.
- a nonvolatile lubricating mineral oil e.g., petroleum spray oil, particularly a refined naphthenic lubricating oil having a viscosity at 100 F. of 1,000 to 2,000 SUS is a suitable additive for the gasoline compositions used with the detergents of this invention and its use is preferred.
- These oils are believed to act as a carrier for the detergent and assist in moving and preventing deposits. They are employed in amounts from about 0.05 to 0.5 percent by volume, based on the final gasoline composition.
- Example A Polyisobutenyl chloride (10,170 lbs.) (polyisobutenyl -1,000 average molecular weight; percent Cl-6.2) was charged to a reaction vessel and warmed to 250 F. To the reaction vessel was then charged 4,360 lbs. of tetraethylene pentamine (a commercial mixture of polyalkylene polyamines having the indicated average composition) and 1,510 lbs. of n-butanol.
- the reaction mixture was, purged with nitrogen and the temperature raised to 300 F. and maintained for 8 hrs. with agitation. At the end of this time, the mixture was cooled to 200 F. and 1,000 gal. of an aromatic solvent (boiling range 316-327 F.) added. While stirring and maintaining the temperature at l70200 F., 108 gal. of isopropyl alcohol and 520 gal. of hot water was added and the mixture stirred for 7 hrs. The aqueous layer was withdrawn and the aqueous isopropyl alcohol wash repeated 3 times. Volatile material was then distilled, raising the temperature to a final temperature of 280 F.
- an aromatic solvent boiling range 316-327 F.
- the product was then mixed with 100 lbs. of flake caustic, followed by the addition of diatomaceous earth. After agitating the mixture, the product was filtered. The filtrate was diluted with the aromatic solvent described above to provide a solution analyzing to 3.13% N; -51 weight percent active.
- Example I Into a reaction vessel was combined one gram of phosphoric acid (86 weight percent) and 13g. of xylenes. To the acidic solution was slowly added 10 g. of a composition prepared as described in Example A (50 weight percent active) 'with agitation. The final product had active material in a concentration of weight percent and the amine was 55.5 percent neutralized.
- Example II Following the procedure of Example I, 0.65 g. of sulfuric acid (96 weight percent) and 11.83 g. of xylene were combined. To the acidic solution was slowly added with agitation 10 g. of a composition prepared as described in Example A. The final solution had 5 weight percent active material and the amine was 90 percent neutralized.
- the titration of the hydrocarbyl substituted alkylene polyamine is carried out as follows.
- the amine is obtained as a 50 weight percent solution of active material (determined by nitrogen analysis, assuming one hydrocarbon group per polyamine molecule) in a C aromatic solvent.
- Approximately 0.5 g. is dissolved in a solution having 20 volumes of benzene, 75 volumes of isopropyl alcohol and 5 volumes of distilled water.
- the solution is potentiometrically titrated with approximately 0.1 normal HCl, graphing the course of the titration.
- the midpoint of the curve (pH -53) determines the amount of titratable nitrogen.
- the acid is titrated in aqueous media to a pH of 7.
- phosphoric acid only the first proton is titrated.
- a base fuel having a boiling range of 102 to 414 F.; 58 percent paraffins, 22 percent aromatics, and 20 percent olefins (by volume) and a vapor pressure (Reid) of 7.4 was employed.
- the additive was added at a concentration of 250 ppm.
- the test is carried outwith a single cylinder CFR engine equipped with throttle.
- the operating conditions for the test are: jacket temperature, 212 F.; oil temperature, 150180 F.; intake air temperature, F; ignition timing, 15 BTC; intake manifold vacuum, 15 in. Hg; fuel/air ratio, 0.07; speed, 1,800 rpm.
- the duration of the test is 12 hrs.
- the intake valve is weighed at the end of the test, cleaned and tared.
- the intake port is washed with hexane, then fitted with a receiver, and the deposits removed mechanically with the aid of chloroform.
- the chloroform is evaporated at about 250 F. and the deposits Weighed.
- the test procedure of ASTM D 104957 was employed.
- the following table indicates the results obtained after 10 minutes, using distilled water.
- the haze rating is a rating based on a rating of 1 to 5; the cylinder is observed against a flat vertical plate of diffused white light. Horizontal black strips are afiixed to the surface of the plate. The graduated cylinder is placed in front of the plate and the haze rating determined by the degree of diffuseness of the black strips. A sharp appearance is rated as 1; an almost totally obscured strip is rated as 5.
- FIGS. 1 and 2 provide a comparison of polyisobutenyl polyamine (the polyamine having an average composition equal to tetraethylene pentamine, there being approximaly 1 polyisobutylene of about 1,000 molecular weight) per alkylene polyamine being neutralized with phosphoric acid to various degrees.
- a liquid hydrocarbon fuel composition having from 50 ppm. to 1000 ppm. of a detergent additive of the formula:
- U is alkylene of from 2 to 6 carbon atoms, usually of from 2 to 3 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms;
- R is a branched chain aliphatic hydrocarbon radical of from about 420 to 5,000 average molecular weight; a is an integer of from to 10; b is an integer of from 0 to l; a+2b is an integer of from 1 to 10; c is an integer of from 1 to and averages in the range of l to 4 over the entire composition and is less than the number of amine nitrogens in the molecule; x is in the range from 0.1 to a+2b; n is the number of acidic protons of the mineral acid Y which can be titrated below pH 7; and Y is sulfuric acid or phosphoric acid.
- R is an oil soluble branched chain aliphatic hydrocarbon radical of from 450 to 5,000 average molecular weight; U is alkylene of from 2 to 3 carbon atoms; Y is phosphoric acid; a is an integer of from 1 to 5; c is an integer of from 1 to 5 and equal to or less than :1 x is in the range from 0.1 to a and n is the number of protons titratable below pH 7 of the mineral acid Y 3.
- composition of matter having the formula:
- U is alkylene of from 2 to 6 carbon atoms, usually of from 2 to 3 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms;
- R is an aliphatic hydrocarbon radical of from about 420 to 5,000 average molecular weight; a is an integer of from 0 to 10; b is an integer of from 0 to l; a+2b is an integer of from 1 to 10; c is an integer of from 1 to 5 and averages in the range of 1 to 4 over the entire composition and is less than the number of amine nitrogens in the molecule;
- x is in the range from 0.1 to a+2b;
- n is the number of acidic protons of the mineral acid Y which can be titrated below pH 7; and, Y is sulfuric acid or phosphoric acid.
- composition of matter having the formula:
- R is an oil soluble branched chain aliphatic hydrocarbon radical of from 450 to 5,000 average molecular weight; U is alkylene of from 2 to 3 carbon atoms; Y is phosphoric acid; a is an integer of from 1 to 5; c is an integer of from 1 to 5 and equal to or less than 11 x is in the range from 0.1 to a and, n is the number of protons titratable below pH 7 of the mineral acid Y 7.
- R is polyisobutenyl.
- a liquid hydrocarbon fuel concentrate composition having from 10 to weight percent of a composition according to claim 5 in a suitable solvent boiling in the range of about to 400 F.
- a liquid hydrocarbon fuel composition having from 50 ppm. to 1000 ppm. of a polyisobutenyl tetraethylene pentamine, wherein said polyisobutenyl group is of from about 400 to 2500 average molecular weight, wherein said polyisobutenyl tetraethylene pentamine is neutralized to from 15 to 60 percent with phosphoric acid.
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Abstract
MINERAL ACID SALTS OF HYDROCARBYL SUBSTITUTED POLYAMINES, WHICH ARE SUBSTANTIALLY FREE OF AROMATIC UNSATURATION AND OF FROM ABOUT 460 TO 10,000 MOLECULAR WEIGHT, FIND USE AS DETERGENTS IN FUELS, PARTICULARLY IN COMBINATION WITH A SMALL AMOUNT OF OIL.
Description
HAZE RATING EMULSIONJTLQ March 30, 1971 MEHMEDBASlCH 3,573,010
ACID SALTS OF POLYISOBUTENYL ALKYLENE POLYAMINES AS FUEL DETERGENTS Filed Aug. 29, 1968 fix-0% THE PERCENT OF TITRATABLE AMINE NEUTRALIZED WITH PHOSPHORIC ACID 1 l I l l I 1 O 2 4 6 8 1O 50 TIME, MINUTES 30 FIG.1
7o K J: I 7 20B 8-13.97
THE PERCENT OF TITRATABLE AMINE NEUTRALIZED WITH PHOSPHORIC ACID *l' 0-41.77o /E" 55.57o
o l l I l I;
O 2 4 6 8 I 10 5O TIME,MINUTES FIG.2
INVENTOR ENVER MEHMEDBAS/CH BY KP.
f Jufti! TORNEYS United States Patent O U.S. CI. 44-63 9 Claims ABSTRACT OF THE DISCLOSURE Mineral acid salts of hydrocarbyl substituted polyamines, which are substantially free of aromatic unsaturation and of from about 460 to 10,000 molecular weight, find use as detergents in fuels, particularly in combination with a small amount of oil.
BACKGROUND OF THE INVENTION Field of the invention Deposits resulting from polymeric materials in fuels remain a continuing problem in the smooth operation of internal combustion engines. Recently, a number of fuel detergent additives have been incorporated into fuels to reduce deposit formation. These additives help by maintaining various parts of the engine in clean condition and reduce incomplete combustion. Thus, the additives contribute to longer engine life, improved fuel performance and reduction in the production of smog-producing exhaust problems.
In co-pending application Ser. No. 647,611, filed on June 21, 1967 and now US. Pat. No. 3,438,757 hydrocarbyl polyamines are reported as detergents in fuels. It is found, however, that when the fuels are shaken with water, the separation of the fuel from the water and the clarity of the fuel phase are not as good as is desired. This phenomenon referred to as water tolerance varies, depending on the composition of the hydrocarbyl polyamine.
The problem of Water tolerance can be acute with fuels which come in contact with water. In many storage tanks, the housekeeping is fairly poor and water collects at the bottom of the tank. When the fuel is introduced into the tank or withdrawn, significant agitation may occur. If the fuel and Water do not separate quickly, significant amounts of water may be withdrawn with the fuel. Or, a cuff results, which means loss of fuel. If water is retained in the fuel phase, the fuel will appear hazy and could be unacceptable.
Also, transferring by means of a centrifugal pump can result in homogenization of water and fuel, if a water phase is present in the holding tank. Rapid separation of the water from the fuel is essential, if the fuel is to be in condition for use.
Since fuel detergents are ordinarily good emulsifiers, the addition of detergents to fuels creates Water tolerance problems. Solutions to the water tolerance problem have varied from modification of the detergent to the addition of a variety of demulsifiers.
Description of the prior art US. Pat. Nos. 2,945,749, 3,050,043 and 3,231,348 disclose relatively low molecular weight amine derivatives as fuel detergents. US. Pat. Nos. 2,905,542, 3,228,758, 3,007,782 and 3,118,745 disclose amine salts as de-icing agents and anti-corrosion agents in fuels.
SUMMARY OF THE INVENTION Mineral acid salts of high molecular weight branched chain aliphatic hydrocarbon N-substituted alkylene polylCC amines are provided as detergents and dispersants having good Water tolerance. These salts are particularly useful for extended detergent action in hydrocarbouaceous liquid fuels for internal combustion engines. The hydrocarbon substituted amine portion of the molecule has average molecular weights in the range of about 460 to 10,000, more usually in the range of about 600 to 5,000.
Brief description of the drawing FIG. 1 is a graph of haze rating versus time for water tolerance determinations according to a modified version of ASTM D 109457, wherein polyisobutenyl tetraethylene pentarnine is neutralized to varying degress with phosphoric acid.
FIG. 2 is a graph of the emulsion volume versus time for the same compositions employed for FIG. 1 and under the same test conditions.
DESCRIPTION OF THE PREFERRED EMBODIMENT The compositions which find use in this invention will, for the most part, have the following formula:
(r/n) Y- (I I{ (Ul l) (-UN N-) b Balm-.1
wherein U is alkylene of from 2 to 6 carbon atoms, more usually of from 2 to 3 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms. R is an aliphatic hydrocarbon radical of from about 420 to 5,000 average molecular weight. a is an integer of from 0 to 10; b is an integer of from 0 to 1; a+2b is and integer of from 1 to 10; c is an integer of from 1 to 5 and is as an average in the range of 1 to 4, and up to the number of nitrogen atoms in the molecule; x is in the range of 0.1 to a+ 212; n is the number of titratable protons of the mineral acid Y; and, Y is sulfuric acid or phosphoric acid.
The alkylene polyamine is titrated to determine the amount of titratable base. The method of titration will be described in the experimental section. From 10 up to about percent, usually 15 to 60 percent, of the titrat able base is neutralized with the mineral acid.
With the polybasic acids used, the acid will be titrated to determine the available acidity and the amine and acid combined in the proportion according to the titrimetric determination.
Preferred compositions will have the following formula:
wherein R is an oil soluble branched chain aliphatic hydrocarbon radical of from about 450 to 5,000 average molecular weight, usually polypropylene or polyisobutylene; U is alkylene of from 2 to 3 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms; Y is phosphoric acid or sulfuric acid; a is an integrer of from 1 to 5; c is an integer of from 1 to 5; x is in the range from 0.1 to a and, n is the number of titratable protons of the mineral acid Y The compositions of this invention are readily prepared by combining in a suitable medium or neat, the acid and the amine. Cooling may be desirable or slow addition of the acid to the amine to avoid undue exothermicity.
The polyamine compositions which find use in this invention are for the most part described by the following formula:
The above symbols are defined as follows:
U -alkylene of from 2 to 6 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms and preferably of from 2 to 3 carbon atoms R an aliphatic hydrocarbon radical, usually a branched chain aliphatic hydrocarbon radical of from about 400 to 5,000 average molecular Weight, preferably of from 400 to 3,000 average molecular weight a an integer of from to b an integer of from 0 to 1 a +2b an integer in the range of from 1 to 5 c -an integer of from 1 to 4, for the average composition being in the range of about 1 to 3, on the average there being fewer R groups than nitrogen atoms The alkylene radical indicated as U will have from 2 to 6 carbon atoms and more usually, from 2 to 3 carbon atoms, the nitrogen atoms connected by U being separated by at least 2 carbon atoms. The alkylene group may be straight or branched chain and is preferably polymethylene of from 2 to 3 carbon atoms.
Illustrative alkylene groups are ethylene, 1,2-propylene, 2,2-dimethyl propylene-1,3, trimethylene, hexamethylene, 2-methyl-l,3-pr0pylene, etc.
The alkylene polyamines which are substituted with the hydrocarbon radical may be derived from such alkylene polyamines as ethylene diamine, diethylene triamine, tetraethylene pentamine, nonaethylene decamine, Z-aminoethyl piperazine, 1,3-propylene diamine, 1,2-propylene diamine, tetramethylene diamine, etc.
In many instances a single compound will not be used as a reactant in the preparation of the compositions of this invention. That is, mixtures will be used in which one or two compounds will predominate and the average composition or molecular Weight is indicated. For example, tetraethylene pentamine prepared by the polymerization of aziridine or reaction of dichloroethylene and ammonia will have both lower and higher members, e.g., triethylene tetramine and pentaethylene hexamine, but the composition will be mainly tetraethylene pentamine and the em pirical formula of the total composition will closely ap proximate that of tetraethylene pentamine. Similarly, the molecular weight reported for the branched chain aliphatic hydrocarbon group is an average for a mixture which is sharply peaked when graphing the number average molecular weight distribution. Also, when the nitrogens of the alkylene polyamines are not equivalent, substitution on different nitrogens will afford different compounds.
As is evident from the above formulae, the alkylene polyamines may have only one hydrocarbon substituent or may be polysubstituted with hydrocarbon radicals. The monosubstituted alkylene polyamine compositions will have the following formula:
The above symbols are defined as follows:
a an integer of from 0 to 5, preferably of from 0 to 4 b --an integer of from 0 to 1, preferably 0 when a is greater than 0 a +2b an integer of from 1 to 5 d-an integer of from 2 to 3 R -a branched chain aliphatic hydrocarbon radical derived from polymerizing olefins of from 2 to 6 carbon atoms, preferably of from 3 to 4 carbon atoms, and particularly preferred of propylene and isobutylene and having an average molecular weight in the range of 400 to 3,000, preferably 400 to 2,5 00
Illustrative compounds within the above formula are as follows: N-polyisobutenyl ethylene diamine, N-polypropenyl ethylene diamine, N-poly(1-butenyl) ethylene diamine, N-(alternating copolymer of ethylene and isobutylene) ethylene diamine (alternating copolymers of ethylene and isobutylene may be achieved by the cationic polymerization of 4-methylpentene-1), N-polypropenyl 2- aminoethylpiperazine, N polyisobutenyl 2 aminoethylpiperazine, N-polypropenyl diethylene triamine, N-polyisobutenyl diethylene triamine, N-po1y(1-pentenyl) diethylene triamine, N-polypropenyl trimethylene diamine, N-
polyisobutenyl trimethylene diamine, N-polypropenyl di(trimethylene) triamine, N-polyisobutenyl di(trimethyl ene) triamine, N-polyisobutenyl 1,2-propylene diamine,
N-polyisobutenyl di(1,2-propylene) triamine, N-polypropenyl triethylene tetramine, N-polyisobutenyl triethylene tetramine, N-(alternating copolymer of ethylene and isobutylene) triethylene tetramine, N-polypropenyl tetraethylene pentamiue, N-polyisobutenyl tetraethylene pentamine, N-polyisobutenyl pentaethylene hexamine, etc.
The polyhydrocarbon radical substituted alkylene polyamine compositions have the following formula:
[-1 I([(CH2)d I I-']=, [(CH2)d1N s N--] e R 2Ha+ a 2 The above symbols are defined as follows:
a an integer of from 0 to 5, preferably an integer of from 1 to 4 b an integer of from 0 to 1, preferably 0 when a is greater than 0 a +2b -an integer of from 1 to 5 c an integer in the range of 1 to 3, on the average there being fewer R groups than nitrogen atoms d an integer of from 2 to 3 R a branched chain aliphatic hydrocarbon radical either free of or having aliphatic unsaturation, e.g., olefinic and of from 400 to 3,000 average molecular weight, preferably of from 400 to about 2,500 average molecular weight (As indicated by the above formula, the number of hydrocarbon substituents need not be a whole number when averaged over a total composition; generally, a mixture will be obtained containing mono-, diand trior higher substituted molecules averaging out to a fractional or whole number.)
Illustrative compounds coming within the above formula are as follows: N,N-di(polypropenyl) diethylene triamine, N,N'-di(polyisobutenyl) diethylene triamine, N, N-di(polyisobutenyl) triethylene tetramine, N,N'-di(polypropenyl) tetraethylene pentamine, N,N'-di(polyisobutenyl) tetraethylene pentamine, N,N,N"-tri(polyisobutenyl) tetraethylene pentamine, N,N' di(polyisobutenyl) 2 aminoethylpiperazine, N,N' di(poly 1- butenyl) triethylene tetramine, N,N'-di(polyisobutenyl) di-(trimethylene) triamine, etc.
The preferred compositions are those having the straight chain alkylene polyamines, particularly ethylene diamine and polyethylene polyamines. These compositions have the following formula:
a an integer of from 1 to 5, preferably of from 1 to 4 c an integer in the range of 1 to 3, on the average over the entire composition being in the range of from 1 to 2, per molecule there being fewer R groups than nitrogen atoms R -a branched chain aliphatic hydrocarbon radical of from 400 to 3,000 average molecular weight, preferably of from 400 to 2,500 average molecular weight, and, particularly preferred, either polypropenyl or polyisobutenyl The preparation of the polyamines is usually carried out by combining a halogenated aliphatic hydrocarbon of the appropriate molecular weight with the desired amine. An extensive discussion of the method of preparation is foud in copending application Ser. No. 647,611, filed on June 21, 1967, and now US. 3,438,757.
The detergent will generally be employed in a hydrocarbon base liquid fuel. The detergent additive may be formulated as a concentrate, using a suitable hydrocarbon alcohol solvent boiling in the range of about to 400 F. Preferably, an aromatic hydrocarbon solvent is used, such as benzene, toluene, xylene or higher boiling aromatics or aromatic thinners. Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol and the like, in combination with hydrocarbon solvents are also suitable for use with the detergent additive. In the concentrate, the amount of the additive will be ordinarily at least 10 percent by Weight and generally not exceed 70 percent by weight.
The amount of the detergent used in the fuel will generally be from about 50 to 1,000 ppm.
In gasoline fuels, other fuel additives may also be included such as antiknock agents, e.g., tetramethyl lead or tetraethyl lead. Also included may be lead scavengers such as aryl halides, e.g., dichlorobenzene or alkyl halides, e.g., ethylene dibromide.
A nonvolatile lubricating mineral oil, e.g., petroleum spray oil, particularly a refined naphthenic lubricating oil having a viscosity at 100 F. of 1,000 to 2,000 SUS is a suitable additive for the gasoline compositions used with the detergents of this invention and its use is preferred. These oils are believed to act as a carrier for the detergent and assist in moving and preventing deposits. They are employed in amounts from about 0.05 to 0.5 percent by volume, based on the final gasoline composition.
EXAMPLES The following examples are offered by way of illustration and not by way of limitation.
Example A Polyisobutenyl chloride (10,170 lbs.) (polyisobutenyl -1,000 average molecular weight; percent Cl-6.2) was charged to a reaction vessel and warmed to 250 F. To the reaction vessel was then charged 4,360 lbs. of tetraethylene pentamine (a commercial mixture of polyalkylene polyamines having the indicated average composition) and 1,510 lbs. of n-butanol.
The reaction mixture was, purged with nitrogen and the temperature raised to 300 F. and maintained for 8 hrs. with agitation. At the end of this time, the mixture was cooled to 200 F. and 1,000 gal. of an aromatic solvent (boiling range 316-327 F.) added. While stirring and maintaining the temperature at l70200 F., 108 gal. of isopropyl alcohol and 520 gal. of hot water was added and the mixture stirred for 7 hrs. The aqueous layer was withdrawn and the aqueous isopropyl alcohol wash repeated 3 times. Volatile material was then distilled, raising the temperature to a final temperature of 280 F.
The product was then mixed with 100 lbs. of flake caustic, followed by the addition of diatomaceous earth. After agitating the mixture, the product was filtered. The filtrate was diluted with the aromatic solvent described above to provide a solution analyzing to 3.13% N; -51 weight percent active.
Example I Into a reaction vessel was combined one gram of phosphoric acid (86 weight percent) and 13g. of xylenes. To the acidic solution was slowly added 10 g. of a composition prepared as described in Example A (50 weight percent active) 'with agitation. The final product had active material in a concentration of weight percent and the amine was 55.5 percent neutralized.
Example II Following the procedure of Example I, 0.65 g. of sulfuric acid (96 weight percent) and 11.83 g. of xylene were combined. To the acidic solution was slowly added with agitation 10 g. of a composition prepared as described in Example A. The final solution had 5 weight percent active material and the amine was 90 percent neutralized.
Titration.The titration of the hydrocarbyl substituted alkylene polyamine is carried out as follows. The amine is obtained as a 50 weight percent solution of active material (determined by nitrogen analysis, assuming one hydrocarbon group per polyamine molecule) in a C aromatic solvent. Approximately 0.5 g. is dissolved in a solution having 20 volumes of benzene, 75 volumes of isopropyl alcohol and 5 volumes of distilled water. The solution is potentiometrically titrated with approximately 0.1 normal HCl, graphing the course of the titration. The midpoint of the curve (pH -53) determines the amount of titratable nitrogen.
The acid is titrated in aqueous media to a pH of 7. For phosphoric acid, only the first proton is titrated.
To demonstrate the eifectiveness of the amine salts of this invention as fuel detergents, a base fuel having a boiling range of 102 to 414 F.; 58 percent paraffins, 22 percent aromatics, and 20 percent olefins (by volume) and a vapor pressure (Reid) of 7.4 was employed. The additive was added at a concentration of 250 ppm.
The test is carried outwith a single cylinder CFR engine equipped with throttle. The operating conditions for the test are: jacket temperature, 212 F.; oil temperature, 150180 F.; intake air temperature, F; ignition timing, 15 BTC; intake manifold vacuum, 15 in. Hg; fuel/air ratio, 0.07; speed, 1,800 rpm. The duration of the test is 12 hrs.
The intake valve is weighed at the end of the test, cleaned and tared. The intake port is washed with hexane, then fitted with a receiver, and the deposits removed mechanically with the aid of chloroform. The chloroform is evaporated at about 250 F. and the deposits Weighed.
The following table indicates the results:
1 The values reported are the average from the number of determinations indicated in parentheses.
To demonstrate the excellent water tolerance of the salt mixtures employed in this invention, the test procedure of ASTM D 104957 was employed. The following table indicates the results obtained after 10 minutes, using distilled water. The haze rating is a rating based on a rating of 1 to 5; the cylinder is observed against a flat vertical plate of diffused white light. Horizontal black strips are afiixed to the surface of the plate. The graduated cylinder is placed in front of the plate and the haze rating determined by the degree of diffuseness of the black strips. A sharp appearance is rated as 1; an almost totally obscured strip is rated as 5.
TAB LE II Additive (250 p.p.m.)
Haze Emulsion To further demonstrate the excellent Water tolerance of the compositions of the invention, FIGS. 1 and 2 provide a comparison of polyisobutenyl polyamine (the polyamine having an average composition equal to tetraethylene pentamine, there being approximaly 1 polyisobutylene of about 1,000 molecular weight) per alkylene polyamine being neutralized with phosphoric acid to various degrees.
The significant improvement in water tolerance is evidenced by the increase in rate at which the Water and fuel layer separate and the haze drops.
Both rapid separation and reduction in haze are important in evaluating water tolerance. For, even in the situation Where the Water separates quickly, if a small residual amount of water remains dispersed in the fuel giving it a hazy appearance, the fuel will be unaccept able. Frequently, haze and water separation do not directly correlate. Therefore, it is important that with the exemplary phosphate salt, great improvement in both the haze rating and separation is achieved, and a rapid reduction in haze and a quick separation between the fuel and water layers is obtained.
It is evident from the above results that while the detergent effectiveness in fuels is substantially retained with the mixture of salt and amine, when the phosphate or sulfate anions are employed, enhanced water tolerance is achieved over the parent amine. Thus, not only is excellent detergency achieved, but the fuel is also found to have excellent water tolerance. This is particularly surprising when one is using a highly detergent material, which generally causes emulsions; and, by going to a more polar situation, one achieves enhanced water tolerance.
I claim:
1. A liquid hydrocarbon fuel composition having from 50 ppm. to 1000 ppm. of a detergent additive of the formula:
wherein U is alkylene of from 2 to 6 carbon atoms, usually of from 2 to 3 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms; R is a branched chain aliphatic hydrocarbon radical of from about 420 to 5,000 average molecular weight; a is an integer of from to 10; b is an integer of from 0 to l; a+2b is an integer of from 1 to 10; c is an integer of from 1 to and averages in the range of l to 4 over the entire composition and is less than the number of amine nitrogens in the molecule; x is in the range from 0.1 to a+2b; n is the number of acidic protons of the mineral acid Y which can be titrated below pH 7; and Y is sulfuric acid or phosphoric acid.
2. A fuel composition according to claim 1, wherein said detergent additive is of the formula:
wherein R is an oil soluble branched chain aliphatic hydrocarbon radical of from 450 to 5,000 average molecular weight; U is alkylene of from 2 to 3 carbon atoms; Y is phosphoric acid; a is an integer of from 1 to 5; c is an integer of from 1 to 5 and equal to or less than :1 x is in the range from 0.1 to a and n is the number of protons titratable below pH 7 of the mineral acid Y 3. A fuel composition according to claim 2, wherein xdoes not exceed 60 percent of the titratable amine nitrogen.
4. A fuel composition according to claim 2, wherein R is polyisobutenyl.
5. A composition of matter having the formula:
(x/ )n( -)b l) c IH-a-ci wherein U is alkylene of from 2 to 6 carbon atoms, usually of from 2 to 3 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms; R is an aliphatic hydrocarbon radical of from about 420 to 5,000 average molecular weight; a is an integer of from 0 to 10; b is an integer of from 0 to l; a+2b is an integer of from 1 to 10; c is an integer of from 1 to 5 and averages in the range of 1 to 4 over the entire composition and is less than the number of amine nitrogens in the molecule; x is in the range from 0.1 to a+2b; n is the number of acidic protons of the mineral acid Y which can be titrated below pH 7; and, Y is sulfuric acid or phosphoric acid.
6. A composition of matter having the formula:
(x /n (-N (-U l l)i c 3+a-c wherein R is an oil soluble branched chain aliphatic hydrocarbon radical of from 450 to 5,000 average molecular weight; U is alkylene of from 2 to 3 carbon atoms; Y is phosphoric acid; a is an integer of from 1 to 5; c is an integer of from 1 to 5 and equal to or less than 11 x is in the range from 0.1 to a and, n is the number of protons titratable below pH 7 of the mineral acid Y 7. A composition of matter according to claim 6, wherein R is polyisobutenyl.
8. A liquid hydrocarbon fuel concentrate composition having from 10 to weight percent of a composition according to claim 5 in a suitable solvent boiling in the range of about to 400 F.
9. A liquid hydrocarbon fuel composition having from 50 ppm. to 1000 ppm. of a polyisobutenyl tetraethylene pentamine, wherein said polyisobutenyl group is of from about 400 to 2500 average molecular weight, wherein said polyisobutenyl tetraethylene pentamine is neutralized to from 15 to 60 percent with phosphoric acid.
References Cited UNITED STATES PATENTS 2,798,045 7/1957 Buck ef al. 4472X 3,384,466 5/1968 Popkin 4472 3,389,980 6/1968 Kautsky 4472X 3,425,815 2/1969 Rosenwald et al 4472 FOREIGN PATENTS 546,875 10/1957 Canada 4472 DANIEL E. WYMAN, Primary Examiner W. J. SHINE, Assistant Examiner US. 01. X.R.
4472; 260-268, 501.2, 268 poly, 268 het
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US75624968A | 1968-08-29 | 1968-08-29 |
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US3767574A (en) * | 1971-12-06 | 1973-10-23 | Phillips Petroleum Co | Gasoline additive |
US4022589A (en) * | 1974-10-17 | 1977-05-10 | Phillips Petroleum Company | Fuel additive package containing polybutene amine and lubricating oil |
EP0558835A1 (en) | 1992-01-30 | 1993-09-08 | Albemarle Corporation | Biodegradable lubricants and functional fluids |
EP2042582A2 (en) | 2007-09-24 | 2009-04-01 | Afton Chemical Corporation | Surface passivation and to methods for the reduction of fuel thermal degradation deposits |
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US20110010985A1 (en) * | 2007-05-22 | 2011-01-20 | Peter Wangqi Hou | Fuel Additive to Control Deposit Formation |
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EP3825387A1 (en) | 2019-11-22 | 2021-05-26 | Afton Chemical Corporation | Fuel-soluble cavitation inhibitor for fuels used in common-rail injection engines |
EP4282937A1 (en) | 2022-05-26 | 2023-11-29 | Afton Chemical Corporation | Engine oil formluation for controlling particulate emissions |
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DE102013013712A1 (en) * | 2013-08-20 | 2015-02-26 | Mann + Hummel Gmbh | Method for increasing the H2O separation efficiency from diesel fuels |
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1969
- 1969-08-22 FR FR6928967A patent/FR2017077A1/fr not_active Withdrawn
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3767574A (en) * | 1971-12-06 | 1973-10-23 | Phillips Petroleum Co | Gasoline additive |
US4022589A (en) * | 1974-10-17 | 1977-05-10 | Phillips Petroleum Company | Fuel additive package containing polybutene amine and lubricating oil |
EP0558835A1 (en) | 1992-01-30 | 1993-09-08 | Albemarle Corporation | Biodegradable lubricants and functional fluids |
EP2272940A1 (en) | 2001-09-14 | 2011-01-12 | Afton Chemical Intangibles LLC | Fuels compositions for direct injection gasoline engines |
US20110010985A1 (en) * | 2007-05-22 | 2011-01-20 | Peter Wangqi Hou | Fuel Additive to Control Deposit Formation |
EP2042582A2 (en) | 2007-09-24 | 2009-04-01 | Afton Chemical Corporation | Surface passivation and to methods for the reduction of fuel thermal degradation deposits |
EP3597726A1 (en) | 2018-07-20 | 2020-01-22 | Afton Chemical Corporation | Fuel-soluble synergistic cleaning mixture for high pressure gasoline engines |
US10774708B2 (en) | 2018-09-04 | 2020-09-15 | Afton Chemical Corporation | Gasoline particulate filters with high initial filtering efficiency and methods of making same |
US10774722B2 (en) | 2018-09-04 | 2020-09-15 | Afton Chemical Corporation | Predictive methods for emissions control systems performance |
US11401855B2 (en) | 2018-09-04 | 2022-08-02 | Afton Chemical Corporation | Predictive methods for emissions control systems performance |
US11441458B2 (en) | 2018-09-04 | 2022-09-13 | Afton Chemical Corporation | Gasoline particulate filters with high initial filtering efficiency and methods of making same |
EP3690009A1 (en) | 2019-01-31 | 2020-08-05 | Afton Chemical Corporation | Fuel additive mixture providing rapid injector clean-up in high pressure gasoline engines |
EP3825387A1 (en) | 2019-11-22 | 2021-05-26 | Afton Chemical Corporation | Fuel-soluble cavitation inhibitor for fuels used in common-rail injection engines |
EP4282937A1 (en) | 2022-05-26 | 2023-11-29 | Afton Chemical Corporation | Engine oil formluation for controlling particulate emissions |
Also Published As
Publication number | Publication date |
---|---|
NL6913264A (en) | 1970-03-03 |
GB1223078A (en) | 1971-02-17 |
DE1943637A1 (en) | 1970-03-05 |
FR2017077A1 (en) | 1970-05-15 |
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