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(11) | EP 0 115 110 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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| (54) |
Liquid fuels and concentrates containing corrosion inhibitors Flüssige Brennstoffe und Korrosionsinhibitoren enthaltende Konzentrate Combustibles liquides et concentrés contenant des inhibiteurs de corrosion |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
[0001] In the past metal corrosion caused by conventional motor fuels such as gasoline was not much of a problem because such hydrocarbon fuels are inherently non-corrosive. However, with the advent of fuels containing alcohols such as gasohol or straight alcohol fuels, corrosion has become a major problem because such fuels are corrosive. It has been reported that this corrosion is due to the presence of acidic contaminants in such fuels such as formic acid. It is almost impossible to avoid such contaminants because they occur in fuel grade alcohols and are also formed in storage as normal alcohol oxidation products.
[0002] It is known from U.S. 4,305,730 polymerized linoleic acid, especially trimer, is an effective corrosion inhibitor for alcohol-type motor fuels. It has now been discovered that the corrosion inhibiting properties of such polymerized polyunsaturated aliphatic monocarboxylic acids are improved by use of the co-additive described herein.
[0003] According to the present invention metal corrosion caused by alcohol-type motor fuels is inhibited by adding to the fuel a combination of (A) polymerized polyunsaturated aliphatic monocarboxylic acid and (B) the reaction product of a polyalkylenepolyamine, a monounsaturated aliphatic monocarboxylic acid and, optionally, an alkenyl succinic anhydride.
[0004] Specifically, the invention provides a liquid fuel adapted for use in an internal combustion engine said fuel comprising from 5 to 100 weight percent alcohol, from 0 to 95 weight percent gasoline and a corrosion inhibiting amount of a combination of (A) a polymer of one or more C16 to C18, preferably a mainly C,8 polyunsaturated aliphatic monocarboxylic acids and (B) a reaction product of (i) about one mole part of one or more polyalkylene polyaniihes having the formula
wherein n is an integer from 1 to 8 the average value of n in a mixture of such polyamines preferably being from 2 to 5, and R is a divalent hydrocarbon group containing 2 to 4 carbon atoms, (ii) about 0.1 to 5 mole parts of one or more C10 to C24, eg. a mainly C18 monounsaturated aliphatic monocarboxylic acids or lower alkyl esters thereof and (iii) 0 to about 4 mole parts of an alkenyl succinic anhydride wherein the alkenyl group contains 8-30 carbon atoms.
[0005] The 'combination' may be a simple mixture or as explained further hereafter, components A and B may react together.
[0006] The additive combination is useful in any alcohol-type motor fuel including gasoline- alcohol mixtures (e.g. "gasohol") as well as straight-alcohol type fuels. Useful alcohols include methanol, ethanol, n-propanol, isopropanol, isobutanol and the like including alcohol mixtures. Gasohol usually contains about 2 to 30 volume percent alcohol. At concentrations above 10 volume percent phase separation is a problem especially in the presence of water which is difficult to avoid. Phase separation can be minimized by including other oxygenates as co-solvents such as ethers, ketones, esters and the like. An especially useful co-solvent is methyl tert-butyl ether (MTBE) which also increases octane value.
[0007] The additive combination may be used at a concentration which provides the required amount of corrosion protection. A useful range is about 1 to 5000 p.p.m. A more preferred range is about 5 to 2000 p.p.m. and the most preferred concentration is 10 to 500 p.p.m.
[0008] Component A is preferably a polymer of a polyunsaturated aliphatic monocarboxylic acid chiefly consisting of C18 acid units. Examples of these are linoleic acid and linolenic acid including mixtures thereof. The polymers comprise mainly dimers and trimers of the polyunsaturated acids. Suitable polymers of linoleic acid are available commercially. Mixtures high in trimer content are most preferred.
[0010] The first reactant is a polyalkylene polyamine. These compounds have the structure
in which n is an integer from 1-8 preferably with an average value in mixtures of 2-5. R is a divalent hydrocarbon group containing 2-4 carbon atoms. Examples of these reactants are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, propylene diamine, dipropylene triamine, tetrapropylene pentamine, butylene diamine and the like including mixtures thereof. The more preferred alkylene polyamines are the polyethylene polyamines especially those in which n is an integer of 1-6 and most preferably mixtures of such polyethylene polyamines in which n has an average value of 2-4.
[0011] The second is a monounsaturated aliphatic monocarboxylic acid. Although such acids containing 10-24 carbons have some utility, it has been found that superior results are achieved using 18 carbon acids or mixtures of acids mainly composed of C18 acids, especially oleic acid, or commercial products high in oleic acid content such as tall oil fatty acids. These acids can also be used in the form of their lower alkyl esters (e.g. methyl, ethyl, propyl, butyl) in which case the alcohol is displaced and distilled out during reaction.
[0012] The third reactant which is optional is an alkenyl succinic acid or anhydride, preferably an anhydride. These are well known compounds and can be made by heating a mixture of maleic anhydride and 1-olefin. The alkenyl group can vary over a wide range from 8-30 carbon atoms. Examples of these are octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl, docosenyl, tetracosenyl, tri- acoulenyl and the like. More preferably, the alkenyl substituent contain 10-14 carbon atoms. The alkenyl succinic reactant can also be used in the form of its lower alkyl ester but this is not the preferred mode.
[0013] The B component is made by reacting the above reactants in the ratio of one mole of polyalkylene polyamine: 0.1 to 5 moles of monounsaturated aliphatic monocarboxylic acid: 0 to 4 moles of alkenyl succinic anhydride; preferably the alkenyl succinic anhydride is used at a mole ratio of 0.5 to 3.5.
[0015] A preferred method of making the (B) component is in a first stage to react the monounsaturated aliphatic monocarboxylic acid with the polyalkylene polyamine; this reaction may preferably be carried out in an inert solvent such as hexane, benzene, xylene and the like at an elevated temperature. On completion of the first stage reaction, any remaining solvent is removed and the resultant product is a substance useful as the B component. In a more preferred method, the first stage product is then further reacted in a second stage with the alkenyl succinic anhydride; this second stage reaction may be carried out in another or the same inert solvent, preferably in mineral oil, to yield a solution of a further product useful as the B component.
[0016] The reaction temperature in making the B component can vary over a wide range. A useful range is about 40 to 200°C. More preferably, the reaction temperature in the first stage is high enough to distill out any water or alcohol displaced in the reaction. Thus, a more preferred range in the first stage is 100 to 190°C.
[0017] One way of forming component B is as follows: in a first stage of react 1 mole of triethylene tetramine with between 1 and 2 moles of commercial oleic acid in hexane at between 100 and 160°C to form primarily the amide. The water formed during the reaction is continually removed together with the hexane. On completion of the reaction, the product is cooled and reacted in a second stage with between 1.5 and 3 moles, of alkenyl succinic anhydride at between 75 and 100°C and at less than 150 mm Hg pressure for at least 1 hour; this second stage is preferably carried out using between 25 and 75 percent by weight of mineral oil as solvent.
[0018] A preferred method of forming the fuel compositions is to formulate the co-additives as a concentrate and then simply add the proper amount of the concentrate to the alcohol-type motor fuel. The concentrate comprises a suitable inert solvent such as alcohols, ethers, esters, aromatic hydrocarbons and the like, and most preferably, aromatic hydrocarbons, such as toluene, xylene and the like, containing about 1 to 50 weight percent of the additive combination. The two active components, A & B, are preferably present in the ratios of between 1 part by weight of A to 10 parts by weight of B and 10 parts by weight of A to 1 part by weight of B. More preferably they are present in the ratios of between 1 part of A to 5 parts of B and 5 parts of A to 1 part of B.
[0019] Of course, it will be realized that any excess amine function and carboxylic acid function in the additive combination will probably exist as an amine salt. This is not detrimental and is considered as part of the invention as long as any such salt results from mixing the A and B components or from adding the A and B components to the fuel. Optionally admixture of the additives may be in a refluxing solvent with the elimination of water so as to form a reaction product.
[0020] To demonstrate the excellent corrosion inhibiting properties of the additive combination, tests were conducted using metal coupons cleaned with carborundum 40, washed with petroleum ether and finally dried in an oven at 40°C for 10 minutes. The coupons were then weighed and immersed in 130 g of fuel in a sealed bottle for a specified period and at a specified temperature; tests in which the coupons were only semi- submersed were also carried out.
[0021] At the end of the test period, the coupons were removed from the fuel; after loose deposits were removed with a light brush, the coupons were washed and dried as at the start of the test and were then reweighed. Any change in coupon weight was recorded. The corrosion was characterised by two modes, either weight loss by loss of metal or weight gain due to deposition of corrosion products, in the tests carried out below, visual examination of the coupons after test indicated that the two modes were mutually exclusive.
[0022] The tests were carried out using as component A a polymer of a C18 polyunsaturated aliphatic monocarboxylic acid which essentially comprised a trimer of linoleic acid and as component B, either component B1, a two stage reaction product of triethylene tetramine with oleic acid and C12 alkenyl succinic anhydride or component B2, a· one stage reaction product of triethylene tetramine with oleic acid containing 6.0% nitrogen and having an acid value of 265 mg KOH/g (IP1 method). Because the second stage of the two stage reaction was carried out in mineral oil, component B1 was made as a 50% concentrate in mineral oil, which concentrate contained 2.5 percent nitrogen and had an acid value of 56 mg KOH/g (lPl method). The components were mixed together and added to the fuel as a concentrate in xylene.
[0023] A series of tests was carried out lasting 2 weeks at 40°C and using Fuel No. 1, comprising methanol containing 100 p.p.m. formic acid and 10 p.p.m. methyl formate. The results of these tests which are set out in Table 1 demonstrate the excellent anticorrosion properties of a fuel containing an additive combination of the invention. Further tests were carried out lasting 6 weeks at ambient temperature and using three different fuels, as follows:-Fuel No. 2-15 wt percent methanol in gasoline containing 0.1 wt percent water.
1. A liquid fuel adapted for use in an internal combustion engine, said fuel comprising
from 5 to 100 weight percent of one or more alcohols, from 0 to 95 weight percent
gasoline and a corrosion inhibiting amount of a combination of (A) a polymer of one
or more C16 to C18 polyunsaturated aliphatic monocarboxylic acids and (B) a reaction product of (i)
about one mole part of one or more polyalkylene polyamines having the formula
wherein n is an integer from 1 to 8 and R is a divalent hydrocarbon group containing 2 to 4 carbon atoms, (ii) about 0.1 to 5 mole parts of one or more C10 to C24 monounsaturated aliphatic monocarboxylic acids or lower alkylesters thereof and (iii) 0 to about 4 mole parts of an alkenyl succinic anhydride wherein the alkenyl group contains 8 to 30 carbon atoms.
wherein n is an integer from 1 to 8 and R is a divalent hydrocarbon group containing 2 to 4 carbon atoms, (ii) about 0.1 to 5 mole parts of one or more C10 to C24 monounsaturated aliphatic monocarboxylic acids or lower alkylesters thereof and (iii) 0 to about 4 mole parts of an alkenyl succinic anhydride wherein the alkenyl group contains 8 to 30 carbon atoms.
2. A liquid fuel as claimed in Claim 1 wherein the monounsaturated aliphatic monocarboxylic
acids or lower alkylesters thereof used in preparing component B are present at 0.5
to 5 mole parts.
3. A liquid fuel as claimed in Claim 1 or Claim 2 wherein the monounsaturated aliphatic
monocarboxylic acids or lower alkylesters thereof used in preparing component B have
from 10 to 20-carbon atoms.
4. A liquid fuel as claimed in any one of Claims 1 to 3 wherein in component (B) of
the combination reactant (ii) is a mixture of the said polyalkylene polyamines such
that the average value of n is from 2 to 5.
5. A liquid fuel as claimed in any one of Claims 1 to 4 wherein component (A) is a
polymer of one or more C18 polyunsaturated aliphatic monocarboxylic acids.
6. A liquid fuel as claimed in any preceding claim wherein said polymer consists mainly
of dimers or trimers of the polyunsaturated aliphatic monocarboxylic acid or acids,
or mixtures thereof.
7. A liquid fuel as claimed in any preceding claim wherein the aliphatic monocarboxylic
acid used in producing component (B) is C18 aliphatic monocarboxylic acid.
8. A liquid fuel as claimed in Claim 7 wherein said polyunsaturated aliphatic monocarboxylic
acid is linoleic acid and said monounsaturated aliphatic acid is oleic acid or tall
oil fatty acid.
9. A liquid fuel as claimed in any preceding claim wherein component (B) of the said
combination is a reaction product of (i), (ii) and from 0.5 to 3.5 mole parts of the
alkenyl succinic acid.
. 10. A liquid fuel as claimed in Claim 9 wherein said alkenyl succinic anhydride
used in preparing component (B) is a C10-14 alkenyl substituted succinic anhydride.
11. A liquid fuel as claimed in Claim 10 wherein said alkenyl succinic anhydride used
in preparing component (B) is a C12 alkenyl substituted succinic anhydride.
12. A liquid fuel as claimed in any preceding claim wherein said polyalkylene polyamine
used in preparing component (B) is a polyethylene polyamine.
13. A liquid fuel as claimed in Claim 9 wherein component (B) is prepared by'reacting
in a first stage at a temperature high enough to displace water (i) about 1 mole part
of the polyalkylene polyamine and (ii) about 0.1 to 5 mole parts of the monounsaturated
aliphatic monocarboxylic acid or lower alkylester thereof to form an intermediate
and then in a second stage reacting said intermediate with (iii) about 0.5 to 3.5
mole parts of said alkenyl succinic anhydride.
14. A corrosion inhibitor concentrate comprising an inert solvent containing 1 to
50 wt percent of a combination of (A) a polymer of one or more C16 to C18 polyunsaturated aliphatic monocarboxylic acids and (B) a reaction product of (i)
about one mole part of one or more polyalkylene polyamines having the formula
wherein n is an integer from 1 to 8 and R is a divalent hydrocarbon group containing 2 to 4 carbon atoms, (ii) about 0.1 to 5 mole parts of one or more CIO to C24 monounsaturated aliphatic monocarboxylic acids or lower alkyl esters thereof and (iii) 0 to about 4 mole parts of an alkenyl succinic anhydride wherein the alkenyl groups contains 8 to 30 carbon atoms, the weight ratio of A:B being from 1:10 to 10:1.
wherein n is an integer from 1 to 8 and R is a divalent hydrocarbon group containing 2 to 4 carbon atoms, (ii) about 0.1 to 5 mole parts of one or more CIO to C24 monounsaturated aliphatic monocarboxylic acids or lower alkyl esters thereof and (iii) 0 to about 4 mole parts of an alkenyl succinic anhydride wherein the alkenyl groups contains 8 to 30 carbon atoms, the weight ratio of A:B being from 1:10 to 10:1.
15. A concentrate as claimed in Claim 14 wherein the monounsaturated aliphatic monocarboxylic
acids or lower alkylesters thereof used in preparing component B are present at 0.5
to 5 mole parts.
16. A concentrate as claimed in Claim 14 or Claim 15 wherein the monounsaturated aliphatic
monocarboxylic acids or lower alkylesters thereof used in preparing component B have
from 10 to 20 carbon atoms.
17. A concentrate as claimed in any one of Claims 14 to 16 wherein component (A) is
a polymer of one or more C18 polyunsaturated aliphatic monocarboxylic acids.
18. A concentrate as claimed in any one of Claims 14 to 17 wherein said polymer consists
mainly of dimers or trimers of polyunsaturated aliphatic monocarboxylic acid or acids
or mixtures thereof.
19. A concentrate as claimed in any one of Claims 14 to 18 wherein the aliphatic monocarboxylic
acid used in producing component (B) is C18 aliphatic monocarboxylic acid.
20. A concentrate as claimed in Claim 19 wherein said polyunsaturated aliphatic monocarboxylic
acid is linoleic acid and said monounsaturated aliphatic acid is oleic acid or tall
oil acids.
21. A concentrate as claimed in any one of Claims 14 to 20 wherein component (B) of
the combination is a reaction product of (i), (ii) and 0.5 to 3.5 mole parts of a
C10-14 alkenyl substituted succinic anhydride.
22. A concentrate as claimed in any one of Claims 14 to 21 wherein said polyalkylene
polyamine is a polyethylene polyamine.
1. Flüssiger Brennstoff, angepaßt an die Verwendung in einem Verbrennungsmotor, enthaltend
von 5 bis 100 Gew.-% einen oder mehrere Alkohole, von 0 bis 95 Gew.-% Benzin und eine,
die Korrosion inhibierende Menge einer Kombination aus (A), einem Polymer aus einer
oder mehreren C16 bis C18 poly-ungesättigten aliphatischen Monocarbonsäuren und (B) ein Reaktionsprodukt aus
(i) etwa einem Molteil aus einem oder mehreren Polyalkylenpolyaminen mit der Formel
wobei n eine ganze Zahl zwischen 1 und 8 und R eine divalente Kohlenwasserstoffgruppe, enthaltend 2 bis 4 Kohlenstoffatome, bedeutet, (ii) etwa 0,1 bis 5 Molteile aus einer oder mehreren Cm bis C24 einfach ungesättigten aliphatischen Monocarbonsäuren oder deren niedrigere Alkyl- . ester und (iii) 0 bis etwa 4 Molteile von einem Alkenylsuccinanhydrid, wobei die Alkenylgrüppe 8 bis 30 Kohlenstoffatome aufweist.
wobei n eine ganze Zahl zwischen 1 und 8 und R eine divalente Kohlenwasserstoffgruppe, enthaltend 2 bis 4 Kohlenstoffatome, bedeutet, (ii) etwa 0,1 bis 5 Molteile aus einer oder mehreren Cm bis C24 einfach ungesättigten aliphatischen Monocarbonsäuren oder deren niedrigere Alkyl- . ester und (iii) 0 bis etwa 4 Molteile von einem Alkenylsuccinanhydrid, wobei die Alkenylgrüppe 8 bis 30 Kohlenstoffatome aufweist.
2. Flüssiger Brennstoff nach Anspruch 1, worin die einfach ungesättigten aliphatischen
Monocarbonsäuren oder ihre niedrigeren Alkylester, die zur Herstellung der Komponente
B verwendet werden, in einer Menge von 0,5 bis 5 Molteilen vorliegen.
3. Flüssiger Brennstoff nach Anspruch 1 oder 2, worin die monoungesättigten aliphatischen
Monocarbonsäuren oder ihre niedrigeren Ester, die zur Herstellung der Komponente B
verwendet werden, 10 bis 20 Kohlenstoffatome aufweisen.
4. Flüssiger Brennstoff nach Anspruch 1 bis 3, worin in der Komponente (B) des Kombinationsreaktionsmittel
(ii) eine Mischung der Polyalkylenpolyamine darstellt, so daß der durchschnittliche
Wert von n 2 bis 5 beträgt.
5. Flüssiger Brennstoff nach Anspruch 1 bis 4, worin die Komponente (A) ein Polymer
aus einer oder mehreren C,8 poly-ungesättigten aliphatischen Monocarbonsäuren ist.
6. Flüssiger Brennstoff nach Anspruch 1 bis 5, worin das Polymer hauptsächlich aus
den Dimeren oder den Trimeren der poly-ungesättigten aliphatischen Monocarbonsäure
oder Säuren oder Mischungen davon besteht.
7. Flüssiger Brennstoff nach Anspruch 1 bis 6, worin die aliphatische Monocarbonsäure,
die zur Herstellung der Komponente (B) verwendet wird, eine C18 aliphatische Monocarbonsäure ist.
8. Flüssiger Brennstoff nach Anspruch 7, worin die poly-ungesättigte aliphatische
Monocarbonsäure Linolsäure und die mono-ungesättigte aliphatische Säure Oleinsäure
oder Tallölfettsäure ist.
9. Flüssiger Brennstoff nach Anspruch 1 bis 8, worin die Komponente (B) der Kombination
ein Reaktionsprodukt aus (i), (ii) und von 0,5 bis 3,5 Molteilen der Alkenylsuccinsäure
ist.
10. Flüssiger Brennstoff nach Anspruch 9, worin das Alkenylsuccinanhydrid, das zur
Herstellung der Komponente (B) verwendet wird, ein C10-14 Alkenyl substituiertes Succinanhydrid ist.
11. Flüssiger Brennstoff nach Anspruch 10, worin das Alkenylsuccinanhydrid, das zur
Herstellung der Komponente (B) verwendet wird, ein C12 Alkenyl-substituiertes Anhydrid ist.
12. Flüssiger Brennstoff nach Anspruch 1 bis 11, worin das zur Herstellung der Komponente
(B) verwendete Polyalkylenpolyamin Polyethylenpolyamin ist.
13. Flüssiger Brennstoff nach Anspruch 9, worin man die Komponente (B) durch Reaktion
in einem ersten Schritt bei einer Temperatur, die hoch genug ist, um das Wasser (i)
zu verdrängen, von etwa 1 Molteil des Polyalkylenpolyamins und (ii) etwa 0,1 bis 5
Molteile der mono-ungesättigten aliphatischen Monocarbonsäure oder den niedrigeren
Alkylestern über die Bildung eines Zwischenproduktes hergestellt und worin man anschließend
in einem zweiten Schritt das Zwischenprodukt mit (iii) etwa 0,5 bis 3,5 Molteile Alkenylsuccinanhydrid
umsetzt.
14. Korrosionsinhibitorkonzentrat, bestehend aus einem inerten Lösungsmittel, enthaltend
1 bis 50 Gew.-% einer Kombination aus (A), einem Polymer aus einer oder mehreren C16―C18 poly-ungesättigten aliphatischen Monocarbonsäuren und (B), einem Reaktionsprodukt
aus (i) etwa einem Molteil aus einem oder mehreren Polyalkylenpolyamin mit der Formel
wobei n eine ganze Zahl von 1 bis 8 und R eine divalente Kohlenwasserstoffgruppe mit 2 bis 4 Kohlenstoffatomen bedeutet, (ii) etwa 0,1 bis 5 Molteile von einer oder mehreren C10―C24 mono-ungesättigten aliphatischen Monocarbonsäuren oder den niedrigeren Alkylester davon und (iii) 0 bis etwa 4 Mol-Teile eines Alkenylsuccinanhydrids, wobei die Alkenylgruppe 8 bis 30 Kohlenstoffatome enthält-und worin das Gewichtsverhältnis von A:B von 1:10 bis 10:1 beträgt.
wobei n eine ganze Zahl von 1 bis 8 und R eine divalente Kohlenwasserstoffgruppe mit 2 bis 4 Kohlenstoffatomen bedeutet, (ii) etwa 0,1 bis 5 Molteile von einer oder mehreren C10―C24 mono-ungesättigten aliphatischen Monocarbonsäuren oder den niedrigeren Alkylester davon und (iii) 0 bis etwa 4 Mol-Teile eines Alkenylsuccinanhydrids, wobei die Alkenylgruppe 8 bis 30 Kohlenstoffatome enthält-und worin das Gewichtsverhältnis von A:B von 1:10 bis 10:1 beträgt.
15. Konzentrat nach Anspruch 14, worin die mono-ungesättigten aliphatischen Monocarbonsäuren
oder die niedrigeren Alkylester davon, die zur Herstellung der Komponente B verwendet
werden, in einer Konzentration von 0,5 bis 5 Molteilen vorliegen.
16. Konzentrat nach Anspruch 14 oder 15, worin die mono-ungesättigten aliphatischen
Monocarbonsäuren oder niedrigeren Alkylester davon, die zur Herstellung der Komponente
B verwendet werden, 10 bis 20 C-Atome aufweisen.
17. Konzentrat nach Anspruch 14 bis 16, worin die Komponente (A) ein Polymer aus einer
oder mehreren C,8 poly-ungesättigten aliphatischen Monocarbonsäuren ist.
18. Konzentrat nach Anspruch 14 bis 17, worin das Polymer hauptsächlich Dimere oder
Trimere der poly-ungesättigten aliphatischen Monocarbonsäure oder Säuren oder Mischungen
davon enthält.
19. Konzentrat nach Anspruch 14 bis 18, worin die aliphatische Monocarbonsäure, die
zur Herstellung der Komponente (B) verwendet wird, eine C18 aliphatische Monocarbonsäure ist.
20. Konzentrat nach Anspruch 19, worin die poly-ungesättigte aliphatische Monocarbonsäure
Linolsäure ist und die mono-ungsättigte aliphatische Säure Oleinsäure oder Tallölsäure
ist.
21. Konzentrat nach Anspruch 14 bis 20, worin die Komponente (B) der Kombination ein
Reaktionsprodukt aus (i), (ii) und 0,5 bis 3,5 Molteile eines C10-14 Alkenyl-substituierten Succinanhydrids darstellt.
22. Konzentrat nach Anspruch 14 bis 21, worin das Polyalkylenpolyamin Polyethylenpolyamin
ist.
1. Combustible liquide apte à être utilisé dans un moteur à combustion interne, ledit
combustible comprenant 5 à 100% en poids d'un ou plusieurs alcools, 0 à 95% en poids
d'essence et une quantité inhibitrice de corrosion d'un mélange formé (A) d'un polymère
d'un ou plusieurs acides monocarboxyliques aliphatiques polyinsaturés en C16 à C18 et (B) d'un produit de réaction (i) d'environ 1 partie molaire d'une ou plusieurs
polyalkylène-polyamines de formule
dans laquelle n est un nombre entier de 1 à 8 et R est un groupe hydrocarboné divalent contenant 2 à 4 atomes de carbone, (ii) d'environ 0,1 à 5 parties molaires d'un ou plusieurs acides monocarboxyliques aliphatiques mono-insaturés en C'o à C24 ou leurs esters alkyliques inférieurs et (iii) de 0 à environ 4 parties molaires d'un anhydride alcénylsuccinique dont le groupe alcényle contient 8 à 30 atomes de carbone.
dans laquelle n est un nombre entier de 1 à 8 et R est un groupe hydrocarboné divalent contenant 2 à 4 atomes de carbone, (ii) d'environ 0,1 à 5 parties molaires d'un ou plusieurs acides monocarboxyliques aliphatiques mono-insaturés en C'o à C24 ou leurs esters alkyliques inférieurs et (iii) de 0 à environ 4 parties molaires d'un anhydride alcénylsuccinique dont le groupe alcényle contient 8 à 30 atomes de carbone.
2. Combustible liquide suivant la revendication 1, dans lequel les acides monocarboxyliques
aliphatiques monoinsaturés ou leurs esters alkyliques inférieurs utilisés dans la
préparation' du composant B sont présents en proportion de 0,5 à 5 parties molaires.
3. Combustible liquide suivant la revendication 1 ou la revendication 2, dans lequel
les acides monocarboxyliques aliphatiques mono-insaturés ou leurs esters alkyliques
inférieurs utilisés dans Ja préparation du composant B ont 10 à 20 atomes de carbone.
4. Combustible liquide suivant l'une quelconque des revendications 1 à 3, dans lequel
le corps réactionnel (ii), dans le composant (B) du mélange, est un mélange desdites
polyalkylène- polyamines choisi de manière que la valeur moyenne de n soit de 2 à
5.
5. Combustible liquide suivant l'une quelconque des revendications 1 à 4, dans lequel
le composant (A) est un polymère d'un ou plusieurs acides monocarboxyliques aliphatiques
polyinsaturés en C18·
6. Combustible liquide suivant l'une quelconque des revendications précédentes, dans
lequel le polymère est principalement formé de dimères ou de trimères de l'acide ou
des acides monocarboxyliques aliphatiques polyinsaturés, ou leurs mélanges.
7. Combustible liquide suivant l'une quelconque des revendications précédentes, dans
lequel l'acide monocarboxylique aliphatique utilisé pour produire le composant (B)
est un acide monocarboxylique aliphatique en C,8.
8. Combustible liquide suivant la revendication 7, dans lequel l'acide monocarboxylique
aliphatique polyinsaturé est l'acide linoléique et l'acide aliphatique mono-insaturé
est l'acide oléique ou l'acide gras du tall oil.
9. Combustible liquide suivant l'une quelconque des revendications précédentes, dans
lequel le composant (B) du mélange est un produit de réaction de (i), (ii) et 0,5
à 3,5 parties molaires de l'acide alcénylsuccinique.
10. Combustible liquide suivant la revendication 9, dans lequel l'anhydride alcénylsuccinique
utilisé dans la préparation du composant (B) est un anhydride succinique à substituant
alcényle en C10 à C14·
11. Combustible liquide suivant la revendication 10, dans lequel l'anhydride alcénylsuccinique
utilisé dans la préparation du composant (B) est un anhydride succinique à substituant
alcényle en C12·
12. Combustible liquide suivant l'une quelconque des revendications précédentes, dans
lequel la polyalkylènepolyamine utilisée dans la préparation du composant (B) est
une poly- éthylènepolyamine.
13. Combustible liquide suivant la revendication 9, dans lequel le composant (B) est
préparé par réaction, dans une première étape à une température assez haute pour déplacer
l'eau, (i) d'environ 1 partie molaire de la polyalkylènepolyamine et (ii) d'environ
0,1 à 5 parties molaires de l'acide monocarboxylique aliphatique mono-insaturé ou
de son ester alkylique inférieur pour former un composé intermédiaire, puis dans une
seconde étape, réaction dudit composé intermédiaire avec (iii) environ 0,5 à 3,5 parties
molaires dudit anhydride alcénylsuccinique.
14. Concentré d'inhibiteur de corrosion, qui comprend un solvant inerte contenant
1 à 50% en poids d'un mélange formé (A) d'un polymère d'un ou plusieurs acides monocarboxyliques
aliphatiques polyinsaturés en C16 à C18 et (B) d'un produit de réaction (i) d'environ 1 partie molaire d'une ou plusieurs
polyalkylènepolyamines de formule
dans laquelle n est un nombre entier de 1 à 8 et R est un groupe hydrocarboné divalent contenant 2 à 4 atomes de carbone, (ii) d'environ 0,1 à 5 parties molaires d'un ou plusieurs acides monocarboxyliques aliphatiques mono-insaturés en C10 à C24 ou de leurs esters alkyliques inférieurs et (iii) de 0 à environ 4 parties molaires d'un anhydride alcénylsuccinique dont le groupe alcényle contient 8 à 30 atomes de carbone, le rapport en poids de A à B ayant une valeur de 1:10 à 10:1.
dans laquelle n est un nombre entier de 1 à 8 et R est un groupe hydrocarboné divalent contenant 2 à 4 atomes de carbone, (ii) d'environ 0,1 à 5 parties molaires d'un ou plusieurs acides monocarboxyliques aliphatiques mono-insaturés en C10 à C24 ou de leurs esters alkyliques inférieurs et (iii) de 0 à environ 4 parties molaires d'un anhydride alcénylsuccinique dont le groupe alcényle contient 8 à 30 atomes de carbone, le rapport en poids de A à B ayant une valeur de 1:10 à 10:1.
15. Concentré suivant la revendication 14, dans lequel les acides monocarboxyliques
aliphatiques mono-insaturés ou leurs esters - alkyliques inférieurs utilisés dans
la préparation du composant B sont présents en proportion de 0,5 à 5 parties molaires.
16. Concentré suivant la revendication 14 ou la revendication 15, dans lequel les
acides monocarboxyliques aliphatiques mono-insaturés ou leurs esters alkyliques inférieurs
utilisés dans la préparation du composant B ont 10 à 20 atomes de carbone.
17. Concentré suivant l'une quelconque des revendications 14 à 16, dans lequel le
composant (A) est un polymère d'un ou plusieurs acides monocarboxyliques aliphatiques
polyinsaturés en C18·
18. Concentré suivant l'une quelconque des revendications 14 à 17, dans lequel le
polymère est principalement formé de dimères ou de trimères d'un ou plusieurs acides
monocarboxyliques aliphatiques polyinsaturés ou de leurs mélanges.
19. Concentré suivant l'une quelconque des 1 revendications 14 à 18, dans lequel l'acide monocarboxylique aliphatique utilisé
dans la production du composant (B) est un acide monocarboxylique aliphatique en C18·
20. Concentré suivant la revendication 19, dans lequel l'acide monocarboxylique aliphatique
polyinsaturé est l'acide linoléique et l'acide aliphatique mono-insaturé est l'acide
oléique ou les acides du tall oil.
21. Concentré suivant l'une quelconque des revendications 14 à 20, dans lequel le
composant (B) du mélange est un produit de réaction de (i), (ii) et 0,5 à 3,5 parties
molaires d'un anhydride succinique à substituant alcényle en C10 à C,4.
22. Concentré suivant l'une quelconque des revendications 14 à 21, dans lequel la
polyalkylène-polyamine est une polyéthylène- polyamine.