Fuel composition

A novel fuel composition contains ethanol or gasohol plus, as a wear-inhibiting additive, a quaternary ammonium reaction product of dilauryl phosphate and a t-alkyl monoamide of iminodiacetic acid.

FIELD OF THE INVENTION 
This invention relates to a fuel composition for internal combustion 
engines particularly characterized by corrosion inhibition. 
BACKGROUND OF THE INVENTION 
As is well known to those skilled in the art, fuel compositions typified by 
gasohol and alcohols which are to be considered for commercial use must 
possess low corrosion activity; and this may be effected by addition 
thereto of various corrosion inhibition systems. It is an object of this 
invention to provide a fuel composition for internal combustion engines 
particularly characterized by corrosion inhibition. Other objects will be 
apparent to those skilled in the art. 
STATEMENT OF THE INVENTION 
In accordance with certain of its aspects, the fuel composition of this 
invention may comprise 
(a) a major portion of a fuel containing (i) at least one alcohol selected 
from the group consisting of ethanol and methanol and (ii) gasoline in 
amount of 0-50 volumes per volume of alcohol; and 
(b) a minor wear-inhibiting amount of, as a wear-inhibiting additive, a 
quaternary ammonium reaction product of (i) an amide of an amino 
carboxylic acid and (ii) as a phosphorus ester, a di-hydrocarbyl 
phosphate. 
DESCRIPTION OF THE INVENTION 
The fuel for internal combustion engines which may be-treated by the 
process of this invention may contain (i) at least one alcohol selected 
from the group consisting of ethanol and methanol and (ii) gasoline in 
amount of 0-50 volumes per volume of alcohol. The fuel may be an 
alcohol-type fuel containing little or no hydrocarbon. Typical of such 
fuels are methanol, ethanol, mixtures of methanol-ethanol, etc. 
Commercially available mixtures may be employed. Illustrative of one such 
commercially available mixture may be that having the following typical 
analysis. 
TABLE I 
______________________________________ 
Component Parts 
______________________________________ 
ethanol 3157.2 
methyl isobutyl ketone 
126.3 
acetic acid 0.256 
methyl alcohol 0.24 
isopropyl alcohol 0.2 
n-propyl alcohol 0.162 
ethyl acetate 0.2 
______________________________________ 
The fuels which may be treated by the process of this invention include 
gasohols which may be formed by mixing 90-95 volumes of gasoline with 5-10 
volumes of ethanol or methanol. A typical gasohol may contain 90 volumes 
of gasoline and 10 volumes of absolute alcohol. 
It is preferred that the fuels to be treated by the process of this 
invention be substantially anhydrous i.e. that they contain less than 
about 0.3 v % water; typically they may contain 0.0001 v %-0.005 v %, say 
about 0.04 v % water. 
It is a feature of these fuels that they may undesirably contain acidic 
contaminants which may cause serious corrosion problems. These 
contaminants are particularly in evidence when the alcohol is a 
commercially available alcohol which contains therein inter alia acids 
concurrently produced as by fermentation processes for producing ethanol 
or acids which have been picked up during handling. Acetic acid is a 
common acid present in the commercially available alcohols produced by 
fermentation; and it may be present in amount of 0.003 w %-0.005 w % of 
the total of the alcohol. 
In accordance with practice of the process of this invention, there may be 
added to the fuel a minor wear-inhibiting amount of, as a wear-inhibiting 
additive, a quaternary ammonium reaction product of (i) an amide of an 
amino mono-carboxylic acid or of an imino dicarboxylic acid or of a 
nitrilo tricarboxylic acid and (ii) as a phosphorus ester a di-hydrocarbyl 
phosphate. 
The amides of the amino carboxylic acids, i.e. of amino monocarboxylic 
acids or imino dicarboxylic acids or of nitrilo tricarboxylic acids, which 
may be used in practice of the process of this invention may be 
characterized by the formula: 
##STR1## 
wherein each of R", R.sup.iv, and R.sup.v is hydrogen, alkyl, cycloalkyl, 
alkenyl, alkaryl, aralkyl, or aryl; a is 0, 1 or 2; and at least one of 
R.sup.iv and R.sup.v is other than hydrogen. 
When a is 2, the formula may be 
##STR2## 
and the compounds may be considered as derivatives of glycine-amino acetic 
acid. 
When a is 1, the formula may be 
##STR3## 
and the compounds may be considered as derivatives of imino diacetic acid. 
When a is 0, the formula may be 
##STR4## 
and the compounds may be considered as derivatives of nitrilo triacetic 
acid. 
In the above compound, R" may be hydrogen or a hydrocarbon radical selected 
from the group consisting of alkyl, aralkyl, cycloalkyl, alkenyl, aryl, 
and alkaryl, including such radicals when inertly substituted. When R" is 
alkyl, it may typically be methyl, ethyl, n-propyl, isopropyl, n-butyl, 
i-butyl, sec-buty, amyl, octyl, decyl, octadecyl, etc. When R" is aralkyl, 
it may typically be benzyl, beta-phenylethyl, etc. When R" is cycloalkyl, 
it may typically be cyclohexyl, cycloheptyl, cyclooctyl, 
2-methylcycloheptyl, 3-butylcyclohexyl, 3-methylcyclohexyl, etc. When R" 
is alkenyl, it may typically be propenyl, butenyl, etc. When R" is aryl, 
it may typically be phenyl, naphthyl, etc. When R" is alkaryl, it may 
typically be tolyl, xylyl, etc. R" may be inertly substituted i.e. it may 
bear a non-reactive substituent such as alkyl, aryl, cycloalkyl, ether, 
halogen, etc. Typically inertly substituted R" groups may include 
3-chloropropyl, 2-ethoxyethyl, carboethoxymethyl, 4-methylcyclohexyl, 
p-chlorophenyl, p-chlorobenzyl, 3-chloro-3-methylphenyl, etc. The 
preferred R" groups may be hydrogen or lower alkyl, i.e. C.sub.1 -C.sub.10 
alkyl, groups including eg methyl, ethyl, n-propyl, i-propyl, butyls, 
amyls, hexyls, octyls, decyls, etc. R" may preferably be hydrogen. 
Although the carbon atom adjacent to the carbonyl groups may commonly and 
preferably bear two hydrogen atoms, it may bear inert substituents. 
Similarly the other carbon atoms in compound I may preferably bear two 
hydrogen atoms or other inert substituents. 
R.sup.iv and R.sup.v may be hydrogen or a hydrocarbon group selected from 
the same group of hydrocarbon groups as that from which R" is selected. 
At least one of R.sup.iv and R.sup.v is other than hydrogen. 
Preferred R.sup.iv and R.sup.v groups may be hydrogen or hydrocarbons 
containing at least 12 carbon atoms, preferably 12-24 carbon atoms. 
Illustrative compositions I may include 
##STR5## 
prepared from imino diacetic acid and primary JMT brand of t-alkyl primary 
amine. 
##STR6## 
prepared from imino diacetic acid and Armeen T brand of tallow (C.sub.12 
-C.sub.18) primary amine. 
##STR7## 
prepared from imino diacetic acid and Armeen O brand of oleyl (C.sub.18) 
primary amine. 
##STR8## 
prepared from imino diacetic acid and Armeen C brand of COCO (C.sub.14 
-C.sub.18 unsaturated) primary amine. 
##STR9## 
prepared from imino diacetic acid and Armeen L-15 brand of secondary 
(C.sub.15 -C.sub.20) alkyl primary amine. 
F H.sub.2 N--CH.sub.2 --CONH(C.sub.12 -C.sub.18) 
prepared from glycine and Armeen O brand of oleyl (C.sub.12 -C.sub.18) 
primary amine. 
G HN(CH.sub.2 CONHC.sub.18 H.sub.37).sub.2 
as prepared from imino diacetic acid and Armeen O brand of oleyl (C.sub.18) 
primary amine. 
H N-(CH.sub.2 CONHC.sub.18 H.sub.37).sub.3 
prepared from nitrilo triacetic acid and Armeen D brand of oleyl (C.sub.18) 
primary amine. 
In the preferred embodiment, the composition I may be composition A of the 
Table above. 
Preparation of the charge amides which may be used in practice of the 
process of this invention may be effected by reacting charge amino acid 
with charge amine. The amino carboxylic acid may be an amino acid, an 
imino dicarboxylic acid or a nitrilo tricarboxylic acid. 
EQU R".sub.a N(CH.sub.2 COOH).sub.3-a 
is reacted with charge amine 
##STR10## 
R".sub.a N(CH.sub.2 COOH).sub.3-a 
##STR11## 
Preparation of the charge amides which may be used in practice of the 
process of this invention in one embodiment may be carried out by reacting 
charge amino acid 
EQU (R").sub.2 N--CH.sub.2 --COOH 
with charge amine 
##STR12## 
(R").sub.2 --N--CH.sub.2 --COOH 
##STR13## 
In a preferred embodiment, the reaction (carried out in the presence of 
refluxing xylene) may be: 
##STR14## 
+(CH.sub.3).sub.3 C(CH.sub.2).sub.8 NH.sub.2 .fwdarw. 
##STR15## 
It will be apparent that the amount of amine employed may depend on the 
number of amide groups to be introduced e.g. whether the charge acid 
contains one, two or three carboxyl groups and whether it be desired to 
prepare imino amides, diamides, etc. 
Reaction may be carried out by adding one equivalent of acid and 1-1.2 
equivalents (preferably 1 equivalent) of amine to a reaction operation 
together with an excess of an inert solvent. Commonly the solvent may be 
present in amount corresponding to 0.3-5 ml per gram of reactants, say 
about 0.45 ml per gram of reactants. Typical inert solvents may include 
hydrocarbons boiling at 65.degree. C.-200.degree. C. Toluene and xylene 
may be preferred. 
The reaction mixture is heated at 65.degree. C.-200.degree. C., typically 
140.degree. C. typically at atmospheric pressure for 8-24 hours, typically 
16 hours. It is preferred to operate at reflux temperature. During 
reaction, by-product water is removed. At the completion of the reaction, 
the mixture is preferably filtered hot and the solvent removed as by 
distillation. Reaction product may be analyzed by infra-red spectroscopy 
and by elemental analysis. 
These novel amides may be used as carburetor detergents, corrosion 
inhibitors for gasoline, etc. 
The novel quaternary products of this invention may be prepared by reacting 
the amides with a phosphorus ester, i.e. a phosphate-ester having the 
formula: 
##STR16## 
In the above formula, R' may be a hydrocarbon radical selected from the 
group consisting of alkyl, aralkyl, cycloalkyl, aryl, and alkaryl, 
including such radicals when inertly substituted. When R' is alkyl, it may 
typically be methyl, ethyl, n-propyl, iso-propyl, n-butyl, i-butyl, 
secbuty, amyl, octyl, decyl, octadecyl, etc. When R is aralkyl, it may 
typically be benzyl, beta-phenylethyl, etc. When R' is cycloalkyl, it may 
typically be cyclohexyl, cycloheptyl, cyclooctyl, 2-methylcycloheptyl, 
3-butylcyclohexyl, 3-methylcyclohexyl, etc. When R' is aryl, it may 
typically be phenyl, naphthyl, etc. When R' is alkaryl, it may typically 
be tolyl, xylyl, etc. R' may be inertly substituted i.e. it may bear a 
non-reactive substituent such as alkyl, aryl, cycloalkyl, ether, etc. 
Typically inertly substituted R' groups may include 2-ethoxyethyl, 
carboethoxymethyl, 4-methyl cyclohexyl, etc. The preferred R' groups may 
be alkyl groups having 1-30 carbon atoms. Preferably the R' group may 
contain 8-20, typically 12-14, say 12 carbon atoms. 
Illustrative phosphates which may be employed may include: 
TABLE 
di-lauryl phosphate 
di-decyl phosphate 
di-pentadecyl phosphate 
di-hexadecyl phosphate 
di-heptadecyl phosphate 
di-octadecyl phosphate 
di-nonadecyl phosphate 
A preferred phosphate may be di-lauryl phosphate. A commercially available 
phosphate may be the mixed di (C.sub.12 -C.sub.14) alkyl phosphate. 
Preparation of the novel quaternary products of this invention may be 
carried out by reacting preferably equimolar quantities of the amide and 
the phosphorus ester: 
##STR17## 
In one typical embodiment wherein dilauryl phosphate is reacted with the 
tertiary C.sub.12 alkyl amide of iminodiacetic acid, the reaction may be 
as follows: 
##STR18## 
Reaction is typically carried out by mixing substantially equimolar 
portions of the phosphorus ester (usually a liquid) and the half-amide 
(also usually a liquid) at 20.degree. C.-100.degree. C., typically 
20.degree. C.-50.degree. C., say 25.degree. C. ambient temperature and 
10-500 psig, preferably 14.7-100 psig, say 14.7 psig atmospheric pressure 
for 0.1-4 hours, say 0.5 hours. If desired, reaction may be carried out in 
the presence of an excess of absolute alcohol, preferably ethanol, or 
hydrocarbon typically toluene or xylene or isooctane. Reaction product may 
be employed without further purification. 
Typical reaction products include: 
TABLE 
__________________________________________________________________________ 
A. 
##STR19## 
##STR20## 
B. 
##STR21## 
##STR22## 
C. 
##STR23## 
##STR24## 
D. 
##STR25## 
##STR26## 
E. 
##STR27## 
##STR28## 
__________________________________________________________________________ 
The so-prepared anti-wear additives may be added to fuels (including 
alcohol, gasoline, gasohol etc.) or to antifreeze. These compositions may 
be particularly found to be effective when added to absolute alcohol fuels 
typified by those available commercially containing compounds including 
ethers, esters, acids, etc. 
The so-prepared anti-wear additives may be added to a fuel in amount of 
1-2500 PTB, preferably 5-2000 PTB, more preferably 100-1000 PTB, say 350 
PTB. (PTB stands for pounds of additive per thousand barrels of fuel). 
Alternatively expressed, the additive may be added to a fuel in minor 
wear-inhibiting amount of about 0.003-10 w % preferably 0.01-6 w %, more 
preferably 0.2-3 w %, say 1 w %. Larger amounts may be employed but may 
not be necessary. 
It is a feature of this invention that the fuel composition so prepared is 
characterized by its increased ability to significantly reduce scar 
diameters (wear) in the Four-Ball Wear Test. 
The Four Ball Wear Test is carried out by securely clamping three highly 
polished steel balls (each 0.5 inch in diameter) in a test cup in an 
equilateral triangle in a horizontal plane. The fourth highly polished 
steel ball, resting on the three lower balls to form a tetrahedron, is 
held in a chuck. A weight lever arm system applies weight to the test cup, 
and this load holds the balls together. In the standard test, the speed of 
rotation is 1800 rpm; the load is 5 kilograms. The assembly is submerged 
in the liquid to be tested. The standard test is carried out at ambient 
temperature for 30 minutes. As the chuck and upper ball rotate against the 
fixed lower balls, the friction of the upper ball rotating in relation to 
the lower balls produces a wear-scar the diameter of which (i.e. the depth 
along a diameter of the ball) is measured. The average of the wear on the 
three lower balls is the rating assigned (in millimeters). 
It is observed that the use of the technique of this invenion permits 
reduction in the average scar diameter by as much as 25%-35%. A reduction 
of 10% is a significant reduction. 
DESCRIPTION OF PREFERRED EMBODIMENTS 
Practice of this invention will be apparent to those skilled in the art 
from the following examples wherein, as elsewhere in this specification, 
all parts are parts by weight unless otherwise specified.

EXAMPLE I 
In this example which illustrates the best mode known to me of practicing 
the process of this invention, there is added to 200 ml of xylene, 120 g 
of iminodiacetic acid and 322 g of the Primene JMT brand of tertiary alkyl 
primary amine 
EQU (CH.sub.3).sub.3 --CH.sub.2 --(CH.sub.2).sub.x --NH.sub.2 
wherein x is 8-10. The reaction mixture was refluxed until 19.5 ml of water 
was recovered. The mixture was filtered hot and the xylene was then 
removed by distillation. Analysis by infrared and by elemental analysis 
revealed substantially stoichiometric yield of 
##STR29## 
EXAMPLE II 
In this example, the monoamide product of Example I is quaternized. There 
is added to a reaction operation 45 g of the product of Example I and 22 g 
of the Ortholeum 162 brand of dilauryl acid phosphate. The mixture was 
thoroughly agitated at ambient temperature of 25.degree. C. for 30 
minutes. The quaternary product, which may be used as is, contains 
##STR30## 
EXAMPLE III 
In this example, a formulation is made up containing 1 w % of the product 
of Example II in absolute ethanol; and this formulation is tested in the 
four ball test for 30 minutes at ambient temperature using a load of 5 Kg 
and a speed of 1800 rpm. The average of five runs is determined. The 
average Scar Diameter is 0.332 millimeter. 
EXAMPLE IV* 
In this control example, the procedure of Example III was carried out 
except that the four ball test was run on pure absolute ethanol. The 
Average Scar Diameter of runs) was 0.4775 millimeter. 
It is apparent that use of the process of this invention desirably 
increased the wear-inhibiting property of the ethanol by 43% (i.e. 
0.4775/0.332). 
Results comparable to those of Example I may be obtained if the amine is: 
TABLE 
______________________________________ 
Example Amine 
______________________________________ 
V Armeen T brand of tallow (C.sub.12 -C.sub.18) amine 
VI Armeen O brand of oleyl (C.sub.18) amine 
VII Armeen C brand of COCO (unsaturated 
C.sub.14 -C.sub.18) amine 
VIII Armeen L-15 brand of C.sub.15 -C.sub.20 secondary 
primary amine 
______________________________________ 
Results comparable to those of Example I may be obtained if the acid is: 
TABLE 
______________________________________ 
Example Acid 
______________________________________ 
IX H.sub.2 NCH.sub.2 COOH 
X N(CH.sub.2 COOH).sub.3 
XI CH.sub.3 NHCH.sub.2 COOH 
XII C.sub.2 H.sub.5 NHCH.sub.2 COOH 
______________________________________ 
Results comparable to those of Example III may be obtained if the 
phosphorus ester is: 
TABLE 
______________________________________ 
Example Phosphorus Ester 
______________________________________ 
XIII di-decyl phosphate 
XIV di-pentadecyl phosphate 
XV di-hexadecyl phosphate 
XVI di-octadecyl phosphate 
XVII di-nonadecyl phosphate 
______________________________________ 
Results comparable to those of Example III may be obtained if the fuel is 
as follows: 
TABLE 
______________________________________ 
Example Fuel 
______________________________________ 
XVIII Gasohol containing 90 v % 
gasoline and 10 v % absolute 
ethanol 
XIX absolute methanol 
XX diesel oil 
______________________________________ 
Although this invention has been illustrated by reference to specific 
embodiments, it will be apparent to those skilled in the art that various 
changes and modifications may be made which clearly fall within the scope 
of this invention.