Fuel composition

An amido alkanolamine composition obtained by reacting, at a temperature of 10.degree. C.-200.degree. C.: (a) a 4-alkyl-2-morpholinone represented by the formula: ##STR1## in which R represents a monovalent aliphatic radical having from 1 to 10 carbon atoms; and (b) a hydrocarbyl oxypolyoxyalkylene amine represented by the formula ##STR2## in which R' represents an alkyl, an alicyclic or an alkyl-alicyclic radical having from 12 to 30 carbon atoms or ##STR3## wherein R" represents a hydrocarbyl radical having from 4 to 30 carbon atoms, x has a value of from about 5 to 50, and R'" is an ethyl radical or a mixture of methyl and ethyl radicals.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a novel additive composition for use in motor 
fuels. The additive comprises the reaction product obtained by reacting a 
4-alkyl-2-morpholinone with a hydrocarbyl oxypolyoxyalkylene amine to 
produce a motor fuel--soluble amidoalkanolamine compound which provides a 
number of valuable properties in a motor fuel composition. 
The combustion of a hydrocarbon motor fuel in an internal combustion engine 
leads to the formation and accumulation of deposits on various parts of 
the combustion chamber as well as on the fuel intake and exhaust system of 
the engine. The presence of deposits in the combustion chamber seriously 
reduces the operating efficiency of the engine. First, deposit 
accumulation within the combustion chamber inhibits heat transfer between 
the chamber and the engine cooling system. This leads to higher 
temperatures within the combustion chamber, resulting in increases in the 
end gas temperature of the incoming charge. Consequently, end gas 
auto-ignition occurs causing engine knock. In addition, the accumulation 
of deposits within the combustion chamber reduces the volume of the 
combustion zone, causing a higher than design compression ratio in the 
engine. This, in turn, can also lead to engine knocking. A knocking engine 
does not effectively utilize the energy of combustion. Moreover, a 
prolonged period of engine knocking can cause stress fatigue and wear in 
pistons, connecting rods, bearings and cam rods of the engine. The 
phenomenon noted is characteristic of gasoline powered internal combustion 
engines. It may be overcome by employing a higher octane gasoline which 
resists knocking for powering the engine. This need for a higher octane 
gasoline as mileage accumulates has become known as the engine octane 
requirement increase (ORI) phenomenon. It is particularly advantageous if 
engine ORI can be substantially reduced or eliminated by preventing or 
modifying deposit formation in the combustion chambers of the engine. 
Another problem common to internal combustion engines is the formation of 
intake valve deposits. Intake valve deposits interfere with valve closing 
and eventually will lead to valve burning. Such deposits interfere with 
valve motion and valve seating and tend to reduce the volumetric 
efficiency of the engine and to limit the maximum design power. Valve 
deposits may be produced from thermally and oxidatively unstable fuel or 
from lubricating oil oxidation products. The hard carbonaceous deposits 
produced collect in the tubes and runners that are part of the exhaust gas 
recirculation (EGR) flow. These deposits are believed to be formed from 
exhaust particles which are subjected to rapid cooling while mixing with 
the air-fuel mixture. Reduced EGR flow can result in engine knock and in 
nitric oxide, NO.sub.x, emission increases. It would therefore be 
desirable to provide a motor fuel composition which minimizes or overcomes 
the formation of intake valve deposits. 
2. Description of the Prior Art 
Various motor fuel compositions and additives for minimizing or overcoming 
the formation of combustion chamber and intake valve deposits are 
described in the prior art. 
For example, co-pending co-assigned application Ser. No. 07/896,700 filed 
Jun. 10, 1992 discloses a motor fuel additive composition of the formula: 
##STR4## 
in which R represents a monovalent aliphatic radical having from 1 to 10 
carbon atoms; R' represents a hydrocarbyl radical having from 4 to 30 
carbon atoms; x has a value of from about 5 to 50; and R" represents a 
methyl radical or a mixture of hydrogen and methyl radicals. 
Co-assigned U.S. Pat. No. 5,203,879, issued on Apr. 20, 1993, discloses a 
motor fuel additive composition of the formula: 
##STR5## 
in which R represents a monovalent aliphatic radical having from 1 to 10 
carbon atoms, R' represents an alkyl, an alicyclic or an alkyl-alicyclic 
radical having from 12 to 30 carbon atoms; x has a value of from about 5 
to 50; and R" represents a methyl radical or a mixture of hydrogen and 
methyl radicals. 
U.S. Pat. No. 4,747,851 discloses a novel polyoxyalkylene diamine compound 
of the formula: 
##STR6## 
where c has a value from about 5-150, b+d has a value from about 5-150, 
and a+e has a value from about 2-12. Motor fuel compositions comprising 
the novel polyoxyalkylene diamine, alone or in combination with a 
polymer/copolymer additive are also disclosed. 
U.S. Pat. No. 4,659,337 discloses the use of the reaction product of maleic 
anhydride, a polyether polyamide containing oxyethylene and oxypropylene 
ether moieties, and a hydrocarbyl polyamine in a gasoline motor fuel to 
reduce engine ORI and provide carburetor detergency. 
The use of a mixture of (i) the reaction product of maleic anhydride, a 
polyether polyamine containing oxyethylene and oxypropylene ether moieties 
and a hydrocarbyl polyamine, and (ii) a polyolefin polymer/copolymer as an 
additive in motor fuel compositions to reduce engine ORI is described in 
U.S. Pat. No. 4,659,336. 
U.S. Pat. No. 4,643,738 discloses a motor fuel composition comprising a 
deposit-control additive which is the reaction product of a dibasic acid 
anhydride, a polyoxyisopropylene diamine of the formula: 
##STR7## 
where x has a value of 2-50, and an N-alkyl-alkylene diamine. 
U.S. Pat. No. 4,631,069 discloses an alcohol-containing motor fuel 
composition which additionally comprises an anti-wear additive which is 
the reaction product of a dibasic acid anhydride, a polyoxyisopropylene 
diamine of the formula: 
##STR8## 
where x has a value of 2-68, and an N-alkyl-alkylene diamine. 
U.S. Pat. No. 4,604,103 discloses a motor fuel deposit control additive for 
use in internal combustion engines which maintains cleanliness of the 
engine intake system without contributing to combustion chamber deposits 
or engine ORI. The additive disclosed is a hydrocarbyl polyoxyalkylene 
polyethylene amine of molecular weight range 300-2,500 having the formula: 
##STR9## 
where R is a hydrocarbyl radical of from 1 to about 30 carbon atoms; R' is 
selected from methyl and ethyl; x is an integer from 5 to 30, and R" and 
R'" are independently selected from hydrogen and --(CH.sub.2 CH.sub.2 
NH).sub.y --H, where y is an integer from 0 to 5. 
U.S. Pat. No. 4,581,040 discloses the use of a reaction product as a 
deposit-inhibitor additive in fuel compositions. The reaction product is 
the condensation product of the process comprising (i) reacting a dibasic 
acid anhydride with a polyoxypropylene diamine of the formula: 
##STR10## 
where x is a numeral of about 2-50, thereby forming a bis-maleamic acid; 
(ii) reacting said maleamic acid with a polyalkylene polyamine, thereby 
forming a condensate product; and (iii) recovering said condensate 
product. 
U.S. Pat. No. 4,357,148 discloses a motor fuel additive useful in 
controlling ORI which is the combination of (a) an oil-soluble aliphatic 
polyamine containing at least one olefinic polymer chain, and (b) a 
polymer, copolymer, or corresponding hydrogenated polymer or copolymer of 
a C.sub.2 -C.sub.6 mono-olefin with a molecular weight of 500-1,500. 
U.S. Pat. No. 4,234,321 discloses a hydrocarbyl-poly(oxyalkylene) ureylene 
carbamate as a deposit control additive for fuels. 
EP 297996 discloses an alkylphenylpoly(oxypropylene) aminocarbamate having 
a molecular weight ranging from 600 to 6000 for use in gasoline or diesel 
fuel compositions. 
OBJECTS AND SUMMARY OF THE INVENTION 
An object of this invention is to provide a novel additive reaction product 
which may be employed in fuel compositions and particularly in a motor 
fuel composition. 
Another object is to provide a fuel additive reaction product and a motor 
fuel composition which inhibit the formation of intake valve deposits in 
an internal combustion engine. 
Another object of this invention is to provide a fuel additive and a fuel 
composition which inhibit or reduce the formation of combustion chamber 
deposits in an internal combustion engine. 
Yet another object of this invention is to provide a concentrate 
composition which may be added to a motor fuel to provide motor fuel 
compositions of the instant invention. 
SUMMARY OF THE INVENTION 
The intake valve and combustion chamber deposit-inhibiting additive of the 
invention is the reaction product prepared by reacting a 
4-alkyl-2-morpholinone with hydrocarbyl oxypolyoxyalkylene amine. 
The 4-alkyl-2-morpholinone reactant used to prepare the reaction product 
additive of the instant invention may be represented by the formula: 
##STR11## 
in which R represents a monovalent aliphatic radical having from 1 to 10 
carbon atoms. 
The hydrocarbyl oxypolyoxyalkylene amine reactant is represented by the 
formula: 
##STR12## 
in which R' represents an alkyl, an alicyclic, or an alkyl-alicyclic 
radical having from 12 to 30 carbon atoms, or 
##STR13## 
wherein R" represents a hydrocarbyl radical having from 4 to 30 carbon 
atoms, x has a value from about 5 to 50, R'" represents an ethyl radical 
or a mixture of methyl and ethyl radicals. 
The final reaction product may be represented by the formula: 
##STR14## 
in which R, R', R", R'", and x have the values noted above. 
The motor fuel composition of the invention comprises a mixture of 
hydrocarbons in the gasoline boiling range and a minor amount of the 
prescribed intake valve and combustion chamber deposit-inhibiting emulsion 
resistant additive of the invention.

DETAILED DESCRIPTION OF THE INVENTION 
The intake valve and combustion chamber deposit-inhibiting additive of the 
invention is the reaction product of a 4-alkyl-2-morpholinone and the 
aminated propylene oxide and 1,2-butylene oxide adduct of a hydrocarbyl 
alcohol. 
The 4-alkyl-2-morpholinone used to prepare the reaction product additive of 
the instant invention may be represented by the formula: 
##STR15## 
in which R represents a monovalent aliphatic radical having from 1 to 10 
carbon atoms. 
The hydrocarbyl oxypolyoxyalkylene amine reactant is represented by the 
formula: 
##STR16## 
in which R' represents an alkyl, an alicyclic or an alkyl alicyclic 
radical having from 12 to 30 carbon atoms or 
##STR17## 
wherein R" represents a hydrocarbyl radical having from 4 to 30 carbon 
atoms, x has a value of from about 5 to 50, R'" is an ethyl radical or a 
mixture of methyl and ethyl radicals. 
R' may be a straight chain, an isomeric branched chain, or a cyclo 
aliphatic hydrocarbyl radical including mixtures of these. Typical 
monovalent alkyl radicals include normal C.sub.16 -C.sub.18 alkyl, 
C.sub.12 -C.sub.20 alkyl, n-nonylcyclohexyl, n-oligomeric species with a 
chain length of C.sub.20 -C.sub.30. Preferably, R' represents a saturated 
monovalent aliphatic radical having from about 12 to 24 carbon atoms, and 
more preferably an aliphatic radical having from about 14 to 20 carbon 
atoms. 
R" may be a monovalent aliphatic radical having from about 6 to 24 carbon 
atoms, and more preferably an aliphatic radical having from about 8 to 20 
carbon atoms. A particularly preferred value for R" is from 9 to 18 carbon 
atoms. 
A preferred value for x is from about 6 to 30, with the most preferred 
value being from about 10 to 20. 
As indicated above, the internal radical represented by the formula: 
##STR18## 
may be a mixture of propylene oxide and butylene oxide radicals. The ratio 
of propylene oxide radicals to butylene oxide radicals employed may range 
from about 0.01:9.99 to 9.99:0.01. A more preferred mole ratio range of 
propylene oxide to butylene oxide is from about 9:1 to 3:2. 
The 4-alkyl-2-morpholinone reactant and the hydrocarbyl oxypolyoxyalkylene 
amine reactant are reacted in about a 1:1 mole ratio. While other mole 
ratios are contemplated, no significant advantage is realized in departing 
from about equimolar reaction ratios. 
The additive reaction product of the invention may be represented by the 
formula: 
##STR19## 
in which R, R', R", R'", and x have the values noted above. 
Having described the invention in general terms, the following examples are 
offered as specific illustrations thereof. It is to be understood that 
these examples are illustrative only and that the invention is not limited 
thereby. 
EXAMPLE I 
A. Preparation of 10.5 Mole Propylene Oxide/3 Mole 1,2-Butylene Oxide 
Adduct of Nonylphenol 
Into a 10 gallon kettle were charged 12 pounds of nonylphenol and 302 grams 
of 45 percent aqueous potassium hydroxide. The reactor was then purged 
with prepurified nitrogen. Maintaining a nitrogen purge, the reactor was 
heated to 110.degree. C. and the nonylphenol initiator dried to a water 
content of less than 0.1 percent using both vacuum and nitrogen stripping. 
A mixture of 33.2 lbs propylene oxide and 11.8 lb 1,2-butylene oxide was 
then reacted at 110.degree.-115.degree. C. at 60 psig over a six hour 
period. The reaction mixture was then digested at 115.degree.-120.degree. 
C. to an equilibrium pressure and purged with nitrogen for 30 minutes. The 
alkaline product was then neutralized at 95.degree. C. by stirring for two 
hours with 951 grams Magnesol 30/40 adsorbent which was added in an 
aqueous slurry. Di-t-butyl p-cresol (7.7 grams) was then added to 
stabilize the product against oxidation. The neutralized product was then 
vacuum stripped to a minimum pressure at 110.degree.-115.degree. C., 
nitrogen stripped, and filtered. Properties of the finished product are 
given in Table I below. 
TABLE I 
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Properties 
______________________________________ 
Acid no., mg KOH/g 0.009 
Hydroxyl no. mg KOH/G 
54.6 
Unsaturation, meq/g 0.036 
Water, Wt. % 0.04 
pH in 10:6 isopropanol-water 
8.1 
Color, Pt-Co 4.0 
Sodium, ppm 0.3 
Potassium, ppm 2.0 
Viscosity, 77.degree. F., CS 
323 
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B. Preparation of Hydrocarbyl oxypolyoxyalkylene Amine 
To a tubular reactor filled with 1250 milliliters of a nickel catalyst was 
fed 1.35 lb/hr of the polyol (preparation A above), 1.35 lb/hr of ammonia, 
and 651/hr of hydrogen. The reactor was at 2000 psig and 215.degree. C. 
The crude reactor effluent was charged to a clean dry kettle. It was then 
nitrogen stripped to 75.degree. C. then placed under vacuum and heated to 
100.degree. C. The product had the following analysis: 
______________________________________ 
meq/gram 
______________________________________ 
Total acetylatables 
1.00 
Total amine 0.964 
Primary amine 0.961 
______________________________________ 
C. Preparation of the Reaction Product of 4-Methyl-2-morpholinone and 
Nonylphenoxypolyoxyalkylene Amine 
To a 5-liter, three-necked flask equipped with a thermometer stirrer and 
nitrogen outlet, was charged 3089.6 g of hydrocarbyl oxypolyoxyalkylene 
amine (preparation B above) and 342.4 g of 4-methyl-2-morpholinone. The 
mixture was heated to 120.degree. C. for three hours. The resulting 
product had the following analysis: 
______________________________________ 
Total Acetylatable 0.87 meq/g 
Total Amine 0.855 meq/g 
______________________________________ 
and may be represented by the formula: 
##STR20## 
While shown as block copolymers, the propylene/butylene oxides can also be 
randomly distributed. 
EXAMPLE II 
A reaction product was prepared similar to Example I except that the polyol 
was prepared by reacting 10.5 moles of propylene oxide and 3.0 moles of 
1,2-butylene oxide with a normal C.sub.16 -C.sub.18 alkanol, which 
reaction product had the following formula: 
##STR21## 
The additive of the invention was tested in motor fuels in comparison to 
commercial fuel compositions to demonstrate its effectiveness for reducing 
intake valve deposits and combustion chamber defaults. 
Honda Generator Test 
A test was developed to determine the intake valve detergency of an 
additive as well as to determine whether the additive will cause the 
intake valves to stick. 
In small four-cylinder gasoline powered engines, the intake valves 
accumulate large amounts of deposits which interfere with the operation of 
the engine. A good detergent/dispersant is required to prevent the buildup 
of these deposits. The Honda Generator test was developed to measure the 
activity of additives in preventing the buildup of intake valve deposits 
(IVD) (keep clean). The measurements are done in two ways: (1) the intake 
valves at the end of the run are rated using the CRC method of rating (a 
valve with a rating of 10 is perfectly clean, and a valve rating of 6 or 
less denotes heavy deposit levels); and (2) intake valve deposit weights 
are obtained and also reported in grams. 
Test Equipment 
The Intake System Deposit/Intake Valve Stickiness Test consists of an 
electrical generator driven by a current technology gasoline engine, 
similar in many characteristics to modern vehicle engines. The generator 
set design allows the engine to be easily loaded by using the electrical 
generator as a dynamometer for the engine. The set operates at a governed 
speed of 3600 rpm and incorporates a twin cylinder, overhead camshaft, 
water-cooled engine described below in Table II. 
TABLE II 
______________________________________ 
Engine Data for ES6500 Honda Generator 
______________________________________ 
Type: 4-stroke Overhead cam, 2 cylinder 
Cooling System: 
Liquid cooled 
Displacement: 359 cc 
Bore .times. Stroke: 
58 .times. 68 mm 
Construction: Aluminum head and block, fixed 
cast iron cylinder liners 
Compression: 8.5:1 
Maximum Power: 9.1 Kw/3600 rpm 
Maximum Torque: 
240 kg-cm 
Fuel System: Carburetor 
Recommended Fuel: 
Unleaded gasoline with min 86 
(R + M)/2 octane 
______________________________________ 
The results of these tests are set forth in Table III below. 
TABLE III 
______________________________________ 
Honda Test Results 
PETROX 
Commercial 
Example I Additive 
______________________________________ 
CRC Valve Rating 
9.99 6.03 
IVD Weight, grm. 
0.0006 0.269 
Stickiness None None 
______________________________________ 
The motor fuel containing the additive of the invention at 100 PTB gave 
excellent CRC valve ratings, virtually no deposits on the intake valves (4 
mg or less), and exhibited no stickiness. The commercial additive package 
at 60 PTB showed a relatively poor CRC rating and had 269 mg IVD deposits. 
The commercial additive was free of valve stickiness. In this test, the 
additive of Example I in a motor fuel demonstrated excellent detergency 
and intake valve deposit keep clean properties. 
Thermal Gravimetric Analysis (TGA) 
TGA establishes the uniqueness of the hydrocarboxypolyoxyalkene 
morpholinones of the invention. Examination of TGA data in Table IV below 
indicates that Run 2 utilizing the additive of Example I is considerably 
more thermally labile than the products tested in Runs 1, and 3 to 5, 
inclusive. For example, at 200.degree. C., 55.39% of Example I is 
decomposed, compared to 41.4-61.1% for Runs 1, 3 and 4, and only 34.5% for 
Run 5. Only 3.3% residue remains for Run 2 (Example I) at 295.degree. C., 
indicating that it does not leave appreciable residue. Therefore, this 
polyether amine-morpholinone detergent should leave very clean intake 
valves and combustion chambers since it does not leave much deposits. 
TABLE IV 
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% Volatility Loss 
Run 200.degree. C. 
295.degree. C. 
______________________________________ 
1 Competitive Additive 
41.4 95.5 
2 Example I 55.3 96.7 
3 Commercial Additive 
61.1 95.1 
4 Commercial Additive 
54.3 89.2 
5 Commercial Additive 
34.5 62.8 
oligomeric polyamine 
______________________________________ 
The above results demonstrate that the additive of the invention, Run 2, 
has an enhanced rate of decomposition as compared to commercial additives, 
and this property leads to surprisingly clean engine combustion chambers. 
It is apparent to those of ordinary skill in the art that variations and 
departures from the exemplary matter described herein can be readily made 
within the scope of the specification and the appended claims.