US3846089A

US3846089A - Motor fuel composition

Info

Publication number: US3846089A
Application number: US00356655A
Authority: US
Inventors: W Machleder; R Kuhn
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1972-08-11
Filing date: 1973-05-02
Publication date: 1974-11-05
Anticipated expiration: 1991-11-05

Abstract

1. A MULTI-FUNCTIONAL ADDITIVE COMPOSITION SUITABLE FOR ADDITION TO DISTILLATE HYDROCARBON FUELS HAVING A MAJOR PROPORTION OF A HYDROCARBON BASE FUEL DISTILLING WITHIN THE GASOLINE DISTILLATION RANGE, THE ADDITIVE COMPOSITIONS COMPRISING A MIXTURE OF (1) ABOUT 20 TO ABOUT 250 PARTS BY WEIGHT OF A TERTIAEY ALKYL PRIMARY AMINE HAVING A BRANCHED BACKBONE AND A TOTAL OF 6 TO 24 CARBON ATOMS; (2) ABOUT 5 TO 100 PARTS BY WEIGHT OF A SURFACE ACTIVE ALKYL AMMONIUM CARBOXYLATE SALT-ETHOXYLATED ALKYL PHENOL ESTER OF A TRIMER OR DIMER ACID; (3) ABOUT 100 TO 650 PARTS BY WEIGHT OF A POLYESTER PREPARED FROM THE REACTION OF A DIMER OR TRIMER ACID AND A MIXTURE OF AN ALIPHATIC ALCOHOL HAVING FROM ABOUT 1 TO 24 CARBON ATOMS AND AN ALKOXYLATED ALKYL PHENOL, SAID DIMER AND TRIMER ACID HAVING BEEN PRODUCED BY THE POLYMERIZATION OF AN UNSATURATED ALIPHATIC MONOCARBOXYLIC ACID HAVING BETWEEN 16 AND 19 CARBON ATOMS.

Description

United States Patent 6 Int. Cl. C101 1/22 US. Cl. 4458 29 Claims ABSTRACT OF THE DISCLOSURE Motor fuel compositions having detergent properties are disclosed and claimed which are particularly useful in spark-ignition, internal combustion engines. The fuel compositions of the present invention contain certain additives which either substantially eliminate, mitigate against, or maintain at a low level, deposits Which would otherwise form in the carburetor, in the intake valves and ports, and in the combustion chamber. Such carburetor and intake system (induction system) depisits are to be avoided since they tend to restrict the flow of air through the carburetor especially at idle and at low speeds and/ or cause improper valve closing and sluggish valve action. These conditions produce rough engine idling, stalling, and can also result in excessive hydrocarbon and carbon monoxide exhaust emissions. Combustion chamber deposits are to be avoided since they cause an increase in octane requirement, emissions and cause preignition. The fuel additives of the present invention include for induction system deposit control an ester selected from a dimer or trimer acid ester or an adipate ester.

This application is a continuation-in-part application of our earlier filed and copending application Ser. No. 279,891, now US. Pat. No. 3,782,912, filed Aug. 11, 1972 and entitled Detergent Motor Fuel.

This invention relates to motor fuel compositions for spark ignition, internal combustion engines. More particularly, this invention relates to a detergent motor fuel containing additives which reduce or prevent the formation of deposits in the carburetor as well as in the induction system and combustion chamber of an internal combustion engine. Thus, the formulations of the present invention are particularly effective as carburetor detergents to clean up and maintain the cleanliness of the carburetor and to prevent, reduce or minimize against deposits forming in the induction system such as the area around the valves and ports. This invention also relates to an additive concentrate of one or more of the additives in mixture, solution or combination.

Modern internal combustion engine design is undergoing and has undergone important changes to meet stricter standards for engine and exhaust gas emissions. A major change in engine design is the feeding or recycling of blowby gases from the crankcase of the engine into the intake air supply to the carburetor rather than the venting of these gases to the atmosphere, as in the past. The blowby gases contain substantial amounts of deposit-forming substances and are known to form deposits in and around the throttle body area of the carburetor. These deposits restrict the flow of air through the carburetor at idle and at low speeds so that an overrich fuel mixture results. This condition produces rough engine idling, stalling and also results in excessive hydrocarbon and carbon monoxide exhaust emissions being emitted to the atmosphere.

In addition to the changes that have already been made, it is anticipated that additional burdens and demands will be placed on present day internal combustion engines and their fuels with the advent of new emission control devices, such as exhaust gas recirculation systems and catalytic exhaust mufflers. Also, the use of certain fuel additives such as the alkyl ammonium phosphate detergents may have to be restricted or eliminated because catalytic exhaust mufflers which utilize metal catalysts will be poisoned by phosphorus-containing compounds.

It is an obiect of the present invention to provide a detergent motor fuel which will have certain carburetor detergent properties and which will clean up and maintain the cleanliness of the carburetor and also the remainder of the fuel induction system such as the valves and ports and reduce the octane requirement increase of an internal combustion engine. It is another obqect of the present invention to provide a detergent fuel Will maintain a loW level of hydrocarbon and carbon monoxide exhaust gas emissions and which will avoid the use of phosphoruscontaining additives. It is still a further object of the present invention to provide a detergent fuel which has other desirable properties such as rust and corrosion protection, water demulsibility properties, anti-icing properties, etc. It is a further object of the present invention to provide multi-functional gasoline additive or additive combination effective in inhibiting the formation of intake valve deposits in addition to being effective as cerburetor detergents, and which can be used at relatively low concentra tions (and thus at relatively low cost) for example at a treating level of about 1000 parts per million (ppm. on a weight basis in the gasoline), or less, and more preferably 600 ppm. or less, and even more preferably 400 ppm. or less There, are, of course, other detergent motor fuel compositions available today, but they generally suffer from one or more deficiencies. Either they are used at very high concentrations, for example, something of the order of 4000 ppm; or if used at the use levels in which We are interested, the available formulations suffer from one or more defects.

We have discovered that the combination of 1) selected tertiary alkyl primary amines having branched backbones and a total of about 6 to 24 carbon atoms; (2) a surface active alkyl ammonium carboxylate salt-ethyoxylated alkyl phenol ester of a trimer or dimer acid; and (3) a dimer or trimer acid ester comprising the essentially esterified polyester of a dimer or trimer acid, or mixture of dimer and trimer acids, produced by the polymerization or condensation of an unsaturated aliphatic monocarboxylic acid having between 16 and 18 carbon atoms per molecule which is esterified with (or incoporates) a mixture of aliphatic and ethoxylated aromatic alcohols, are effective in reducing or preventing the formation of carburetor and other induction system deposits.

According to one aspect of the present invention, therefore, We provide a normally liquid, multi-functional, additive composition for addition to a leaded, low lead, or unleaded gasoline, i.e., to a distillate hydrocarbon fuel comprising a major proportion of a hydrocarbon base fuel distilling within the gasoline distillation range. The three component composition ranging from a total of about 125 to about 1000 parts, on a weight basis, is comprised of about 20 to about 250 parts, and more preferably, about 50 to parts by Weight of (l) a tertiary alkyl branched chain primary amine, as above described; about 5 to about 100 parts and, more preferably, about 10 to about 25 parts by Weight of (2) a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid, as above described; and about 100 to about 650 parts by weight and, more preferably, about 200 to 400 parts by weight of (3) a trimer acid or dimer acid mixed ester as above described. In an alternative embodiment of the invention and Where induction system control, per se, is primarily desired, then components (1) and (2) can be omitted, and component (3) can be utilized itself in the fuel, on a total weight basis of about 100 to about 650 p.p.m., more preferably about 200! to 400 p.p.m., or component (3) can be used in con-- junction with component (1) to provide a two-com-- ponent package or blend providing good carburetor detergency and good induction system deposit control, or component (3) can be used with other carburetor detergents and/or other rust inhibitors. When using a combination or mixture of components 1) and (3), they are used in the same amount as noted above, i.e., about 20 to 250 p.p.m. of (1), more preferably, about 50 to 100 p.p.m. of (1) and about 100 to 650 p.p.m., more preferably, about 200 to 400 p.p.m. of (3).

On a fuel treating level basis, i.e., on a level related to the gasoline, the three component additive composition should be added to or used in the gasoline at a total level of about 125 to about 1000 p.p.m. (weight basis) and, on an individual or component basis, in an amount of from about 20 to 250 p.p.m., and more preferably 50' to 100 p.p.m. of (1); about to about 100 p.p.m., more preferably about to about 25 of (2); and about 100 to about 650 p.p.m., more preferably 200 to 400 p.p.m. of (3 On a pounds per barrel of gasoline basis, this is about 5 to 62.5, more preferably 12.5 to 25 lbs/1000 barrels; (bbls). of gasoline of (1); 1.25 to 25, more preferably 2.5 to 6.25 lbs/1000 bbls. of gasoline of (2); and 25 to 162.5, more preferably 50 to 100 lbs/1000 bbls. of gasoline of (3).

For the concentration of the additive component (3), above (when used alone) the p.p.m. concentration and the pounds per barrel of gasoline treating level is the same as noted for component (3) above, i.e., about 25 to 162.5, more preferably about 50 to 100 lbs/1000 bbls. (barrels) of gasoline, or about 100 to 650 p.p.m., more preferably about 200 to about 400 p.p.m. of (3).

For the concentration of the additive mixture (1) and (3) in gasoline, the treating level should be in the range of about to 250 p.p.m., more preferably about 50 to 100 p.p.m., of component (1), and about 100 to 650 p.p.m., more preferably about 200 to 400 p.p.m. of component (3). On a pounds per barrel of gasoline basis. this amounts to about 5 to about 62.5 lbs., more preferably about 12.5 to lbs. per 1000 bbls. of gasoline of component (1); and about 25 to 162.5 lbs., more preferably to 100 lbs. per 1000 bbls. of gasoline of component (3).

The tertiary (tert.) or t-alkyl primary amine, having at least one branched chain, may be represented by the general formula (I).

in which R R and R are alkyl groups whose total carbon atom content ranges from 6 to 24. It is preferred that two of the R groups, for example, the R and R of the t-alkyl primary amine be methyl groups.

The t-alkyl primary amines with branched chains and which may be used in the compositions of the presentinvention include, for example, t-octylamine, t-nonylamme, t-dodecylamine, t-tetradecylamine, t-octadecylamine, t-docosylamine, t-tetracosylamine and mixtures of two or more of such amines. These amines are commonly prepared by reactions known to those skilled in the art such as the reaction of nitriles with alkenes or secondary or tertiary alcohols in strongly acidic media. Commercially available t-alkyl primary amines are often mixtures. t-Octylamine having a branched structure has the formula:

and the alkyl group of this amine will hereinafter be referred to as t-octyl. One form of t-nonylamine is prepared as a mixture containing 4 a 13 3 2NH2 and and has a neutral equivalent of about 142. A commercial preparation which can be used in the present invention is readily available under the trademark Primene 8l-R which is the trademark used for a mixture of t-dodecyl-, t-tridecyland t-tetradecylamines or principally a mixture of t-C H NH to t-C H NH amines having a neutral equivalent of about 191. Another commercial preparation which is useful in the present invention is available under the trademark Primene JM-T. Primene I'M-T is principally a mixture of t-C N NH to t-C H NH amines and has a neutral equivalent of about 315. The important consideration is that in a t-alkyl primary amine, the NH group is always attached to a carbon atom containing no hydrogen atoms and in the present invention at least one of the alkyl groups is branched.

The alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid (or mixture thereof) is added or included primarily to provide rust and/ or corrosion protection although there is also some modest carburetor detergency activity, has the following formula cog Nrnnn X where n is an average number from about 1 to 12.5 and more preferably from about 3 to 10;

and in the case of a salt-ester derived from a trimer acid x is 1 or 2, and y is 1 or 2, the sum of x and being 3;

and in the case of the salt-ester derived from a dimer acid,

both x and y are each 1;

R is an alkyl group containing 4 to 12 carbon atoms;

R is H or an alkyl group containing 4 to 12 carbon atoms;

R is an alkyl group containing 2 to 24 carbon atoms which may be straight or branched chain or an amine substituted alkyl group of 2 to 24 carbon atoms. Preferably, R contains 12 to 22 carbon atoms; and

Z is a saturated or unsaturated hydrocarbon residue of the acid, said hydrocarbon residue having 34 to 51 carbon atoms. (Z will ordinarily have 51 carbon atoms in the case of a trimer acid, and ordinarily 34 carbon atoms in the case of a dimer acid.)

The alkyl ammonium carboxylate salt-ester, i.e., component (2), may be used as all trimer acid derivative or all dimer acid derivative, or any mixture of the dimer and trimer acid derivatives may be used in the present inventron.

Also, the presence of some monocarboxylic C acids or the like in the ester or salt form, or mixtures of both ester and salt form, may be tolerated in minor amounts, about 5% or less.

Specific embodiments of the alkyl ammonium carboxylate salt-ester of the general formula II, above, and Where- :in, R is substantially or essentially all octyl, i.e. C H and R is H and which are usable in the present invention are given in Table I below:

TABLE IContinued Alkyl ammonium carboxylate saltester The alkyl ammonium carboxylate salt ester can be made in known fashion, by the acid catalyzed esterification of a suitable dimer or trimer acid, or mixture thereof, for example, in the case of the diester-monosalt, with two moles of a suitable ethoxylated alkyl phenol followed by conversion of the remaining carboxylic acid functionality to an alkyl ammonium carboxylate salt with the addition of a suitable amine. The trimer acid may be the product derived from the trimerization reaction of a C unsaturated fatty acid; an example of a suitable trimer acid is that available under the trademark Empol 1041. The preparation of such dimer and trimer acids is described in U .8. Pat. 2,632,695. A generalized reaction scheme for the preparation of an alkyl ammonium carboxylate salt-ester is shown below using a trimer acid for illustrative purposes:

R 4 1 Acid C51(CO2H)3 2110 (CHQcHaO) Q E2 (2) 2H2O where n, R R and R have the values given previously, and C is the carbon atom content of the hydrocarbon residue.

In order to provide induction system and combust on chamber deposit control, there is included in the additive or additive combination, a mixed polyester of a dimer or trimer acid, or mixture of such dimer and trimer acids. The mixed polyesters as well as the dimer and trimer acids may be prepared in known fashion. For example, an unsaturated aliphatic monocarboxylic acid having between about 16 and 18 carbon atoms per molecule, for example linoleic acid can be polymerized or condensed to form essentially the dimer of linoleic acid, a dicarboxylic acid, and also the aliphatic monocarboxylic acid can be polymerized to form essentially the trimer of linoleic acid, a tricarboxylic acid. Mixtures of such dicarboxylic and tricarboxylic acids may also be formed. Similarly, other C and C unsaturated aliphatic monocarboxylic acids, in-

cluding ricinoleic and linolenic acid can be polymerized to dimer and trimer acids or mixtures of such dimer and trimer acids. The preparation of such dimer and trimer acids is described in US. Pat. 2,632,695. The mixed polyesters used in the present invention are prepared by reacting a suitable amount of a mixture of an aliphatic alcohol and an ethyloxylated aromatic alcohol with the polycarboxylic acid to esterify essentially all of the carboxyl groups in the acid. Esterification is conducted according to conventional, known methods, The aliphatic alcohols which are suitable for this purpose are preferably saturated aliphatic alcohols, having from about 1 to 24 carbon atoms. Representative aliphatic alcohols include methyl alcohol, propyl, alcohol, n-butyl, alcohol, isobutyl alcohol, hexyl alcohol, Z-ethylhexyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, isodecyl alcohol, lauryl alcohol, stearyl alcohol, hexadecyl alcohol, and nondecyl alcohol. Preferably, the aromatic or aromatic containing alcohols which are used are alkylated phenols which have been ethoxylated with varying amounts of an alkylene oxide such as ethylene oxide. (These materials are known generally as alkylphenoxypolyethoxy ethanols.) The number of moles of ethylene oxide which may be condensed with the alkylated phenol may vary from about one to about 20 ethylene oxide units, and more preferably from about one to four moles of ethylene oxide. While the presence of some unreacted alcohols and some completely esterified all-aliphatic or all-ethyloxylated aromatic esters will be present in the esterification mixture, the principal active ingredient or the principal active mixed polyester has the following general formula:

wherein n is an average number of from about 1 to 20 and, more preferably, of from about 1 to about 4;

and in the case of the mixed polyester derived from a trimer acid, J is l or 2 and q is 1 or 2, the sum of p and q being 3;

and in the case of the mixed ester derived from a dimer acid, both p and q are each 1;

and where Z is a saturated or unsaturated hydrocarbon residue having an average of 34 to 51 carbon atoms, said residue being the residue of a dimer or trimer acid of linoleic acid, or mixture of said dimers and trimers of linoleic acid;

R is an alkyl group containing 4 to 12 carbon atoms,

more preferably 8 or 9 carbon atoms;

R is H or an alkyl group containing 4 to 12 carbon atoms,

more preferably H;

R is an alkyl group containing 1 to 24 carbon atoms which may be straight or branched chain.

The aromatic alkoxylated alkyl phenols are preferably based on either octyl or nonyl phenol and can contain approximately 1 to 20 moles of ethylene oxide, and more preferably about 1 to about 4 moles of condensed ethylene oxide. Also, the mixed polyester when based on a mixture of dimer and trimer acids, as hereinabove described, are preferably based on a mixture containing at least about 60% trimer acid, and more preferably, at least about trimer acid.

In the following examples which illustrate this invention, all parts and percentages are by weight, unless otherwise stated. The ability of the additive or additive combinations of this invention to clean up and maintain the cleanliness of the carburetor of an internal combustion engine is illustrated, and its ability to remove or protect against the formation of induction system deposits is also illustrated below. Also illustrated below is the ability of the additives to reduce octane requirement increase in an internal combustion engine. Unless otherwise stated, an MS-08 gasoline fuel is used for the Blowby carburetor detergency Keep Clean engine test and a Howell Unleaded Gasoline is used for the Induction System Deposit Test. The Howell Unleaded Gasoline has the following properties:

HOWELL UNLEADED GASOLINE: FUEL SPECIFICATION EL-72-l Aromatic content percenL- 30.2 Olefins do 11.6 Saturates do 58.2 Lead g./gal 0.03 Sulfur wgt. percent 0.009 Gravity API 57.9 Reed vapor pressure 8.1 Research octane 91.7 Motor octane 83.8 Initial B.P. F 94 50% distilled F 228 90% distilled F 351 Distillation end point F 426 ENGINE TEST EVALUATION OF MULTIPURPOS-E CARBURETOR DETERGENTS (A) Blowby Carburetor Detergency Keep Clean Engine Test (1) Engine test procedure.The Blowby Carburetor Detergency Keep Clean Engine Test (BBCDT-KC) measures the ability of a gasoline additive to keep clean the carburetor throttle body area, and is run in a 1970 Ford 351 CID V-8 engine equipped by means of a special Y intake manifold with two one-barrel carburetors, which can be independently adjusted and activated. With this arrangement, a separate test fuel can be evaluated by each carburetor which feeds four of the eight cylinders via the non-interconnected intake manifold. The carburetors are modified with removable aluminum sleeves in order to facilitate weighing of the deposits which accumulate in the throttle body area. The severity of the test is adjusted to an appropriate level by recycling the entire amount of blowby gases, approximately 90-110 c.f.h., to the top of the air cleaner so that each carburetor receives an equal volume of these gases. Equal intake mixture flow through each carburetor is adjusted during the first hour of operation of means of intake manifold differential pressure and CO exhaust gas analysis. The following test cycle and operating conditions are employed:

Test cycle:

Phase I 650 engine r.p.rn., 8 min. Phase II 3000 engine rpm, 1 min. Test duration, hrs 10. Intake air, F 135:10. Jacket water, F 190i10. Engine oilsump, F. 210:10. Percent CO in exhaust 3.0:02. Blowby, c.f.h 90-1 10.

The weight (mgs.) of deposits accumulated on the aluminum sleeve is measured, and the average value of four tests per additive or additive mixture is reported.

The gasoline used in the BBCDTKC test is an MS-O8 gasoline having the following properties:

Gravity:

API 59.7 Sp. gr. at 60 F 0.74

ASTM D-86 distillation, F:

I.B.P. 93

BR 405 Percent recovered 98 Percent residue 1 Percent loss 1 Percent sulfur 0.11 Lead, gm./ gal. 3.08 PIA composition:

Aromatics, percent 23.1

Olefins, percent 20.0

Saturates, percent 56.9

Oxidation stability, minutes 600+ ASTM gum (unwashed), mg./ 100 ml 1.0

Research octane number 95.5

Percent H 13.10

Percent C 86.61

(B) Induction System Deposit Engine Test (1) Engine test procedure.-The Induction System Deposit Test (ISDT) which is used to evaluate the ability of gasoline additives or mixtures of additives to control induction system deposits, is run using a new air-cooled, single cylinder, 4 cycle, 2.5 H.P. Briggs and Stratton engine for each test. The engine is run for hours at 3000 rpm. and 4.2 ft. lbs. load, with a 1 hour shutdown every 10 hours to check the oil level. Carbon monoxide exhaust emission measurements are made each hour to insure that a constant air to fuel (A/F) ratio is being maintained.

Upon completion of a test run, the engine is partially disassembled, and the intake valve and port are rated and valve and port deposits are collected and weighed.

(C) Rusting Test Method A rusting test method for fuel additive rust inhibition is used which follows military specification MIL-I-25 017C (Section 4.6.3). This procedure which utilizes a type B medium hard water is a modification of the basic ASTM method D665. The object of the test is to evaluate the ability of a gasoline additive to inhibit rusting of ferrous parts such as encountered in gasoline storage and transportation systems. The method involves stirring a mixture of 300 ml. of an additive blend in depolarized isooctane with 30 ml. of de-ionized-distilled water, medium hard water, or synthetic sea-water, for 5 hours at a temperature of 100 F. (37.8 C.) with a cylindrical steel specimen completely immersed therein. Test results are reported as percent area rusted and a pitting rating is also optionally reported on a scale of 1 to 3, with 3 being the worst degree of pitting and 0 being the best. The type B medium hard water is prepared as follows:

3 stock solutions using ACS reagent-grade chemicals in distilled water containing, respectively, 16.4 g./liter NaI-ICO 13.2 g./liter CaCI -ZH O, and 8.2 g./liter MgSO -7H O. Ten ml. of the NaHCO stock solution are pipetted into 800 ml. of distilled water in a 1-liter volumetric flask, and then shaken vigorously. While swirling the contents of the flask, 10 ml. of the CaCl stock solution are pipetted into the flask and then 10 ml. of the MgSO stock solution are also pipetted into the flask, distilled water is then added to bring the volume to 1 liter and mixed thoroughly. The final blend should be clear and free of precipitate.

(D) Combustion Chamber Deposit Engine Test (1) Engine test procedure.The Combustion Chamber Deposit Engine Test (CCDET) is used to evaluate the ability of a gasoline additive, or mixture of additives to control or reduce the octane number requirement in- 9 crease (ONRI), in an internal combustion engine, the 'test is run using a 1972 Chevrolet 350 CID V-8 engine equipped with a two barrel carburetor and a 1972 Turbo Hydromatic 350 transmission which is connected to a l42 WIG dynamometer equipped with a 200.3 lb.ft. inertia wheel. The following test cycle and operating conditions are employed and are intended to simulate an urban taxi cab.

Test cycle:

Phase I Start-idle, 650-750 r.p.m.

Phase II Accelerate1 to 2 shift, 5.5

sec., 29003000 r.p.m.

Phase III Accelerate2 to 3 shift, 9.5

sec., 2800-2900 r.p.m.

Phase IV 3rd gear, 10.0 sec., 2600 r.p.m.

Phase V Decelerate to idle, 15.0 sec.

Test duration 200 hrs.

Fuel consumption 1000 gallons (Howell unleaded gasoline plus additive treatment). Intake air F Ambient. Jacket water, F 180. Engine oil-sump, F. 220110.

Octane number requirement is determined at 24 hrs. interval under the following engine conditions: transmission in 3rd gear with an output shaft speed controlled at 1500 r.p.m. and the engine throttle wide open. The octane number requirement of the engine is determined at trace knock in terms of primary reference fuels, i.e., the engine is run on a series of blends of isooctane and nheptane of known octane number until audible knock is perceived. The lowest standardized octane number blend at which the engine does not knock is recorded as the octane number requirement. Octane number requirement increase is then the difference between the initial octane number requirement and the final octane number requirement for a particular test.

The novel fuel compositions may be prepared by adding the individual additives directly to the fuel, or an additive blend or mixture of one or more of the components may be prepared or a concentrate of one or more of the additives in a suitable solvent such as toluene or xylene may be prepared. Also, all of the additive components are normally liquid materials at room temperature and are soluble or miscible with each other and may be distributed Without any solvent.

The preparation of a typical mixed polyester employed in the fuel of the invention is as follows:

PREPARATION OF TRIMER ACID, DIISODECYL,

MONO OCTY'LPHENOXYPOLYETHOXYETHA- NOL (3 MOLES ETHYLENE OXIDE)TRIESTER To a 3-l. three-necked round bottom flask fitted with a mechanical stirrer, thermometer, and Dean-Stark trap with reflux condenser are charged 845 g. (1 mole) of a trimmer acid mixture (Emery Industries 1834-18R trimer acid), comprising 70-80% trimer acid and 30 to 20% dimer acid, 316 g. (2 moles) of isodecyl alcohol, 338 g. (1 mole) of octylphenoxypolyethoxyethanol containing about 3 moles of condensed ethylene oxide, 200 ml. of toluene, and 1.0 g. of p-toluenesulfonic acid. The reaction mixture is heated to reflux (with stirring which occurs near 135 C. Refiuxing is continued for 6 hours during which time the theoretical quantity of water is evolved. Toluene solvent is stripped under vacuum, 3.0 g. of Na CO added to neutralize the p-toluenesulfonic acid, and the product filtered. The material prepared in this way generally has an acid number near 1.0.

The theoretical product distribution assuming that equilibrium has been obtained and that there are no free energy formation differences between the various esters is the following:

Wt. Mole percent percent Trimer acid, triisodecyl triester 25. 9 29.6 Trirner acid, diisodecyl/monooctylphenoxypolyethanol (3 moles ethylene oxide) 44. 5 44. 5 Trimer acid, isodecyl dioctylphenoxypolyethoxyethanol (3 moles ethylene oxide) triester 25.0 22. 2 Trimer acid, trioctylphenoxypolyethoxyethanol (3 moles ethylene oxide) 4. 6 3. 7

Actual analysis shows the diisodecylmonooctylphenoxypolyethoxyethanol ester to be present in the preponderant numerical percentage amount, and actual chromatographic analysis conforms substantially with the predicted amount. Changes in the ratio of the ester components may be obtained, by altering the esterification conditions.

The following Table II lists typical mixed polyesters prepared for use with the present invention and in accordance with the above general method:

TABLE II Example:

1 Dimethyl/monobetylphenoxy polyethoxyethanol containing average of 3 moles of condensed ethylene oxide.

2 Dibutyl/mono-octylphenoxy polyethoxyethanol with average of 3 moles of ethylene oxide.

3 Di-2-ethylhexyl/mono-octylphenoxy polyethoxyethanol with 3 moles of ethylene oxide.

4 Diisodecyl/mono-oetylphenoxy polyethoxyethanol with average of 3 moles of ethylene oxide.

5 Dl-C15-20 aliphatic alcohol/monooctylphenoxy polyethoxyethanol with 3 moles of ethylene oxide.

6 Mono-isodeeyl/di-octy1phenoxy polyethoxyethanol with 3 moles of ethylene oxide.

7 Diisodeeyl/monooctylphenoxy polyethoxyethanol with average of 5 moles of ethylene oxide.

8 Dimethyl/mono-octylphenoxy ethoxyethanol with average of 1 mole of ethylene oxide.

9 Mono-isodecyl/mono-octylphenoxy polyethoxy ethanol with 3 moles of ethylene oxide.

Ester of trimer of linoleic acid.

Ester of the dimer of linoleic acid.

The esterification reaction is usually acid catalyzed and can be carried out over a broad range of temperatures, but usually the temperature will vary from about C., to about C. The mixture of aliphatic alcohol and ethoxylated aromatic alcohols can also vary fairly widely depending on the products desired, but ordinarily the ratio of the aliphatic alcohol to the ethoxylated aromatic alcohol will vary from about (on a molar basis) one to four to about four to one, and more preferably about one to two to about two to one. The quantity of mixed alcohols used should be sufficient to essentially completely esterify the polycarboxylic acid (i.e. the trimer or dimer acid, or mixture thereof) and there can be used an equivalent amount or slight molar excess of alcohols in relation to the polycarboxylic acid during the esterification reaction.

The base fuel employed in the following examples (Tables III, IV, and V below) is a Howell unleaded gaso line as described hereinabove, except for the BBCDT-KC tests wherein an MS-08 gasoline as described hereinabove is used. Induction System Deposit Test results (ISDT) are reported in milligrams (mg.) of deposit as are the Blowby Carburetor Detergency Keep Clean Engine Test results. Percent rusting is also reported. These test procedures are described above.

ii I Md TABLE III ISDT, mg. deposit (valve and BBODI -KC, Example Fuel additive and concentration p.p.m. gasoline port) mg. deposit Control Untreated gasoline i.e. base fuel 365 13 Comparative Triisodecyl ester of trimcr of linoleic acid, 300 p.p.m 170 Example A. 1. Mixed dimethyl polyester of Example 1 (see Table II), 300 72 p.p.m. 11 Mixed dibutyl polyester of Example 2 (Table 11 above) 300 35 18.1

p. p.m. 12 Mixed diisodeeyl polyester 01 Example 4 (Table II above) 300 37 14. 2

p.p.m. 13 Mixed diisodeeyl polyester of Example 7 (Table 11 above) 300 475 p.p.m. 14 Tri-octylpolyethoxycthanol ester of ti'iiner oi linoleic acid 186 with 3 moles ethylene oxide, 500 p.p.m. Comparative Commercially available and used alkyl ammonium phosphate, 435 4. 0

Example B. 50 ppm. Comparative Commercially available and used polybutene succinimide, 1, 247 3. 3

Example C. 140 p.p.m.

1 Induction System Deposit Test, as described above. 2 Blowby Carburetor Detergency Keep Clean Engine Test, as described above.

In Table IV, below, there are shown results obtained 20 18, 20, 21, and 22 show higher levels of induction system with a combination or mixture of additives according to deposits than the base fuel their total performance 18 sigthe present invention. nificantly better than the base fuel treated with currently TABLE IV ISDT, mg. Busting deposit, BBCDT- (percent Pitting Example valve and KC, mg. area designanumber Fuel additive and concentration, p-p.m. in gasoline port deposit rusted) tion 15 1 -50 p.p.m., 11 p.p.m., IIIa-Mixed diisodecyl cthoxylated polyester of Example 95 2. 8, 2. 6 0 0 4 (Table II above)-O p.p.m.

16 I p.p.m., 11-10 p.pxn, IIIb-Mixed dibutyl ethoxylated polyester of Example 2 264 3. 4 0 0 (Table II above)300 p.p.ml

17- I-50 p.p.m., II-20 p.p.m., IIIc-Mixed di-Z-ethylhexyl ethoxylatcd polyester of Ex- 487 0 0 ample 3 (Table II above)300 p.p.m.

l8 I50 p.p.m., 11-20 p.p.m., IlId-Mixed di it-C20 aliphatic alcohol ethoxylated poly- 374 4. 0 4 0 ester of Example 5 (Table II above)300 ppm.

19 I-50 p.p.m., II-lO p.p.m., IIIe-Mixed mono-isodccyl ethoxylated polyester of Ex- 320 2.3 0 0 ample 6 (Table II above)-300 p.p.ml

20 I50 p.p.m., 11-15 p.p.m., IIIf-Mixed diisodeeyl etlioxylated polyester of Example 912 4.2 1 0 7 (Table II above)-300 p.p.m.

21 I-50 p.p.m., 11-5 p.p.m., llIg-Mixed dimethyl ethoxylated polyester of Example 1 414 2 0 (Table II above)300 ppm.

22 50 p.p.m., 11-20 p.p.m., IIIh-Mixed dimethyl ethoxylated polyester of Example 8 981 1 0 (Table II above)-300 p.p.m.

Control Untreated gasoline, l.e., base fuel 365 13 100 0 Component I (used in the additive package or blend of components I, II, and III, above) is a t-Cn-Czz alkyl amine with a highly branched backbone, a neutral equivalent of 315, and a molecular weight principally in the 260-325 range.

2 Additive component II is essentially an alkyl ammonium carboxylate di-salt-ester of the formula where Z1 is the hydrocarbon residue of the product of trimerization of an unsaturated C18 fatty acid, such as linoleic acid, which is a mixture of about 70-80% trimer acid (C54) and about 30-20% of dimer acid (030), all parts by weight.

TABLE V used commercial additives such as the alkyl ammonium phosphates and the polybutenc succinimides. It is irn- [Octane number requirement increase] portant to remember that untreated gasoline is rarely used 9 252 2 3 in present day automobiles and that gasoline treated with Fuel additiveandconcentration,p.p.m., requirement 55 conventional carburetor detergents and rust inhibitors Example in gasoline Increase will normally give higher levels of induction system de- Control Untreated gasoline i.e. base fuel i0 posits than the base gasoline as is shown in Comparative arats. imitatealilitftittlptff 1W 8 Examples B and C of liable 22 Same additive package or blends as in 4 Although the mechanism of activity 15 not clear, it is g fg gl 15 (Tablelv) (tta1=37 evident from the data in Table V that the additive com- 23 Same additive as Example No. 2, Table 5 bination of our invention is effective in modifying the II at 300 deposits in the combustion chamber such that the octane As measured by the Combustion Chamber Deposit Engine Test number requirement increase Of the engine is less than AS is evident from the data in Table III, the mixgd with either untreated gasoline or base gasoline treated polyesters of this invention while individually afiording Wlth a Commercially s d polybutene succinimide. no carburetor detergencw activity per Se, are Very effec Ina specific example of an alternative embodiment of tive at controlling induction system deposits in an internal P Inf/6mm, Wherem f carburetorfiewrgem and combustion engine induction system deposit control additive (3) are used when th mixed polyesters are used in combination (without any added rust inhibitor) in gasoline, at a total with rust inhibitors and carburetor detergents as shown in Concentratlon of about 350 P-P- (5O P'P- of 1 and 300 Table IV so that a multipurpose additive package is P-P- of the following results 8Y6 Obtained! for th formed, the activity of Examples l5, l6, and 19 is sig- ISDT Test, 201 milligrams of deposits; and for the nificantly better than the base fuel in all three perform- C Test, mg of dfiPOSitS- In this test, ance categories, i.c., rust inhibitor, carburetor detergency, ponent (1) was a t-C C alkyl amine such as was used and induction system detergency. Although Examples 17, in Example 15, and component (3) was the mixed poly- 13 ester of Example 4. As noted previously, a Howell unleaded gasoline is used for the ISDT tests, and MS8 gasoline is used for the BBCDT-KC tests.

In another alternative embodiment of this invention, other dicarboxylic acid esters, such as an adipate diester may be substituted in whole or part for component (3) of the detergent composition, noted above, to provide induction systems deposit control. Thus, an adipate diester comprising the mono-isodecyl, mono-octyl phenoxy polyethoxy ethanol (containing an average of 3 moles of condensed ethylene oxide) mixed ester of adipic acid and made by a conventional acid esterification process, gave the following result: in the ISDT test, 160' mg. of deposit. Other adipic acid esters, e.g., the mixed adipic acid esters comprising a mixed C C alkyl/alkyl phenoxy (alkyl of C to C polyethoxy ethanol (containing 1 to 20 moles, and more preferably about 1 to moles condensed ethylene oxide) ester may also be used to provide induction system deposit control either alone, or in combination with components (1) and (2) above. The adipic acid ester is used in the same amount as component (3) noted above, either alone in gasoline or in combination with components (1) and (2) noted above.

Other results using 300 p.p.m. of the specific monoisodecyl, mono-octyl phenoxy polyethoxy ethanol (3 moles ethylene oxide) adipic ester noted above in combination with 50 p.p.m. of the t-C C alkyl amine (component (1) above) are as follows: in the ISDT test, 225 mg. of deposit, and in the BBCDT-KC test, 2.3 mg. of deposit. When 10 p.p.m. of the rust inhibitor component (2) of Example No. is added to the mixture of the LC -C alkyl amine and the adipic acid ester, noted above, to give a three component system, the following results are obtained: in the ISDT test, 327 mg. of deposit, 2.2 mg. of deposit in the BBCDTKC test, and 0% area rusted in the rust test described above.

In another example using 50 p.p.m. of the t-C- -C alkyl amine (component (1) above), 5 p.p.m. of the rust inhibitor component (2) of Example No. 15, and 300 p.p.m. of the mono-isodecyl, mono-octyl phenoxy polyethoxyethanol (containing 5 moles of ethylene oxide) adipate ester the following results were obtained: in the ISDT test, 237 mg. of deposit, in the BBCDT-KC test, 3.5 mg. of deposit, and 0 area rusted in the rust test.

What is claimed is:

1. A multi-functional additive composition suitable for addition to distillate hydrocarbon fuels having a major proportion of a hydrocarbon base fuel distilling within the gasoline distillation range, the additive composition comprising a mixture of (1) about to about 250 parts by Weight of a tertiary alkyl primary amine having a branched backbone and a total of 6 to 24 carbon atoms;

(2) about 5 to 100 parts by weight of a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid;

(3) about 100 to 650 parts by weight of a polyester prepared from the reaction of a dimer or trimer acid and a mixture of an aliphatic alcohol having from about 1 to 24 carbon atoms and an alkoxylted alkyl phenol, said dimer and trimer acid having been produced by the polymerization of an unsaturated aliphatic monocarboxylic acid having between 16 and 18 carbon atoms.

2. A multi-functional additive composition suitable for addition to gasoline, said additive composition comprising a mixture of (1) about 20 to about 250 parts by weight of a tertiary alkyl primary amine having a branched backbone and a total of 6 to 24 carbon atoms;

Component (1) refers to the t-alkyl amine (of 6 to 24 carbon atoms) carburetor detergent component and component (2) refers to the surface active alkyl ammonium carboxylate saltethoxylated alkyl phenol ester rust inhibitor component, hereinbefore described.

14 (2) about 5 to about parts by weight of a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid of the formula o o on on 0 a I 0? Z R5 [002 a tly x where n is an average number from 1 to 12.5;

and wherein in the case of the salt-ester derived from a trimer acid x is 1 or 2, and y is 1 or 2, the sum of x and y being 3;

and in the case of the salt-ester derived from a dimer acid, both x and y are each 1;

R is an alkyl group containing 4 to 12 carbon atoms;

R is H or an alkyl group containing 4 to 12 carbon atoms;

R is an alkyl group containing 2 to 24 carbon atoms which may be straight or branched chain or an amine substituted alkyl group of 2 to 24 carbon atoms; and

Z is a saturated or unsaturated hydrocarbon residue of the acid, said hydrocarbon residue having 34 to 51 carbon atoms; and

(3) about 100 to 650 parts by weight of a polyester prepared from the reaction of a dimer or trimer acid and a mixture of an aliphatic alcohol having from about 1 to 24 carbon atoms and an alkoxylated alkyl phenol, said dimer or trimer acid having been produced by the polymerization of an unsaturated aliphatic monocarboxylic acid having between 16 and 18 carbon atoms.

3. A composition according to claim 2 wherein the tertiary alkyl primary amine has a carbon atom content of 12 to 22 carbon atoms.

4. A composition according to claim 3 wherein the tertiary alkyl primary amine is present in an amount of from about 50 to 100 parts by weight.

5. A composition according to claim 2 wherein the polyester is a mono-ethoxylated alkyl phenol, di-isodecyl ester of the trimer of linoleic acid, the ethoxylated alkyl phenol having an alkyl group of 8 or 9 carbon atoms and an average of about 3 ethylene oxide units.

6. A composition according to claim 2 wherein the formula of component (2), n is 3 to 10, x is 1, y is 2 and Z is a hydrocarbon acid residue having about or an average number of 51 carbon atoms.

7. A composition according to claim 6 wherein n is 3.

8. A composition according to claim 2 wherein com ponent (1) is present in an amount of about 50 to about 100 parts by weight, component (2) is present in an amount of about 10 to about 50 parts by weight, and component (3) is present in an amount of about 200 to about 400 parts by weight.

9. A composition according to claim 1 wherein the mixed polyester has the general formula:

where Z is a saturated or unsaturated hydrocarbon residue having 34 to 51 carbon atoms and is the residue of a dimer or trimer acid, or mixture thereof;

and n is an average number of from about 1 to 20 and more preferably from about 1 to 4;

in the case of the mixed polyester derived from a trimer acid, p is 1 or 2 and q is 1 or 2, the sum of p and q being 3;

R is an alkyl group containing 4 to 12 carbon atoms,

more preferably 8 or 9 carbon atoms;

R is H or an alkyl group containing 4 to 12 carbon atoms, more preferably H;

10. An improved detergent motor fuel composition comprising (a) a major proportion of a hydrocarbon base fuel boiling in the gasoline boiling or distillation range and (b) about 125 to about 1000 p.p.m. of the additive composition of claim 2.

11. An improved detergent motor fuel composition comprising (A) a major proportion of a hydrocarbon base fuel boiling in the gasoline boiling or distillation range and (B) about 15 0 to about 750 p.p.m. of the multifunctional additive composition of claim 2.

12. A detergent additive composition suitable for addition to gasoline comprising a mixture of (1) about to about 250 parts by weight of a tertiary alkyl primary amine having a branched backbone and a total of 6 to 24 carbon atoms; and

(2) about 100 to about 650 parts by weight of a mixed polyester of the formula wherein n is an average number of from about 1 to 20, and more preferably, from about 1 to about 4; and

in the case of the mixed polyester derived from a trimer acid p is l or 2 and q is 1 or 2, the sum of p and q being 3; and

in the case of the mixed ester derived from a dimer acid, both p and q are each 1;

R is an alkyl group containing 4 to 12 carbon atoms, more preferably 8 or 9 carbon atoms;

R is H or an alkyl group containing 4 to 12 carbon atoms, more preferably H;

R is an alkyl group containing 1 to 24 carbon atoms which may be straight or branched chain; and

Z is a saturated or unsaturated hydrocarbon residue having about 34 to about 51 carbon atoms, said residue being the residue of the dimer or trimer of linoleic acid, or mixture of dimers and trimers of said linoleic acid.

13. A composition according to claim 12 wherein (l) is present in an amount of about 50 to about 100 parts by weight and (2) is present in an amount of about 200 to about 400 parts by weight.

14. A composition according to claim 12 wherein (1) is a tertiary alkyl primary amine having a carbon atom content of 18 to 22 carbon atoms, and wherein (2) is the diisodecyl mono-octylphenoxypolyethoxyethanol, containing 3 moles of ethylene oxide, ester of the trimer of linoleic acid.

15. An improved detergent motor fuel composition comprising (A) a major proportion of a hydrocarbon base fuel boiling in the gasoline or distillation range and (B) about 120 to 900 p.p.m. of the additive composition of claim 12.

16. As a novel composition of matter a mixed polyester 0f the formula 16 wherein n is an average number of from about 1 to 20, and

more preferably, from about 1 to about 4; and

in the case of the mixed polyester derived from a trimer acid p is 1 or 2 and q is 1 or 2, the sum of p and q being 3; and

R is an alkyl group containing 4 to 12 carbon atoms,

more preferably 8 or 9 carbon atoms;

R is H or an alkyl group containing 4 to 12 carbon atoms, more preferably H;

17. A composition comprising (A) a major amount of a hydrocarbon base fuel boiling in the gasoline range and (B) a minor amount of about to about 650 p.p.m. of the mixed polyester of claim 16.

18. A composition according to claim 17 wherein the mixed polyester is the diisodecyl mono-octylphenoxypolyethoxyethanol, containing an average of 3 moles of ethylene oxide, ester of the trimer of linoleic acid.

19. A multi-functional additive composition suitable for addition to distillate hydrocarbon fuels having a major proportion of a hydrocarbon base fuel distilling within the gasoline distillation range, the additive composition comprising a mixture of (1) about 20 to about 250 parts by weight of a tertiary alkyl primary amine having a branched backbone and a total of 6 to 24 carbon atoms; and

(2) about 100 to 650 parts by weight of an adipic acid ester comprising a C -C alkyl/C to C alkyl phenoxy polyethoxyethanol, containing 1 to 20 moles of ethylene oxide, ester of adipic acid.

20. A multi-functional additive composition according to claim 19 suitable for addition to gasoline, said additive composition comprising a mixture of 1) and (2) and wherein (2) is the mono-isodecyl, mono-octyl phenoxy polyethoxyethanol, containing 3 moles of ethylene oxide, ester of adipic acid.

21. Composition according to claim 19 wherein the composition is used in gasoline at a concentration of about to 900 p.p.m.

22. An improved detergent motor fuel composition comprising (a) a major amount of a hydrocarbon base fuel boiling in the gasoline boiling or distillation range and (b) about 100 to about 650 p.p.m. of the mono-isodecyl, mono-octyl phenoxy polyethoxyethanol, containing about 3 moles of ethylene oxide, ester of adipic acid.

23. Composition according to claim 19 wherein (2) is the mono-isodecyl mono-octyl phenoxy polyethoxyethanol, containing about 5 moles of ethylene oxide, ester of adipic acid.

24. A multi-functional additive composition suitable for addition to distillate hydrocarbon fuels having a major proportion of a hydrocarbon base fuel distilling within the gasoline distillation range, the additive composition comprising a mixture of (1) about 20 to about 250 parts by weight of a tertiary alkyl primary amine having a branched backbone and a total of 6 to 24 carbon atoms;

(2) about 5 to 100 parts by weight of a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of trimer or dimer acid;

(3) about 100 to 650 parts by weight of a diester prepared from the reaction of adipic acid and a mixture of an aliphatic alcohol having from about 1 to 24 carbon atoms and an alkoxylated alkyl phenol.

25. A composition according to claim 24 wherein (3) is the mono-isodecyl, mono-octyl phenoxy polyethoxy- 17 ethanol adipate, with an average of 3 moles of ethylene oxide.

26. A composition according to claim 24 wherein (3) is the mono-isodecyl, mono-octyl phenoxyethanol adipate, with an average of moles of ethylene oxide.

27. A composition according to claim 24 wherein (1) is a tertiary alkyl primary amine having a carbon atom content of about 18 to 22 carbon atoms, (2) is the monooctylphenoxypolyethoxyethanol, containing about 3 moles of ethylene oxide, ester diammonium carboxylate salt of the trimer of linoleic acid and wherein (3) is the mono isodecyl, mono-octylphenoxypolyethoxyethanol adipate, with an average of 3 moles of ethylene oxide.

28. A composition according to claim 24 wherein (l) is a tertiary alkyl primary amine having a carbon atom content of about 18 to 22 carbon atoms, (2) is the monooctylphenoxypolyethoxyethanol, containing about 3 moles of ethylene oxide, ester diammonium carboxylate salt tertiary alkyl primary amine having a carbon atom content of about 18 to 22 carbon atoms of the trimer of linoleic acid and wherein (3) is the mono-isodecyl, monooctyl phenoxyethanol adipate, with an average of 5 moles of ethylene oxide.

29. An improved detergent motor fuel composition comprising (a) a major amount of a hydrocarbon base fuel boiling in the gasoline boiling or distillation range and (b) about 100 to about 650 p.p.m. of an ester, said ester comprising a C C alkyl/C to C alkyl phenoxy polyethoxyethanol, containing 1 to 20 moles of ethylene oxide, ester of adipic acid.

References Cited UNITED STATES PATENTS 1,692,784 11/1928 Orelup et a1 4466 2,049,062 7/1936 Howard 4462 X 2,718,503 '9/1955 Rocchini 44-71 X 2,758,086 8/1956 Stuart et a1. 4466 X 2,830,021 4/195'8 Smith et a1. 4471 X 2,922,706 1/ 1960 Durr, Jr. et a1. 4458 3,231,348 1/1966 Lindstrom et al. 4472 3,399,982 9/1968 Kautsky 4469 3,438,757 4/ 1969 Honnen et al. 4458 3,574,574 4/1971 Moore 4458 OTHER REFERENCES Rohm & Haas Brochure: t-Alkyl Primary Amines.

DANIEL E. WY MAN, Primary Examiner Y. H. SMITH, Assistant Examiner US. Cl. X.R. 4466, 71, 72