US 3923474 A
Gasoline fuel compositions containing a dual additive comprising a composition having the general formula R-NHCH2CH2CH2NHCO-R' is improved by incorporation therewith of a second additive having the general formula R''OCH2CH2CH2NHCH2CH2-CH2NHCOR' in which R is an aliphatic hydrocarbon radical having 10-20 carbon atoms; R' is an aliphatic hydrocarbon radical having 9-19 carbon atoms and R'' is an aliphatic hydrocarbon radical having 10-15 carbon atoms. The carburization systems of internal combustion engines operating on gasolines containing these additives remain low in harmful deposits of varnish scale which normally results from untreated fuel.
Description (OCR text may contain errors)
United States Patent 1 Yount 1 1 Dec.2, 1975  Inventor: Joseph B. Yount, Newark, Del.
 Assignee: ICI United States Inc., Wilmington,
 Filed: Nov. 11,1974
 Appl. No.: 522,709
 US. Cl. 44/66; 44/DIG. 1; 44/7]  Int. Cl. COIL 1/22  Field of Search 44/66, 71, 72
 References Cited UNITED STATES PATENTS 3,035,907 5/1962 Halter et al 44/71 3.468.639 9/1969 Lindstrom et al. 44/71 3,655,351 4/1972 Jamieson 44/66 3,681,038 8/1972 Gaydasch 44/71 3,765,850 lO/l973 Badin et al 44/71 Primary Examiner-Daniel E. Wyman Assistant E.\'aminerY. Harris Smith ABSTRACT Gasoline fuel compositions containing a dual additive comprising a composition having the general formula R-NHCH CH CH NHCOR is improved by incorporation therewith of a second additive having the general formula R"OCH CH CH NHCH C- H CH NHCOR in which R is an aliphatic hydrocarbon radical having 10-20 carbon atoms; R' is an aliphatic hydrocarbon radical having 9-19 carbon atoms and R" is an aliphatic hydrocarbon radical having 10-l5 carbon atoms. The carburization systems of internal combustion engines operating on gasolines containing these additives remain low in harmful deposits of varnish scale which normally results from untreated fuel.
4 Claims, N0 [Drawings ALKYLDIAMINOAMIDS OF FATTY ACIDS AS GASOLINE ADDITIVES This invention relates to an improved gasoline composition for internal combustion engines. Particularly, the invention relates to the discovery that the incorporation of a combination of additives in gasoline produces a lower formation of deposits in the upper portion of the induction system, including the carburetor bore area, than that found for gasolines containing a single additive selected from the combination.
Modern internal combustion engine design is undergoing important changes to meet certain standards concerning engine and exhaust gas emissions. A major change in the engine design presently being widely adopted is the feeding of blow-by gasses from the crank case out of the engine into the intake air supply to the carburetor rather than venting these gases to the atmosphere as in the past. These blow-by gases contain substantial amounts of deposit forming substances, and it has been observed that some of the substances in the blow-by gases form deposits in and around the throttle plate area of the carburetor. These deposits restrict the flow of air through the carburetor and idle in low speed so that an over-rich fuel mixture results. This condition produces rough idling, engine stalling, and also results in excessive hydrocarbon exhaust emissions to the atmosphere. In addition to overcoming the foregoing problem, it is felt that the incorporation of these additives will provide corrosion inhibition and anti-icing.
The use of amine derivatives such as amides, imides, amines, imidazolines, triazines, pyrimidines, polyamids, low molecular weight polymers, organophosphates, and amine phosphates as well as ordinary ammonium salts of such materials are well known fuel additives which in part increase the operating efficiency of the carburetor system. Representative of US. patents teaching the use of alkyl substituted diaminoamid derivatives are US. Pat. Nos. 2,805,135; 2,922,707; 2,996,365; 3,251,853; 3,313,607; 3,589,877; 3,653,853; 3,704,109; 3,707,361; and 3,813,228.
The deposits which are formed in the carburetor system may be due in part to the make up of the motor fuel which is used; but it is believed that deposits are due to a greater extent, at least to foreign matter introduced into the carburetor, through the air intake system since air cleaners are not completely effective. Major contributors to air contamination are crank case vapors formed from the crank case, exhaust vapors, dust, smoke and the like. The problem with respect to carburetor deposits resulting from air contamination is further aggravated by the positive crank case ventilating system which is employed in many of the recently introduced automotic engines. In engines equipped with a positive crank case ventilating system, fumes and vapors from the crank case are passed through a metering valve into the air intake system of the engine. While this system helps to cut down on the fumes escaping to the atmosphere, the system adds the problem of deposits formed in the carburetor. Deposits are encountered not only in the carburetor, but also in the components of the metering valve employed in connection with the positive crank case ventilating system.
Another source of carburetion deposit is derived from the composition and history of the fuel. Trace contaminants in the fuel which result from its process of manufacture, storage and geographical origin are thought to be responsible for the high molecular varnishes and gums which are deposited over long periods of use.
Many commercially available gasolines and fuel oils contain additives which are used to either keep the intake system free from additional deposits (stay clean) and/or to clean off existing deposits (clean up) and thereafter keep the system clean. Clean up detergency requires much higher dosages of additives than are needed for stay clean detergency.
It is a major objective of this invention to provide a fuel such as gasoline which contains a minor amount of an additive combination which performs as a detergent to keep the intake system of an internal combustion engine free from additional deposits or to clean off existing deposits and thereafter keep the system relatively clean.
Another objective of the invention is to provide gasoline compositions comprising hydrocarbons boiling in the gasoline boiling range with a combination of detergents comprising alkoxy substituted derivatives of propylamides and alkylamine substituted derivatives of propylamides.
These and other objectives of the invention are accomplished by introducing into a hydrocarbon fuel a by-component detergent composition comprising a blend of monoamides A and B having the general struc- The first component (A) of the blend is a propylene diamine derivative wherein R and R is a C C fatty aliphatic hydrocarbon radical.
The second component (B) of the blend is a propylene diamine derivative wherein R is a C C fatty aliphatic hydrocarbon radical and R is a hydrocarbon radical having 10-15 carbon atoms.
The first detergent component referred to above can be made by reacting a monoalkyl N-substituted propylenediamine derivative with mono carboxcylic acids to form the N,N amide derivative. Specific examples of such N-aliphatic substituted propylene diamines are N-nonyl propylenediamine, N-tetradecylpropylenediamine, N-tetradecenlpropylenediamine, N-hexadecylpropylenediamine, N-eicosylpropylenediamine, N-cicosenylpropylcnediamine, N- docosylpropylenediamine, and N-docosenylpropylenediamine. Preferably those in which the aliphatic N- substituent is an alkyl or alkenyl group containing at least 12 and preferably 16-20 carbon atoms are considered to be most effective. Examples of the N-aliphatic substituted propylenediamines which are considered to form especially effective materials are the N-dodecyl, N-hexadecyl, propylenediamines, and especially the 18 carbon alkyl--, alkenyland the alkadienyl-substituted propylenediamines such as the N- octadecyl-, N-octadecenyl, and N-octadecadienyl propylenediamine. Mixtures of N-aliphatic substituted propylenediamine such as are formed when the aliphatic N- substituent is derived from mixed fatty acids obtained from naturally occuring fats and oils, form highly effective materials for use in the composition of the invention. In such instances the aliphatic N- substituent is a straight chain, monovalent and hydrocarbon radical containing from 10-20 carbon atoms. Examples of such mixtures of N-aliphatic substituted propylenediamines are N-tallow propylenediamine,
propylenediamine 3 propylenediamine where the respective N- substituents are mixed alkyl and unsaturated alkyl groups derived from animal tallow (C -C fatty acids, soybean (C -C fatty acids and coconut (C -C fatty acids. These N- aliphatic substituted propylenediamines can be prepared by converting commerially available fatty acids to their corresponding nitriles and thereafter reducing the nitriles with hydrogen to form the primary amine. This primary amine is then treated with acrylonitrile to obtain the corresponding cyanopropyl aliphatic amine which is then hydrogenated to obtain the alkyl substituted propylenediamine. Exemplary commercially available N-aliphatic substituted propylenediamines are Duomeen-T and Duomeen-S (products of Armour and Company.) which have gen- N-octadecylpropylenediaminemonooleate N- octadecylpropylenediamin estearate, N-tallow propylenediaminemonoole ate, 'N-soya' propylenediaminemonooleate, and N-coco propylenediaminestearate. I y
A preferred detergent derivative representative of the above described is prepared by reacting 1 mol of oleic acid which is commercially available and sold under the trademark ACINTOL No. l with 1 mol of N-tallow propylenediamine sold under the trademark KEMAMINE D-974 at a temperature ranging between 50 and 105C. until the removal of 1 mol of water is accomplished. v
The second detergent component of the blend is made byreacting compounds having the general forwherein R" is an aliphatic hydrocarbon radical having -15 carbon atoms with a monocarboxylic acid having 10-20 carbon atoms selected from those described above. Such starting-materials are readily commercially available and can be reacted'together at temperatures up to about 105C. in equal molar quantities to eliminate 11 mol of water. A preferred material is prepared by reacting 1 mol of oleic acid (Acintol FA. No. l) with N-tridecyloxypropylethylenediamine ('Adogen 583). t
The detergent compositions of the invention can also be made by simultaneously reacting in one vessel equal molar portions'of the N-a'lkyl substituted propylenediamine compounds along with the N-alkoxypropylpropylenediamine derivatives with 2 equivalents of the monocarboxylic acid to form a mixture of the detergent combination. In making the combined detergents, it is preferred that the A and B diamine derivatives be present in the final combination in weight ratios of 1:9 to 9:1. Of course, the individually prepared detergents can be mixed together in these weight ratios for addiis present in concentrations ranging from 0003-015 4 percent by weight of the fuel. Of course each individual detergent can be added directly to the gasoline in the appropriate weight ratios and concentrations.
The advantages offered by the invention can be more readily understood by reference to the following examples which are designed to indicate the improved results offered by the addition of the second detergent component to the first. Unexpectedly it was found that the combination of the detergents produced results superior to that found for the exclusive use'of either one in similar fuels carbonized under similar conditions.
EXAMPLE 1 In a test device called an Induction System Deposit (ISD) bench apparatus, the performance of the detergent blends was measured in a gasoline designed specifically for lube oil engine tests. The bench test apparatus was designed specifically for military and commercial organizations and is described in detail in a publication entitled A Bench Technique for Evaluating the Induction System Deposit Tendencies of Motor Gasolines by A. A. Johnston and E. Dimitroff, SAE Transactions, Vol. (1967), paper No. 660783. The test operates by impinging a stream of air propelled fuel onto a preweighed heated deposit-collecting tube made of aluminum tubing. As the gasoline impinges on the tube, thin film, flash evaporation occurs and varying amounts of deposits remain, depending upon the fuels deposition tendencies.
To demonstrate this synergistic effect of one component upon the otherfor increasing their individual effectiveness as an antideposition detergent, varying concentrations of .-N-tallow propylenediaminemonooleate, designated Component A, and N-(3-tridecyoxypropyl)-propylenediaminemonooleate, designated Component B, were run in the above-described bench test in gasoline having the analysis described in Table I, In Table II, the results of the bench test employing a blend of the detergents indicate a deposition rate substantially lower than that found for either component additive used singly. 1
EXAMPLE 2 The effectiveness of the additive blend is more realistically demonstrated by comparing their effectiveness as a detergent in maintaining valves and carburetor cleanliness in a standard operating V-8 automobile engine modified slightly such that two gasolines may be compared simultaneously. Removable aluminum sleeves are placed in the throttle bores of two test carburetors and the weight of deposit accumulated on these sleeves is a measure of fuel additive performance. The results of a 24 hr. test are indicated in Table III using low lead gas as described in Table I. The results obtained in Table III for the performance test suggests that Additive A is improved by a factor of about 10 percent whileAdditive B is improved by a factor of 20 percent.
TABLE'I Test Gasoline Characteristics Fuel M808 Low Lead .Gravity, API 59.7 60.0
Tetraethyl Lead 3.08g/gallon 0.50g/gallon RVP- 8.4 9.8
Composition 7 7r Aromatics 23.1 23.0
7: Olefins 20.0 6.1
% saturates 56.9 70.9
TABLE l-continued Test Gasoline Characteristics lSD bench test data showing the deposit weights (mg) obtained for the individual amides and amide bination consisting of at least one compound having the general formula A: RNHCl-l Cl-l CH NHCoR and at least one compound of the general formula B: R)\ 'OCH Cl-l Cl-l Nl-lCH CH Cl-l -NHCOR, wherein R is an aliphatic hydrocarbon radical having -20 carbon atoms; R is an aliphatic hydrocarbon radical having 9-19 carbon atoms; and R" is an aliphatic hydrocarbon radical having 10-15 carbon atoms in said formulas.
2. A gasoline fuel of claim 1 wherein the weight ratio of additive formula A to additive formula B ranges from 1:9 to 9:1.
blend. Detergent Stay Clean Clean Up" Additive Fuel at l6ptb at lOOptb at 16ptb at l00ptb A* MSO8+O.15% 6.1*** 3.3*** 19.6*** 1.8***
used oil B** MSO8+0.15% 126.96.36.199 0.30.3 3.75.3 188.8.131.52
used oil 20%Az807zB MSO8-HJ.15% 0.2.0.1 0.2.0.3
used oil %A;70%B MSO8+0.15% 0. 1,0.2 0.1.0.2
used oil None MSO8+0.15% 7.5 to 9.0 21 w 24 used oil ptb is pounds of additive per thousand barrels of fuel *A is Acintol F.A. No. 1 amide of Kcmaminc D-974 **B is Acintol FA. No. 1 amide of Adogen 583 *Avg. of two determinations 3. A gasoline fuel of claim 1 wherein the additive of TABLE III formula A is N-tallow propylenediaminemonooleate and the additive of formula B is N-( 3-tr1decyloxy- Comparative engine test data for amides and amide blend/rum propyl )propylenedraminemonooleate. Active Carburetor 4. A dual additive comprising the simultaneous reac- Cmpound ptb Fuel Dams Reducm" tion product of a monocarboxylic having 10-20 carbon 28 k k 32 atoms with a mixture of an N-alkyl substituted 15 Ptb A W propylenediamine derivative wherein said alkyl substit- 35 ptb B 50 Low Lead 36 uent is an aliphatic group having 10-20 carbon atoms,
What is claimed is: 1. A gasoline fuel composition comprising from 0.003 to 0.15 percent by weight of a dual additive comwith N-( 3-tridecyloxyp ropyl) propylenediamine such that the molar ratio of the monocarboxylic acid present in the reaction mix toeach of the propylenediamine derivatives is 2:1.