US3746520A

US3746520A - Di(hydrocarbon substituted)polyamine fuel detergents

Info

Publication number: US3746520A
Application number: US00095962A
Authority: US
Inventors: E Mehmedbasich
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1970-12-07
Filing date: 1970-12-07
Publication date: 1973-07-17
Anticipated expiration: 1990-07-17

Abstract

BIS(OIL SOLUBILIZING HYDROCARBON) SUBSTITUTED ALKYLENE POLYAMINES HAVING FROM 2 TO 5 AMINE NITROGEN ATOMS, WHEREIN THE OIL SOLUBILIZING HYDROCARBON GROUPS ARE OF FROM 25 TO 50 CARBON ATOMS, ARE EFFECTIVE FUEL DETERGENTS HAVING GOOD WATER TOLERANCE.

Description

United States Patent 01 fies 3,746,520 Patented July 17, 1973 1970, Ser. No. 95,962

Int. Cl. C101 1/22 U.S. CI. 44-58 6 Claims ABSTRACT OF THE DISCLOSURE Bis(oil solubilizing hydrocarbon) substituted alkylene polyamines having from 2 to 5 amine nitrogen atoms, wherein the oil solubilizing hydrocarbon groups are of from 25 to 50 carbon atoms, are effective fuel detergents having good water tolerance.

This application is a streamlined continuation of Ser. No. 750,765, filed Aug. 7, 1968, now abandoned.

BACKGROUND OF THE INVENTION Field of the invention Fuel detergents have been used for a long time to maintain clean carburetors in gasoline internal combustion engines. Further efforts have been employed to obtain detergents which not only clean the carburetor but also clean the intake ports and valves. These detergents are referred to as having extended detergent action (EDA).

By cleaning the ports and valves, the engine operates more efiiciently. Thus, the useful life of the engine is extended before major repairs are required. The fuel is used more efficiently, reducing the amount of unburned fuel which is exhausted. More efficient use of fuel reduces the extent of pollution of the air.

Co-pending application Ser. No. 538,571, filed Mar. 30, 1966, now abandoned, discloses a wide variety of hydrocarbon substituted alkylene polyamines for use as fuel detergents. However, some improvement in water tolerance was found to be desirable.

Description of the prior art U.S. Pat. No. 3,275,554, patented Sept. 7, 1966, discloses a wide variety of hydrocarbon substituted alkylene polyamines for use as detergents in lubricating oils.

SUMMARY OF THE INVENTION Alkylene polyamines having from 2 to 5 amine nitrogen atoms and at least 70 percent of the alkylene polyamines being disubstituted with hydrocarbon solubilizing groups of from 25 to 50 carbon atoms are used as fuel detergents showing good'water tolerance.

DESCRIPTION OF THE PREFERRED Q EMBODIMENTS The compositions of the this invention will have at least 70 weight percent of a composition of the formula:

[HN .11] Ruin-1 ably branched, having not more than about 2 sites of allphatic unsaturation, e.g., ethylenic. Usually, R will be a branched chain aliphatic hydrocarbon group having at least one branch of about 1 to 4 carbon atoms per four atoms along the longest chain. Preferably, the branch is methyl.

Depending on the method of preparation, small amounts of chlorine may be present on the hydrocarbon group R. Usually, residual chlorine will be less than about 2 Weight percent.

The preferred alkylene polyamines are polyethylene polyamines, such as triethylene tetramine and tetraethylene pentamine. Equivalent to the alkylene polyamine are compositions which frequently are formed concurrently in the preparation of the alkylene polyamines, such as N- aminoethyl piperazine.

The compositions of this invention may be prepared in a variety of ways which insure that at least 70 Weight percent of the composition is disubstituted. The other materials present will ordinarily be mono-substituted alkylene polyamines and trior higher substituted alkylene polyamines.

To insure that the predominant product is the disubstituted compound, the compositions may be conveniently prepared stepwise. That is, the alkylene polyamine is reacted with alkenyl chloride in the presence of excess of alkylene polyamine to prepare the mono-substituted product. The excess amine is then removed and an additional stoichiornetric equivalent of alkenyl halide is added to provide the disubstituted prod-uct. Of course, the same or different alkenyl groups may be used, as long as they are within the indicated carbon range.

Usually, the amine reactants will not be individual compounds but mixtures of compounds having an average composition. Ordinarily, these compositions have a predominant compound present with minor amounts of other materials to provide the average composition indicated. When polymers are used as the hydrocarbon substituent, the average molecular weight is indicated and usually at least 70 weight percent of the polymer will be within plus or minus 20 weight percent of the average composition indicated.

The preparation of the compositions is carried out in a manner analogous to that described in co-pending application Ser. No. 538,571. The aliphatic halide, preferably alkenyl chloride, is combined with the desired alkylene polyamine, either neat or in the presence of an alkanol of from 3 to 6 carbon atoms, aromatic hydrocarbon or mixtures thereof.

Elevated temperatures are ordinarily used in the range of about 50 to 150 C., more usually from about to C. The time for the reaction will generally vary from 2 to 12 hrs.

The detergent will generally be employed in a hydrocarbon base liquid fuel. The detergent additive may be formulated as a concentrate, using a suitable hydrocarbon or alcohol solvent boiling in the range of about to 400 F. Preferably, an aromatic hydrocarbon solvent is used, such as benzene, toluene, xylene or higher boiling aromatics or aromatic thinners. Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol and the like, in combination with hydrocarbon solvents are also suitable for use with the detergent additive. In the concentrate, the amount of the additives will be ordinarily at least 10 percent by weight and generally not exceed 70 percent by Weight.

The amount of the detergent used in the fuel will generally be from about 100 to 1,000 ppm.

-In gasoline fuels, other fuel additives may also be included such as antiknock agents, e.g., tetramethyl lead or tetraethyl lead. Also included may be lead scavengers such as aryl halides, e.g., dichlorobenzene or alkyl halides, e.g., ethylene dibromide.

A nonvolatile lubricating mineral oil, e.g., petroleum spray oil, particularly a refined naphthenic lubricating oil having a viscosity at 100 F. of 1,000 to 2,000 SUS, is a suitable additive for the gasoline compositions used with the detergents of this invention and its use is preferred. These oils are believed to act as a carrier for the detergent and assist in removing and preventing deposits. They are employed in amounts from about 0.05 to 0.5 percent by volume based on the final gasoline composition.

EXAMPLES The following examples are offered by way of illustration and not by way of limitation.

EXAMPLE I Into a reaction vessel was charged 454 g. (0.75 mole) of polyisobutenyl chloride (75 weight percent active; polyisobutenyl of about 570 average molecular weight), 567 g. (3 moles) of tetraethylene pentamine and 200 ml. of xylene and the mixture refluxed at 150 C. for 12 hrs. The product was then repeatedly washed with water and isopropyl alcohol and the water azeotroped off. The solution was analyzed, having 4.03 weight percent nitrogen indicating 43.7 weight percent active material.

The above product (550 g.; 0.32 mole) was combined with 319 g. (0.40 mole) of polyisobutenyl chloride (the same as described above) diluted with xylene and heated at 150 C. for 12 hrs. The product was then washed with 0.4 molar sodium hydroxide, followed by repeated washes with water and isopropyl alcohol. The water was then azeotroped off. The solution was analyzed for nitrogen (percent): N, 1.83, 1.83; theoretical N, 5.27. The solution had, therefore, 34.72 percent active material.

EXAMPLE II Mono-substituted polyisobutenyl triethylene tetramine was prepared as described in Example I. The solution used was 60.9 percent active.

Into a reaction vessel was charged 880 g. (0.75 mole) of polyisobutenyl triethylene tetramine (polyisobutenyl of about 570 average molecular weight) and 757 g. (0.94 mole) of polyisobutenyl chloride (75 percent active; polyisobutenyl of about 570 average molecular weight), the mixture purged with nitrogen and volatile materials removed. Xylene was then added and the temperature raised to reflux (150 C.) and maintained for 12 hrs.

The reaction solution was then washed with 300 ml. of water containing about one gram of sodium hydroxide, followed by repeated washings with water and isopropyl alcohol. Water was then azeotroped off and the product filtered through diatomaceous earth.

The product was analyzed for nitrogen (percent): N, 1.74, 1.77; theoretical N, 4.37. The final solution, therefore, contained 42 weight percent active material.

To demonstrate the effectiveness of the disubstituted alkylene polyamines of this invention as fuel detergents, a base fuel having a boiling range of 102 to 414 F.; 58 percent parafiins, 22 percent aromatics and 20 percent olefins (by volume) and a vapor pressure (Reid) of 7.4 was employed. The additive was added at a concentration of 250 p.p.m.

The test is carried out with a single cylinder CFR engine equipped with throttle. The operating conditions for the test are: jacket temperature, 212 F.; oil temperature, 150-180 -F.; intake air temperature, 95 F.; ignition timing, 15 BTC; intake manifold vacuum, 15 in. Hg; fuel/air ratio, 0.07; speed, 1,800 r.p.m. The duration of the test is 12 hrs.

The intake valve is weighed at the end of the test, cleaned and tared. The intake port is washed with hexane then fitted with a receiver, and the deposits removed mechanically with the aid of chloroform. The chloroweighed.

The following table indicates the results:

TABLE I Port Valve deposit, deposit,

Additive (250 p.p.m.) mg. mg.

Base fuel 150 161 Example:

1 Contains 19.9 g. of petroleum spray oil per 2.89 g. of detergent.

To demonstrate the excellent water tolerance of the detergents employed in this invention, the test procedure of ASTM D 1049-67 was employed. The following table indicates the results obtained after 10 minutes and 45 minutes, using distilled water. The haze rating is a rating based on a rating of 1 to 5; the cylinder is observed against a flat vertical plate of diffused white light. Horizontal black strips are afiixed to the surface of the plate. A flask is placed in front of the plate and the haze rating determined by the degree of difluseness of the black strips. A sharp appearance is rated as 1; an almost totally obscured strip is rated as 5.

The excellent water tolerance is evidenced by the rapid rate at which the water and fuel layer separate and the hazevalue drops.

Both rapid separation and reduction in haze are important in evaluating water tolerance. For, even in the situation where the water separates quickly, if a small residual amount of water remains dispersed in the fuel giving it a hazy appearance, the fuel will be unacceptable. Frequently, haze and water separation do not directly correlate. Therefore, it is important that with the compositions of this invention, great improvement from the initial ratings in both the haze rating and separation is rapidly achieved.

Furthermore, the compositions of this invention show excellent extended detergent action in a test devised for evaluating fuel detergents.

I claim:

1. A fuel composition comprising a major amount of a liquid hydrocarbon fuel and from p.p.m. to 1,000 p.p.m. of a detergent composition having at least about 70 weight percent of a composition of the formula:

[H1 1 (U1 1) nHRzHn-l] wherein U is alkylene of from 2 to 6 carbon atoms, n is an integer of from 1 to 4 and R is a hydrocarbon fuel solubilizing group of from 25 to 50 carbon atoms, the remainder of said detergent composition being monoand trior higher-substituted alkylene polyamines, and wherein said detergent composition is prepared by reacting an alkenyl chloride with an excess of alkylene polyamine and the reaction product is then reacted with about a stoichiometric equivalent amount of alkenyl chloride.

2. A fuel composition according to claim 1 wherein in said detergent composition U is alkylene of from 2 to 3 carbon atoms; n is an integer of from 2 to 3 and R is of from 30 to 45 carbon atoms.

3. A fuel composition according to claim 1 wherein in said detergent composition R is polypropenyl or polyisobutenyl.

4. A fuel composition according to claim 1 having from 0.05 to 0.5 percent by volume of a nonvolatile lubricating mineral oil.

5. A fuel composition concentrate having from 10 to 70 Weight percent of a composition of the formula:

[HI I nIdiom-1 wherein U is alkylene of from 2 to 6 carbon atoms, n is an integer of from 1 to 4 and R is a hydrocarbon fuel solubilizing group of from 25 to 50 carbon atoms, the remainder of said detergent composition being monoand trior higher-substituted alkylene polyamines, and where- 10 6. A composition according to claim 5, wherein in said detergent composition, R is polypropenyl or polyisobutenyl and U is alkylene of from 2 to 3 carbon atoms.

References Cited UNITED STATES PATENTS 3,438,757 4/1969 Honnen et al. 44-72 X 3,565,804 2/1971 Honnen et al. 4472 X 3,574,576 4/1971 Honnen et al. 4472 DANIEL E. WYMAN, Primary Examiner W. J. SHINE, Assistant Examiner US. Cl. X..R.

3 3 7 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Petent: No. 3,74 ,520 Dated July 17', 1973 Inventor(s) ENVE R MEHMEDBASICH It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 4, line 13, "ASTM D-l049" should read -ASTM D 1094 I I I Claim 1, [HN (UN) HR H should r ead -f (HN (UN) H) R H Signed and sealed thisBth day of March 19m.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. C, MARSHALL DANN I Attesting offic$r Commissioner of Patents