US3126261A - Gasoline compositions - Google Patents

Description

United States Patent O-fiice 3, ,2 1 Patented Mar. 24, 1964 3,126,261 GASOLINE COMPOSITIONS Patrick J. Friel, Broomall, Pa., assignor to Sun Oil Company, Philadelphia, Pa., a corporation of New Jersey No Drawing. Filed Mar. 28, 1958, Ser. No. 724,517 4 Claims. (Cl. 44-69) This invention relates to novel gasoline compositions containing additives which suppress surface ignition and spark plug fouling in spark ignition internal combustion engines.

Surface ignition is the ignition, prior to normal ignition by the spark plug, of engine fuel by glowing or burning carbonaceous material which is deposited on engine combustion chamber surfaces. These carbonaceous deposits are derived from decomposition of the fuel and/ or lubricant used in the engine. Also contained in engine deposits are products resulting from decomposition of fuel or lubricant additives. The presence in engine deposits of decomposition products of organometallic anti-knock additives such as tetraethyl lead is especially deleterious since these products catalyze ignition of carbonaceous fuel and/ or lubricant decomposition products at low temperatures thereby greatly increasing surface ignition in an engine. Surface igintion is deleterious in that it causes loss of power, increased engine wear and increased engine fuel octane requirement necessary for knock-free performance. The octane requirement increase (O.R.I.) of an engine while operating on a particular fuel is indicative of the surface ignition promoting tendencies of that fuel.

Spark plug fouling is caused by the deposition on spark plugs of lead anti-knock additive decomposition products either which themselves conduct electricity, or which are reduced under combustion chamber conditions to products which conduct electricity. A build-up on the spark plugs of such products provides an alternate path for spark plug current and results in fouling or shorting out of the spark plugs.

Now, in accordance with the present invention, a dialkyl borino-phosphine or mixture of such compounds is added in minor amount to gasoline containing organo-lead anti-knock additives to suppress surface ignition and spark plug fouling.

In an embodiment of the invention, one or more dialkyl borino phosphine is incorporated in a gasoline containing an organo-lead anti-knock agent whereby spark plug fouling, O.R.I., and surface iginition are substantially suppressed.

Included in the novel gasoline compositions of the invention is a small amount, SlllfiClGll't to suppress engine O.R.I. surface ignition and spark plug fouling, of a dialkyl borino phosphine or a mixture of such compounds. Dialkyl borino phosphines have the general formula:

Rn wherein R and R are alkyl radicals, i.e., saturated aliphatic hydrocarbon radicals. In accordance with the practice of this invention, the alkyl radicals, R and R can be the same or different, but each radical preferably contains not more than 6 carbon atoms in either straight or branched chain configuration. These alkyl radicals can also contain halogen substituents. Examples of dialkyl borino phosphines which can be employed as additives include dimethyl borino phosphine, diethyl borino phosphine, di-n-propyl borino phosphine, di-i-propyl borino phosphine, di-n-butyl borino phosphine, di-n-pentyl borino phosphine, di-n-hexyl borino phosphine, methylethyl borino phosphine, methyl-n-propyl borino phosphine, ethyl-n-butyl borino phosphine and the like. The

use of di-n-butyl borino phosphine is particularly preferred in the practice of this invention.

The dialkyl borino phosphines can be prepared by reacting a trialkyl borine with phosphorus trichloride to produce the corersponding dialkyl borino chloride, generally a high boiling liquid. A solution of the latter product in solvents such as a mixture of benzene and triethylamine, when reacted with gaseous phosphine, yields the corresponding dialkyl borino phosphine. The latter compounds are generally high boiling liquids which are sufliciently soluble in gasoline hydrocarbons, within the range of concentrations contemplated by the instant inven tion, so as not to require the use of mutual solvents or dispersants. Where necessary, however, such mutual sol vents and dispersants can be employed in order to incorporate amounts of the additive in excess of its solubility in the leaded gasoline composition.

The novel gasoline compositions of the invention comprise mainly petroleum hydrocarbons boiling in the gasoline range of from about F. to about 440 F. at atmospheric pressure, and usually from about F. to about 400 F. Both automotive gasoline and aviation gasoline are within the scope of this invention. Aviation.

gasoline has a more closely specified atmospheric boiling range, generally extending from a minimum of about F. to a maximum of about 350 F.

The gasoline compositions of the invention also contain an anti-knock amount of an organo-lead anti-knock agent. Tetraethyl lead (TEL) is the most commonly used organo-lead anti-knock compound although other organo-lead compounds such as tetramethyl lead, tetraphenyl lead, tetraisopropyl lead, triethyl methyl lead, diethyl dimethyl lead and tetramethyl lead are sometimes used. Mixtures of these compounds can also be used. In automotive gasolines the organo-lead anti-knock compounds are used in amounts ranging from about 0.5 to 3.0 cc. of the compound per gallon of gasoline, while in aviation gasolines a greater amount can be used, viz., up to about 6.0 cc. per gallon. Along with the organolead anti-knock compound, various volatile halohydrocarbons are normally incorporated in the gasoline in lead scavenging amounts, i.e., in amounts theoretically calculated to convert the lead in the organo-lead compound to volatile compounds, viz., lead dihalides. Examples of such halohydrocarbon lead scavengers are: organobromides and -chlorides such as ethylene dibromide, ethylene dichloride, acetylene tetrabromide, hexachloropropylene and mixtures thereof; monoand polyhalopropanes, butanes and pentanes; polyhaloalkyl benzenes; and mixtures thereof with each other and the like. It is therefore to be clearly understood that the novel additives of this invention can be used in leaded gasoline compositions either with or without all such lead scavengers as are commonly employed, and in such amounts as may be required.

It is to be understood that all other gasoline additives commonly employed in the art such as, for example, anti-icing agents, scavengers, detergents, corrosion inhibitors, stabilizers, dyes and the like, can also be employed in the novel gasoline compositions of the invention containing an organo-lead anti-knock agent.

The novel additives of this invention, viz., the dialkyl borino phosphines, are added to the gasoline composition containing an organo-lead anti-knock additive in a small amount suflicient to suppress surface ignition, O.R.I., and spark plug fouling in subsequent engine operation. The amount of additive employed will normally depend upon the amount of organo-metallic anti-knock agent also present in the fuel composition. Generally, amounts of the additive, or mixture of additives, in the range of from about 0.005% to about 1.0% by weight 3 of the resulting gasoline composition, and preferably 0.01% to 0.50% give good results. On occasion, amounts outside of the above-cited ranges can be used.

In order to illustrate a specific embodiment of this invention, di-n-butyl borino phosphine is produced by reacting tri-n-butyl borine with phosphorus trichloride and subsequently reacting a solution of the di-n-butyl borino chloride in benzene and triethylamine with phosphine gas.

The benzene and triethylamine are removed by distil lation leaving a liquid product boiling above about 250 C. and consisting of di-n-butyl borino phosphine. The above-prepared additive is incorporated in a commercial high octane automotive gasoline in an amount equivalent to 0.01% by weight of the resulting gasoline composition. The commercial gasoline employed also contains 3 cc. per gallon of tetraethyl lead and the customary accompanying amount of halohydrocarbon lead scavengers. The resulting fuel composition has a Research octane number of 103.2 (ASTM-D908) and illustrates the novel gasoline compositions of the instant invention.

A standard Oldsmobile engine employing a commercially available high compression S.A.Ev No. W30 petroleum lubricating oil is used in evaluating the above novel gasoline composition. This engine has a compression ratio of 10:1 and an initial fuel Research octane number requirement (for knock-free performance) of 96. When the engine is operated according to a standard simulated high speed test procedure for a period of 95 hours on the novel gasoline composition of the invention, the final octane requirement is 98 ON, equivalent to an octane requirement increase (O.R.I.) of only 2 numbers. However, when the engine is operated according to the same procedure and for the same period of time on the identical leaded base gasoline, but without the additives of the invention, the O.R.I. is found to be 4 numbers. Thus it can be seen that employment of the novel gasoline compositions of this invention results in a substantial reduction in engine O.R.I. which, in turn, is indicative of a significant decrease in the surface ignition tendencies of the leaded base fuel.

Other fuel compositions within the scope of this invention, when employed as herein described, give substantially equivalent results.

The invention claimed is:

1. Spark ignition internal combustion engine fuel composition consisting essentially of mainly petroleum hydrocarbons boiling within the gasoline range; an anti-knock amount of an organo-lead anti-knock compound, and a small amount, sufiicient to suppress engine surface ignition and octane requirement increase of an additive material having the general formula:

R2 wherein R and R are alkyl radicals containing not more than 6 carbon atoms each.

2. Composition according to claim 1 wherein said organ-lead compound is tetraethyl lead.

3. Composition according to claim 2 wherein said additive material is di-n-butyl borino phosphine.

4. A gasoline containing an antiknock quantity of tetraalkyl lead and a small amount, sufficient to suppress preignition, of an organic boronand phosphorus-containing compound having the general formula:

wherein R and R are lower molecular weight alkyl radi cals.

References Cited in the file of this patent UNITED STATES PATENTS 2,257,194 Rosen Sept. 30, 1941 2,265,819 Rosen Dec. 9, 1941 2,368,866 Nygaard et al Feb. 6, 1945 2,710,251 Darling June 7, 1955 2,720,448 Arimoto Oct. 11, 1955 2,797,153 Bereslavsky June 25, 1957 2,818,417 Brown et al. Dec. 31, 1957 2,821,463 Scott et al. Ian. 28, 1958 FOREIGN PATENTS 795,067 Great Britain May 14, 1958 OTHER REFERENCES Chemical Society Journal (London), February 1953, The Reaction of Diborane With Alkyl Derivatives of Some Group V-B Elements, by Hewitt et al., pages 530 to 534.

Chemical Reviews, vol. 58, No. 1, February 1958, Stability Relationships Among Analogous Molecular Addition Compounds of Group III Elements, by Stone, pages 101 to 129.

Claims (1)

1. SPARK IGNITION INTERNAL COMBUSTION ENGINE FUEL COMPOSITION CONSISTING ESSENTIALLY OF MAINLY PETROLEUM HYDROCARBONS BOILING WITHIN THE GASOLINE RANGE; AND ANTI-KNOCK AMOUNT OF AN ORGANO-LEAD ANTI-KNOCK COMPOUND, AND A SMALL AMOUNT, SUFFICIENT TO SUPPRESS ENGINE SURFACE IGNITION AND OCTANE REQUIREMENT INCREASE OF AN ADDITIVE MATERIAL HAVING THE GENERAL FORMULA: R1-B(-R2)-PH2 WHEREIN R1 AND R2 ARE ALKYL RADICALS CONTAINING NOT MORE THAN 6 CARBON ATOMS EACH.