US3160592A - Engine operation and compositions therefor - Google Patents

Description

Dec. 8, 1964 J. E. BROWN ENGINE OPERATION AND COMPOSITIONS THEREFOR Filed Oct. 16, 1959 FIGURE I IN V EN TOR.

' JEROMEE BROWN United States Patent 3,16%,592 ENGENE @PERATIGN AND CGMPGdlTlGN THERAFQR Jerome E. Brown, Detroit, Mich assignor to Ethyl Corporation, New York, N.Y., a corporation of Virginia Filed Get. 16, 1959, Ser. No. 847,618 11 Claims. (Cl. 252-49.?)

This invention relates to a method of operating a spark ignition internal combustion engine which utilizes novel compositions of matter containing certain nonionic metal polycarbonyl compounds which enable an engine to give knock-free performance and which possess numerousbenefits in connection with improved combustion characteristics and the alleviation of modern day engine problems.

Concurrent with the development of the modern high eficiency, high compression ratio, internal combustion engine of the spark ignition type, it was necessary to develop fuels which would permit the knock-free operation required to utilize most effectively these advances in engine design. The approach to this problem has been in two directions. On the one hand, improvements in refining operations have been undertaken to provide hydrocarbon fuels, wherein the ingredients or mixtures thereof possess high antiknock quality. There exists, however, a limit, depending on a number of factors, beyond which the fuels cannot be econonncflly improved. 0n the other hand, additives have been provided for such fuels whereby a further increase in the antiknock quality of the mixture is produced.

The most successful antiknock additive from a practical standpoint has been tetraethyllead. From time to time, a number of other antiknock materials have been proposed, but none of them has attained commercial significance in this country.

It is an object of this invention to provide an improved method for operating an internal combustion engine. Another object is'to provide new compositions of matter. A more specific object is to provide new gasoline compositions. It is also an object of this invention to provide a gasoline containing certain metal polycarbonyl antiknock compounds or mixtures of such compounds which possess greatly reduced wear causing characteristics. A still further object is to provide gasoline suitable for use in high efiiciency, spark ignition internal combustion engines requiring a fuel of high antilmock quality. Still another object is to provide a lubricating oil which acts to reduce the octane requirement of an internal combustion engine. Among the other objects of this invention is the alleviation of engine problems including octane requirement increase, spark plug ionic manganese polycarbonyl compounds or mixtures of said manganese polycarbonyl compounds as antiknock agents.

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Thus, among the important compositions contemplated by the present invention are included a hydrocarbon fuel of the gasoline boiling range for use in spark ignition internal combustion engines containing a small amount of non-ionic manganese polycarbonyls of the type defined sufiicient to improve the antiknock properties of said hydrocarbon fuel. For most purposes this amount of manganese compound will range from about 0.01 gram to about 6 grams of manganese per gallon of fuel.

In a preferred embodiment of the invention the amount of manganese compound is regulated so as to be equivalent to from 0.2 gram to 4 grams of manganese per gallon. More specifically, the present invention contemplates a hydrocarbon of the gasoline boiling range for use in spark ignition internal combustion engines con taining substantially 1.77 grams of manganese in the form of a non-ionic manganese polycarbonyl of the type defined per gallon of fuel. Further compositions which are contemplated by the present invention include antiknock fluids which consist of organolead antiknock agents, usually alkyllead compounds such as tetraethyllead, together with non-ionic manganese polycarbonyls of the type defined. Also within the purview of the invention are gasolines containing mixtures of said organelead compounds and said manganese polycarbonyls. Both the fuels and the antiknock fiuids may contain additional ingredients such as halogenated hydrocarbon scavengers, phosphorus deposit modifying compositions, antioxidants such as alkylated phenols and the like. The present invention also embraces the process of obtaining improved operating characteristics. of a spark ignition internal combustion engine which comprises operating said engine on a fuel composition which consists of a hydrocarbon fuel of the gasoline boiling range containing a small amount of non-ionic manganese polycarbonyl sufiicient to improve the antiknock properties of said hydrocarbon fuel.

Among the manganese carbonyl compounds suitable for use in the present invention are those which have the empirical formula R Mn(CO) where R is an organic radical, x is l and y is 5. These compounds and their usefulness as antiknock agents are described in my copending application, Serial No. 683,759, now Patent Number 2,913,413, filed September 13, 1957, of which this application is a continuation-in-part. Application Serial No. 683,759 is in turn a continuation-in-part of my earlier copending application, Serial No. 645,828, now abandoned. R is most preferably a monovalent hydrocarbon radical, such as an alkyl or aryl radical, or a monovalent acyl radical. Examples of these compounds include methyl manganese pentacarbonyl, benzoyl manganese pentacarbonyl, phenyl manganese pentacarbonyl, acetyl manganese pentacarbonyl, and the like. These and other manganese polycarbonyl compounds exhibit extraordinary antiknock effect and other unexpected properties which render them of interest as commercial antiknock agents.

The relative size of the organic radical in the manganese carbonyl compounds, while not too important, is best limited to .thosehaving from 1 to about 20 carbon atoms, as it is found that these are best suited to the practice of this invention. Compounds having organic groups containing from 1 to 13 carbon atoms are preferred as these compounds are found to best combine the qualities of volatility and inductibility which are prerequisites to proper functioning as gasoline additives.

Compounds having the formula RMn(CO) where the 3 R represents an organic radical from the group consisting of organic hydrocarbon radicals and organic oxygen containing radicals, are conveniently prepared from manganese carbonyl in an ethersolution. Manganese carbonyl is first converted to an alkali metal salt such as the sodium salt by treating the solution with an alkali metal present by an alkali metal dispersion or amalgam.

The alkali metal salt is then reacted with an alkylating agent such as a dialkyl sulphate to form an alkyl manganese pentacarbonyl.- Alternatively, the alkali metal salt of manganese carbonyl is reacted with an acyl halide to form an acyl manganese pentacarbonyl compound. These acyl manganese pentacarbonyl compounds are converted to the corresponding lower alkyl or aryl manganese pentacarbonyl compounds by pyrolysis accornpanied by the loss of CO at elevated temperatures. Thus, phenyl manganese pentacarbonyl is conveniently produced by the pyrolysis of benzoyl manganese pentacarbonyl.

The lowest molecular weight compound having the formula RMn(CO) is methyl manganese pentacarbonyl which is a crystalline solid melting at about 95 C. and which is highly volatile and soluble in gasoline. Another compound of this class is benzoyl manganese pentacarbonyl, also a soluble crystalline solid, which melts at about 38 C. Propyl manganese pentacarbonyl and acetyl manganese pentacarbonyl are other representative members.

It is essential that the manganese polycarbonyl compounds-used in the practice of this invention be'nonionic in nature in order that they produce the desired efiect. For example, ionic manganese carbonyl compounds such as those having halogen bonded directly to manganese are not suiiiciently volatile to be readily inductible into the cylinders of a multi-cylinder engine using a manifold type intake valve. These compounds are unable to give the benefits attributable to non-ionic manganese polycarbonyl compounds.

An unexpected feature of this invention is that the nonionic manganese polycarbonyls are among the most efiective antiknock agents tested to date. This is particularly surprising when it is considered that manganese is located in the Periodic Table next to the element chromium. Chromium carbonyl exhibits a pro-knock effect when employed as a gasoline additive for use in a spark ignition internal combustion engine. 7

Even when a compound has exceptional antiknock activity, the chances of its becoming a useful product remain extremely remote. This is due to the fact that many other properties must be taken into consideration due to the excessive engine wear caused by their use. As a further example, many aromatic amines exhibit antiknock activity, but their use is not feasible due to the fact that they exude a particularly objectionable odor.

Therefore, to be commercially successful, an antiknock must possess many auxiliary properties in addition to outstanding antiknock activity. Any compound under con sideration must undergo extensive tests to insure that it meets the important secondary qualifications.

It has been found that the non-ionic manganese polycarbonyl compounds which are the subject of the present invention, possess all the requirements of a successful antiknock to a remarkable degree. That is, they not only exhibit outstanding antiknock effectiveness, but in addition have the properties (including volatility, gasoline solubility, lack of gum forming tendencies, minimization of engine deposits and engine wear and susceptibility to preparation from available materials) required of commercial additives.

The fuels and lubricants used in todays high compression automotive engines cause deposits to be formed during combustion. These deposits which are derived from the fuels and lubricating oils and the additives therein collect on essentialy all parts of the combustion chamber including the valves, the spark plugs and the cylinder Walls. The formation of these deposits leads to several problems such as octane requirement increase, deposit induced'ignition and spark plug fouling. These problems prevent maximum utilization of the potential of a fuel and limit the designer from providing engines which will accomplish this end.

Not only do the non-ionic manganese polycarbonyl compounds of this invention exhibit the properties required of a successful antiknock, but they also have valuable and unexpected auxiliary efiects on the operation of a spark ignition internal combustion engine. It has been found that these compounds when used either as fuel or lube oil additives, minimize octane requirement increase and deposit induced ignition and increase the spark plug life of the modern high compression spark ignition internal combustion engine.

An important embodiment of this invention is gasoline containing, in amounts sufiicient to improve the octane quality thereof, a' non-ionic manganese polycarbonyl compound which is soluble in the-gasoline. It has been found that non-ionic manganese polycarbonyl compounds are of outstanding effect as antiknock agents. The amount of the manganese polycarbonyl compound present in the compositions of this invention is regulated such that at least about 0.01 gram of manganese is present per gallon of the finished gasoline, and ordinarily up to about 6 grams of manganese per gallon is provided. In a preferred embodiment the amount of manganese polycarbonyl is regulated to provide from 0.2 gram to 4.0 grams of manganese per gallon of fuel.

The upper limit of beneficial use of the non-ionic manganese polycarbonyl compounds is, as a practical matter, limited due to the fact that at high concentrations the magnitude of the octane number benefit obtainable per unit weight of compound decreases to some extent. Thus, the most beneficial antiknock effect of the nonionic manganese polycarbonyl compound is realized' when these compounds are employed in concentrations such that there is from about 0.03 to about 10 grams of manganese per gallon of the finished gasoline. At higher concentrations the antiknock effect per unit weight is diminished, and the other beneficial effects are also reduced. When used as a primary additive, the best results are obtained when from about 0.01 to about 6 grams of manganese are present in the gasoline.

As the non-ionic manganese polycarbonyl compounds find outstanding and unexpected utility as additives to both gasoline and crankcase lubricating oil, this invention gives rise to novel compositions of matter comprising a liquid hydrocarbon mixture useful in a spark ignition internal combustion engine, which mixture contains a non-ionic manganese polycarbonyl compound of the type defined in amount sufiicient to improve the combustion characteristics of the engine. 7

The non-ionic manganese polycarbonyl antiknock agents of this invention are also conveniently introduced into the cylinders of an internal combustion engine by utilizing a separate system of supply in conjunction with the system which supplies fuel to the cylinders. Thus, the non-ionic manganese polycarbonyl compounds are supplied to the cylinders by atomizing, vaporizing or directly spraying the compound or a solution thereof, directly into the cylinders or into the intake manifold which supplies the cylinders with fuel. Introduction of the non-ionic manganese polycarbonyl compound into the manifolding system may be. acomplished either prior or subsequent to carburetion or injection of the gasoline. When the non-ionic manganese polycarbonyl compound is a solid, it is often possible to vaporize it by passing a stream of air over or through a supply of the compound. When the compound is a liquid, it is conveniently supplied to the intake manifold through a wick which is supplied from a reservoir of the liquid. 7

FIGURE 1 is illustrative of a method of introducing a non-ionic manganese polycarbonyl compound into a combustion chamber of an internal combustion engine having a plurality of combustion chambers equipped with movable pistons wherein the walls of the chambers are lubricated with a crankcase lubricating oil and wherein gasoline is introduced into the combustion chamber and ignited and the products of combustion act upon the pistons and produce a driving force. With reference to FIGURE 1, the numeral 11 generally represents a cylinder and cylinder head of a multi-cylinder spark ignition internal combustion engine which contains a piston 11, combustion chamber 12, spark plug 13 which is under the influence of an ignition system (not shown), intake valve 14 and intake port 15 through which gasoline and combustion air are supplied by a carburetion system (not shown), an exhaust valve 16 and an exhaust port 17. These components make up the basic parts required in a conventional four-cycle spark ignition internal combustion engine.

To effectively conduct the process of tais invention, a non-ionic magnanese polycarbonyl compound is conveniently injected into the combustion chamber 12 by the utilization of a separate system which consists of a supplemental opening 18 which has fitted thereto a valve 19 shown for purposes of illustration as a poppet valve held closed by a spring 20 and having an elongated stem 21 which places the valve under the influence of a solenoid 22. The solenoid 22 is conveniently arranged to be under the influence of a set of breaker points (not shown) coordinated with the ignition system of the engine so that the valve 19 will be open during the intake stroke of the piston 11 for a time suihcient to permitthe required amount of non-ionic manganese polycarbonyl compound to enter the combustion chamber 12. The non-ionic manganese polycarbonyl compound is supplied through the opening 18 by means of a vaporizing system 23 which terminates in an inlet port 24 through which the valve stem 21 operates by means of the aperture 25. The valve stem 21 is sealed in the aperture 25 in any convenient manner. To supply a non-ionic manganese polycarbonyl compound as a vapor to the combustion chamber 12 through the opening 18, a reservoir 26 of any convenient form contains a supply of manganese polycarbonyl compound to a convenient level 27. The container 26 is fitted with a means for passing vaporizing gas through the manganese poly carbonyl compound as shown by the conduit 28 which is attached to an opening 29 in the container 26. Back-up in the conduit 28 is prevented by any convenient means, such as a diaphragm valve 3G. To the upper portion of the container 26 is attached a plurality of conduits 31 corresponding to the number of cylinders in the engine. The conduits 31 terminate in the inlet port 24. A vaporiz ing gas, such as nitrogen, air, carbon dioxide and the like, supplied from any convenient means such as a compressor or tank (not shown) through the conduit 28 passes through the manganese polycarbonyl compound 27 and carries the compound as a vapor through the conduit 31 to the inlet port 24 where at the appropriate time it passes through the aperture 18 into the combustion chamber 12 where it mixes with the gasoline and combustion air and improves the combustion which takes place under the influence of spark plug 13 at the end of the comprcssion stroke of the piston 11. The manganese polycarbonyl compound shown at 27 may be in the form of a solid such as methyl manganese pentacarbonyl or may be a liquid which contains a non-ionic manganese polycarbonyl which may be blended with an antiknock fluid containing halogen scavenger material and an organolead antiknock agent such as tetraethyllead.

Fuels containing organolead antiknock agents ordinarily contain, in addition to the antiknock agent, corrective agents commonly termed scavengers. Thus, when organolead antiknock agents are present in the compositions of this invention, it is desirable to include therewith such scavengers. These scavengers consist of organo bromine and/0r chlorine compounds such as ethylene dibromide, ethylene dichloride and like material. They function to inhibit the build-up of lead deposits on the interior surface of internal combustion engines.

Halogen containing hydrocarbons are useful as scavengers in conjunction with the manganese polycarbonyl antiknock agents and are conveniently blended therewith to form fluids which are added to gasoline to give the benefits of this invention. These fluids also may contain small amounts of such hydrocarbon solvents as kerosene as well as dyes, antioxidants and the like. The proportion of halogen in such compositions is adjusted such that an atom ratio of halogen to manganese of from about 0.221 up to 12:1 is achieved. However, the octane enhancement of the manganese polycarbonyl compounds is realized even in the absence of such scavengers.

Organolead antiknock agents are commonly provided as fluids for addition to hydrocarbon fuels. These fluids ordinarily contain the organolead compound and the halogen scavenger agents referred to above. In addition,

' these fluids also often contain solvents comprising mixtures of hydrocarbons as well as antioxidants and the like. invention is the provision of an antiknock fluid comprising an organolead compound and a manganese polycarbonyl compound. These fluids are convenientlyblended with hydrocarbon fuels to prepare the improved fuels to this invention.

Because of the property inherent in the manganese polycarbonyl compounds within the scope of this invention of being highly soluble in gasoline, such blending operations present little or no difiiculties. It is generally necessary only to add the requisite quantity of an improved antiknock fluid of the present invention to gasoline; and, by stirring, shaking or otherwise mechanically agitating these components, homogeneous improved fuel compositions are obtained. As a result of the high solubility of the antiknock fluids of this invention in gasoline such fluids can be utilized in any commercially available gasoline including straight run, catal ytically cracked, catalytically reformed and thermally cracked base stocks and likewise, blends thereof.

in order to illustrate the utility and some of the commercial advantages of employing the manganese carbonyl compounds used in the practice of this invention, a great number of tests have been conducted. The results of some of the most significant are presented below.

A most important feature of the present invention is the outstanding antikrrock activity'exhibited by the non-ionic manganese polycarbonyl compounds.

To demonstrate this antiknock effectiveness, tests were Thus, another variant within the purview of this 4 TABLE I Antiknock Efiectiveness of Compounds of This Invention H. The initial boiling points (BF) and final boiling 'Oetane r F E Numbgr of Mn, Resulting points (1 B?) o the gasonnes used are mdicated as Well AddltlVB p s as the particular manganese polycarbonyl compounds and additive their concentrations in terms of grams of manganese per gallon of gasolme. Other such improved gasoline com- IMethyl manganese pentaearbonyl 91.8 0.18 93. 1 PQSitions will be PF to one Skilled in the IMethyl manganese pentacarbonyL. 91.8 0.36 93.8 10 IMethyl manganese pentaearbonyl 01. S 1. S16. 0 Methyl manganese pentacarb0nyl 91. 8 2.0 97. 1 Methyl manganese pentaearbonyL. 91.8 3.0 99.9 TABLE II lgiethyil manganese pentaeaigionyiln 91. 8 0. 59 9-1. G

enzy manganese pentacar ony 91.8 0.58 94.3 I 4 Acetylmanganese pentawbonylm 9L8 0 23 92. 9 Gasame Coma nzng Manganese Polycarbonyl Acetyl manganese pentacarb0nyl 91. 8 0. 47 94. O Compounds Aeetyl manganese pentacarbonyl.-- 91.8 1.0 05.5 Trifluoroacetyl manganese pentacarbonyl 98. 7 0. S9. 4 Gasoline Grams Trilluoroacetyl manganese penta- Example Manganese Polycarbonyl Mn per carbonyl 9S. 7 1. 0 101. 0 Compound gal Trifluoroacetyl manganese penta- IBP FBP carbonyl es. 7 2. 0 103. 3 Methyl manganese pentacarbonyl 80 1.02 94.3 20 Methyl manganese pentacarbony1 S0 2. 01 100.0 II 90 406 Phenylaeetyl manganese 0.01 Propionyl manganese pentapentacarbonyl.

carbonyl 91.8 0.28 94.5 III 9a 390 Benzoyl manganese penta- 10.0 Propionyl manganese pentacarbonyl.

carbonyl V 91.8 0.56' 95.3 IV 5'4 390 Aoetyl manganese ponta- 6.0 Phenyl manganese pentacarbonyL. 91. 8 0.50 94.4 carbonyl, Phenyl manganese pentacarbonyL- 91.8 1.0 05.9 V 8a 392 Ethyl manganese penta- 0.1

2D carbonyl. VI S9 385 Methyl manganese penta- 2.0 The antiknock properties of manganese polycarbonyl VU 8 a l y a compounds are even more unexpected when it is con- 9 g z f pcma v sidered that some other compounds of manganese are in- VIII 9 390 ni y s p 18 effective. For example, manganese naphthenate exhibits m on} a slight pro-knock quality. 7

The following examples are illustrative of the novel gasolines, lubricating oils and antilmock fluids which are EXAMPLES IX XIX within the Scope of thls mvennon' Table 111 illustrates typical gasolines of this invention EXAMPLE I V which contain a non-ionic manganescpolycarbonyl com- A typical method of providing fuels containing a dispound in conjunction with an organolead compound. solved manganese polycarbonyl compound is as follows: The organolead antilmocks which are ingredients of To a gasoline hav ng a final boiling point of 406 in a certam of the compositions of this invention are prefervessel provided with an agitator is added 6.29 parts of ably hydrocarbon lead compounds such as tetraphenylethyl manganese pen-taoarbonyl per gallon of the gaso- 40 lead, tetratolyllcad and particularly tetraalkyllead ,cornline. After agitating the mixture for approximately fifteen pounds such as tetramethyllead, tetraethyllead, tetraprominutes, the ethyl manganese pentacarbonyl is completely pyllead, and the like. Tetraethyllead is preferred. In dissolved and uniformly distributed throughout the fuel. general, the amount of organolead antiknock agent is se- This is demonstrated by analysis of a portion of the fuel lectcd so that its content of the gasoline is equivalent to for manganese, which shows the fuel to contain 1.77 grams about 0.1 to about 8 grams of lead per gallon of gaso of manganese per gallon of fuel mixture. line.

7 TABLE III EXAMPLES IIVIII Other improved gasoline compositions of this invention prepared as in Example I are illustrated in Table Improved Gasolines Containing a Lead Amiknock Agent and a N0n-0nic Manganese Polycarbonyl Compound Gasoline M- .ga- Grams Scavenger Example Manganese Polyearhenyl nese, Lead Antilmoek of Pb Scavenger Cone, Per- Gravity, Additive g./ al. Agent per gal. gJgal. cent FBP API Benzyl man anese penta- Ethylene dichloride- 1.48 426 61.4 carbon. 0.20 Tctraethylleadnu 3.17 {gg k g fi? g L5 Trifiuorometh lman anese t yene ic ori e 1.48 426 pentaearbon yl b t {Etlgylene Sibfipmiale--. 1.5

. Meth l man' mese en aa t yene ie ori e 1.48 426 carb onyl. & p Et ylene dibromide 1.5 390 59.0 p-Octyl benzyl manganese 2.4 Tetramethyllead 2.0 Dibromebutane 2.1

pentaearoonyl. 366 54. Nonoyl mangmese penta- 4.0 Tetraphenyllead 0.05'

t t i I t il d in 'd 43 .ee 1 man anese en a- .myene ie on e. 380 54.4 cartbonyL 0.03 Tet.ae..hylleed 3.00 Dibmmmmem L4 XV 420 61.4' Benzoyl mangmese penta 8.0 Tetrabutylleed 0.1

carbonyl. XVI 416 63.2 Phenyl manganese penta- 0.9 Tetraethyllead 5.1

carbonyl. XVII 0.02 426. 61.4 Methyl mangwese penta 0.05 --.,do 0.95

- carbonyl. I XVIII 00.8 Ethyl manganese pent-a- 0.10 (lo 0.90

carbonyl. XL 0.001 395 58.6 Tolyl manganese penta- 0.30 do 2.70 do a carbonyl. I

Antiknock activity of mixtures of my manganese additives with organolead antiknocks is shown in Table IV.

TABLE IV EXAMPLE XX To 11 parts of methyl manganese pentacarbonyl is Antiknock Efiectiveness of Mixtures Compounds of This Invention With Organolead Antl'knock Agents TEL=tetraethyllead. TML=tetramethyllead.

Other compositions of this invention comprising an improved gasoline containing a non-ionic manganese polycarbonyl compound are prepared in a manner similar to that described above and illustrated in Examples 1 through XIX. Further, illustrative examples of the non-ionic manganese polycarbonyl compounds utilized alone or in admixture in such improved gasolines include propionyl manganese pentacarbonyl, phenyl manganese pentaoarbonyl, benzoyl manganese pentacarbonyl, benzyl manganese pentacarbonyl, m-ethylbenzyl manganese pentacarbonyl and the like.

Where halohydrocarbon compounds are employed as scavenging agents, the amounts of halogen used are given in terms of theories of halogen. A theory of halogen is defined as the amount of halogen which is necessary to react completely with the metal present in the antiknock mixture to convert it to the metal dihalide, as, for example, lead dihalide and manganese dihalide. In other words, a theory of halogen represents two atoms of halogen for every atom of lead =and/ or manganese present. In like manner, a theory of phosphorus is the amount of phosphorus required to convert the lead present to lead orthophosphate, Pb (PO that is, a theory of phosphorus based on lead represents an atom ratio of two atoms of phosphorus to three atoms of lead. When based on manganese, a theory of phosphorus likewise represents two atoms of phosphorus for every three atoms of mangamess, that is sufficient phosphorus to convert manganese to manganese orthophosphate, M11 (PO The scavenger compounds can be halohydrocarbons both aliphatic and aromatic in nature, or a combination of the two, with halogens being attached to carbons either in the aliphatic or the aromatic portions of the molecule. The scavenger compounds may also be carbon, hydrogen and oxygen-containing compounds, such as haloalkyl others, halohydrins, halo esters, halonit-ro compounds, and the like. Still other examples of scavengers that may be used in conjunction with my manganese compounds either with or without hydrocarbolead compounds are illustrated in US. Patents 2,398,281 and 2,479,900-903, and the lii: Mixtures of different scavengers may also be used. These fluids can contain other components as stated hereinabove.

In like manner, manganese-containing fluids are prepared containing from 0.01 to 1.5 theories of phosphorus in the form of phosphorus compounds. To make up the finished fuels, the concentrated fluids are added to the gasoline in the desired amounts and the homogeneous fluid obtained by mixing, agitation, etc.

added 5 parts of ethylene dichloride and the mixture agitated until a homogeneous fluid results. The manganese to chlorine atom ratio in this fluid is 1:12 and represents 6 theories of halogen based on the manganese.

In like manner, a fluid is prepared comprising benzyl manganese pentacarbonyl and ethylene dibromide in which the manganese to bromine ratio is 1:6, representing 3 theories of bromine based on the manganese. Likewise, a fluid containing isobutyryl manganese pentacarbonyl, ethylene bromohydrin, and 2,3-dichloro 1,4-dimethylbenzene is prepared in such proportions that for every 75 atoms of manganese, there are one atom of bromine and two atoms of chlorine, representing a total of 0.02 theory of halogen.

The above fluids are added to hydrocarbon fuels in amounts so as to provide improved fuels containing 0.015 gram, 0.25 gram, 1.00 gram, 6 grams and 10 grams of manganese per gallon.

EXAMPLE XXI .To 8.0 parts of lead in the form of tetraethyllead in an antiknock fluid containing 0.5 theory of bromine as ethylene dibromide and 1.0 theory of chlorine as ethylene dichloride, wherein the theories of halogen are based upon the amount of lead present, is added 0.015 part of manganose in the form of an equimolar mixture of benzyl manganese pentacarbon l and acetyl manganese penta carbonyl.

This fluid is then added to a commercial hydrocarbon fuel havin an initial boiling point of 82 F. and a final boiling point of 420 F. in an amount so as to provide 8.0 grams of lead and 0.015 gram of manganese per gallon.

EXAMPLE XXII A concentrated fluid is prepared as in Example XX containing kerosene, a blue dye, and 10 parts by weight of manganese as an equimoiar mixture of methyl manganese pentacarbonyl and benzoylmanganese pentacarbonyl for every 0.02 part of lead in the form of dicthyldimethyllead. This fluid is then blended with a commercial hydrocarbon fuel having an initial boiling point of F. I

and a final boiling point of 394 F. in an amount suflicient to provide 10 grams of manganese and 0.02 gram of lead per gallon- EXAMPLE XXIII Tetraethyllead and manganese penfiacarbonyl are admixed so that the ratio is 2.0 grams of lead as tetraethyl lead present for every 1.0 gram of manganese present l l as phenyl manganese pentaoarbonyl. This composition is found to possess superior antiknock and deposit modify ing properties when added to gasoline.

' EXAMPLE YXIV such as passenger cars, trucks, buses and the like, amounts 7 of any of the compositions of this invention equivalent to from between about 0.1 and about 4.3 grams of lead per gallon are satisfactory. It will be appreciated, however, that in most cases the lead content of such improved fuels is preferably from between about 1.06 and about 3.17 grams of lead per gallon which, when the organolead constituent of such fuels is tetraethyllead, is equivalent to from between about 1 and about 3 milliliters of tetraethyllead per gallon. When the improved gasolines of this invention are designed primarily for use in aviation engines, somewhat greater concentrations can be tolerated and are frequently preferred. In such instances, it is advantageous to employ an amount of improved antiknock fluid of this invention equivalent to from between about 3.17 grams and about 6.34 grams of lead per gallon. That is to say, when utilizing a tetraethyllead-containin antiknock fluid of the present inven- 1 tion in an aviation fuel, amounts of such a fluid equivalent to from between about 3 and about 6 milliliters of tetraethyllead per gallon are satisfactory. Concentrations above these limits can be employed in both motor and aviation fuels, practical considerations being the prime criterion for establishing the upper concentration limit.

Use of antiknock fluids containing my non-ionic manganese polycarbonyls in addition to resulting in great convenience in storage, handling, transportation, blend- 4 and branched chain; olefins; cycloaliphatics containing paraffin or olefin side chains; and aromatic containing aliphatic side chains. The gasoline type depends on the base stock from which it is obtained and on the method of refinin For example, it can be a straight run or processed hydrocarbon, including thermally cracked, catalytically cracked, reformed fractions, etc. When used for spark-fired engines, the boiling range of the components of gasoline can vary from zero to about 430 F., although the boiling range of the fuel blend is often found to be between an initial boiling point of from about 80 F. to 100 F. and a final boiling point of about 430 F. .While the above is true for-ordinary gasoline, the boiling range is a little more restricted in the case of aviation gasoline. Specifications for the latter often call for a boiling range of from about 82 F. to about 338 F., with certain fractions of the fuel boiling away at particular intermediate temperatures. All commercial gasolines including all those embraced within the present invention, always contain a great number of individual hydrocarbon compounds as components and always have a final boiling point of at least 300 F.

The gasolines in which the 'antiknock agents of this invention can be employed often contain minor quan-;

titles of various impurities. One such impurity is sulfur which can be present either in a combined form as an i2 organic or inorganic compound or as the elemental sulfur. The amounts of such sulfur can vary in various fuels from about 0.003 percent to about 0.30 percent by weight. Fuels containing quantities of sulfur, both lesser and greater than the range of amounts referred to above, are also known.

For best results interms of spark plug life, the improved gasolines of this invention should contain at least 0.015 weight and 0.065 weight percent of this element. These gasolines may also contain organolead antiknock agents in the amounts specified above.

It will be apparent that the present invention is susceptible of additional variations. Some of these variants include the utilization in the antiknock fluid embodiments of solubilizing agents, such as kerosene, petroleum cuts or fractions, and in general various aromatic solvents including those containing diphenyl and the like. In addition to this, various orgauolead stabilizers can be used in such embodiments. Among such materials are included styrene, naphthalene, lecithin, aminodiphenyl amines, phenyl-ot-naphthyl amine and analogous materials. Likewise, in both the antiknock fluid and antiknock fuel embodiments of this invention it is frequently advantageous to employ minor proportions of antioxidants, particularly those of the phenylene diamine type as well as the various alkyl phenols, such as 2,6-di-tertbutyl ph nol, 2,4,6-tri-tert-butyl phenol, o-tert-butyl phenot, etc. A still further variant within the contemplation of this invention relates to the utilization of various organic dyestufis in the antiknock fluid embodiments of this invention, which materials serve primarily as a means of product identification, although frequently the coloration produced by suchdyestutfs imparts to the composition a degree of stabilization against deterioration resulting from exposure to light. Furthermore, under certain circumstances benefits are to be obtained by utilizing as the scavengers in the diverse compositions of the present invention, organic halides possessing volatilities comparable to that of the organolead antiknock agent utilized. Such scavengers are described in several of the patents cited hereinbefore.

The improved gasolines and fluids of the present in- Vention can be utilized in conjunction with other well known motor fuel adiuvants. Of such materials, the various catalytically active substances, such as phosphorus compounds comprising various phosphates, phosphites, phosphonates and the like can thus be used in various embodiments of this invention. Other variants within the contemplation of this invention will be apparent to those skilled in the art.

The manganese polycarbonyl containingadditives of this invention may be mixed with antioxidants, such as alkylated phenols and amines, metal deactivators, phosphorus compounds; antiknock agents, such as amines as well as the alkyllead compounds mentioned above antirust and anti-icing agents, and wear inhibitors.

EXAMPLE XXV To 500 parts of a commercially available neutral crankcase lubricating oil is added a quantity of methyl manis stirred until a homogeneous solution is obtained.

EXAMI E XYV II To 1000 parts of a mixed-base, solvent-refined lubricatingv oil containing bright stock and which has an SAE 13 viscosity grade of 20, an API gravity of 305 and a viscosity index of 107.4 is added 0.05 percent manganese as benzyl manganese pentacarbonyl.

EXAMPLE XXVIII To 2162 parts of a wholly-distilled lubricating oil having an API gravity of 30.3", a viscosity index of 154.2 and an SAE number of W2O is added percent manganese as 'benzoyl manganese pentacarbonyl and the mixture is stirred until the benzoyl manganese pentacarbonyl is dissolved.

EXAMPLE XXIX To 216 parts of a wholly-distilled lubricating oil having an API gravity of 29.1, an SAE number of l0W-30 and a viscosity index of 138.9 is added 3 percent of manganese as phenyl butyryl manganese pentacarbonyl. The mixture is agitated until a homogeneous solution is obtained. 7

The lubricating oils used in the practice of this invention include those fractions or blends of fractions from mineral oils which are used for lubricating purposes in the crankcase of an internal combustion engine. Lubricatin oil stock is usually considered to include all the distillate obtainable from crude oils after the lower boiling fractions and gas oils have been expelled, as well as some of the residues that are left in the still when non-asphaltic crudes are distilled.

Generally lubricating oils are made from distilled fractions of a crude, but often these distilled fractions are combined with refined residium, such as bright stocks, to yield oils having excellent lubricating qualities.

In addition to the non-ionic manganese pentacarbonyl compound, the lubricating oils of this invention may contain other additives. These other additives may include, for example, viscosity index improvers, detergents, corrosion inhibitors, metal deactivators, rust inhibitors, color stabilizers, pour depressants, emulsifiers, dyes, etc.

The non-ionic manganese poly carbonyl compounds used in the practice of this invention are prepared by various methods. Examples of these are indicated below.

EXAMPLE XXX Sodium manganese pentacarbonyl was prepared by treating a 5 percent solution of manganese carbonyl in tetrahydrofuran with an excess of one percent sodium amalgam. After removal of the excess amalgam, the supernatent liquid was treated with dimethyl sulfate and the resulting mixture, after standing overnight, was added to ice water and filtered. The precipitate was carefully dried in air and recrystallized forming a lowboiling petroleum ether to give a 59.5 percent yield of methyl manganese pentacarbonyl.

Similar methods are employed to give excellent yields of benzyl manganese pentacarbonyl, benzoyl manganese pcntacarbonyl, styryl manganese pentacarbonyl and the like.

EXAMPLE XXX I Benzoyl manganese pentacarbonyl is prepared in a manner similar to that describal in Example m by reacting benzoyl chloride with sodium manganese pentacarbonyl. The benzoyl manganese pentacarbonyl is gently heated to above 90 C. at which temperature a strong evolution of gas is readily identified as carbon monoxide. When the gas evolution ceases, the remaining product is found on analysis to be phenyl manganese pentacarbonyl.

EXAMPLE XXXII When 8.7 parts of NaMn(CG) contained in 88 parts of tetrahydrofuran was treated with 3.2 parts of allyl chloride in a nitrogen atmosphere and the resulting mixture cautiously heated to reflux for one hour, the mixture became turbid. Removal of the solvent by distillation through a helix-packed column followed by distillation of the residues at reduced pressure gave a small yield of pale yellow liquid (allyl manganese pentacarbonyl) which solidifies on cooling to ice bath temperature. The

compound has a boiling point of 32 C. at 2 millimeters. Analysis.Calcd. for C H MnO Mn, 23.3. Pound:

EXAMPLE XXXIII The sodium salt of 4.1 parts of manganese carbonyl was reacted with three parts of acetyl chloride to give 3.5 parts of a pale yellow solid melting between 43 and 48 C. This material was purified by successive sublimation to give 2.6 parts (a 51 percent yield) of pure acetyl manganese pentacarbonyl which melted at 54 to 56 C. Analysis of this compound showed that it contained 35.2 percent carbon, 1.28 percent hydrogen and 23.1 percent manganese. This corresponds very well with a calculated content of 35.32 percent carbon, 1.27 percent hydrogen and 23.17 percent manganese for the formula CH COMn(CO) EXAMPLE XXXIV A solution of 21.8 parts of sodium manganese pentacarbonyl was prepared by reacting 19.5 parts of manganese pentacarbonyl in 133 parts of anhydrous tetrahydrofuran with an excess of freshly prepared one perpercent sodium amalgum under nitrogen in a reaction vessel. This solution was then transferred under nitrogen into a reaction vessel equipped with a stirrer, dropping funnel, reflux condenser and nitrogen sweep. To the stirring solution from the funnel was slowly added 31.5 parts of trifluoroacetic anhydride. An exothermic reaction occurred and a color change from opaque green/ brown to an almost transparent yellow took place. The solution was allowed to stir overnight at room temperature after which it was poured into ice water. A pale yellow solid separated, was filtered oil, and pressed dry. This yellow material, when recrystallized from carbon tetrachloride, gave 21.5 parts (81.4 percent yield) of white, flulfy crystalline product, perfiuoroacetyl manganese pentacarbonyl'having a melting point of 56.5- 57.5 C.

EXAMPLE XXXV Two samples of perfluoroacetyl manganese pentacarbonyl, 3.1 parts and 2.0 pantsrespectively, were weighed separately into reaction vessels which were subsequently cooled and evacuated. The vessels were then heated carefully to the temperature of hot water, and then rapidly heated to 140 C. Both samples melted into yellow liquids and gas evolution was observed. Immediately after this evolution slowed, the vessels were cooled. Yellow-white solids covered the vessel interiors and these were recrystallized from carbon tetrachloride and combined to give a total of 2.9 parts (63.0 percent yield) of white crystalline perfluoromethyl manganese pentacarbonyl, M.P. 8284 C. The infrared spectrum supported the proposed structure.

Analysis.-Calcd. for C F O Mn: Mu, 20.8. Found: Mn, 21.3.

When the non-ionic manganese polycarbonyl compounds used in the practice of this invention contain an organic radical, such radical has, in general, from 1 to about 20 carbon atoms. Thus, compounds suitable for use in the process of this invention include pelargonyl manganese pentacarbonyl, dibutyl manganese tetracarbonyl, methyl manganese pentacarbonyl, and the like. These compounds have a molecular weight from about 194 to about 500.

When the organic group is a hydrocarbon radical, it preferably has from 1 to about 13 carbon atoms and the manganese polycarbonyl compound which contains it has a molecular weight up to about 450. Examples of such non-ionic manganese polycarbonyl compounds inelude ethyl manganese pentacarbonyl, allyl manganese pentacarbonyl, phenyl manganese pentacarbonyl, p-hexyl benzyl manganese pentacarbonyl, and the like.

Likewise, when the organic group is an acyl radical or an acylated hydrocarbon radical, it preferably contains up to about 13 carbon atoms and the non-ionic manganese polycarbonyl compound has a molecular weight up to about 465. Examples of these compounds include benzoyl manganese pentacarbonyl, stearoyl manganese pentacarbonyl, and the like.

The present invention resides in the discovery that the non-ionic manganese polycarbonyl compounds are unexpectedly beneficial with regard to antiknock efiect when used in conjunction with the operation of a spark ignition internal combustion engine. The invention gives rise to a number of embodiments including a novel process for operating such an engine by means of introducing a nonionic manganese polycarbonyl compound into the combustion chambers, and a number of novel compositions which are of particular benefit in such a process. These novel compositions include a liquid hydrocarbon mixture for use in such an engine which mixture contains a nonionic manganese polycarbonyl compound. This liquid hydrocarbon mixture, as has been pointed out, may be a gasoline or a lubricating oil. When the hydrocarbon 'is a gasoline it may contain an organolead antiknock agent and appropriate halohydrocarbon scavengers in addition to the manganese polycarbonyl compound. Suitable organolead compounds include the alkyllead compound, tetraethyllead, which may be present in amount such that up to 6.34 grams or more of lead are present per gallon of fuel. The atom ratio of manganese to lead may be from about 0.05 to 1 to 64 to 1, or, expressed differently, from about 1 to 20 to about 64 to 1. Applicable halohydrocarbon scavengers include ethylene dichloride and ethylene dibromide.

Further novel compositions of particular benefit in conducting the process of this invention comprise antiknock fluids containing a non-ionic manganese polycarbonyl. Fluids containing halohydrocarbon scavengers along with the non-ionic manganese polycarbonyl compound are also within the scope of this invention, as are fluids containing organolead antiknock agents in addition to the non-ionic manganese polycarbonyl compounds. Illustrative of such fluids are those containing methyl manganese carbonyl and tetraethyllead such that the atom ratio of manganese to lead is from about 0.05 to about 64 to 1. These fluids are conveniently added to gasolines to give compositions containing up to 6.34 o more grams of lead per gallon.

A variant in the practice of the present invention comprises the use of a non-ionic manganese polycarbonyl compound wherein the organic group is substituted with a non-ionic, non-reactive group.

Having fully described the nature of the presentinven tion, the need therefor, and the best modes derived for carrying it out, it is intended that this invention be ganese as a non-ion-ic manganese polycarbonyl compound having the formula RMn(CO) wherein R is an organic radical selected from the group consisting of hydrocarbon radicals and acyl radicals and contains from 1 to about 20 carbon atoms.

2. The composition of claim 1 wherein R is an aliphatic hydrocarbon radical.

3. The composition of claim 1 wherein R is an aryl hydrocarbon radical.

4. The composition of claim 1 wherein R is an acyl radical.

5. Hydro-carbons of the gasoline boiling range containing from 0.01 to about 10 grams of manganese per gallon as a non-ionic manganese polycarbonyl compound having the formula wherein R is an organic radical selected from the group consisting of hydrocarbon radicals and acyl radicals and contains from 1 to about 20 carbon atoms.

6. The composition of claim 5 wherein R is an aliphatic hydrocarbon radical.

7. The composition of claim 5 wherein R is an aryl hydrocarbon radical.

8. The composition of claim 5 wherein R is an acyl radical;

9. The composition of claim 5 additionally containing from about 0.1 to about 8.0 grams of lead per gallon as an organo-lead antiltnock agent.

10. An antiknock composition comprising a mixture of an organolead antiknock agent and a non-ionic manganese polycarbonyl compound having the formula RMn(CO) 5 wherein R is an organic radical selected from the group consisting of hydrocarbon radicals and acyl radicals and containing from 1 to about 20 carbon atoms, wherein the atom ratio of manganese-to-lead is from about 1:20 to about 64:1.

11. Gasoline containing a small antiirnock quantity of methyl manganese pentacarbonyl, said antiknock quantity being between equivalent to about 0.01 to about 10 grams of manganese per gallon.

References Cited in the file of this patent UNITED STATES PATENTS 1,954,865 Danner Apr. 17, 1934 2,398,282 Bartholomew Apr. 9, 1946 2,434,578 Miller Jan. 13, 1948 2,763,617 Scott et al Sept. 18, 1956 FOREIGN PATENTS 1,092,700 France Nov. 10, 1954 1,095,084 France Dec. 15, 1954 7 OTHER REFERENCES Journal of the Institute of Petroleum Technologists, vol. 13, l927-,pages 24-4 255.

Journal of the American Chemical Society, vol. 71, 1949, page 1899.

Claims (1)

1. A LIQUID HYDROCARBON CRANKCASE LUBRICATING OIL CONTAINING FROM ABOUT 0.05 TO ABOUT 10 WEIGHT PERCENT MANGANESE AS A NON-IONIC MANGANESE POLYCARBONYL COMPOUND HAVING THE FORMULA

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