US 2134625 A
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Patented Oct. 25, 193% UNITED STATES PA ENT-or METALLO nearva'rlvss Sol Shappirio, Washington, D. O. No Drawing. Application November 5, 1986,
Serial No. 109,395
This invention relates to motor fuels, lubricating oils and related materials and methods of making the same, and more particularly to motor fuels, et'c. containing metal organo compounds to improve their properties.
In more recent years, motor fuels containing tetraethyl lead have become widely used. More recently, the production of metallo organo derivatives within the motor fuel, in situ, have been m developed eliminating the hazards and expense of the prior methods of making tetraethyl lead extraneously of the fuel, and also yielding motor fuels of pronouncedly improved characteristics.
Among the objects of the present invention is the production of motor fuels or other hydrocarbon distillates and fractions, such as lubricating oils, which contain novel types of metallo organo derivatives, widely departing from the metallo aryls and alkyls of the prior art, and giving to such products as motor fuels, not only improved characteristics but new properties.
Still further objects and advantages will appear from the more detailed description set forth below, it being understood however that such more detailed description is given by way of illustration and explanation only, and not by way of limitation, since various changes therein may be made by those skilled in the art, without departing from the scope and spirit of the present invention.
In. accordance with the present invention, metallo organo compounds are produced in which the organic radicle contains an unsaturated linkage, such as the olefinic -C=C, or the acetylenic -C=- -C, the organic radicles containing such groups being of any desired character, such as aliphatic or acyclic, aromatic or isocyclic, heterooyclic, etc., and the metallo component being any desired metal, but preferably one of the metals and non-metals of accepted use for antidetonants in motor fuels, such as lead, tin, antimony, zinc, phosphorus, silicon, arsenic, mercury and thallium, etc.
In producing these modified motor fuels, for
example, various methods are available, but the simplest is that in which the motor fuel or other hydrocarbon fraction containing the metallo aryl or.alkyl, is reacted with the desired unsaturated compound under conditions wherein the unsaturated compound forms a radicle containing the olefinic or acetylenic linkage, and the latter replaces the saturated alkyl or aryl group of the original metallo organo compound, producing new types of metallo organics. Where the unsaturated reactant is a gas like ethylene, propylene or acetylene, a current of said gas may be through the liquid metallo organic or a solution of the metallo aryl or alkyl, either in a solvent therefor or in the motor fuel or other hydrocarbon distillate. Where the unsaturate is 5 a liquid or solid, such as cyclo pentadiene, for example, the liquid or solid may be added to the solution containing the metallo alkyl or aryl, or the latter may be dissolved in the liquid unsaturate. The-reactions involving the gaseous un- 10 saturates, such as ethylene, propylene and acetylene, may be carried out at ordinary room temperatures and pressures, the gases being well dried to remove any moisture. Higher tempera tures and superatmospheric pressures may be 15 used, particularly where unsaturate liquids are being treated; while even low temperatures and subatmospheric pressures may be used.
The process will be exemplified by the treatment of .lead tetraethyl and Grignards, such as 20 ethyl magnesium chloride (or other halide), with the gaseous unsaturates, it being understood that such illustrative reactions are exemplaryof the use of other types of metallo organics.
, Thus, a well dried current of acetylene is passed 25 through the ethereal solution of ethyl magnesium bromide (prepared in the usual way) at ordinary temperatures, until the extent of reaction desired has taken place. The maximum conversion is reached after about twenty-four hours. acetylenic magnesium bromide is produced together with ethane. The Grignard may be recovered and used for organic synthesis, or it may be added to motor fuel. It may be converted into any of the other metallo acetylenic derivatives 35 by double decomposition in the usual way. See
Patent 2,012,356, page 3, lines 3-25. Thus lead acetylenic derivatives may be produced and added to motor fuels.
Or the lead tetraethyl in solution in any de- 40 sired solvent is treated with a current of well dried acetylene at ordinary temperatures. The
' lead acetylenic derivative is formed together with ethane.
Similarly zinc diethyl may be treated with 45 acetylene to give the corresponding zinc acetylene derivative, ethane being formed at the same time.
In an analogous way the olefinic derivatives may be produced of the Grignards, of lead, zinc,
tin, etc., and utilized in motor fuels or other 50 hydrocarbon fractions and distillates.
To exemplify the production of an olefinic metallic derivative, a liquid olefine will suffice. One
- molecular weight of ethyl magnesium bromide is prepared in the usual way. Cyclopentadiene 55 The 30 (1.3) is maintained at the boiling point, and the ethyl magnesium bromide introduced. The reaction takes about 12- hours for completion. Cyclopentadienyl magnesium bromide is formed together with ethane. If in lieu of using an ethereal solution of the ethyl magnesium bromide, part of the ether is distilled 011' and replaced by benzol (desirably free from thiophene), the reaction is more rapid, being completed in 5 or 6 hours .at 60 C. The process can be further improved by using ligroin (boiling 60 to 80 C.) as the medium, and dissolving the cyclopentadiene therein and reacting with the Grignard. Even though the latter is not soluble in the ligroin, by the use of agitation, the reaction is very rapid, and is completed in 3 hours at temperatures of to C.
Other unsaturated compounds, such as indene and fluorene, may be used to give corresponding Grignard type reaction products. Or as pointed out above, the metallo alkyls, for example, may be similarly treated with these various oleiinic materials to give corresponding metallo olefinic compounds.
Many of these metallo derivatives are new compounds including; for example, the lead acetylenic and olefinic derivatives, the Grignard olefinic derivatives of ethylene and propylene, etc. They are desirably used herein in motor fuels, lubricating oils, etc., but may be used in organic syntheses of far reaching importance.
While the preparation of these metallo organics has been illustrated above in the production of individual organic compounds, more desirably they are produced in situ in the motor fuel, for
example. In such cases, complex mixtures 01' metallo derivatives are produced, and at the same time the hydrocarbons which are formed, favorably aifect the motor fuel as, for example, in octane number. In producing such products in situ, the Grignards or metallo aryls may be produced in situ in the motor fuels for example by any desired method, as for example the methods described in U; S. Patents 2,012,356 and 1,974,167.
In such cases, the motor fuel or other hydrocarhon fraction contains complex mixtures of metallo organo derivatives, such as, for example, various lead alkyls which will include lead butyls, lead pentyls, lead hexyls, etc. Such complex organo derivatives of the metal, when treated with the unsaturate yields lead derivatives of the unsaturate, such as lead ethylenic or lead propylenic or lead acetylenic, etc. derivatives, while higher hydrocarbons are formed. The latter raise the octanemumber of the motor fuel, while the metallo derivatives act not merely as antidetonants, but they are antigum and antioxidants as well. For example, a well dried stream of acetylene is passed through a motor fuel containing lead alkyls produced in situ, normal temperatures being employed, and the reaction being continued for six hours. Lead acetylide is formed, together with parafiln hydrocarbons. The alkyl radicles set free in nascent condition recombine in various ways.
Analogously, a gasoline containing a complex mixture of Grignards produced in accordance with Patent 2,012,356 is treated at 40-70 C. with a current of ethylene for three to six hours. The corresponding magnesium ethylene halide is produced, together with parafiins of various types.
In lieu of using pure gaseous unsaturates, gaseous mixtures containing the unsaturates may be employed. Gases from cracking units may thus be used, since they contain relatively high con-' tents of olefines, and may be directly applied to the production of the olefinic plumbanes and other metallo organics. Thus, in one case, the gas from a vapor phase cracking plant contained 6% of butylenes, 17% propylene, 27% ethyleneand 50% methane. It is desirably employed to treat a complex lead alkyl motor fuel produced in situ by the methods of Patent 2,012,356. Thegas is run through the motor fuel at a temperature of from 20-50 C., and if desired some pressure may be used, as for example, about The current of gas is run through for five hours to produce theconversion. More desirably countercurrent contact of gas with liquid is utilized, and with slightly elevated temperatures and pressures, the process of conversion is quite rapid. By the use of still gases, vapor phase cracking gases, etc., utility is made of products readily available in the refinery. Very complex mixtures of metallo ethenyls, propenyls, butenyls, etc. are produced.
Where polymerization of the unsaturates takes place, the motor fuels may be redistilled. But the conditions of reaction can be chosen to avoid so extensive polymerization as to require distillation.
While motor fuel fractions, such as gasoline, have been particularly mentioned, other hydrocarbon fractions and distillates may be similarly treated. For example, a lubricating oil used for cylinder lubrication may be given a complement of the lead organics. Or Diesel fuels may be so treated. The ethylene, propylene, etc. are illustrative oi the class of oleflnic materials, while acetylene illustrates the class of compounds containing the -CEC- group. The term oleiinyl like the term ethylenyl and similar terms is intended to cover compounds in which the metal is joined directly to carbon of olefin group such as ethylene, etc. Furthermore, the term metal is used herein to cover both metals and nonmetals of the character set forth above which are found to be useful in motor fuels in connection with anti-detonating and other types of metal derivatives.
The processes given above in which alkyl or aryl groups of metallo alkyls or aryls are replaced by unsaturated organic radicles are illustrative of the wide variety of processes which can be utilized to modify the metallo organo ingredients of motor fuels, lubricating oils, etc., by simple means in view of the great reactivity of the metallo organo derivatives such as lead alkyl, zinc alkyl, the Grignard reagents, etc. Processes can further be employed to modify the ingredients along other lines, and to introduce either other substituent groups, or partially to replace alkyls or alkylene groups in-such metal derivatives.
An important process in this connection is'that in which an organic derivative containing a ni-- trogen group, is employed to replace alkyl or aryl or alkylene or acetylene groups in the corresponding metal derivatives, either completely or partially by nitrogen containing radicles, in which thenitrogen is directly attached .to the metal. As a result amides or amido derivatives are readily produced. Amido derivatives of the metals, such as lead, zinc, etc. can be readily produced by direct treatment of the metal aryls or alkyls with ammonia, whereas if amines are employed, including, for example, primary and secondary amines, substituted .amino derivatives of the metals are obtained. As noted, if the substitution for the alkyl or aryl or alkylene groups, is carried to the total elimination of such alkyl, aryl or alkylene or acetylene groups, metal amides or metal amido derivatives are produced containing no alkyl or aryl or other radicles, except those which may be attached to the nitrogen. A wide variety of different types of compounds can thus be produced, and by control of the processes, mixtures of complex substances of the character can all he produced simultaneously by simple means in the motor fuels themselves, and preferably are so produced. While these reactions can be carried out utilizing individual compounds, the simplicity of reactions by which the metal derivatives are treated in the motor fuels themselves, particularly when they have been produced in situ therein along lines indicated above, make such methods preferable to others. Various of these processes are illustrated below.
It should be kept in mind in this connection that where the metal derivative is being treated in situ in a motor fuel, hydrocarbon oil, etc., that such metallo organo derivative may be present in a concentrated degree in such vehicle, and after the modification of the metallo derivative, the resulting material containing a concentration of the new metallo derivative may be diluted with motor fuels, gasolines, etc., of any desired type, to reduce the content of metal derivative to the small amount required, such as only a fraction of a percent in the final commercial product.
For example, a motor fuel fraction containing lead alkyls produced in situ in such motor fuel by the methods set forth in Patent 2,012,356, is subjected to treatment with ammonia by passing a dry current of ammonia into the motor fuel containing the metallo alkyls and aryls. The process can be carried out at ordinary temperatures and under ordinary pressures, but if desired the reaction mediums can be heated to moderate temperatures and superatmospheric pressures can be employed. Counter-current methods can be utilized for contact of the gas with the liquid here as in other cases illustrated above. As a result of such treatment, depending on the extent to which the replacement is permitted to occur, that is the length of time treatment, there is produced as an ulimate derivative lead amide, in which the metal is directly attached to the nitrogen of the amido group. If the reaction, however, is interrupted before complete displacement of the alkyls and aryls by the amido group, mixed compounds represented by the amido metallo alkyls or amido metallo aryls are obtained.
If it is desired to treat the metallo alkyls or aryls individually, and subsequently to add the produced products to motor fuels or other compositions, an analogous process may be employed. Thus a current of well dried ammonia is led into an ether solution of zinc ethyl under conditions analogous to those described immediately above with the production of zinc amide.
.and the metal hydrazide is produced, in which event, in this instance, lead hydrazide would be obtained. Here too, the reaction may be interrupted before the complete replacement of alkyl or aryl groups as obtained by means of the hydrazide radicle, so that mixed hydrazide metallo alkyls or hydrazide metallo aryls are obtained.
Analogously, the lead ethylenyl, and other metallo organo derivatives produced as set forth above, which contain an unsaturated group, and in which the metal is joined directly to the carbon, may be treated with ammonia, hydrazin, or other nitrogen containing bases to obtain displacement, either completely or in part of the carbon-containing radicles by the nitrogen containing group.
In lieu of using ammonia, hydrazin, or similar types of compounds, the substituted ammonias and hydrazines may also be employed. Thus any of the amines, particularly the primary and secondary amines may be employed for reaction with the metallo derivatives of organic radicles to produce substituted compounds in which the metal is attached to the nitrogen of the amino radicle. Where the amines employed are gaseous or easily vaporized, as in the case of methylamine, ethylamine, etc., the gaseous amine may be conducted into the solution containing the metallo aryl, alkyl or analogous compound at ordinary temperatures, the reaction readily taking place, and producing corresponding metallo derivatives in which the metal is joined to the nitrogen of the amino group producing an alkyl amino metal derivative. Again, if the reaction is not permitted to go to completion, the substitution is effected in part only with the result that mixed derivatives, corresponding to alkyl or aryl, amido metallo alkyls or aryls are obtained. Where the amines are liquids and not readily vaporized, they may be utilized in liquid condition for reaction with the solution, such as the gasoline solution of the metal alkyls, etc.
By the methods set forth above, therefore, motor fuels and other hydrocarbon vehicles carrying metallo derivatives of carbon and nitrogen containing radicles are readily produced, most desirably in situ in the motor fuel, lubricating oil, or similar fractions with which they are to be employed. Metallo derivatives of unsaturated organic compounds in which the metal is joined directly to the carbon, or metallo organic derivatives, including nitrogen-containing radicles, in which the metal is attached directly to the nitrogen, or combinations of such materials are readily produced in the motor fuels, etc., or may be produced externally of the motor fuel, for example, and subsequently added thereto. These various metallo derivatives are of great importance in the modification of motor fuels giving them new properties, particularly as antidetonating agents, anti-gumming compounds, etc.
Having thus set forth my invention, I claim:
1. A gasoline type motor fuel containing a small amount of amido metallo derivative of an anti-knock metal.
2. A gasoline-type motor fuel containing small amount of lead amid.
3. A gasoline type motor fuel containing a small amount of lead hydrazide.
4. A lubricating oil of hydrocarbon type containing lead amid.-
5. A hydrocarbon vehicle containing an'amido metallo derivative of an anti-knock metal.