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United States atent O "ice 3,086,038 ’ Patented Apr. 16, 1963 2 1 materials of a the ‘sesquichloride type, and particularly wherein the alkyl groups contain two to about six 3,086,038 carbon atoms. An additional object of the invention is ORGANOALUMINUM COMPOUNDS to provide a new class of novel complex compounds suit Merle L. Gould, Baton Rouge, La., assignor to Ethyl: able for conversion to the desired alkyl aluminum chlo ‘Clorporation, New York, N.Y., a corporation of ride products. An additional object of certain embodi No Drawing. Filed Mar. 29, 1960, Ser. No. 18,251 ments is to provide a process for making alkyl aluminum 12 Claims. (Cl. 260-448) sesquichloride compounds wherein the alkyl groups can include at least two diiferent alkyl radicals, and further, This invention relates to the manufacture of organo 10 wherein the identity of alkyl groups can be rigorously controlled or directed. Still another object of certain aluminum compounds. More particularly, the invention / relates to the manufacture of a new and novel complex material, and also a new and improved process for the embodiments of the invention is to provide a novel proc ess wherein a mixture of a trialkyl aluminum with a of this nature hasbeen ethyl aluminum sesquichloride (C2H5)3A12C13. This versatile material is useful in its a dialkyl aluminum hydride and aluminum chloride. The products are homogeneous, clear liquids, except when ; of other materials. Ethyl aluminum sesquichloride can be reacted readily with aluminum chloride to provide from ambient temperatures to moderately elevated dialkyl aluminum hydride, is converted to high purity manufacture of alkyl aluminum sesquichloride com 15 trialkyl aluminum. pounds and other aluminum alkyl materials. In all forms of the process, a new composition is ?rst Organoaluminum compounds have, in recent years, produced, having the formula RzAlaClal-l wherein R is grown in commercial importance. Thus, organoalu a lower alkyl radical, that is, having from one to, usually, minum compounds have been employed extensively as about six carbon atoms, although higher alkyl groups components of catalysts for the generation of polyole?n 20 are permissive‘. Such compositions are produced by re resinous material, or as alkylation catalysts. acting together approximately equimolal proportions of Outstanding among the organoaluminum compounds the alkyl groups all have ?ve or more carbon atoms, in own right, as a component of catalysts, for example, and also as a highly e?ective intermediate for the production 25 which cases, the compounds have melting points ranging temperatures. These new materials can then be further reacted, by treating with an ole?n, particularly a l-alkene', thus ethyl aluminum dichloride, (C2H5)AlCl3. Alternatively it can be reacted with triethyl aluminum to provide diethyl aluminum chloride, (C2H5)2A-lCl. Ethyl alu producing an alkyl aluminum sesquichloride, RSAIQCIS. minum sesquichloride can also be readily reduced with‘ an alkali metal to provide a high purity triethyl alu ferent than the two alkyl groups in the new composition. The alkyl group thus established may be the same as or dif The best mode of operations of the several embodi minum. In the preparation of ethyl aluminum sesqui chloride, heretofore, metallic aluminum has been directly 35 ments of the present invention will be clearly understood from the detailed examples below and the detailed de reacted with ethyl chloride at elevated temperatures to scription hereinafter, wherein all parts and concentra form the ethyl aluminum sesquichloride. tions are by weight, unless otherwise noted. While the foregoing reaction of ethyl chloride and aluminum is quite effective, it suifersfrom the disadvan Example I tages that relatively expensive ethyl chloride is required 40 A relatively pure fraction of diethyl aluminum hydride, as a reagent. This disadvantage is more pronounced (CQHQZAIH, is reacted with ?nely subdivided anhydrous when production of higher alkyl compounds is desired. aluminum chloride, in the proportions of 150 parts of , In such instances, the alkyl chlorides are, apparently, for aluminum chloride to 100 parts of the diethyl aluminum alkyl bromides or alkyl iodides appear to be essential. 45 hydride, or approximately in a 1:1 mole ratio. The two materials were vigorously mixed and combination oc In other words, materials such as n-propyl aluminum curred with the evolution of a small amount of heat, a sesquichloride, isobutyl aluminum sesquichloride, and all practical purposes, inoperable, and the quite expensive clear, viscous liquid being produced. Analysis of a por tion of this liquid shows the composition corresponding minum iodide have been reported. It is thus apparent 50 to diethyl dialuminum trichlorohydride (C,H,),A1,C1,H. higher alkyl aluminum sesquichlorides have not been prepared, although products such as di-n-propyl alu that a more efficient procedure for the manufacture of The product of the foregoing operation, diethyl dialu the alkyl aluminum sesquichlorides is desirable, not only minum trichlorohydride, is a clear, mobile liquid. Upon standing, however, gelling sometimes occurs. Aliquot portions of this product were then taken and to provide utilization of lower price raw materials, but also to make it possible to effectively manufacture such compounds having more than two carbon atoms in the 55 reacted with alpha ole?n gases as follows: Ethylene-a pressure of, initially, about 150 pounds alkyl group. Ruthru?, in US. Patent 2,271,956, de per square inch of ethylene was applied and was rapidly scribes a process wherein an ole?n, hydrogen, and an absorbed in proportions corresponding to 1 mole per aluminum halide is reacted with metallic aluminum ostensibly to produce alkyl aluminum halides. How ever, no illustration shows a good production of the al 60 mole of the diethyl dialuminum trichlorohydride form ing ethyl aluminum sesquichloride therefrom in good leged compounds, and in fact, it appears that signi?cant yield. polymerization of the ole?n involved would occur. Sig ni?cant need has thus existed for a'more direct and about 125° C. The process is carried out at a temperature of ' Propylene—in this operation a similar technique is employed, and a good conversion to diethyl propyl' dialu effective process for producing alkyl aluminum sesqui chloride compounds, without being restricted to two 65 minum trichloride is provided. Other ole?ns-when n-butene, isobutylene, hexene, or carbon atom alkyl radicals, and without necessitating the other lower alpha ole?ns are reacted with the diethyl di employment of expensive alkyl halides. aluminum trichlorohydride, as above, comparable reaction A general object of the present invention is to provide is encountered and ari alkyl aluminum sesquichloride is a new and more direct process for the manufacture of alkyl aluminum chloride materials. More particularly, 70 produced, wherein one of the three alkyl groups, is of an object of the present invention is to provide a process course, corresponding to the ole?n reacted. which is capable of producing alkyl aluminum chloride of reacting alpha ole?ns of normally liquid character, the In the case 8,086,038 proportionate quantity is mixed with the diethyl dialumi occurs“ Accordingly, the present process" alfords ahighly I num trichlorohydride, the reaction vessel closed and heat .' ef?cient route to producing a very pure grade of triethyl ' aluminum without the necessity of utilizing ethyl chloride . is applied to initiate reaction. ' as a starting material. Example I! In this operation a supply of dimethyl aluminum hy Example V _ dride, 100 parts, is-mix‘ed with 235 parts of ‘aluminum In this operation, the reactants are di-n-pentyl alumi chloride, and a smooth, heat evolving, reaction occurs, num hydrideand aluminum chloride.‘ Upon reacting this similar to the reaction in Example I, resulting in forma material with anhydrous aluminum chloride in equimolal tion of dimethyl dialuminum trichlorohydride. Treat 10 proportions, a good yield of di-n-pentyl dialuminum tri ' ment of aliquot portions of this compound with ethylene, chlorohydride is obtained. This product reacts readily propylene, n-butene, and other alpha ole?ns as in Ex with ole?nic hydrocarbons, as is the case with the other ample I above, results in comparable generation of di vmethyl alkyl dialuminum trichloride materials. Example III dialkyl dialuminum trichlorohydride compounds available 15 by this process. The step of forming the new compounds of the present invention, viz., the dialkyl dialuminum trichlorohydride compounds, is relatively simple. In virtually all instances In this embodiment 96 parts of anhydrous aluminum chloride is reacted with 100 parts of diisobutyl aluminum the dialkyl aluminum hydride and aluminum chloride are diisobutyl dialuminum trichlorohydride, which is succpti 20 ‘fed together in approximately equimolecular proportions. The aluminum chloride should be an anhydrous material, , ble to prompt and efficient reaction with ethylene, n-bu— preferably ?nely divided. In continuous operations a tene, n-pentene-l, n-hexene-l, propylene and other lower slight excess or de?ciency of any individual component alpha ole?ns to make the corresponding trialkyl dialumi present in the reaction zone at one time is not particularly num trichloro compounds, or alkyl aluminum sesquichlo rides wherein one of the alkyl groups corresponds to the 25 deleterious to the operation, the overall consumption being almost identically on an equimol-al basis. . Normally, un ole?n mentioned. less production rates are quite high, it is most convenient As previously indicated, one of the most signi?cant bene hydride, again resulting in relatively rapid production of to carry out the preparation in a batch manner, viz., by ?ts of the present invention is its application to a mixture of a dialkyl aluminum hydride with a corresponding tri alkyl aluminum compound. Such mixtures are the prod uct of certain synthesis processes, involving the direct combination of aluminum metal, hydrogen, and an ole?n, usually carried out in the presence of a reaction medium which includes at least some corresponding alkyl alumi num compound as a component. ' 35 Example IV In this operation, ?nely subdivided aluminum metal is provided in a reaction zone suspended in a liquid system comprising approximately equimolar proportions of tri ethyl aluminum and diethyl aluminum hydride. Ethylene and hydrogen pressure are applied to the system jointly, while vigorously stirring and maintaining the liquid phase at a temperature of about 140° C. Concurrent reac tion of these components results in the formation of ad feeding together batch quantities of aluminum chloride and the dialkyl aluminum hydride, and vigorously agitat ing while heating atimoderate temperatures. It will be‘ readily apparent that, if desired, a plurality of dialkyl aluminum hydride feed components can ‘be provided, whereby a corresponding plurality of dialkyl dialuminum trichlorohydride components are obtained. The reaction is carried out at temperatures from about ambient conditions to about 130° C., in the ordinary op- ' cration, but the temperatures are not thus limited. It is ordinarily preferred not to exceed a temperature of about 100° C., and in some instances pressure operation will be ' 40 necessary to accomplish the desired reaction. Vigorous agitation is highly desirable, as the aluminum chloridef component is normally fed as a subdivided solid. In ad ' dition, adequate cooling is necessarily provided, as the reactions are exothermic in character. ditional quantities of triethyl aluminum and diethyl alumi 45 In those operations wherein the formation of the di alkyl dialuminum trichlorohydride is followed by its num hydride, in approximately equimolar proportions, reaction with an ole?n hydrocarbon, the particular oper resulting in additional production of a liquid phase, where ating conditions will vary with the identity of the com in the triethyl aluminum concentration is of the order of ponents or reactants involved. In the case of the lower 60 percent and the diethyl aluminum hydride in the pro 50 ole?ns, which are normally gaseous, pressure operation portions of about 40 percent. is desired. Pressures of about 50 to 500 pounds per The liquid phase is withdrawn, and separated from square inch are usually employed, at temperatures of 50 any unreacted solid aluminum present by ?ltration or up to about 140 or 150° C. The temperature is not as sedimentation and decanting. The components are sep critical in the present process, employing ethylene, as in arated into relatively pure diethyl aluminum hydride and triethyl aluminum by fractionation at a pressure of below 55 other processes in which ethylene is added to a dialkyl aluminum hydride. In the latter case, ethylene is well 10 mm. mercury, and at a temperature of from 60 to known to exhibit a tendency to form higher alkyl groups 100° C. and this tendency is affected by the temperature of opera ~"I‘he diethyl aluminum hydride fraction is then reacted tion. In the present process, ethylene exhibits virtually with aluminum chloride in equimolar proportions, re sulting in a virtually stoichiometric yield of diethyl di 60 no tendency to “chain grow” or form longer alkyl groups. In addition to the peculiar utility of the new compounds aluminum trichlorohydride, which is then reacted with of the invention, with respect to the ellicient and eco~ ethylene as in Example I, forming ethyl aluminum sesqui nomical formation of an alkyl aluminum sesquichloride, chloride, (Cilli), Al=Cl,. This product is then treated these materials are highly suitable as economical and with ?nely subdivided alkali metal, resulting in the re convenient sources of organoaluminum materials for pur duction thereof to a pure grade of triethyl aluminum, which is combined or mixed with the triethyl aluminum fraction from the original operation, if ‘desired, providing poses such as components of polymerization catalysts, re ducing agents, and for organic syntheses generally. As already noted, a particular and highly advantageous a good overall yield of pure triethyl aluminum. utility is their use as intermediates in an overall process In contrast, when the equimolar mixture of triethyl aluminum and diethyl aluminum hydride, for the ?rst 70 for producing a highly selective and puri?ed grade of a tialkyl aluminum by a sequence of operations as in step of the operation, is treated, as is, with ethylene pres Example IV. In addition to the formation of, for ex sure, it is found that a substantial quantity of higher alkyl ample, a very pure grade of triethyl aluminum, the re substituents are produced in the product. 0n the other action of the dialkyl dialuminum trichlorohydrides with hand, when ethylene is reacted with the separated diethyl dialuminum trichlorohydride, virtually no chain growth 75 ole?n having an odd number of carbon groups provides 3,086,038 5 a highly effective route to the formation of straight chain substituents having an odd number of carbon atoms. In addition to the technique illustrated by Example IV wherein the trialkyl aluminum and dialkyl aluminum hydride of a ?rst synthesis operation are separated, for separate formation, from the latter, of a dialkyl d-ialu minum trichlorohydride, this operation can be conducted without such a separatory step. In such instances, suf ?cient aluminum chloride is mixed with the ?rst step product mixture to correspond to the dialkyl aluminum 10 dialkyl aluminum hydride is di-n-pentyl aluminum hy dride. 6. The process of making an alkyl aluminum sesqui chloride having alkyl groups of from one to ?ve car bon atoms, comprising reacting together, in approxi mately equimolal proportions, and at a temperature of not over about 130° 0., aluminum chloride and a dialkyl aluminum hydride having alkyl groups of from one to ?ve carbons atoms, and forming thereby a homogeneous liquid composition having the empirical formula hydride, whereby a mixture including the trialkyl alu minum and dialkyl dialuminum trichlorohydride is pro duced. Some of the aluminum chloride will also com plex with the trialkyl aluminum. Reaction of this mix RgAlzClgH wherein R represents the alkyl groups of the dialkyl aluminum hydride, and then reacting said composition ture with a desired ole?n results in a selective, or partly 15 with an ole?n having up to ?ve carbon atoms, and form selective reaction thereof with the dialkyl dialuminum trichlorohydride component, resulting in a mixture in cluding the trialkyl aluminum with alkyl aluminum chlo rides, the composition of which is determined by the starting material compositions. In the case of ethylene, 20 ing the alkyl aluminum sesquichloride. 7. The process of claim 6 further de?ned in that the dialkyl aluminum hydride is diethyl aluminum hydride and the ole?n is ethylene. 8. A process for making triethyl aluminum substan as the added ole?n, there is some tendency for reaction to also occur with the trialkyl aluminum component, tially free of hydrocarbon radicals of more than 2 car desired. Thus butene-2, isobutylene, pentene-Z, Z-methyl butene-l, 2-methyl butene-2, 2-methyl pentene-l, 2-ethyl' alkaline reducing metal. employed as reactants. in R is an alkyl radical of 1 to 5 carbon atoms. bon atoms, comprising forming a mixture of diethyl alu minum hydride and triethyl aluminum by the direct re forming longer alkyl substituent groups. When the added action of aluminum, hydrogen and ethylene, then sepa ole?n is, however, a higher ole?n, this tendency is much 25 rating the diethyl aluminum hydride of said mixture and less apparent. reacting with aluminum chloride in approximately equi With respect to the ole?ns suitable for reacting with molecular proportions thereto, forming thereby a cor the dialkyl dialuminum trichlorohydride compounds, the responding quantity of a composition having the empirical simple lower alkene compounds are most common, such formula of (C2H5)2AlzCl3H, and then reacting said as ethylene, propylene, butene-l, pentene-l, hexene-l and the like. However, alpha branched chain ole?ns, 30 composition with ethylene and producing thereby ethyl aluminum sesquichloride, and then reducing said ethyl or internal ole?ns, both straight and branched, are also aluminum sesquichloride to triethyl aluminum with an fully operable when the corresponding alkyl groups are 9. As a new composition, a homogeneous liquid ma hexene-l, and other ole?n hydrocarbons can be effectively 35 terial having the empirical composition R2Al2Cl3H, where 10. As a new composition, the homogeneous liquid Having fully described the invention and the best mode having the empirical formula (C2H5)2Al2Cl3H. of working the several embodiments thereof, what is 11. As a new composition, the homogeneous liquid claimed is: 1. The process of making a composition having the 40 having the empirical formula (CHahAlaClsH. 12. As a new composition, the homogeneous liquid empirical formula RgAlgClgH, wherein R is an alkyl hy having the empirical formula (i-C4H9)2Al2Cl3H. drocarbon radical having from 1 to 5 carbon atoms, comprising reacting together, at a temperature of not over References Cited in the ?le of this patent about 130° C., a. dialkyl aluminum hydride, wherein the 45 UNITED STATES PATENTS alkyl radicals correspond to said R, and aluminum chlo ride, in approximately equimolal proportions. 2. The process of claim 1 further de?ned in that the dialkyl aluminum hydride is diethyl aluminum hydride. 2,786,860 2,826,598 Ziegler et al ___________ .... Mar. 26, 1957 Ziegler et al ___________ __ Mar. 11, 1958 2,835,689 Ziegler et al _____ __.‘ ____ __ May 20, 1958 3. The process of claim 1 further de?ned in that the 50 OTHER REFERENCES dialkyl aluminum hydride is dirnethyl aluminum hydride. 4. The process of claim 1 further de?ned in that the dialkyl aluminum hydride is di-isobutyl aluminum hydride. 5. The process of claim 1 further de?ned in that the Grosse et al.: J. Organic Chemistry, vol. 5 (1940), pp. ‘109-111. Coates: “Organo-Metallic Compounds” (1956), p. 81.