US3687994A - Method of manufacturing alkylaluminum compounds - Google Patents

Method of manufacturing alkylaluminum compounds Download PDF

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US3687994A
US3687994A US98954A US3687994DA US3687994A US 3687994 A US3687994 A US 3687994A US 98954 A US98954 A US 98954A US 3687994D A US3687994D A US 3687994DA US 3687994 A US3687994 A US 3687994A
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aluminum
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weight
hydrogen
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Paul Kobetz
Warren E Becker
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Ethyl Corp
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Ethyl Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/065—Aluminium compounds with C-aluminium linkage compounds with an Al-H linkage

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  • alkylaluminum com- 3,535,108 which is a continuation-in-part of pounds from ternary or quaternary alloys, comprising Ser. No. 653,622, July 17, 1967, abandoned. as principal elements aluminum, silicon and titanium, and aluminum, silicon, titanium and iron, respectively, [52] U.S. Cl. ..260/448 A wherein said all ys ar reacted with hydrogen and an [51] Int. Cl. ..C07f 5/06 aluminum alkyl.
  • An olefin and/or a catalyst may also [58] Field of Search 4.260/448 A be added in the reaction.
  • organo aluminum and/or aluminum alkyl compounds may be produced .by reacting aluminum with an organo aluminum compound and hydrogen or with an olefin and hydrogen in the presence of an organoaluminum compound. See, for example, U. S. Pat. Nos. 2,787,626; 2,900,402; 2,930,808; 3,000,919; 3,016,396; 3,032,574; 3,207,770; 3,207,772; 3,207,773; 3,207,774; 3,393,217; and 3,505,375.
  • U. S. Pat. No. 3,393,217 discloses the production of organo aluminum compounds using an aluminum-silicon binary alloy containing more than 13 percent by weight of silicon.
  • the patent further discloses that impurity amounts of iron, copper, titanium and magnesium may also be present in the binary alloy. These impurity amounts are quite small however, usually about 0.1 percent by weight or less of the binary aluminum-silicon alloy.
  • U. S. Pat. No. 3,393,217 further discloses that binary aluminum-silicon alloys of 13-60 percent by weight silicon produce far greater depletions during hydroalumination than binary aluminum-silicon alloys containing less than 13 percent silicon by weight. Extremely poor depletions or aluminum extractions are obtained (less than percent) when the silicon content of the binary alloy is as low. as about 8 percent silicon by weight.
  • alkylaluminum compounds which relates to a method for manufacturing alkylaluminum compounds utilizing certain activators or catalysts, discloses that with the use of such catalysts, namely alkoxides of lithium, sodium or potassium, alkylaluminum compounds can be made from multi-component alloys such as aluminumsilicon-iron or aluminum-silicon-iron-titanium, the alloys having the composition of 13-40 percent by weight of silicon, l-15 percent by weight of iron, 0-10 percent by weight of titanium and the remaining amount being aluminum. Small amounts of other metals such as magnesium and calcium may also be included in the alloy.
  • multi-component alloys such as aluminumsilicon-iron or aluminum-silicon-iron-titanium, the alloys having the composition of 13-40 percent by weight of silicon, l-15 percent by weight of iron, 0-10 percent by weight of titanium and the remaining amount being aluminum.
  • Small amounts of other metals such as magnesium and calcium may also be included in the alloy.
  • an organo aluminum compound or aluminum alkyl can be prepared from a ternary or quaternary alloy, namely an alloy comprising as its principal elements aluminum, silicon and titanium, or aluminum, silicon, titanium and iron.
  • the titanium must also be present in an amount of at least 0.2 percent by weight of the ternary or quaternary aluminum alloy.
  • the remaining elements may be present in varying amounts, however, aluminum must be present in at least about 33 percent by weight and the other components proportionately.
  • the ternary or quaternary alloy of the present invention consists essentially of, by weight percent, aluminum 33-94, silicon 5-58, titanium 0.2-4 and iron 0-5. Accordingly this invention provides a method for producing alkylaluminum compounds, which comprises reacting an aluminum-silicon ternary or a quaternary alloy comprising 33 to 94 percent by weight of aluminum, 5 to 58 percent by weight of silicon, 0 to 5 percent by weight of iron, and 0.2 to 4 percent by weight of titanium with an alkylaluminum compound, hydrogen and a catalytic substance. An olefin may also be added in the reaction.
  • Titanium must be present in more than impurity amounts and in an amount sufficient to speed up or enhance the hydroalumination reaction.
  • the titanium must also be in sufficiently small amounts that it does not have a deleterious effect on the reaction.
  • both titanium and iron be in as small amounts as will effectively enhance vthe hydroalumination reaction.
  • the titanium unexpectedly overcomes the deleterious effect of silicon in a hydroalumination reaction using binary aluminum-silicon alloys as taught in U. S. Pat. No. 3,393,217.
  • the present invention consistently provides depletions of percent or more in the hydroalumination reaction. It should be noted that increases of depletions of even 1 percent are extremely important in a commercial process.
  • the ternary aluminum-silicon-titanium alloy or the quaternary aluminum-silicon-iron-titanium alloy is preferably activated for use in the reaction, as in the case of aluminum, and the activation may be carried out according to any of the known processes proposed in the case of aluminum metal which are effected by I triphenylaluminum,
  • shavings or small particles of a ternary or quaternary aluminum alloy comprising as principal elements aluminum, silicon and titanium or aluminum, silicon, titanium and iron, respectively, are reacted with 1.5 times the theoretical amount of triisobutylaluminum with hydrogen at 1500 psig at 120C for about 7 to 15 hours.
  • a more reactive aluminum alkyl such as triethylalurninum
  • good results are obtained at a hydrogen pressure of 1000 psig at 140C for about 1 to 3 hours.
  • the ternary or quaternary alloy may contain impurity amounts of copper, magnesium, calcium, zirconium, vanadium and other elements.
  • the amount of aluminum to be contained in the alloy is preferably more than 50 percent by weight, but can be as low as 33 percent by weight.
  • the amount of silicon to be contained in the alloy can be any amount from about 5 to about 58 percent by weight of the alloy.
  • the amount of titanium in the alloy is at least 0.2 percent by weight and preferably not more than about 4 percent by weight.
  • a weight percent of titanium from about 0.6 to about 3 is especially preferred.
  • the amount of iron in the alloy is preferably as little as possible but may be from to 5 percent by weight, and alloys containing less than 4 percent iron are preferred. A weight percent of iron of about 1 to about 4 is especially preferred.
  • the alloy may be finely divided or in any desired shape such as chipped-like fragments obtained by use of a shaper, lathe or drilling machine, or chunks or small particles obtained by simple crushing or cutting.
  • alkylaluminum compound employed as one of the materials used in the present invention is represented by the general formula, RR'AIR", wherein R and R are respectively selected from alkyl radicals having two to 20 carbon atoms and R" is selected from the group consisting of alkyl radicals, hydrogen or halogen.
  • Preferred alkylaluminum compounds are triethylalurninum, diethyl-aluminum hydride, di-npropylaluminum hydride, trim-propylaluminum, triisobutylaluminum, diisobutylaluminum hydride and mixtures thereof.
  • alkylaluminum compounds are ethyl-di-propylaluminum, diethylaluminum chloride, diethyl-aluminum bromide, diisobutylaluminum chloride, diisobutylalurninum bromide, dioctylaluminum chloride, dioctylaluminum bromide, dipentadecylaluminum chloride, dipentadecylaluminum bromide, didocosylaluminum chloride, diphenylaluminum hydride, diphenyl-aluminum chloride, dipara-tertiary-butylphenylaluminum hydride, di-paratertiary-butylphenylaluminum chloride, phenyloctylauminum hydride, phenyloctylaluminum chloride,
  • tripara-tertiary-butylphenylaluminum tripara-tertiary-butylphenylaluminum, diphenyloctylaluminum, dioctyl-aluminum hydride, dipentadecylaluminum hydride, didocosylaluminum hydride, ditetracontylaluminum hydride, trioctylaluminum, tripentadecylaluminum and tridocosylaluminum.
  • the olefin which may be employed in the present invention is preferably an alpha olefin having two to twenty carbon atoms of which typical examples are ethylene, propylene, normal and isobutylene, 2-methyll-pentene, and 2-ethyl-l-hexene. Olefins having internal double bonds are less reactive and are thus not as desirable.
  • Catalysts employed in the present invention may be selected from the group of alkali metals and alkaline earth metals and their hydrides, halides, alkyls and alkoxides or complexes of these compounds with alkylaluminum compounds.
  • a preferred catalyst for use in the present invention has the formula MYn.Al(C H )RX, wherein M is an alkali metal or an alkaline earth metal; Y is hydrogen (H), chlorine (Cl), fluorine (F), hydroxyl group (OH), cyanide group (CN), alkyl group (R) or alkoxy group (OR n is an integer in accordance with the valences of M and Y; R is hydrogen or a hydrocarbyl group selected from alkyl, alkenyl, alkynyl, aralkyl, aryl and alkaryl having up to twenty carbon atoms; and X is halogen or the same as R. Catalysts of hydrocarbyl groups of C to C are preferred.
  • a most preferred catalyst is a sodium alkylaluminum hydride, e.g., sodium triethylalurninum hydride, sodium tetraethylaluminum and sodium diethylaluminum dihydride.
  • TEA is triethylalurninum
  • DEAH diethylaluminum hydride.
  • Preferred alkali metals are sodium, potassium and lithium, with sodium being the most preferred.
  • Preferable alkaline earth metals are magnesium and calcium, with calcium being the more preferred.
  • MY compounds are sodium hydride, sodium hydroxide, sodium cyanide, potassium chloride, sodium ethoxide, sodium butoxide and potassium butoxide.
  • alkyl groups (R) are ethyl, propyl, isobutyl, n-butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, octadecyl, and eicosyl. Alkyl groups having from two to four carbon atoms are most preferred.
  • alkoxy groups are ethoxy, n-propoxy, isopropoxy, n-butoxy, phenoxy and ptolyloxy.
  • hydrocarbyl groups (R) and (X) are ethyl, propyl, isobutyl, n-butyl, sec-, pentyl, hexyl, heptyl, octyl, decyl, eicosyl, lauryl, benzyl, cyclohexyl, vinyl, ethynyl, phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, and indenyl.
  • halides are chloride, bromide and fluoride.
  • the complex metal compound catalyst may be prepared or formed in situ or may be added to the hydroalumination reactants.
  • R MY Another suitable catalyst or activating agent which may be employed in the present invention is represented by the general formula, R MY, wherein R is selected from the group of alkoxy, aroxy, aralkoxy, alkaroxy, alkyl, aryl, aralkyl, and alkaryl radicals, Y is selected from the group of alkoxy, aroxy, aralkoxy and alkaroxy radicals, M represents a metal element having valency of n 1, and n is a whole number selected from 0, 1 and 2.
  • Typical examples of the catalyst include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, phenoxy, and p-tolyloxy compounds of lithium, sodium and potassium; dimethoxy, diethoxy, diisopropoxy, din-butoxy, methoxy-ethoxy, ethyl-ethoxy, diphenoxy, methyl-phenoxy, and ethyl-tolyloxy compounds of magnesium and zinc; trimethoxy, triisopropoxy, tri-nbutoxy, dimethoxy-ethoxy, methyl-dimethoxy, ethyl diethoxy, dimethyl-methoxy, diethyl-ethoxy, n-butyldi-n-butoxy, diisobutyl-n-butoxy, triphenoxy, tribenzyloxy, and methyl-diphenoxy compounds of boron and aluminum.
  • reaction temperatures to be adopted in the production of alkylaluminum compounds from the ternary or quaternary aluminum alloy are in the range of from 70C to 250C, preferably from 100C to 180C.
  • Suitable reaction pressures are in the range of from to 300 kglcm Under pressures of less than 10 kilograms per square centimeter, the reaction velocity is low, whereas under pressures of more than 300 kglcm the reaction apparatus should necessarily be made complex and is not practical.
  • small particles of a quaternary aluminum alloy about -100 mesh in size comprising, by weight percent, 78 aluminum, 20 silicon, 1 iron and 1 titanium are reacted with triethylaluminum, ethylene and hydrogen at 1000 psig at 140C for about 1 hour.
  • a metal residue containing a large amount of silicon, which has been used in the production of the alkylaluminum, is separated from the reaction mixture, formed into an alloy of a suitable proportion and then may be used again.
  • the metal residue may be recycled in the form of silicon containing impurity amounts of iron and titanium by converting the free aluminum present in the alloy into an alkylaluminum compound, or may be recycled in the form of an alloy or mixture comprising aluminum, silicon and titanium, with and without iron, by converting only a part of alu' minum present in the alloy.
  • Each alloy was prepared by weighing the calculated amount of commercially pure metals into a graphite crucible which was heated in an induction furnace to 1400-1450C for series (A) or l800-1950C for series (B). The molten mixture was stirred with a graphite rod and allowed to cool. The ingot was treated with a rasp to remove the graphite crucible and then taken down on a lathe to remove the ends and outer skin.
  • the alloy ingots were comminuted by means of a lathe, taking a cut of about 0.004 inch (4 mils).
  • the tumings were found to be thicker than 4 mils, smooth on one side and jagged on the other. They were of similar dimensions, about one-sixteenth inch wide, roughly one-eighth to one-fourth inch long, and averaging 6 to 8 mils thick.
  • Two exceptions were Samples 1(A) and 2(A), which gave larger, thicker chips averaging about 9-13 mils thick. In general, the higher silicon alloys gave shorter, more brittle chips.
  • the 16 mesh fines were removed from all of the alloy tumings. Samples for testing in the hydroalumination reaction were split out by quartering from the bulk sample.
  • the catalyst solution was prepared from the reaction of sodium with a mixture containing approximately 70 percent diethyl-aluminum hydride (DEAH), 30 percent triethylaluminum (TEA), and filtering off the aluminum metal formed. It analyzed 8.1 percent sodium.
  • the composition of the catalyst is not stoichiometric and is best represented by the general formula NaH-x- Et Al-yEt AlH (x y 5, but may equal at least 1 and preferably equals 3 to 5
  • TIBA and catalyst the autoclave was closed, pressurized to 1000 psig with hydrogen and heated to C with stirring. Then more hydrogen gas was introduced into the autoclave until the pressure became 1500 psig. This pressure and temperature were maintained for 5 hours. The pressure was then increased to 1750 psig and the reaction carried out for an additional 10 hours.
  • the pressure at shut-down time (unattended) ranged from 1500-1750 psig.
  • the total reaction time was 15 hours.
  • reaction mixtures were worked up under nitrogen with special care to recover all of the solid residue.
  • a benzene stream from a wash bottle was used to remove solids adhering to the stirrer, and to transfer the solids to a medium frit Buchner funnel.
  • the residues were washed well with benzene and petroleum ether, vacuum dried on the filter and weighed.
  • a NaHx TEA-y DEAH "Based on weight loss EXAMPLE E A Hydroalumination reaction was carried out using triethylaluminum (TEA) as the aluminum alkyl and the procedure described in Example A.
  • TEA triethylaluminum
  • Four grams of quaternary alloy No. 4 were reacted with 87 milliliters TEA and 6 milliliters of the sodium ethylalurninum hydride catalyst at 140C under 2000 psig hydrogen pressure for 3 hours.
  • the reaction mixture was worked up as described in Example A and yielded 1.75 grams of solid residue. This weight of residue corresponds to a 90.4 percent depletion of the aluminum values present in the original aluminum-silicon quaternary alloy.
  • EXAMPLE F A sample of aluminum-silicon quaternary alloy was prepared by melting the calculated amounts of commercially pure metals to achieve the target composition. by percent by weight of 56 Al 31 Si 2 Ti 11 Fe. The molten alloy was cooled, crushed and ground and sieved through a -l00 mesh screen. X-ray fluorescence (XRF) analysis showed the actual iron content to be 7.9 percent and the titanium to be 2.2 percent. Four grams of this alloy were .reacted with 87 milliliters TEA in the presence of sodium ethyl-aluminum hydride catalyst at 140under 2000 psig hydrogen pressure for 3 hours. The reaction mixture was worked up as described in Example E.
  • XRF X-ray fluorescence
  • Aluminum tied up as interrnetallics is unreactive and preferably the amount of these interrnetallics should be kept as low as possible by keeping the amount of iron and titanium as low as possible.
  • crude aluminum or an aluminum-silicon alloy is converted into a dialkyl-aluminum hydride-containing liquid phase and a residual solids phase.
  • the crude aluminum or aluminum-silicon alloy must contain some metallic aluminum which is not held in the tightly bound form of an interrnetallic compound.
  • Aluminum-silicon alloys are especially preferred as materials to be refined in this process. Aluminum-silicon alloys can readily be produced at low cost by various electrotherrnic reduction processes and thereby serve as an economical source for purified aluminum metal.
  • the residual solids formed in the present process will comprise metallic silicon (usually but not necessarily associated with other common impurities such as iron, titanium and the like).
  • metallic silicon usually but not necessarily associated with other common impurities such as iron, titanium and the like.
  • Such residual solids which can be readily recovered, are of considerable utility in the chemical and allied arts, for example, in steel making processes.
  • the by-product silicon from the process tends to be very active and thus may be reacted directly with alkyl halides to produce alkyl halosilanes.
  • the use of the preferred aluminum-silicon alloys, especially those which contain small amounts of titanium and/or iron is of advantage in that they are an economical source for low cost aluminum and yield in the present process useful silicon-containing by-products which are likewise of industrial and economical importance.
  • the crude aluminum or aluminum-silicon alloy is preferably employed in subdivided or particulate form, although effective use may be made of turning, chips, flakes, ribbons, and the like.
  • the other, and more preferred, method for converting the aluminum-silicon alloy into the dialkylaluminum hydride-containing liquid phase involves reacting the crude aluminum with appropriate quantities of trialkylaluminum and hydrogen. This reaction proceeds very smoothly and under proper conditions, quite rapidly, whereby dialkylaluminum hydride can be formed in good yield. Moreover, the use of this type of process makes it possible to recycle or reutilize the trialkylaluminum co-product which is formed in the aluminum-producing step.
  • a preferred embodiment of the decomposition process involves converting the aluminumsilicon alloy into an alkylaluminum hydride-containing liquid phase and residual solids by reacting the aluminum with trialkylaluminum and hydrogen under appropriate reaction conditions.
  • Such conditions preferably include use of aluminum-silicon alloy, activation of the aluminum by common techniques, and utilization of suitable elevated temperature and pressure conditions.
  • the foregoing first step may be modified, if desired, so as to produce other suitable alkylaluminum hydridecontaining liquid phases.
  • the liquid phase may contain a significant proportion of dialkylaluminum hydride, this liquid phase may contain in addition to or in lieu thereof other alkylaluminum hydrides.
  • the reaction among the aluminumsilicon alloy, trialkylaluminum and hydrogen may be effected in admixture with a tertiary amine, such as those described above. In this case, the alkylaluminum hydride product(s) (and the trialkylaluminum almost always copresent) will tend to exist in the form of alkylaluminum-tertiary amine complexes.
  • thermal dissociation catalysts in any thermal decomposition operation, inasmuch as these added catalysts insure that the aluminum, gaseous hydrogen and trialkylaluminum coproduct will be produced very rapidly without appreciable liberation of free hydrocarbon (e.g., olefin).
  • thermal decomposition processes wherein an aluminum-silicon-titanium-iron or quaternary alloy is employed in the hydroalumination step are set forth hereinafter in Examples G through J.
  • EXAMPLE G An essentially equimolar mixture of diethylaluminum hydride and triethylaluminum was prepared by hydroalumination of an aluminum-silicon-iron-titanium quaternary alloy with triethyl-aluminum and hydrogen at 110C and 2000 psi. A solution (40 ml) containing about 75 weight percent of this diethylaluminum hydride-triethylaluminum mixture and about 25 weight percent of trimethyl amine was heated to C and at this temperature 5 milliliters of N,N,N,N" tetramethylethylene diamine and 0.0005 milliliters of titanium tetraisopropoxide were added. Within 3 minutes at 70C decomposition had occurred as evidenced by the formation of aluminum powder and evolution of gaseous hydrogen. In this reaction 1.1 grams of aluminum, an essentially quantitative yield, was obtained.
  • EXAMPLE H In this operation a quaternary aluminum-silicon alloy was used to produce a reaction system composed of diethylaluminum hydride and triethylaluminum. In this hydroalumination reaction tertiary amine was present throughout. More particularly, in a 300-milliliter Magne-Stir autoclave were placed milliliters of triethylaluminum, 10 milliliters of N,N,N,N- tetramethylethylene diamine, 0.2 gram of sodium, and 10 grams of powdered alloy (below 325 mesh) containing 68 weight percent aluminum, 27 weight percent silicon, 3 weight percent iron, and 2 weight percent titanium. The bomb was closed and stirring was started.
  • the contents of the bomb were heated to 110C under a hydrogen atmosphere at 2000 psi. Reaction occurred immediately. After one hour of continuous heating and stirring the autoclave was cooled to room temperature and the hydrogen gas vented. The contents of the bomb were filtered to remove the residual silicon, iron, titanium and unreacted aluminum. This solid residue was washed with benzene and vacuum dried. X-ray analysis of this metallic residue showed 77 percent silicon, 8 percent aluminum and 15 percent others (iron and titanium intermetallics). This corresponds to approximately 95 percent utilization of the free aluminum present in the initial alloy.
  • Example I The hydroalumination procedure of Example H was repeated except that 0.01 milliliter of titanium tetraisopropoxide was added to the hydroalumination reactants. On reaching reaction temperature (110C) the reaction commenced immediately and was allowed to proceed for 1 hour. The residual solids were filtered off, washed with benzene and dried yielding a total of 4.57 grams. On analysis, this residue was found to contain 74 percent silicon, 13 percent aluminum, 13 percent others, corresponding approximately to a 92 percent utilization of the free aluminum of the initial alloy.
  • a method for producing alkylalurninum compounds which comprises reacting an aluminum-silicon ternary or a quaternary alloy comprising 33 to 94 percent by weight of aluminum, 5 to 58 percent by weight of silicon, 0 to 5 percent by weight of iron, and 0.2 to 4 percent by weight of titanium with an alkylalurninum compound, hydrogen and a catalyst containing an alkali metal or alkaline earth metal.
  • said aluminum-silicon alloy is a quaternary alloy comprising 0.6 to 3 percent by weight of titanium, and l to 4 percent by weight of iron.
  • said catalyst has the formula MY,,-Al(C H )RX, wherein M is an alkali metal or alkaline earth metal; Y is hydrogen, chlorine, fluorine, hydroxyl group, cyanide group, alkyl group or alkoxy group; n is an integer in accordance with the valences of M and Y; R is hydrogen or a hydrocarbyl group having up to 20 carbon atoms; and X is hydrogen, halogen or hydrocarbyl group having up to twenty carbon atoms.
  • said catalyst has the general formula of R My wherein R is a member selected from the group consisting of alkoxy, aroxy, alkaroxy, aralkoxy, alkyl, aryl, aralkyl and alkaryl radicals, Y is a member selected from the group consisting of alkoxy, aroxy, aralkoxy and alkaroxy radicals, M is a metal element selected from the group consisting of lithium, sodium, potassium and magnesium and n is 0 when M is sodium, potassium or lithium and 1 when M is magnesium.
  • said catalyst is selected from the group consisting of sodium metal and sodium hydride.
  • a method of making alkylaluminum compounds comprising: reacting a ternary of quaternary aluminum alloy, comprising by weight 33 to 94 percent aluminum, 5 to 58 percent silicon, 0.2 to 4 percent titanium and up to 5 percent iron, with a mixture selected from the group consisting of an alkylaluminum compound and hydrogen or an alkylaluminum compound, hydrogen and an olefin, the said alkylaluminum compound having the general formula of RR'AlR"; wherein R and R are alkyl radicals having from two to carbon atoms, and R" is an alkyl radical or in the presence of an olefin, hydrogen; in the presence of a catalyst or activating agent having the general formula MY 'AKCH )RX, wherein M is an alkali metal or alkaline earth metal; Y is hydrogen, chlorine, fluorine, hydroxyl group, cyanide group, alkyl group or alkoxy group; n is an integer in accordance with the valences of M
  • said olefin is an alpha-olefin having 2 to twenty carbon atoms.
  • reaction is effected at a temperature between 70C and 250C.
  • alkali metal is selected from the group consisting of sodium, potassium or lithium.
  • alkaline earth metal is selected from the group consisting of calcium or magnesium.
  • alkylaluminum compound is a member selected from the group consisting of triethylaluminum, di-n-propyaluminum hydride, tri-n-propylaluminum, triisobutylaluminum, diisobutylaluminum hydride and mixtures thereof.
  • a method for producing alkylaluminum compounds which comprises reacting an aluminum-silicon ternary alloy containing as the third principal element titanium in an amount sufficient to speed up the reaction, with an alkylaluminum compound, hydrogen and a catalyst containing an alkali metal or alkaline earth metal.
  • olefin is an alpha-olefin having from 2 to twenty carbon atoms.
  • said catalyst has the formula MY,,'Al(C H -,)RX, wherein M is an alkali metal or alkaline earth metal; Y is hydrogen, chlorine, fluorine, hydroxyl group, cyanide group, alkyl group or alkoxy group; n is an integer in accordance with the valences of M and Y; R is hydrogen or a hydrocarbyl group having up to 20 carbon atoms; and X is hydrogen, halogen or hydrocarbyl group having up to twenty carbon atoms.
  • a method for producing alkylaluminum compounds which comprises reacting a quaternary alloy comprising 33 to 94 percent by weight of aluminum, 5 to 58 percent by weight of silicon, l to 5 percent by weight of iron, and 0.2 percent to 4 percent by weight of titanium, with a catalyst containing an alkali metal or alkaline earth metal, an aluminum alkyl compound and hydrogen at an elevated temperature.
  • olefin is an alpha-olefin having from 2 to twenty carbon atoms.
  • the source of the aluminum for the reaction is an aluminum-silicon-iron-titanium alloy which contains at least about 3 weight percent iron, at least about 2 weight percent titanium, and at least some metallic aluminum which is not held in the tightly bound form of an interrnetallic compound.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853542A (en) * 1973-01-08 1974-12-10 Aluminum Co Of America Process for promoting reactivity of aluminum
US3853931A (en) * 1973-01-15 1974-12-10 Aluminum Co Of America Production of hydrocarbyl aluminum hydrides

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JPS558588U (enrdf_load_stackoverflow) * 1978-07-04 1980-01-19
JPS5721346U (enrdf_load_stackoverflow) * 1980-07-09 1982-02-03

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3050540A (en) * 1958-07-30 1962-08-21 Ethyl Corp Manufacture of alkyl aluminum compounds
US3050541A (en) * 1958-07-30 1962-08-21 Ethyl Corp Manufacture of alkyl aluminum compounds
US3381024A (en) * 1963-07-12 1968-04-30 Sumitomo Chemical Co Method for directly manufacturing alkylaluminum compounds
US3393217A (en) * 1963-08-30 1968-07-16 Sumitomo Chemical Co Method for producing alkylaluminum compounds
US3402190A (en) * 1963-06-18 1968-09-17 Sumitomo Chemical Co Method for manufacturing alkylaluminum compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3050540A (en) * 1958-07-30 1962-08-21 Ethyl Corp Manufacture of alkyl aluminum compounds
US3050541A (en) * 1958-07-30 1962-08-21 Ethyl Corp Manufacture of alkyl aluminum compounds
US3402190A (en) * 1963-06-18 1968-09-17 Sumitomo Chemical Co Method for manufacturing alkylaluminum compounds
US3381024A (en) * 1963-07-12 1968-04-30 Sumitomo Chemical Co Method for directly manufacturing alkylaluminum compounds
US3393217A (en) * 1963-08-30 1968-07-16 Sumitomo Chemical Co Method for producing alkylaluminum compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853542A (en) * 1973-01-08 1974-12-10 Aluminum Co Of America Process for promoting reactivity of aluminum
US3853931A (en) * 1973-01-15 1974-12-10 Aluminum Co Of America Production of hydrocarbyl aluminum hydrides

Also Published As

Publication number Publication date
AU3700371A (en) 1973-06-21
CA965432A (en) 1975-04-01
NO137277C (no) 1978-02-01
NO137277B (no) 1977-10-24
AU470875B2 (en) 1973-06-21
JPS5133892B1 (enrdf_load_stackoverflow) 1976-09-22

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