Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
  • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
• • 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
• • 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

Definitions

• the present invention relates, in general, to an im proved process for preparing organoaluminum con pounds. More particularly, the invention relates to the use of catalytic elements which provide improved reaction rates in the preparation of organoaluminum compounds. In a preferred embodiment, the invention relates to aluminum alloys containing catalytic elements, Which aluminum alloys provide improved reaction rates in the preparation of dialkylaluminum hydrides. In another em- 7 72 2 2 5 3 3A1 a s 2 Belgian Patent No. 546,432, issued March 24, 1956, to
• diethylaluminum hydride formed in the process of this invention can be reacted with ethylene 'to produce triethylaluminum as follows:
• the over-all efifectcf the two reactions is to produce three moles of triethylaluminurn for each two moles of triethylalmninurn initially present. 7
• the triethylaluminum gained from these processes can then be subjected to a growth reaction with additional olefin and the .growth product in turn is converted into high-molecularweight alcohols and a-oleiins.
• organoaluminum compounds e.g., triethylaluminum
• organoaluminum compounds e.g., triethylaluminum
• a process for preparing triethylalurninum comprises contacting comminuted aluminum (e.g., as aluminum shavings prepared under nitrogen) with sufficient triethylaluminum to Wet the metal surface and then heating the reaction zone to a temperature between about 30 and 130 C. under 10 to 300 atmospheres pressure of a gaseous mixture containing hydrogen and ethylene. It is an object of the present invention to provide aluminum ,alloys which containa reaction-promoting amount of one or more added catalytic' metals.
• the present invention resides in our discovery that the use of a reaction-promoting amount of one or more catalytic elements in conjunction with aluminum gives improved reaction rates in processes wherein aluminum is used in the production of organoaluminum compounds.
• the use of aluminum alloys containing a reaction-promoting amount of one or more catalytic elements is more'effective than the use of aluminum and the catalytic elements separately (i.e., not in alloyed form).
• some elements do not increase the reactivity of aluminum when said aluminum (in alloy form) is used in the production of organoaluminum compounds.
• some elements decrease the efficacy of the catalytic elements in the aluminum. By inference, then, we believe that these elements show a retarding or negative effect on the aluminum. We have discovered that by increasing the amount of the catalytic elements, the effect of these negative elements can be overcome.
• organoaluminum compounds as used herein refer to compounds having the general formula wherein R is a hydrocarbon radical, and R and R are hydrogen, halogen, or a hydrocarbon radical.
• the aforementioned hydrocarbon radical can contain from 2 to 40 carbon atoms andcan be alkyl, aryl, alkaryl, or aralkyl.
• organoaluminum compounds such as the following:
• these elements conform to the following designation: (1) they are hydride formers; (2) most of the elements (at least titanium, zirconium, vanadium, and niobium) form peritectic binary systems with aluminum, and (3) they are apparently electronegative to aluminum even though :scandium, uranium, and hafnium appear to be above aluminum in the usual chart. While most of the elements which work are peritectic-forrners with aluminum, all of the elements which form peritectics with aluminum do not work. For example, barium, lanthanum, and cerium will form a peritectic with aluminum. Yet, they do not work in our invention. It should be noted that, while we have tested some fifty-one metallic elements in aluminum alloys, only the above-listed seven have been found to work.
• titanium, zirconium, niobium, vanadium, scandium, and uranium are preferred.
• titanium and zirconium are the most preferred.
• combinations of the elements can be used.
• Table I gives the lower limits of efiicacy for the catalytic elements when incorporated in very pure (99.99 percent) aluminum.
• Table 11 gives the lower limits of efficacy for the catalytic elements when incorporated in aluminum of about 99.4 percent purity, which corressponds to commercially available aluminum.
• each increase in the amount of catalytic element in the aluminum alloy to a certain level gives an improvement in reactivity.
• the higher the concentration of the catalytic element in the aluminum alloy the greater the reactivity.
• the addition of more catalytic elements produces only a slight increase in reactivity.
• levels of catalytic elements at least equal to or greater than the preferred levels, but the plant levels will, for purposes or economy, be less than the 2 percent indicated as the muimum.
• titanium or zirconium it is desirable, when using titanium or zirconium, to use these elements in an amount of at least 0.02 percent, preferably 0.05 percent, by weight.
• aluminum alloy refers to aluminum alloys wherein the catalytic elements have been deliberately added to the aluminum.
• the catalytic elements can be added to the aluminum by any of the means known to those skilled in the art. Examples of metallurgical means by which the catalytic elements can be added include the following (1) the elements can be added directly; (2) the elements, alloys, or inorganic salts can be added to the primary electrolysis cells; and (3) reductive compounds or mixtures of the elements can be added to the melting furnace.
• aluminum alloy as used herein and in the appended claims refers to aluminum alloys containing at least 98 percent by weight of aluminum.
• catalytic elements can be used is by blending aluminum alloys containing a higher than-necessary concentration of the catalytic elements with aluminum or aluminum alloys containing none, or less than a reaction-promoting amount, of the catalytic elements. By this means, reaction-promoting amounts of the catalytic elements can be maintained in the reaction system.
• catalytic elements has been used herein in order to have a generic term for the elements which work effectively for reaction acceleration in the aluminum alloys used in preparing organoalurninum compounds. From the evidence we have obtained, it appears that the observed catalytic effect is not due to reduction in grain size, which coincidentally occurs in most of the catalytic aluminum alloys used.
• the shape or form of the aluminum alloy used in preparing organoaluminum compounds does not fall within the scope of our invention.
• workers in this field have used comminuted aluminum (e.g., atomized particles or machined shavings) because a large surface area per unit of weight is afforded.
• Example II The procedure of Example II was followed with the exception that 28 grams (1.04 moles) of the pure aluminum rod of Example I was used. Approximately 26 grams of unreacted aluminum was recovered at the end of the procedure. The yield of diethylaluminum hydride was 7 percent of theoretical based on the aluminum conum EXAMPLE 1v in order to more rapidly evaluate the efficacy of various aluminum alloys, a screening test was used.
• the equipment consisted of a standard, one liter, stirred (640 rpm.) autoclave. A stainless steel sample holder was mounted upon the stirrer shaft so as to hold eight cylindrical test specimens of %-inch diameter by l-in. length.
• each of these cylinders was metallographically polished to afford a sensitive means to study the surface topography after the triethylaluminum-hydrogen solution attacks.
• the polished cylinders were placed on the sample holder, 500 milliliters of triethylaluminum was added to the autoclave, and the autoclave was pressured with hydrogen or previous treatment of the aluminum, the addition of the catalytic elements improves the reactivity of the aluminum.
• reaction-promoting amount as used herein term is synonymous with catalytic amount; however, in view of the term catalytic element, the alternative term has been used.
• the reaction of the trialkylaluminum and hydrogen with the aluminum alloy is conducted at a temperature of 80 to 200 C., more preferably 100 to 150, C., and at a pressure of 60 to 350 atmospheres. An excess of hydrogen is used.
• the reaction will occur at any mole ratio of aluminum to trialkylaluminum of from 0.1 to 1, to 10 to 1.. More preferably, the mole ratio of aluminum to triethylaluminum is from 1 to 1, to 4 to 1.
• the aluminum alloys of our invention can also be used in the process of Redman (U.S. Patent No. 2,787,626),
• EXAMPLE H I Thirty grams (1.1 moles) of the aluminum rod containing 0.15 percent titanium'of Example I was cut into to 2000 p.s.i.g. and 250 F. The run was conducted for three hours. A standard coupon of alloy of 1000 ppm, titanium in 99.99 percent aluminum was used as a reference in each run. Each coupon was weighed before and after the run.
• the alloys tested were prepared by air melting in a pure graphite crucible heated by an electric resistance furnace. A Weighed amount of the alloying element was added to a weighed amount of aluminum of 99.99 percent purity. r
• EXAMPLE XIII Charge 150 grams growth product 1 (sample No. RGR-3-178) 12 grams aluminum powder (99.99% pure) Procedure: The procedure was the same as in Example IX. Results: An aluminum analysis of the product indicated that 9.2 percent of the growth product had been converted to the tdialkylaluminum hydride.
• growth product refers to a mixture of alkylalum num compound made by repeated addition of ethylene to trialkylaluminum.
• a typical sample of growth product has the following analysis (alkyl groups).
• Example XII 150 grams growth product (same as used in Example XII) 12 grams aluminum alloy powder (99.99% aluminum containing 2,000 ppm. zirconium) Procedure: The procedure was exactly the same as used in Example IX.
• EXAMPLE XV V In this example, three samples of aluminum powder were atomized by the Aluminum Company of America. Two of the samples were prepared from 99.99 percent pure aluminum. The third sample was prepared from 99.99 percent purity molten aluminum ,to which had been added 0.078 percent of titanium.
• the aluminum powder corresponded to Reynolds 120 commercial powder, with the exception of the added titanium.
• five samples of Reynolds 120 commercial (993+ percent purity) aluminum powders were tested for reactivity. These powders had no titanium added; whatever titanium present occurred naturally.
• the powder contained small amounts of iron and silicon.
• Example XIV eight samples of aluminum powder were ballmilled and were tested for reactivity in the manner de scribed in Example XIV. The results are shown in Table IX. The data therein show the time in hours required to obtain an percent conversion of triethylaluminum to diethylaluminum hydride.
• pounds said compounds being characterized as having the general formula wherein R and R are hydrocarbon radicals containing from 2' to 40 carbon atoms and R is selected from the group consisting of hydrogen and a hydrocarbon radical containing from 2 to 40 carbon'atoms, by the reaction of at least an organic compound and aluminum, the im provement comprising carrying out the process in the presence of an added reaction-promoting amount of at least about 5 parts per million of at least one catalytic element selected from the group consisting of titanium, zirconium, niobium, vanadium, scandium, uranium, and hafnium.
• organoaluminum compounds said compounds being characterized as having the general formula wherein R and R are hydrocarbon radicals containing from 2 to 40 carbon atoms and R is selected from the group consisting of hydrogen and a hydrocarbon radical containing from 2 to 40' carbon atoms, by the reaction of at least an organic compound and aluminum, the im provement comprising carrying out the process with an aluminum alloy containing at least 98 weight percent of aluminum and a reaction-promoting amount, at least about 5 parts per million, of at least one added catalytic element selected from the group consisting of titanium,
• dialkylaluminum hydride by the reaction of a trialkylaluminum, the alkyl radicals of said trialkylaluminum containing from 2 to 40 carbon atoms, with hydrogen and aluminum at an elevated temperature and superatmospheric pressure, the improvement comprising carrying out the reaction with an aluminum alloy containing at least 98 weight percent aluminum and a reaction-promoting amount, at least about 5 parts per million, of at least one added catalytic element selected from the group consisting of titanium, zirconium, niobium, vanadium, scandium, uranium, and hafnium.
• diethylaluminum hydride comprising reacting triethylaluminum with hydrogen and an aluminum alloy at an elevated temperature and superatmospheric pressure, wherein said aluminum alloy comprises about 98 to about 99.98 percent by weight of aluminum and a reaction-promoting amount in the range of about 0.02 to about 2 percent by weight of at least one added catalytic element selected from the group consisting of titanium, zirconium, niobium, vanadium, scandium, uranium, and hafnium.
• catalytic element is titanium
• catalytic element is zirconium.
• catalytic element is vanadium
• catalytic element is scandium
• catalytic element is uranium.
• catalytic element is hafnium
• a process for the preparation of diethylaluminum hydride comprising reacting triethylaluminum with hydrogen and an aluminum alloy at an elevated temperature and superatmospheric pressure, wherein said aluminum alloy comprises about 99 to about 99.95 percent by weight of aluminum and a reaction-promoting amount in the range of about .05 to about 1 percent by weight of at least one added catalytic element selected from the group consisting of titanium, zirconium, niobium, vanadium, scandium, uranium, and hafnium.
• the process, as defined in catalytic element is titanium.
• catalytic element is niobium.
• catalytic element is scandium.
• catalytic element is uranium.
• catalytic element is hafnium.
• dialkylaluminum hydride the alkyl radicals of said dialkylaluminum hydride containing from 2 to 40 carbon atoms, by the reaction of a trialkylaluminum with hydrogen and aluminum at an elevated temperature and superatmospheric pressure, the improvement comprising carrying out the process in the presence of a reaction-promoting amount of at least about 5' parts per million of at least one added catalytic element selected from the group consisting of titanium, zirconium, niobium, vanadium, scandium, uranium, and hafnium.

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