US3576832A

US3576832A - Preparation of organoaluminum compounds

Info

Publication number: US3576832A
Application number: US723911A
Authority: US
Inventors: Warren E Becker; Paul Kobetz
Original assignee: Ethyl Corp
Current assignee: Ethyl Corp
Priority date: 1968-04-24
Filing date: 1968-04-24
Publication date: 1971-04-27
Anticipated expiration: 1988-04-27

Abstract

IMPROVEMENTS IN PROCESSES FOR PRODUCING ORGANOALUMINUM COMPOUNDS ARE DESCRIBED. THESE IMPROVEMENTS INVOLVE THE USE OF PARTICULAR ALUMINUM ALLOYS AS A SOURCE OF ALUMINUM IN THE PROCESSES. IN PARTICULAR, THE ALUMINUM ALLOYS CONTAIN ABOUT 50-98 PERCENT BY WEIGHT OF ALUMINUM AND AT LEAST THREE OF THE ELEMENTS COPPER, IRON, LEAD, MANGANESE, NICKEL, SILICON AND TIN, THE TOTAL QUANTITY OF SAID ELEMENTS BEING ABOUT 0.75 TO 20 PERCENT BY WEIGHT, THE QUANTITY OF SILICON PRESENT BEING 0 TO 10 PERCENT BY WEIGHT.

Description

United States Patent 3,576,832 PREPARATION OF ORGANOALUMINUM COMPOUNDS Warren E. Becker and Paul Kobetz, Baton Rouge, La., assignors to Ethyl Corporation, New York, NY. No Drawing. Filed Apr. 24, 1968, Ser. No. 723,911 Int. Cl. C07f /06 U.S. Cl. 260--448 10 Claims ABSTRACT OF THE DISCLOSURE Improvements in processes for producing organoaluminum compounds are described. These improvements involve the use of particular aluminum alloys as a source of aluminum in the processes. In particular, the aluminum alloys contain about 50-98 percent by weight of alumi num and at least three of the elements copper, iron, lead, manganese, nickel, silicon and tin, the total quantity of said elements being about 0.75 to percent by weight, the quantity of silicon present being 0 to 10 percent by weight.

This invention relates to the production of organoaluminum compounds. More particularly, this invention relates to the use of aluminum alloys as a source of aluminum in processes for producing organoaluminum compounds.

Processes wherein an organoaluminum compound is produced by reacting aluminum with an organoaluminum compound and hydrogen or with olefin and hydrogen in the presence of an organoaluminum compound are well known. See for example U.S. 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 and 3,207,774.

U.S. 3,104,252 discloses the addition to commercially available aluminum of certain catalytic elements viz., titanium, zirconium, niobium, vanadium, hafnium, scandium, and uraniumand the use of the resultant alloys for preparing organoaluminum compounds. In British Patent 1,044,735 the production of organoaluminum compounds using aluminum-silicon binary alloys containing more than 13 percent by weight of silicon is disclosed.

In accordance with the present invention, organoaluminum compounds are produced by reacting aluminum with an organoaluminum compound and hydrogen or with olefin and hydrogen in the presence of an organoaluminum compound employing as aluminum feed to the process an aluminum alloy containing about 50 to 98 percent by weight of aluminum and at least three of the elements copper, iron, lead, manganese, nickel, silicon and tin. The total qauntity of said elements present is about 0.75 to 20 percent by weight and the quantity of silicon when present is up to 10 percent by weight. These aluminum alloys are usually employed in subdivided form. Thus, the aluminum alloys used pursuant to this invention will generally be in the form of turnings, chips, powders, shavings, flakes, chunks, filings, or other type of relatively small pieces or fragments.

The reactivity of any given form of these alloys in the process is as good as, if not better than, the reactivity of the corresponding form of commercially available aluminum. As brought out in U.S. 3,104,252, the purity of commercially available aluminum corresponds to about 99.4 percent aluminum, although nowadays even higher purity grades of aluminum are commercially available.

It will be noted from Table VI of U.S. 3,104,252 that each of the elements copper, iron, lead, manganese, nickel, silicon and tin, when tested individually in a highly pure aluminum-titanium alloy was found to be a negative Patented Apr. 27, 1971 the patentees teach (column 2, lines element and that 40-42 By inference, then, we believe that these elements show a retarding or negative elfect on the aluminum.

In the case of silicon the foregoing teachings of U.S. 3,104,252 are reinforced by results reported in British 1,044,735 which show that addition to aluminum of amounts of silicon up to about 12 or 13 percent gave unfavorable results as compared to the use of aluminum itself as a raw material in the manufacture of organoaluminum compounds.

It is also worth noting that from the information tabulated in column 10 of U.S. 3,104,252 it would not be expected that the alloys used in this invention would react at all.

Another feature of this invention is that the aluminum alloys utilized as feed in the process tend to be quite inexpensive, oftentimes much less expensive than regular commercially available aluminum. Moreover, it is not necessary to add one or more of the catalytic elements titanium, zirconium, niobium, vanadium, hafnium, scandium, and uranium disclosed in U.S. 3,104,252, which catalytic elements themselves tend to be expensive. However, one or more such elements may be present in the alloys used pursuant to this invention.

As noted above, the aluminum alloys used pursuant to this invention as a source of aluminum in the above noted processes contain about 50 to 98 percent by weight of aluminum and at least three of the elements, copper, iron, lead, manganese, nickel, silicon and tin. Another feature of these alloys is that the total quantity of these elements present ranges from about 0.75 to 20 percent by weight, the quantity of silicon, if present, not exceeding about 10 percent by weight. Thus, the aluminum alloys utilized pursuant to this invention may contain 3, 4, 5, '6 or 7 of these elements although from the standpoint of cost and availability alloys containing at least six of these elements are generally most preferable. By the same token, aluminum alloys containing all seven of these elements are especially preferred.

Insofar as aluminum content is concerned, preferred alloys for use in accordance with this invention are those which contain about to 98 percent by 'weight of aluminum as they contain a high proportion of aluminum and are available from various existing commercial sources. Particularly preferred alloys contain about to 96 percent by weight of aluminum.

The total quantity of three or more of copper, iron, lead, manganese, nickel, silicon and tin is about 0.75 to 20 percent by weight, although it is usually preferable that this quantity fall Within the range of 0.75 to 12 percent by weight. Particularly preferred are alloys containing from about 1 to about 10 percent of three or more of these elements. And in all cases, the greater the number of these elements present, the more preferred is the alloy.

From the cost effectiveness standpoint it is usually desirable to use alloys wherein three or more of the foregoing elements are present up to certain maximum respective quantities as follows:

all of the percentages being expressed by weight. From a practical standpoint the alloys will contain three or more of the following elements within the following ranges or proportions:

Element: Weight percent Copper 0.1- Iron 0.1-2.5 Lead 0.1-1.5 Manganese 0.05-3 Nickel 0.05-25 Silicon 0.1- Tin 0.05-1

It will be understood and appreciated that still other elements may be present in the aluminum alloys employed in accordance with this invention. For example, besides containing aluminum and at least three of the elements copper, iron, lead, manganese, nickel, silicon, and tin, the alloys may contain one or more other common alloying elements or impurities such as zinc, magnesium, titanium, boron and the like. Ordinarily the amounts of these other elements present will varye.g., titanium, if present, will usually not be in excess of about 0.15 percent and the amount of zinc, if present, will normally range up to about percent. The character of the variety of aluminum alloys which may be used in the practice of this invention will become even further apparent from the illustrative examples set forth hereinafter.

The aluminum alloys employed pursuant to this invention may be made by conventional metallurgical techniques and many such alloys are available from a wide variety of commercial sources at exceedingly low cost. It is not necessary that the composition of the aluminum alloy fed to the process be uniform. Indeed, a feature of this invention is that a plurality of different aluminum alloys may be fed to the process with or without purer forms of aluminum provided that the overall composition of the feed averages out in accordance with the proportions described above.

Another feature of this invention is the fact that it enables the economical recovery of certain desirable metals from sources in which it is customarily found. By way of example, typical aircraft aluminum alloy contains significant quantities of zinc and copper along with lesser quantities of magnesium, manganese, iron, silicon and chromium. Use of such alloy in accordance with this invention makes possible the recovery of these elements, especially the zinc, copper and manganese values.

When conducting the processes of this invention it is desirable that the reaction system contain an alkali metal catalyst. These catalysts shorten the induction time of the reaction and also tend to speed up the reaction rate. The nature of many of these alkali metal adjuvants and the modes by which they are employed are fully discussed in the prior art. See for example US. 2,892,738; 3,026,345; 3,050,540; 3,050,541; 3,077,490; and 3,100,786. Of these catalytic materials, those based on sodium are most preferable for use in accordance with this invention because of their considerable effectiveness and generally lower cost.

The processes of this invention can be effectively used to prepare a wide variety of different organoaluminum compounds including for example hydrocarbon aluminum hydrides, hydrocarbon aluminum halides, trihydrocarbon aluminum compounds, and mixtures thereof. Thus the organoaluminum compounds produced by the processes of this invention may be depicted by the formula R R R AI wherein from 1 to 3 of R R and R are hydrocarbon radicals and the balance, if any, are halogen or hydrogen. Each hydrocarbon radical may contain up to 40 or more carbon atoms. The invention is particularly well suited for the preparation of alkyl aluminum compounds, especially dialkylaluminum hydrides, or aluminum trialkyls, or mixtures of both. However, the hydrocarbon radicals present in the products may be aryl, alkaryl, aralkyl, cycloalkyl or the like.

The reaction conditions utilized in practicing the process of this invention are susceptible to considerable variation. For example when employing the present aluminum alloys to prepare organoaluminum compounds by reaction among aluminum, organo aluminum compound and hydrogen with or without the co-utilization of olefin the reaction temperature will generally fall within the range of about 90 to about 170 C., temperatures between about 120 and about 150 C. being preferred. By the same token, the reaction pressures used in these process embodiments will generally be in the range of about 500 to about 5000 p.s.i., with pressures of from about 700 to about 2500 p.s.i. being generally preferred.

The proportions of the reactants are not critical although it is desirable that there be an excess amount of hydrogen and of olefin (if used) relative to the amount of aluminum contained in the reaction system.

Reaction times may likewise be varied to suit the needs of the occasion. Ordinarily, the reaction time may be in the range of about 5 minutes up to about 6 or 8 hours, or even longer if desired. However, for an eflicient commercial installation reaction times falling within the range of about minutes to about 3 hours are generally most suitable and are therefore preferred.

It is very desirable to provide ample agitation or turbulence in the reaction system to insure thorough mixing of the reactants and intimate contact between the gaseous and liquid phases involved. If desired, suitable anhydrous solvents which do not adversely affect the desired reaction may be employed. Exemplary of such solvents are saturated aliphatic hydrocarbons (e.g., paraffinic hydrocarbons, cycloparaflinic hydrocarbons, or mixtures thereof), aromatic hydrocarbons, saturated fiuorocarbons, silicone oils, and other similar materials which are inert to the reactants and the organoaluminum product. It is feasible, although ordinarily not recommended, to conduct the reaction can be readily controlled in the absence of such as amines, ethers, or the like so long as there is an insufiicient amount of such material present to complex with all of the organoaluminum compound(s) initially present in the system.

In preferred form the various process embodiments of this invention are carried out in the absence of an ancillary solvent such as those referred to above. The reaction canb e readily controlled in the absence of such solvents. Moreover, the lack of an ancillar solvent means that the reactors need not be sized to accommodate such materials.

As noted above, it is preferable to conduct the various process embodiments of this invention in the presence of an alkali metal adjuvant or catalyst. For best results, the alkali metal content of the system will generally be in the range of about 0.1 to about 2 percent by weight (expressed in terms of alkali metal although it will normally be present in the form of a chemical compound or complex) based on the Weight of the organoaluminum compound(s) initially present in the reaction system. Among the preferred catalysts for addition to the reaction system are metallic sodium, sodium hydride, sodium aluminum tetrahydride, sodium aluminum hexahydride, sodium fluoride, sodium aluminum tetraalkyl, sodium aluminm dialkyl dihydride, sodim aluminum trialkyl hydride, and the like, especially where the alkyl groups (if present in the catalyst) each contain up to about 18 carbon atoms. The corresponding sodium aluminum aryls and cycloalkyls are also entirely suitable. Indeed, lithium, potassium, rubidium and cesium are suitable catalysts, whether charge into the system in metallic form or in the form of a chemical compound or complex corresponding to the sodium derivatives already referred to. Mixtures of different alkali metals or compounds thereof may be used.

For best results, clean, essentially anhydrous particulate aluminum alloys of the makeup described herein are employed. Inasmuch as the reaction should be conducted in an essentially anhydrous environment it is desirable to insure that the aluminum alloy feed to the process is itself free from excess moisture. In addition (the alloy should be essentially free from any oily residue, dirt, soil or other extraneous contaminants which would tend to interfere with intimate contact between the aluminum alloy and the other reactants being used.

Although the size of the particulate alloy is not critical, it is generally desirable that the particles range in size from fine particles up to about 4 mesh. This enables the achievement of the most rapid reaction rates. It will be clearly understood and appreciated however that even larger sized particulate aluminum "alloys may be successfully used in the practice of this invention.

In order to demonstrate the practice and advantages of this invention, the following illustrative examples are presented.

EXAMPLE I An autoclave was charged with 75 ml. of triethylaluminum, 1 gram of sodium, and 1 grams of aluminum alloy turnings having the following composition:

Components: Weight percent Aluminum 86.68 Copper 3.50 Iron 0.50 Manganese 0.50 Silicon 0.50 Chromium 0.30 Magnesium 2.50 Titanium 0.02 Zinc 5.50

The autoclave was sealed and the contents heated to 140 C. under 2500 psi. hydrogen pressure for about one hour. After discontinuing the reaction, the metallic residue was isolated, washed, dried and weighed andit was found that about 2.4 grams of aluminum had been consumed in forming diethyl aluminum hydride.

EXAMPLE II The procedure of Example I was repeated except that the aluminum alloy turnings had the following composition:

Components: Weight percent Aluminum 86.99

Copper 3.50 Iron 1.00

Silicon 8.50 Titanium 0.01

In the course of this reaction about 2.9 grams of aluminum were consumed in forming diethyl aluminum hydride.

EXAMPLE III The procedure of Example I was repeated using turnings of an aluminum alloy of the following composition:

Components: Weight percent Aluminum 95.09

Iron 0.25

Manganese 0.25 Silicon 0.25 Chromium 0.15 Magnesium 4.00 Titanium 0.1

The reaction resulted in the consumption of about 2.8 grams of aluminum and the formation of diethyl alumi num hydride.

6 EXAMPLE IV The procedure of Example I was applied to turnings of an alloy of the following composition:

Component: Weight percent Aluminum 97.29 Iron 0.50 Manganese 1.00 Silicon 0.50 Chromium 0.20 Magnesium 0.50 Titanium 0.01

Approximately 2.6 grams of aluminum was consumed in producing diethyl aluminum hydride.

EXAMPLE V A reaction as in Example I was conducted except that the alloy turnings had the following composition:

Component: Weight percent Aluminum 86.75 Copper 3 .50 Iron 0.5 0 Manganese 0.50 Silicon 0.50 Chromium 0.30 Magnesium 2.50 Zinc 5 .5 0

In forming diethyl aluminum hydride about 2.8 grams of aluminum was consumed.

EXAMPLE VI The procedure of Example I was repeated except that the aluminum alloy turns were produced from an aluminum scrap which analyzed as follows:

It was found that approximately 4.1 grams of aluminum was consumed in forming diethyl aluminum hydride.

EXAMPLE VII The procedure of Example I was repeated except that the aluminum alloy turnings were prepared from an alummum alloy scrap of the following composition:

Component: Weight percent Copper 0.3 Iron 0.8 Manganese 0.4 Silicon 1.5 Chromium 0.6 Magnesium 1.5 Titanium u 0.03 Zinc 2.5 Lead 0.2 Nickel 0.05 Silver 0.01 Aluminum and other impurities 92.11

The reaction resulted in the production of diethyl alu' minum hydride and the consumption of about 3.1 grams of aluminum. It is interesting to observe that when the procedure of Example I was applied to turnings made from commercially available aluminum 99'.4 percent aluminum) essentially the same results were obtainedabout 3.4 grams of aluminum was consumed in forming the diethyl aluminum hydride.

The organoaluminum compounds which can be prepared by the process of this invention are of known utility as ingredients for polymerization catalysts and as chemical intermediates in the production of olefins, alcohols, and other valuable products. For further details, reference may be made to the patent literature, including the disclosures of the US. patents cited above.

We claim:

1. In a process wherein an organoaluminum compound is produced by reacting aluminum with an organoaluminum compound (hereinafter defined) and hydrogen or with olefin and hydrogen in the presence of an organoaluminum compound (hereinafter defined), the improvement which comprises employing as aluminum feed to the process an aluminum alloy containing about 50 to 98 percent by weight of aluminum and at least six of the following elements in the amounts shown:

Element: Weight percent Copper 0. 15 Iron 0.1-2.5 Lead 0. 11.5 Manganese 0.05-3 Nickel 0.052.5 Silicon 0.1--10 Tin 0.05-1

the total quantity of said elements present being about 0.75 to 20 percent by weight; the organoaluminum compound utilized in the process having the formula R R R Al wherein from 1 to 3 of R R and R are hydrocarbon radicals and the balance, if any, are halogen or hydrogen, each such hydrocarbon radical containing not more than about 40 carbon atoms.

2. The process of claim 1 wherein all of said elements are present in the aluminum alloy.

3. The process of claim 1 wherein said alloy contains about 80 to 96 percent by weight of aluminum.

4. The process of claim 1 wherein said total quantity is about 0.75 to 12 percent by weight.

5. The process of claim 1 wherein said aluminum alloy contains about 80 to 96 percent by Weight of aluminum and wherein said total quantity is about 0.7 5 to 12 percent by weight.

6. The process of claim 1 wherein an alkali metal catalyst is employed in the reaction.

7. In a process wherein an organoaluminum compound is produced by reacting aluminum with an organoaluminum compound (hereinafter defined) and hydrogen or with olefin and hydrogen in the presence of an organoaluminum compound (hereinafter defined), the improvement which comprises employing as aluminum feed to the process an aluminum alloy containing about 50 to 98 percent of aluminum and at least six of the elements copper nickel Iron silicon Lead tin manganese the total quantity of said elements present being about 8 0.75 to 20 percent, the maximum quantity of those of said elements present being as follows:

Percent Copper Iron 2.5 Lead 1.5

Manganese Nickel Silicon Tin 1 all of the percentages being expressed by weight; the organoaluminum compound utilized in the process having the formula R R R A1 wherein from 1 to 3 of R R and R are hydrocarbon radicals and the balance, if any, are halogen or hydrogen, each such hydrocarbon radical containing not more than about 40 carbon atoms.

8. In a process wherein an alkyl aluminum compound is produced by reacting aluminum with an alkyl aluminum compound and hydrogen in the presence of an alkali metal catalyst or with olefin and hydrogen in the presence of copper iron lead manganese the total quantity of said elements present being about 0.75 to 20 percent, the quantity of those of said elements present being as follows:

Element:

Copper Iron Weight percent 0.1-5 0.1-2.5 Lead 0.1-1.5 Manganese 0.05-3 Nickel 0.05-2.5 Silicon 0.1-10 Tin 0.05-1

all of the percentages being expressed by weight.

9. The process of claim 8 wherein all of said elements are present in the aluminum alloy.

10. The process of claim 8 wherein a sodium catalyst is employed in the reaction.

References Cited UNITED STATES PATENTS 5/1962 Ziegler et al. 9/1963 Radd et al. 7/1968 Ichiki et al. 260-448A FOREIGN PATENTS 1/ 1961 Great Britain 260-448A TOBIAS E. LEVOW, Primary Examiner H. M. S. SNEED, Assistant Examiner U.S.C1.X.R. -139 j 9;

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 576,832 Dated April 2l l97l Inventor(s) Warren E. Becker and Paul; Kobetz It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 5 reads "organo aluminum", should read organoaluminum --5 line 37 reads "action can be readily controlled in the absence of such", should read action 1 the presence of certain basic substances such line &5 reads "canb e readily", should read can be readily --3 line 68 reads "charge", should read charged Column line 71 reads "Titanium --O. 1', should read Titanium "-0.01 Column 6, line 20 reads "Aluminum --86.75", should read Aluminum -86.7O

Signed and sealed this Zhth day of August 1971.

(SEAL) Attest:

EDWARD M.FIETCHER,JR. WILLIAM E. SGHUYLER, JR. Attesting Officer Commissioner of Patents