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US3254009A - Production of metal alkyls - Google Patents

Production of metal alkyls Download PDF

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US3254009A
US3254009A US262285A US26228563A US3254009A US 3254009 A US3254009 A US 3254009A US 262285 A US262285 A US 262285A US 26228563 A US26228563 A US 26228563A US 3254009 A US3254009 A US 3254009A
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aluminum
compound
lead
sodium
metal
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Ziegler Karl
Lehmkuhl Herbert
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ZIEGLER AG
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/13—Organo-metallic 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/90—Antimony 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
    • C07F5/062—Al linked exclusively to C
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/94—Bismuth compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals

Definitions

  • This invention relates to new and useful improvements in the production of metal alkyls and particularly of alkyls of the metals lead, tin, antimony, bismuth, zinc,
  • One preferred embodiment of the 4 invention concerns the production of lead tetraalkyls.
  • Such mixtures are for instance typically formed in the electrolytic production of metal alkyls and especially alkyls of the metals lead, tin, antimony, bismuth, zinc, cadmium, mercury.
  • an alkali metal aluminum alkyl complex as for instance sodium or potassium aluminum tetraethyl to electrolysis using one of these metals, such as, for instance lead, as the anode
  • the corresponding metal alkyl compounds such as tetraalkyl lead are formed.
  • Trialkyl aluminum is formed or liberated at the same time. If the alkali metal aluminum tetraalkyl compound was a tetraethyl compound, triethyl aluminum is liberated which establishes its own independent liquid layer and does not intermix with the sodium aluminum tetraethyl complex which under the conditions of reaction is normally present in molten condition.
  • the aluminum trialkyl, and particularly aluminum triethyl may thus be readily separated from the metal aluminum tetraalkyl complex.
  • the separation of the aluminum trialkyl and particularly of the aluminum triethyl from the other metal alkyl compounds, and particularly the metal ethyl compounds, which are formed during electrolysis offers in most ⁇ cases considerable difliculties. This is particularly'true for the mixture of lead tetraalkyl and aluminum trialkyl and most specifically for lead tetraethyl and aluminum triethyl because the boiling points of these products are normally so relatively closely adjacent that separation by distillation of mixtures of these materials is difficult if not impossible.
  • mixtures of tetraalkyl lead and aluminum trialkyl and particularly mixtures of tetraethyl lead and aluminum triethyl will decompose relatively readily because the lower aluminum trialkyls and particularly aluminum triethyl will slowly degenerate with heat, being dissociated into dialkyl aluminum hydride and the corresponding hydrocarbon.
  • a mixture of tetraethyl lead and triethyl aluminum will, with heat, form diethylaluminum hydride and ethylene.
  • diethylaluminum hydride has a reducing effect upon the tetraethyl lead converting the same to metallic lead with the formation of ethane.
  • One object of the invention comprises an improvement United safes Patent o 3,254,009 Patented May 31, 1966 JCC in the production of metal alkyls with an alkylating agent l
  • a further object of the invention comprises a novel process for the separation of metal alkyls from aluminum-trialkyls in mixtures containing the same.
  • Still further objects of the invention comprises novel electrolytic processes for the production of metal alkyls.
  • a metal alkyl production with the use of an alkyl radical supplying agent having the general grouping Me[Al(R)3-] is effected, at a point between the metal alkyl formation and the separation of formed metal alkyl, in the presence of a complex compound of the general formula: Me [Al(R)3OR] in which Me is an alkali metal of the group consisting of sodium and potassium, R is an alkyl radical with up to 6 carbon atoms and R is an organic radical selected from the group consisting of alkyl and cycloalkyl radicals to thereby substantially assure freedom from A1R3 and to react said complex compound to form AIRZOR.
  • one limiting case of the metal alkyl production in accordance with the invention is that in which the alkylating agent itself is said alkali metal alkyl aluminum alkoxy complex compound.
  • the formation of trialkyl aluminum is avoided ab initio as for instance in an electrolytic alkylation in which the metal of the desired metal alkyl is used as anode and the said complex compound constitutes the electrolyte.
  • the other limitiing case is that in which a mixture of the desired metal alkyl and aluminum trialkyl (regardless of its derivation) is present and is to be used for the metal alkyl production.
  • the trialkyl aluminum is eliminated byreaction with said alkoxy complex compound i.e.
  • alkali metal tetraalkyl aluminum complex compound it is converted to an alkali metal tetraalkyl aluminum complex compound.
  • This is accomplished in an electrolytic alkylation .in which the metal of the desired metal alkyl is used as anode and an alkali metal aluminum tetraalkyl is employed as alkylating electrolyte.
  • the trialkyl aluminum containing electrolysis product being acted with said alkoxy complex compound for the elimination of the aluminum trialkyl.
  • a further case of metal alkyl production in accordance with the invention is presented by conducting the alkylation, as for example electrolytic alkylation, with the use of alkali metal tetraalkyl aluminum and said alkali metal trialkyl aluminum alkoxy complex compound. In that case the products resulting from the alkylation are substantially free from trialkyl aluminum.
  • a mixture containing aluminum trialkyl and an alkyl of a metal other than aluminum is reacted with a complex compound of the general formula Me[Al(R')3OR], in which Me is an alkali metal preferably sodium or potassium, R is an alkyl radical up to 6 carbon atoms and advantageously a straight chain alkyl radical with up to 4 and preferably 2-4 carbon atoms and in which R is a member of the group consisting of alkyl and cycloalkyl radicals, the alkyl radicals having advantageously 2 to 12 preferably 2 to 8 and especially 4 carbon atoms.
  • Me is an alkali metal preferably sodium or potassium
  • R is an alkyl radical up to 6 carbon atoms and advantageously a straight chain alkyl radical with up to 4 and preferably 2-4 carbon atoms and in which R is a member of the group consisting of alkyl and cycloalkyl radicals, the alkyl radicals having advantageously 2 to 12 preferably 2 to 8 and especially 4 carbon atom
  • reaction thus results in the elimination of the trialkyl aluminum compound and the formation of an alkali metal tetraalkyl aluminum compound and an alkoxy aluminum dialkyl compound in admixture with the desired metal alkyl compound.
  • This mixture may now be further treated for the separation, such as by distillation of the desired alkali metal compound.
  • the invention in its application readily lends itself to the separation of the alkyls and particularly lower alkyls of the metals lead, zinc, mercury, cadmium, antimony, bismuth and tin.
  • One electrolytic embodiment of the invention concerns the electrolytic production of alkyls of metals other than aluminum and particularly of the metals lead, tin, antimony, bismuth, Zinc, cadmium, mercury and especially of lead tetraalkyls from complex compounds of the general formula Me[Al(R)4] in which Me and R have the above given connotation.
  • the metal, as for instance, lead, of which the alkyl compound is to be produced is used as the anode together with the alkali metal aluminum tetraalkyl compounds preferably present in substantially molten condition as the electrolyte.
  • the preferred electrolyte is a mixture of potassium and sodium aluminum tetraalkyl compounds with the potassium component predominating.
  • n is the valence of the metal the alkyl compound of which is produced
  • lead tetraalkyl such as, for instance 4 mol aluminum triethyl and lead tetraethyl which is practically insoluble in the electrolyte mixture of, for instance, potassium and sodium aluminum tetraethyl with the Ipotassium component predominating.
  • n is the valence of the metal the alkyl compound of which is produced
  • lead tetraalkyl such as, for instance 4 mol aluminum triethyl and lead tetraethyl which is practically insoluble in the electrolyte mixture of, for instance, potassium and sodium aluminum tetraethyl with the Ipotassium component predominating.
  • the resulting mixture is, on the other hand, not readily separable by distillation into its components for the recovery of the desired metal alkyls because, for instance, aluminum triethyland tetraethyl lead have boiling points that are closely adjacent. If, however, in accordance with the invention, there is added to this mixture 4 molecules of alkali metal alkoxyalu-minum-triethyl, immediately the following double reaction takes place:
  • the tetraethyl lead is mixed with the alkoxy-aluminum-diethyl while the alkali metal aluminum tetraethyl, in case the sa-me is sodium, for instance, will separate at temperatures above 110 C. as a liquid layer while the same will be separated in substantially solid form when operating at temperatures below 110 C.
  • a separation of the mixture of tetraethyl lead and the diethyl-alkoxy-aluminum is then readily possible.
  • Tetraethyl lead may be removed by distillation, particularly with the suitable selection of the OR to assure an advantageous boiling point differential. Good results are thus obtained when there is selected for R a butyl radical.
  • the -mixture containing the three components may be subjected to distillation for the removal of the tetraethyl lead whereupon the alkoxy aluminum dialkyl, such as the alkoxy-aluminum-diethyl, is distilled off or separated out by mechanical separation of nonmiscible phases.
  • the sodium aluminum tetraethyl is returned to the electrolyte and balances the amount of this material used up in the electrolysis.
  • the compound of ⁇ the general for-mula ROAl(C2H5)2 may then be worked up and reconverted into the compound as below set forth in detail in connection with an alternative embodiment of the invention.
  • An alternative electrolytic embodiment of the invention concerning the electrolytic production of alkyls of metals other than aluminum and particularly of lead, tin, antimony, bismuth, zinc, cadmium, mercury and especially of lead tetraalkyls resides in the use as electrolyte of the said complex compound of the general formula Me[Al(R)3OR], using as anode, the metal of which the desired alkyl is to be formed.
  • metallic potassium or preferably sodium are deposited at the cathode, either as such or in the form of their alloys, while there is deposited at the anode a mixture of the alkyl compound of the metal of the anode together with n molecules of the .compound of the formula Al(R')2OR, n being the valence of the metal in the formed metal alkyl.
  • n being the valence of the metal in the formed metal alkyl.
  • a 'lead anode and an alkali metal alkoxy aluminum triethyl as the material in the electrolysis, there results at the anode a mixture composed of tetraethyl lead and four molecules of the compound Al(C2H5)2OR.
  • the equation of the complete chemical reaction involved in the electrolysis is in this case as follows:
  • alkyl of other metals such as zinc, mercury, cadmium, antimony, bismuth, and tin
  • specific examples are thus, for instance, lead tetraethyl, zinc diethyl, mercury diethyl, cadmium diethyl, antimony triethyl, bismuth triethyl, tin tetraethyl, and the corresponding propyl and lower and higher alkyl derivatives of these metals.
  • the compounds of the formula ROAl(R)2 do normally not possess the reactivity of aluminum trialkyls. Especially, they will not give the characteristic sodium uoride compounds of the aluminum trialkyls which possess an excellent conductivity. Accordingly the electrolytic conductivity of the complex compounds of the formula Me[Al(R)3OR] is relatively bad so that when electrolyzing these compounds alone a relatively high current consumption Will have to be taken into account. In spite of the higher current consumption, the advantages of the process according to the invention are so considerable because of the facilitated separability of the reaction products, that in comparison thereto the disadvantages are unimportant.
  • the current consumption may be appreciably lowered when using as the electrolyte a mixture of the complex compounds Me[Al(R)3OR] With complex compounds of the general formula Me [Al(R)4] of which the latter possess a much better conductivity. For this reason there is to be used as the principal electrolyte a compound of the formula Me[Al(R)4] to which the compound of the formula Me[Al(R)3OR] has been given as an addition.
  • OR By a suitable selection of the residue OR the boiling points of both components may be xed at any desired, suitable diiferential. In selecting OR, however, it may be necessary to obtain an optimum cornpromise. OR should not be too small because otherwise the boiling point Will be too low. OR, on the other hand, shall not be too large because otherwise the ballast of the OR which is otherwise immaterial for the process becomes too large and the conductivity of the complex electrolyte will be reduced. As compound for the production of, for instance, tetraethyl lead, thebutoXy-diethylaluminum may be used successfully.
  • the 1:4 mixture Pb(C2H5)4-(C2H5)2AlOC4H9 has the weight proportionate composition ratio of 323:632, that is, the same consists of approximately 1A of tetraethyl lead and ZA of the butoXydiethyl-aluminum.
  • a simple single and very easily entirely continuously conductible distillation will yield the -lead compound as the distillate and the lead free aluminum compound as the residue. In this manner, the problem of the separation of the tetraethyl lead is solved in the most simple manner.
  • there should be used in this case as an essential component of the electrolyte preferably a compound It is, of course, understood that depending upon the reaction conditions other corresponding compounds may be used in accordance with the invention.
  • the compounds of the general formula may be produced in various ways.
  • One mode of production comprises the reaction of complex compounds of the formula Me[Al(R)4] with alcohols in accordance with the following equation:
  • the practical execution of this embodiment may be effected :by transferring the spent electrolyte, or, when operating with a diaphragm separating the cathode and anode spaces, the catholyte, together with thesodium or potassium into a pressure reactor and, after the addition of the compoundl (C2H5)2AlOR obtained in the anode space, convert by treatment with hydrogen into the cornpound Me[(C2H5)2AlH(OR)] and to treat the same with ethylene.
  • the amount of alkali metal separated at the cathode during the electrolysis is just suflicient for this regeneration.
  • the treatment with ethylene is preferably carried out at 130 to 220 C., particularly 150 to 200 C. with a pressure of up to 100 atmospheres, particularly 1 to 20 atmospheres.
  • a substantially closed cycle process may be carried out in accordance with the illustrated cycle for, for instance, tetraethyl lead:
  • the molten sodium complex compound is stirred with powdered potassium chloride at about 120 C. whereupon the same is -decanted from undissolved sodium chloride.
  • the molten sodium complex compound is stirred with powdered potassium chloride at about 120 C. whereupon the same is -decanted from undissolved sodium chloride.
  • the cathodically deposited sodium runs downwardly on the cathode as a liquid lm and can there easily be removed from the electrolytic device.
  • the anode and cathode are vertically concentrically arranged tubes, the anode portion being composed of perforated electrically insulated material :behind which the metal to lbe dissolved is arranged in the form of granules.
  • the diaphragm is equally present in tubular -for-m and is inserted between anode and cathode.
  • the electrolysis itself may be thus constituted relatively simply.
  • the anode space may be appropriately separated from the cathode space by a diaphragm. There is then preferably.
  • the anolyte is advantageously saturated with (R)2A1OR so that upon electrolysis, already the rst small amount of the metal alkyls and of the compounds of the formula (R)2A1OR which are formed will separate in substantially liquid form.
  • a valuable composition of the electrolyte for the production of the ethyl compounds of different metals may be the following: Sodium 100 to 20%, potassium 0 to 80%, [(C2H5)4Al]- 95 to 50%, [(C2H5)3A1OR] 5 to 50%.
  • Suitable electrolytes are, for instance, the following mixtures, indicated in mols:
  • a particularly preferred method according to the inv Vention is carried out by electrolyzing the mixture of the electrolyte compounds ina cellunder vacuo, whereby the metal alkyl formed or the metal alkyl together with the alkoxy aluminum dialkyls is continuously distilled ott.
  • the second described electrolytic embodiment of the invention possesses a number of considerable advantages.
  • One of the principal benefits is the relatively simple, readily immediate separability of the desired metal alkyls from the electrolysis ⁇ lay-products, which are formed in accordance with the invention, which advantage is particularly true and of great value for the production of tetraalkyl lead such as tetraethyl lead.
  • a further advantage resides in the preferred embodiment involving the regeneration of compounds of the general formula Me [Al(R')3OR] however avoiding the necessity of making aluminum trialkyl from aluminum hydrogen and olens.
  • the method in accordance with the invention is characterized by a better space time yield in the hydrogenation phase of the cyclic process.
  • the sodium hydride formation under pressure proceeds more rapidly than the synthesis of the diethylaluminum hydride in accordance with the equation
  • a still fur-ther advantage resides in the relatively small current requirement of the electrolysis in View of the relatively high conductivity of the electrolyte.
  • a most important advance, however, when proceeding in accordance with the method of the invention, is the fact that by depositing an alkali metal preferably sodium at the cathode there a liquid metal is obtained, the separation and removal of which liquid metal can be effected without any difculties and does not involve any more any danger or problem of short circuiting Within the cell.
  • the elec- Itrolyte in accordance with said second described embodiment, has ⁇ a decidedly lower electric conductivity than the substantially pure alkali aluminum tetraalkyl complex electrolyte in accordance with the first described embodiment. It is thus possible when proceeding, in accordance withthe latter, to electrolytically produce the desired metal alkyl compounds with materially lowered energy requirements of the electrolysis cell for the same yields or, alternatively, to obtain yields of about 50% higher with the same energy.
  • the mutual miscibility of the phase aluminum triethyl and methal ethyl, on the one hand, molten alkali aluminum tetraethyl, on the other, is less than is normally the case for the miscibility of the phases Al(OR)(C2H5)2, metal ethyl, on the one hand,
  • Example 1 3320 g. (220 mol) of sodium aluminum tetraethyl are stirred with 740 g. mol) of potassium chloride for five hours at 150 C. After settling of the sodium chloride which forms, the resultant equimolar mixture of sodium aluminum tetraethyl and potassium aluminum tetraethyl is subjected to electrolysis While in molten condition.'
  • the cathode is a copper cylinder and at a distance of about 1 centimeter a perforated synthetic resin cylinder of teon, polypropylene or high molecular Weight low pressure polyethylene is positioned.
  • a diaphragm consisting of hardened lter paper or of a line textile or glass lter fabric is stretched over the synthetic resin cylinder.
  • the ⁇ anode space is situated behind the diaphragm and is lled with lead spheres and any lead dissolved during electrolysis can be continuously replenished with additional lead spheres in the anode space.
  • the heating of the electrolyte or removal of any current produced heat during the electrolysis is eiected by circulating a liquid having a temperature of about 100 C. through the interior of the closed cathode cylinder. Heat input or heat removal at the outer cylinder is so regulated that the temperature within the anode space does not exceed about 70 C.
  • the temperature Within the anode space is preferably maintained at about 100 C. while that within the anode space is maintained at about 70 C.
  • the conductivity of the electrolyte mixture used is 4.5 10"2 (D cm.)1 at 100 C. Current intensity is adjusted to about 20 A. corresponding to a cell voltage of 2 volts.
  • the ow-oif from the anode space is adjusted to cc. per ampere hour so that a reaction mixture with about lead tetraethyl runs olf.
  • about 3,600 g. electrolyte are flown through the electrolytic cell at 20 A.
  • the electrolyte drained from the anode space consists of two layers. , The upper layer which mainly consists of sodium aluminum tetraethyl is freed from small amounts of dissolved lead tetraethyl and aluminum triethyl under a vacuum of 0.5 mm. Hg and 120 C. and may subsequently be again used as electrolyte for a new electrolysis.
  • the distillate is combined with the lower layer which now consists of 700 g. lead tetraethyl and 1,020 g. aluminum triethyl.
  • the separation of the mixture of lead tetraethyl and aluminum triethyl may be effected in accordance with the process described in the following examples.
  • Example 2 A mixture of 700 g. lead tetraethyl and 1,020 g. aluminum triethyl is stirred for 1 hour at 100l C. with 1,880 g. of sodium butoxy aluminum triethyl.
  • the reaction mixture separates into 2 liquid layers. The upper layer is freed from small amounts of dissolved lead tetraethyl under a vacuum of 0.5 mm. Hg and at 100 C.
  • the distillation residue is v
  • Example 3 instead of the 1880 g. sodium bu-toxy aluminum triethyl used in Example 2, the mixture of 700 g. lead tetraethyl and 1020 g.
  • aluminum triethyl formed according to Examplel may, for example, also be reacted with 2130 g. of sodium-hexyl-oxy-aluminum triethyl Pure lead tetraethyl distills under these condi-' or 2130 g. sodium isohexyl-oxy-aluminum 'triethyl H Na(C2H5)3A10oH2 l3-(CHmong A t...
  • Example 4 3320 g. of sodium aluminum tetraethyl and 740 g. of potassium chloride are stirred for 5 hours at 140 C. After settling of the sodium chloride which forms the mixture comprising equivalent amounts of sodium aluminum tetraethyl and potassium aluminum tetraethyl is subjected to electrolysis in the apparatus described in Example 1 using an anode of lead. The procedure is the same as in Example 1 except tha-t the ow-off from the anode space Iis so adjusted that a reaction mixture with 10% lead tetraethyl is obtained, i.e. 30 cc. per ampere hour are withdrawn. After 6 hours, the total electrolyte stock has passed through the apparatus.
  • the reaction mixture withdrawn consists of two phases.
  • the upper layer consisting preponderantly of potassium aluminum tetraethyl is freed from lead tetraethyl and aluminum triethyl by distillation at a mercury pressure of 0.5 mm. and C.
  • the distilla'te is combined with the lower layer.
  • the separation of the lower layer consisting of 350 g. of lead tetraethyl and 510 g. of aluminum triethyl may be effected by the procedures set forth in Examples 2 and 3.
  • Lead tetra-n-butyl can be obtained in an analogous A manner, it being only necessary to start with the butyl compounds corresponding to the propyl compounds mentioned above.
  • auxiliary materials needed for the process of the invention can be prepared as follows:
  • Example 6 The procedure is the same as in Example 1 except that zinc, cadmium, tin, antimony and bismuth, preferably in granular form, are used as the anode metal instead of lead.
  • mercury the anode metal
  • the anode space of the apparatus described in Example 1 is provided with superposed channels of an insulating material
  • Example 7 A mixture of 123 g. of zinc diethyl and 228 g. of aluminum triethyl is stirred 'at 100% C. together with 364 g. of sodium ethoxy raluminum triethyl 'for' 30 minutes. Then the Zinc diethyl is distilled off frornthe mixture at a mercury pressure of 100 mm. and 80 C. The distillation residue consis-ts of 2 phases.
  • the upper layer is ethoxy aluminum diethyl and the lower layer consists of sodium aluminum tetraethyl with a small amount of dissolved ethoxy aluminum diethyl.
  • Example 9 With the same procedure set forth in Example 8, mixture of 170 g. of cadmium diethyl (boiling point, 54 C. at 11 mm. mercury) and 228 g. of aluminum triethyl; 258 g. of mercury diethyl (boiling point, 60 C. at 10 mm. mercury) and 228 g. of aluminum triethyl; and 209 g. of antimony triethyl (boiling point, 60 C. at 10 mercury) and 342 g. of aluminum triethyl are separated.
  • Example 10 The procedure is the same as in Example 5 except that anodes of zinc instead of lead are used.
  • the mixture of 330 g. of Zinc dipropyl Iand 1370 g. of aluminum tripropyl separated by distillation from the residual electrolyte is stirred by distillation from the residual electrolyte is stirred at 100 C. for 1/2 hour together with 2710 g. of Na[(CaHq)3AlOCH2CH(C2H5)C4H9] and then distilled at a mercury pressure of 0.1 mm. and 100 C., the distillation being most preferably carried out in a continuously operating lm evaporator.
  • Example 11 By ⁇ a procedure analogous to that of 'Example 10, a mixture consisting of 314 g. of mercury dibutyl, 396 g. rof
  • the complex compound is filled, preferably in molten condition into an electrolysis arrangement as shown on the appended drawing.
  • This arrangement is provided with an opening 1 for introducing the electrolyte, a further opening 2 for adding the metal the alkyl compound of which is intended to be produced, means 3 for withdrawing the separated alkali metal and an outlet 4 for the reaction mixture from the anode space.
  • 5 is the overflow for the cathode liquid and 6 that for the anode liquid.
  • a perforated cylinder of an insulating material 7 and a diaphragm Between the cathode 8 and the anode metal 11 is arranged a perforated cylinder of an insulating material 7 and a diaphragm.
  • Heat- -ing and cooling means 9 are provided within the cathode space to heat the cathode liquid to the appropriate temperature while the anode liquid is maintained at the temperature desired by means of the heating device 10 using a recirculated medium.
  • the cathode I is a copper cylinder 8 l and at a distance of about 1 centimeter a perforated synthetic resin cylinder 7 of polypropylene or high molecular weight low pressure polyethylene is positioned.
  • a diaphragm consisting of hardened lter paper or of a line textile or glass filter fabric is stretched over the synthetic resin cylinder
  • the anode space is situated behind the diaphragm and is filled with lead sp-heres 11 and any lead dissolved during electrolysis can be continuouslyreplenished through opening 2 with -additional lead spheres in the anode space
  • the heating of the electrolyte or removal of any current produced heat during the electrolysis is etfected by a liquid 9 having a temperature of about 100 C. in the interior of the closed cathode cylinder. Heat input or heat removal at the outer cylinder is so regulated that the temperature within the anode space does not exceed about 70 C.
  • the temperature within the cathode space is preferably maintained at about 100 C. while that within the anode space is maintained at about 70 C.
  • Current intensity is adjusted to about 15 A. at 30 volts between electrodes which corresponds to an anodic current intensity of 4 A./dm.2 and a cathodic current intensity of 10 A./dm.2.
  • the cathodically formed sodium will flow away from the cathode into the lower cathode -space from which it may be removed in molten condition from time to time.
  • the flow away from the anode space is so adjusted that a reaction mixture with about 10% lead tetraethyl runs o whereby the inflow into the cathode space is so adjusted that the liquid level within the cathode space is by ⁇ about 4-5 centimeters higher than that within the anode space.
  • the entire electrolyte has own through the electrolysis cell.
  • the tetraethyl lead can be separated from the Al(C2H5)2(CO4H9) and the remaining complex compound.
  • the aluminum diethylbutoxy is separated by distillation at in vacuo at 0.5 mm. merphases.
  • This electrolyte is subjected to electrolysis in the arrangement described in accordance with Example 12 between a copper cathode and a lead anode at the conditions of temperature there set forth.
  • a current passage of A. is obtained which corresponds to an anodic current intensity of 5.3 A./dm.2 and a cathodic current intensity of 13 A./cm.2.
  • the cathodically formed sodiu-m is removed in liquid condition from time to time and the efflux from the anode space is so adjusted that a reaction mixture with 20% tetraethyl lead flows o'.
  • By adjusting appropriately the inflow into the cathode space a liquid level differential between cathode and anode liquid of about 4 centimeters is maintained.
  • the entire electrolyte has passed through the electrolysis cell.
  • the tetraethyl lead is removed from the reaction mix -by distillation at 40 C. and 0.5 to 0.3 mm. mercury.
  • the lead free distillation residue separates into two The upper is practically pure A1(C2H5)2(OC4H9) which may be converted into Na[A1(C2H5)3(OC4H9)] by the following operation:
  • A1(C2H5)2(OC4H9) -i-NQH* Na [Hal(C2H5)2(OC-1H9) l Na[Hal(C2H5)2(OC4H9) l +C2H4 Na [A1(C2H5)3(OC4H9)] 742 g. ( 4.7 mol) Al(C2H5)2(OC4H9) are heated with 4.7 mol sodium hydride Linder stirring in a nitrogen or argon atmosphere at 120 to 140 C. for 1/2 hour. After this time the reaction mix is transferred into a two liter autoclave filled with nitrogen and 10 atmospheres of The autoclave is then heated with rolling and shaking at 170 C. until no pressure change is further observable. This is usually the case after about 4 to 5 hours. The autoclave con- 14 tent is pure Na[Al(C2H5')3(OC4H9)]. The yield is 990 g. of theory).
  • the separation of tetraethyl lead is effected by distillation in high vacuum as described in Example 13.
  • the conversion of the butoxy aluminum diethyl into sodium butoxy aluminum triethyl may be effected in accordance with the procedure set out in Example 12 to 14.
  • Example 16 When proceeding in the same manner, set forth in Example 13, except that instead of lead there are used as anodic materials the metals: Zinc, tin, antimony, bismuth, cadmium, and mercury respectively, the ethyl compounds of these metals were obtained as set forth in the following tab e:
  • Example 17 1140 g. of aluminum triethyl are diluted with l liter of dry and air-free hexane. Then 1580 g. of n-decyl alcohol are added dropwise with stirring. The heat of the reaction causes the hexane to boil vigorously. Therefore, a reflux condenser is used. ⁇ The hexane is subsequently withdrawn under a moderate vacuum. There is left the decyl oxy aluminum diethyl as rather iiuid oil.
  • the 2420 g. of the decyl oxy aluminum diethyl obtained are mixed with 1 liter of a 24 wt. percent sodium hydride suspension in decaline or with a corresponding amount of a similar suspension of different sodium hydride content and the entire mixture is filled into a pressure vessel.
  • Ethylene of 20 to 50 atmospheres is pressed on with stirring and the mixture is heated to 170 C.
  • the ethylene is absorbed and the pressure is maintained at a constant level by pressing on additional ethylene until an ethylene absorption does no longer occur. This is the case after about 6 hours.
  • a sample drawn of the reaction mixture, when carefully hydrolized, should now furnish only ethane but no hydrogen.
  • the cathode and anode spaces of the electrolysis cell described in Example 12 lirst contain sodium aluminum tetraethyl in molten state.
  • Sodium decyl oxy aluminum triethyl or, optionally, .sodium isohexyl oxy aluminum triethyl is allowed to iiow continuously into the anode space from above at a rate which is tobe adapted to the current flowing through.
  • the current circuit is closed as this addition starts.
  • An amount of l1 g./hr. of sodium decyl oxy aluminum triethyl (or 8.9 g. of sodium isohexyl oxy aluminum triethyl) is allowed to iiow in per ampere of current flowing through.
  • the anode space there separates a liquid layer consisting of a mixture of decyl oxy aluminum diethyl (or isohexyl oxy aluminum diethyl) and lead tetraethyl, which contains rather exactly 25% (30%) by Weight of lead tetraethyl.
  • This layer is continuously withdrawn at a rate that the main electrolyte, the molten alkali aluminum tetraethyl, remains unchanged in the anode space.
  • the electrolyte level in the cathode space should be higher by about 4 centimeters than that in the anode space.
  • Both of the spaces are preferably provided with overows and sodium aluminum tetraethyl, preferably in molten state, is continuously introduced into the cathode space at a rate that only a small amount flows over.
  • the amount owing over from the cathode space is returned into the stock of the sodium aluminum tetraethyl.
  • sodium aluminum tetraethyl will also llow over in the anode space, this amount being the higher the more permeable the diaphragm is. This portion of the sodium aluminum tetraethyl is not capable of being directly returned into the stock since it contains lead. It must irst be freed from lead tetraethyl -by heating to aboutv 100 Q. under vacuum.
  • about 10 to 30 A. are allowable, i.e., on an hourly base, to 330 g. of sodium decyl oxy aluminum triethyl (or 89 to 267 g.
  • the electrolysis cell used simply consists of a vacuum-resistant steel container, in the center of which a cathode of a copper plate and on both sides of the cathode at a distance of about 1 to 2 centimeters therefrom anodes consisting of thick lead plates are arranged.
  • the cathode is connected with the steel shell of the container to provide metallic conduction.
  • the cathode is of sufficient length as to contact the bottom of the container while between the container and the lower end of .the anode a free space of about 20 centimeters is left.
  • the container is tilled under nitrogen with an electrolyte consisting of 80% of potassium aluminum tetraethyl and 20% of sodium aluminum tetraethyl.
  • a larger quantity of sodium aluminum ethoxy is prepared as follows: 1140 g. of aluminum triethyl are mixed under lnitrogen with 680 g. of completely dry and alcohol free sodium ethylate and the mixture is heated to about 100 C. until a clear melt has formed. Upon cooling, the melt solidies at 80 C.
  • the container By means of a descending cooler, the container is connected with a cooled receiver tank and a vacuum pump. The container is heated to to 140 C. and evacuated to less than 0.1 mm. mercury if possi-ble. Now, through a special line mounted at the container and provided with a valve, the molten sodium aluminum ethoxy triethyl iS allowed to flow in slowl)l and the current is applied in that moment where the content of this compound added at least has reached 5% in the contents of the container. The current is now adjusted to a current density of 10 to 30 A./dm.2 and now the second electrolyte is allowed to iiow in continuously at a rate corresponding to the current density, i.e. 6.78 grams per ampere hour.
  • the sodium may also be dissolved out of the container in liquid state after temporary interruption of the vacuum and the current supply.
  • the distillate is separated into lead tetraethyl (boiling point, 38 C./l mm.,) and ethoxy aluminum ⁇ diethyl (boiling point, 72 C./ l mrn.) using a column which needs not be very eflicient.
  • the sodium formed in the electrolysis is further processed in conventional manner to form sodium hydride which is added to the electrolyte for regeneration as described above (Examples 12-14).
  • Example 19 1560 g. of aluminum tripropyl are mixed under nitro-
  • Example 20 2780 ⁇ g. of sodiumY aluminum tetrabutyl are dissolved in 3 liters of dry benzene. To the solution, 790 g. of ndecanol-l are slowly added dropwise with vigorous stirring. After the total amount is added, the benzene solvent is distilled off at 120 C. (measured in the liquid). There is obtained a mixture of equimolar amounts of the complex compounds sodium aluminum tetrabutyl and sodium decyloxy aluminum tributyl.
  • Example 12 rllhis mixed electrolyte is subjected to electrolysis between a copper vcathode and a lead anode using the apparat-us described in Example 12. The procedure is otherwise the same as set out in Example 12. The resulting reaction mixture with 10% of lead tet-rabutyl is freed from lead tetrabutyl at a mercury pressure of 10-3 mm. and 120 C. (measured in the liquid). The yield of lead tetrabutyl is 80% of ltheory.
  • Example 21 The equimolar mixture of sodium aluminum tetrapropyl and sodium hexyl oxy aluminum tripropyl obtained in accordance with Example 19 is subjected Ito electrolysis by the procedure set forth in Example 12 using an anode of antimony.
  • Example 23 The mixed electrolyte produced in accordance with Example 20 is subjected to electrolysis by the procedure set forth in Example 20 using zinc granules as the anode material. With a current intensity of 10 A., 33 g. of reaction mixture are withdrawn from the anode space per ampere hour. This corresponds to a content of zinc dibutyl of about 10%.
  • the reaction mixture consists of a liquid phase in which the insoluble NaAl-(CH3)4 formed is suspended.
  • the solids are separated by ltration in an inert gas atmosphere.
  • the solids are identified by analysis as pure NaAl(CH3)4 and may thus be used as electrolyte in another electrolysis operation.
  • the ltrate which consists of -a mixture of Pb(CH3)4 and (CH3)2A1OC4H9 is separated lby fractional distillation in a 50 cm. Vigreux column at about 100 mm. Hg.
  • the rst fraction obtained comprises 250 gms. Pb(CH3).,y corresponding to 93.5% of the theory.
  • the intermediate fraction is preferably combined with the next batch to be separated.
  • Example 25 If 'the separation of fthe mixture of 267 gms. of Pb(CH3)4 and 288 gms. of Al(CH3)3 obtained by electrolysis is effected by reaction with 784 gms. of
  • the yields of lead -tetramethyl arel R an alkyl radical, said complex compound being other than an alkoxy derivative, the improvement which comprises effecting such production, at a point Ibetween the metal alkyl formation and the separation of formed metal alkyl, in the presence of a complex compound of the general formula: Me[Al(R)3OR] in'which Me is an alkali metal of the group consisting of sodium and potassium, R is ⁇ an alkyl radical with up to 6 carbon ⁇ atoms and R is an organic radical selected from the group consisting of alkyl and cycloalkyl radicals to thereby substantially assure freedom .from AlR3 and to react said complex compound to form AlRzOR.
  • R represents an alkyl radical with four carbon atoms.
  • alkyls of metals selected from the group consisting of lead, tin, antimony, bismuth, zinc, cadmium and mercury from a material containing such metal alkyl and aluminum trialkyl
  • the improvement comprising reacting said material with a compound of the general formula: Me[Al(R)3OR] in which Me is an alkali metal of .the group consisting of sodium and potassium, R is a straight chain alkyl with up to 6 carbon atoms and R is an organic radical selected from the group consisting of alkyl and cycloalkyl radicals and separating said metal alkyl compound from the reaction lproduct formed.
  • R is an alkyl with from 2'to 12 carbon atoms.
  • R is an alkyl with from 2 to 8 carbon atoms.
  • R represents an alkyl radical with four carbon atoms.
  • R ⁇ represents a straight chain alkyl with up to 4 carbon atoms.
  • the improvement which comprises subjecting to electrolysis, while using as an anode 'a metal selected from the group consisting of lead, tin, antimony, bismuth, zinc, cadmium, and mercury, an electrolytey comprising a com- -pleX compound of the general formula Me[Al(R)3OR] containing admixed therewith an amount of a compound 'having the general formula Me[Al(-R')4] suflicient to increase its electric conductivity, in said general formulas R representing a member selected from the group con sisting of alkyl and cycloalkyl, Me representing a member selected fromthe group consisting of potassium and' sodium, and each R' representing a straight chain alkyl radical containing from 26 carbon atoms, to thereby form at the anode an alkyl compound of said ⁇ anode metal together with an alkoxy aluminum dialkyl compound of the general formula Al ⁇ (R')2OR,
  • said olefin is ethylene, in which said anode metal is lead, in which R is an ethyl radical, in which said alkali metal hydride is sodium hydride and in which said sodium hydride is obtained by hydrogenation of the cathodically produced sodium.
  • R is an alkyl with from 2 to 8 carbon atoms.
  • R represents a-n alkyl radical with four carbon atoms.
  • R represents a straight chain alkyl with up to 4 carbon atoms.
  • R is an alkyl radical with from 2 to 12 carbon atoms.
  • R is the ethyl radical, in which R is analkyl radical, in Which -anodically produced liquid' is permitted to separate into layers one of which containsl said metal alkyl compound and. said alkoxy aluminum dietlhyl compound, and in which said metal alkyl compound is recovered from said last-mentioned layer.
  • the improvement which comprises subjecting the electrolysis, while using as an anode a metal' selected,- fromr the group consisting of lead, tin, antimony, bismuth, zinc, cadium and mercury, an electrolyte comprising a complex compound of the general formula containing admixed therewith ⁇ an amount ofa compoundI of the general formula Me [Al(R')4] suiicientV to increase;
  • R is the ethyl radical and the electrolyte during the electrolysis saturated with the alkoxy aluminum diethyl compound.
  • the improvement which comprises subjecting the electrolysis, while using as an anode a metal selected from the group consisting of lead, tin, antimony, bismuth, zinc, cadmium andmercury, an electrolyte comprising a complex compound having the general formula Me[Al(R)3OR] containing admixed therewith a suicient amount of a compound having the general formula Me[Al(R)4] to increase its electrical conductivity, in said general formulas, R representing a member selected from the group consisting of alkyls and cycloalkyl radicals, Me representing an alkali metalselectcd from the group consisting of potassium and sodium, and R representing a straight chain alkyl radical containing from 2 to 6 carbon atoms, yto thereby form at the anode an alkyl compound of said anode meta-l, together with an alkoxy aluminum dialkyl compound of the general form'ula Al(R)2OR

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DEZ6509A DE1127900B (de) 1958-02-13 1958-02-13 Verfahren zur Herstellung von Alkylen der Metalle der Gruppen ób bis ó§b des Periodischen Systems, insbesondere Bleitetraalkylen
DEZ6510A DE1153754B (de) 1958-02-13 1958-02-14 Verfahren zur Herstellung von Alkylen der Metalle der ó. Nebengruppe und der ó¾. bis ó§. Hauptgruppe, insbesondere Bleitetraalkylen

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3392093A (en) * 1964-06-23 1968-07-09 Du Pont Electrolytic process for producing tetraalkyl lead compounds
US3493592A (en) * 1968-01-15 1970-02-03 Ethyl Corp Preparation of dialkyltins and dialkyltin oxides
US20030233004A1 (en) * 2002-06-13 2003-12-18 Crompton Gmbh Process for the preparation of alkali metal tetraalkylaluminates and use thereof
US6960677B1 (en) 2003-10-28 2005-11-01 Albemarle Corporation Preparation of aluminates

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Publication number Priority date Publication date Assignee Title
BE606111A (xx) * 1960-07-13
DE1146258B (de) * 1961-06-30 1963-03-28 Dr Karl Ziegler Metallorganischer Elektrolyt hoher Leitfaehigkeit zur kathodischen Abscheidung von Natrium

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US2849349A (en) * 1955-06-13 1958-08-26 Ziegler Process for the electrolytic deposition of aluminium
US2944948A (en) * 1956-02-06 1960-07-12 Ethyl Corp Method of purifying organometallic complexes and their use in the preparation of organolead compounds

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NL202273A (xx) * 1954-11-26

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2849349A (en) * 1955-06-13 1958-08-26 Ziegler Process for the electrolytic deposition of aluminium
US2944948A (en) * 1956-02-06 1960-07-12 Ethyl Corp Method of purifying organometallic complexes and their use in the preparation of organolead compounds

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3392093A (en) * 1964-06-23 1968-07-09 Du Pont Electrolytic process for producing tetraalkyl lead compounds
US3493592A (en) * 1968-01-15 1970-02-03 Ethyl Corp Preparation of dialkyltins and dialkyltin oxides
US20030233004A1 (en) * 2002-06-13 2003-12-18 Crompton Gmbh Process for the preparation of alkali metal tetraalkylaluminates and use thereof
US6734317B2 (en) * 2002-06-13 2004-05-11 Crompton Gmbh Process for the preparation of alkali metal tetraalkylaluminates and use thereof
US6960677B1 (en) 2003-10-28 2005-11-01 Albemarle Corporation Preparation of aluminates

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GB864393A (en) 1961-04-06

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