EP0162908A4 - Preparation de composes organo-metalliques de metaux alcalino-terreux. - Google Patents

Preparation de composes organo-metalliques de metaux alcalino-terreux.

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Publication number
EP0162908A4
EP0162908A4 EP19850900283 EP85900283A EP0162908A4 EP 0162908 A4 EP0162908 A4 EP 0162908A4 EP 19850900283 EP19850900283 EP 19850900283 EP 85900283 A EP85900283 A EP 85900283A EP 0162908 A4 EP0162908 A4 EP 0162908A4
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EP
European Patent Office
Prior art keywords
magnesium
alkaline earth
barium
hydrocarbon
earth metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19850900283
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German (de)
English (en)
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EP0162908A1 (fr
Inventor
Conrad W Kamienski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lithium Corp of America Inc
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Lithium Corp of America Inc
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Filing date
Publication date
Priority claimed from US06/655,226 external-priority patent/US4634786A/en
Priority claimed from US06/669,675 external-priority patent/US4555498A/en
Application filed by Lithium Corp of America Inc filed Critical Lithium Corp of America Inc
Publication of EP0162908A1 publication Critical patent/EP0162908A1/fr
Publication of EP0162908A4 publication Critical patent/EP0162908A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/02—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/68—Preparation of metal alcoholates
    • C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/28—Metal alcoholates
    • C07C31/30—Alkali metal or alkaline earth metal alcoholates
    • 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
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/02—Magnesium 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

Definitions

  • This invention is directed to the preparation of novel alkaline earth metal alkoxides and to complexes thereof with metal alkyl of Groups I , II and III of the Periodic Table.
  • Alkaline earth metal alkoxides and their metal alkyl complexes have a variety of applications.
  • certain barium alkoxides in conjunction with alkyllithium or dialkylmagnesium compounds promote the polymerization and copolymerization of, for example, 1,3-butadiene to a polymer having a high trans-1,4 microstrueture and possessing unique beneficial properties in its use as a tire rubber.
  • barium or calcium compounds particularly for the foregoing purposes, must be present as an alkoxide and that, generally, the barium or calcium alkoxide interacts strongly with the alkyllithium or dialkylmagnesium compounds to form complexes of, presumably, alkylbarium or alkylcalcium alkoxides with the alkyllithium or dialkylmagnesium compounds.
  • barium alkoxides which possess a high solubility in liquid hydrocarbon media.
  • Initial experimental work was done utilizing barium tert-butoxide (A. Onishi et al, U.S. Patent No. 3,629,213, December 21, 1971).
  • barium tert-butoxide by itself, was found to possess a low order of solubility in liquid aliphatic hydrocarbon solvents (U.S. Patent No. 4,044,900, July 5, 1977); while barium ethoxide is even less soluble (Z.M. Baydakova, et al (a) High Molecular Wt. Compounds 1976 Vol.
  • Barium or calcium alkoxides are generally prepared by reacting a solution of barium or calcium metal in liquid ammonia or methylamine, with the desired alcohol, followed by evaporation of the solvent and subsequent drying in vacuo. Solutions of the barium or calcium alkoxides are then made up in the desired hydrocarbon solvent.
  • magnesium alkyl alkoxides and magnesium dialkoxides have been found to possess utility as precursors for magnesium chloride support materials utilized in the preparation of Ziegler-Natta catalysts for alpha-olefin polymerization.
  • ethylene has been polymerized at 80° C. in hexane using a magnesium alcoholate-TiCl 4 reaction product (MgCl 2 ) and a trialkylaluminum as the catalyst system.
  • MgCl 2 magnesium alcoholate-TiCl 4 reaction product
  • a trialkylaluminum as the catalyst system.
  • solid magnesium diethoxide, suspended in carbon tetrachloride is treated with ethyl benzoate and titanium tetrachloride, and the resulting solid product is used in combination with trialkylaluminum and p-methoxybenzoate as a catalyst to polymerize propylene
  • B. L. Goodall, A. vander Nat, and W. Sjardyn, U.S. Patent No. 4,414,132, to Shell Oil Co. B. L. Goodall, A. vander Nat, and W. Sjardyn, U.S. Patent No. 4,414,132, to Shell Oil Co.
  • Certain magnesium alkyl alkoxides and dialkoxides have also been generated by reaction of complexed magnesium dialkyls, coated on an inert support material, with an alcohol. These supported magnesium alkoxides are then further reacted with HCl and/or titanium tetrachloride to give a supported magnesium chloride catalyst which can be dried and used to polymerize ethylene (R. Hoff , U.S. Patent No. 4,402,861 and R. A. Dombro, U.S. Patent No. 4,378,304 to Chemplex Co.; and M. Bahadir and W. Payer, Ger. Offen. DE 3223331, to Ruhrchemie).
  • magnesium dialkoxides soluble in hydrocarbon solvents, have known utility for the preparation of MgCl 2 which forms a useful support for catalysts to polymerize alpha-olefins, as shown by Goodall (U.S. Patent Nos. 4,216,383; 4,426,316; and 4,387,200).
  • D. Gessell (U.S. Patent Nos. 4,246,383; 4,426,316; and 4,244,838, to Dow Chemical Company) also describes the preparation of a useful alpha-olefin polymerization catalyst by reacting a dialkylmagnesium compound (in the presence of at least 50 mole % of a trialkylaluminum compound) with sufficient n-propyl alcohol to convert all of the alkyl groups to n-propoxy groups, thus forming a hydrocarbon-soluble solution of magnesium and aluminum n-propoxides, followed by reaction of the resulting solution with a titanium ester and a chlorinating agent, ethylaluminum dichloride, to give an MgCl 2 -supported titanium catalyst.
  • a dialkylmagnesium compound in the presence of at least 50 mole % of a trialkylaluminum compound
  • n-propyl alcohol to convert all of the alkyl groups to n-propoxy groups
  • magnesium alkyl alkoxides are known to be soluble in hydrocarbon solvents, as described in U.S. Patent Nos. 4,410,742 and 4,133,824, and by G. E. Coates, J. A. Heslop, M. E. Redwood and D. Ridley, J. Chem. Soc, 1968, 1118 (see also B. J. Wakefield in Advances in Inorganic Chemistry and Radiochemistry, Vol. ii, 1968, p. 396 (Academic Press) , little is known about the solubility of magnesium dialkoxides. It is known that both magnesium methoxide and ethoxide are insoluble in ethers and hydrocarbon solvents, as described in Kirk Othmer's Encyclopedia of Chemical Technology, vol.
  • Magnesium isopropoxide was found by D. Bryce-Smith and B. J. Wakefield, J. Chem. Soc., 1964, 2483, to be insoluble in methylcyclohexane, benzene and ether, and only sparingly soluble in isopropanol.
  • Magnesium t-butoxide is not soluble in ethyl ether ( see Coates reference, as well as D. C. Bradley in Advances in Inorganic Chemistry and Radiochemistry, Vol. 15, 1972, p. 265 (Academic Press), and, thus, presumably, would be even less soluble in hydrocarbons.
  • 3,932,545 describes, among other things, the preparation of magnesium 2-ethoxyethoxide in an excess of 2-ethoxyethanol; and, further, its use in dry form as an additive to promote the hydrocarbon solubility of arylmetallics such as phenylsodium, but does not teach its preparation and solubility in hydrocarbon solvents without such additives. (See, also, article in Organometallics, Vol. 3, 904-907, 1984) .
  • magnesium dialkoxides can be prepared directly in liquid hydrocarbon or chlorinated hydrocarbon solvents, and possess a relatively high solubility therein.
  • a still further object of my invention is to provide a process for the preparation of liquid hydrocarbon or chlorinated hydrocarbon-soluble stable complexes of these alkaline earth metal alkoxides with alkyllithium, alkylsodium, alkylpotassium, dialkylmagnesium and trialkylaluminum compounds and mixtures thereof.
  • certain alcohols are reacted with alkaline earth metals, barium, calcium, and strontium amides, and magnesium dialkyls or alkylmagnesium alkoxides in liquid aliphatic or aromatic hydrocarbon or chlorinated hydrocarbon solvent media to form highly soluble, stable solutions of novel and highly useful alkaline earth metal alkoxides.
  • linear alkaline earth metal primary alkoxides possess little or essentially no solubility in liquid hydrocarbon or chlorinated hydrocarbon solvents
  • those with 2-alkyl-substituents in the alcohol moiety of said alkoxides possess a much higer solubility when the alkaline earth metal is magnesium.
  • This solubility is promoted by the presence of minor amounts of aluminum alkoxides and lithium or potassium alkoxides derived from the same said alcohol moiety; that is, those alcohols with 2-alkyl substituents.
  • calcium or barium alkoxides of this type see my copending U.S. Patent Application Serial No.
  • TMEDA N,N,N',N'-tetramethylethylenediamine
  • barium tert-alkoxides were found to possess a high solubility in hydrocarbon solvents, in my hands this was not the case.
  • solubility of barium tert-butoxide in toluene was found by me to be only 0.37M at ambient temperature; that of barium tert-amylate, 0.23M in toluene; and that of barium 3-methyl-3-pentanolate, only 0.08M in cyclohexane.
  • the stability of these solutions deteriorated with time (precipitation of product within a few days).
  • magnesium tert-alkoxides possess a low to intermediate solubility in liquid hydrocarbon or chlorinated hydrocarbon solvents when prepared by the process of my invention:
  • Butoxide forms which sets to solid mass on standing.
  • barium salts of certain secondary alcohols have an improved solubility in liquid hydrocarbon solvents compared with the solubility of barium tert-alkoxides.
  • Barium see-butoxide and barium 4-methyl-2-pentyloxide can be dissolved in cyclohexane to the extent of 0.8M, or even higher, at ambient temperature, without the aid of agents such as TMEDA.
  • the highly-branched secondary alkoxide, barium 2,6-dimethyl-4-heptyloxide, sterically hindered like the tertiary alkoxides was found to have a low solubility in these solvents, even in the presence of TMEDA.
  • magnesium secondary alkoxides were found to be of a low order of solubility in hydrocarbon or chlorinated hydrocarbon solvents:
  • a dialkylmagnesium dissolved in a liquid hydrocarbon solvent is treated first with a catalytic amount (about 3 mole %, based on magnesium) of a trialkylaluminum compound, and then with slightly more than twice the molar equivalent, based on magnesium, of a C 4 -C 12 2-alkyl-substituted primary monohydric alkanol or alcohol, or a mixture of these alkanols or alcohols, either neat or in solution in a liquid hydrocarbon or chlorinated hydrocarbon solvent.
  • Alkanes are rapidly generated, and can be driven off by heating to the boiling point if low boiling (ca 0-5° C) , or absorbed by the solution itself.
  • barium or calcium amide is suspended in the liquid hydrocarbon solvent of choice; and a slightly less than stoichiometric quantity of 2-alkyl substituted C 4 -C 12 normal monohydric alcohol, or in admixture with various proportions of C 3 -C 12 secondary monohydric alcohol in which the OH group is attached to the second carbon atom, alone as to such alcohols or in solution in a liquid hydrocarbon solvent, are added to the stirred barium amide or calcium amide suspension.
  • Ammonia is rapidly evolved; and the mixture is heated to the boiling point for such period of time (commonly several hours) to be certain that essentially all ammonia is gone from the solution.
  • TMEDA or equivalent agents, may be added during the reaction as a complexing agent, as required, to promote solubility, especially in the case of the lower molecular weight (C 4 and C 5 ) 2-alkyl-substituted alkoxides.
  • the resulting barium or calcium alkoxide solutions are filtered to remove unreacted barium or calcium amide and other solid impurities.
  • secondary alcohols can be used, such as isopropanol or sec-butanol, most favorably, up to about a 1:1 molar ratio, based on the 2-alkyl-substituted primary alkanol, although somewhat more may be employed.
  • the excess of 2-alkyl-substituted primary alkanol employed, over and above twice the molar equivalent (based on magnesium) is generally in the range of 0.01 to 2.0 molar equivalents, based on magnesium, but will more preferably lie in the range of 0.1-1.0 molar equivalents.
  • This addition of an excess of the 2-alkyl-substituted primary alkanol possesses an unusually beneficial action on the viscosity and/or solubility of many of these branched magnesium dialkoxides and mixtures thereof.
  • metallic alkoxides which can be used, for example, are those of Na, K, Ca, Ba, B and Zn.
  • 2-alkoxy-substituted 1-alkanols such as 2-methoxy-1-ethanol and 2-ethoxy-1-ethanol
  • liquid hydrocarbon or chlorinated hydrocarbon solvent-soluble alkaline earth metal 2-alkoxyalkoxides by reaction with suitable alkaline earth metal-containing precursors, such as magnesium and calcium metals, magnesium and barium amides, dialkylmagnesium compounds and magnesium and calcium monoalkoxides, such as magnesium ethoxide.
  • suitable alkaline earth metal-containing precursors such as magnesium and calcium metals, magnesium and barium amides, dialkylmagnesium compounds and magnesium and calcium monoalkoxides, such as magnesium ethoxide.
  • no added aluminum, lithium or potassium compounds or TMEDA are necessary to maintain solubility and fluidity of the resulting liquid hydrocarbon or chlorinated hydrocarbon solvent solutions of the alkaline earth metal 2-alkoxyalkoxides .
  • the magnesium-2-alkoxyalkoxides are prepared by simple mixing of solid magnesium monoalkoxides, such as magnesium diethoxide, with slightly more than two molar equivalents of the 2-alkoxyalkanol, such as 2-ethoxyethanol, followed by dissolution of the liquid product in the desired hydrocarbon or chlorinated hydrocarbon solvent.
  • solid magnesium monoalkoxides such as magnesium diethoxide
  • 2-alkoxyalkanol such as 2-ethoxyethanol
  • the process is less expensive and less hazardous than that which uses dialkylmagnesium compounds, as contrasted to a lengthy reaction using magnesium metal in place of the lower magnesium alkoxides.
  • hydrocarbon or chlorinated hydrocarbon solvent-soluble magnesium-2-alkoxyalkoxides can be prepared from relatively less expensive and generally more readily available starting materials.
  • magnesium 2-ethoxy-ethoxide prepared by reaction of magnesium ethoxide with slightly more than two equivalents of 2-ethoxy-ethanol in the absence of solvents such as heptane or chlorobenzene has been found to be a clear, mobile, liquid product, essentially corresponding to the chemical formula Mg(OCH 2 CH 2 OCH 2 CH 3 ) 2 (CH 3 CH 2 OH) 2 , a novel product having utility in catalyst ( ⁇ -olefin) preparations.
  • the product can be dispersed in mineral oil and chlorinated to give essentially uniformly-sized particles of magnesium chloride which can serve as a support for a deposited titanium catalyst for alpha-olefin polymerization.
  • This form of magnesium alkoxide is totally different from the solid product produced by the above-mentioned Screttas patent, and is also different from the chlorobenzene solution of the magnesium 2-ethoxyethoxide produced by reaction of slightly more than two equivalents of 2-ethoxyethanol with magnesium metal in an essentially neat reaction, followed by dissolution of the resulting product in a minimum of chlorobenzene, according to my invention. Similar results are obtained, for instance, with calcium and barium 2-ethoxyethoxide.
  • alkaline earth metal alkoxides in a hydrocarbon or chlorinated hydrocarbon solvent-soluble form when mixed with alkyllithium, aIkyIsodium, dialkylmagnesium, alkylpotassium and trialkylaluminum compounds form stable, soluble complexes which are useful mixtures thereof.
  • 2-alkyl-substituted primary monohydric normal alcohols or alkanols are 2-methyl-1-pentanol and 2-ethyl-1-hexanol and mixtures thereof.
  • Other alcohols which advantageously can be admixed with the above 2-alkyl-substituted primary alkanols and co-reacted with alkaline earth metals and their compounds are C 3 -C 12 aliphatic secondary and tertiary alcohols, notably C 3 -C 12 aliphatic secondary or tertiary branched alcohols such as isopropanol, sec-butanol, 4-methyl-2-pentanol,
  • Cycloaliphatic alcohols may also be used, such as cyclopentanol and cyclohexanol.
  • Still other alcohols which may be mixed with the above 2-alkyl-substituted primary alcohols and co-reacted with alkaline earth metals and their compounds are C 1 -C 12 aliphatic primary (linear, unsubstituted) alcohols, such as, for example, methanol, ethanol, n-butanol, n-hexanol, n-octanol and the like.
  • the amounts of said primary (unsubstituted), secondary and tertiary alcohols, which are co-reacted with said C 4 -C 12 2-alkyl-substituted primary alcohols may be varied from 0.1 to 2 moles per mole of said C 4 -C 12 2-alkyl-substituted primary alcohols, but will preferably be in the range of 0.5 to 1 mole per mole of said alcohol, and most in the preparation of polymerization initiators.
  • hydrocarbon or chlorinated hydrocarbon solvent-soluble magnesium alkoxides ean be readily mixed with hydrocarbon or chlorinated hydrocarbon solvent-soluble magnesium alkyls to form soluble alkylmagnesium alkoxides which are useful in the preparation of halogen-free Ziegler catalysts which are useful as co-catalysts for the polymerization of olefins, diolefins, or olefin oxides.
  • Such a procedure for forming alkylmagnesium alkoxides is deemed superior to that described in either Malpass (U.S. Patent No. 4,133,824) or Mueller (U.S.
  • Patent No. 4,410,742 to Schering A.G. in that no insoluble magnesium alkoxide need be employed which would tend to slow the reaction with dialkylmagnesium compounds or incompletely react therewith.
  • the resulting alkyl-magnesiurm alkoxides when complexed with alkali metal alkyls, also form useful initiators for the polymerization of 1,3-dienes and vinylaromatic compounds.
  • 2-alkyl-substituted primary monohydric (normal) alcohols or alkanols (C 4 -C 12 ) which are reacted with alkaline earth metals or their compounds in various of the embodiments of my invention are exemplified by isobutyl alcohol, 2-methyl-1-pentanol,
  • an excess of the alcohol or mixture of alcohols, above that necessary to react with all of the alkaline earth metal precursors present, is employed in order to gain an increased fluidity or solubility of the resulting alkaline earth metal alkoxides in hydrocarbon or chlorinated hydrocarbon solutions.
  • This excess of alcohol can vary from 0.01 to 2 moles of alcohol per mole of alkaline earth metal precursor reacted, but preferably varies from 0.05 to 1 mole of alcohol per mole of alkaline earth metal precursor reacted, and most advantageously from 0.1 to 0.5 moles of alcohol per mole of alkaline earth metal precursor reacted.
  • the said alcohols can be added to the alkaline earth metals or their compounds in either neat form or dissolved in a liquid hydrocarbon or chlorinated hydrocarbon solvent of choice. favorably in the range of 0.7 to 1 mole per mole of said alcohol.
  • 2-alkoxyl-1-alkanols ROCH 2 CHR'OH (R is C 1 -C 12 hydrocarbyl and R' is hydrogen or C 1 -C 3 hydrocarbyl), such as, for example, 2-methoxy-1-ethanol, 2-ethoxy-1-ethanol, 2-butoxy-1-ethanol,
  • 2-butoxyethoxyethanol are alcohols of the type belonging to the generic group of ⁇ -alkoxy poly(ethyleneoxy)-1-ethanols, RO(CH 2 CH 2 O) n CH 2 CH 2 OH, where R is C 1 -C 12 hydrocarbyl but most desirably ethyl, n-butyl and n-hexyl, and n may vary from 0 to 4.
  • R is C 1 -C 12 hydrocarbyl but most desirably ethyl, n-butyl and n-hexyl, and n may vary from 0 to 4.
  • dialkylmetallic compounds employed in the reaction with the above alcohols can be varied widely. For convenience, they are generally soluble in liquid hydrocarbon or chlorinated hydrocarbon media, although it is not outside the scope of this invention to employ dialkylmetallic compounds or even arylmetallic compounds which are insoluble in liquid hydrocarbon or chlorinated hydrocarbon media.
  • dialkylmagnesiums such as n-butyl-sec-butylmagnesium, n-butyl-ethylmagnesium, di-n-hexylmagnesium, diisopropylmagnesium, di-n-butylmagnesium, di-sec-butylmagnesium, di-2-methyl-butylmagnesium, di-n-amylmagnesium, n-butyl-n-octylmagnesium, ethyl-isoamyl-magnesium, and typical arylmagnesium compounds, such as diphenylmagnesium, phenylmagnesium chloride and the like. Also included are phenylcalcium iodide, isopropylcalcium bromide, isopropylcalcium chloride, and the like.
  • dialkylmetallic compounds when they are dialkylmagnesium compounds, can also contain sufficient added trialkylaluminum compounds to maintain solubility and fluidity of the resulting magnesium alkoxides in the liquid hydrocarbon or chlorinated hydrocarbon solutions after reaction with the desired alcohols. It is, in any case, preferred that such trialkylaluminum compounds be added to the said dialkylmagnesium compounds, when not originally present, prior to reaction with said alcohols.
  • amounts of trialkylaluminum to be added or maintained can be varied from 0.005 to 2 moles per mole of magnesium compound, but are preferably in the range of 0.01 to 1 mole per mole of magnesium compound, and most advantageously in the range of 0.02 to 1 mole of trialkylaluminum per mole of dialkylmagnesium compound.
  • Typical trialkylaluminum compounds employable are triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethyl-n-butylaluminum, tri-n-octylaluminum, and the like.
  • trialkylaluminum can be added after reaction of the alcohol with the dialkylmagnesium is complete and then further reacted with the alcohol or alcohols, if required.
  • trialkylaluminum compounds mentioned above which are added to the dialkylmagnesium compounds prior to reaction with the desired alcohols, there can be added other organometallic compounds or metallic alkoxides, such as trialkylboron, dialkylzinc, alkyllithium, alkylsodium, potassium alkoxide, sodium alkoxide, calcium alkoxide, and barium alkoxide compounds and the like to maintain solubility and fluidity of the resulting magnesium alkoxides in the liquid hydrocarbon or chlorinated hydrocarbon solvent solutions.
  • organometallic compounds or metallic alkoxides such as trialkylboron, dialkylzinc, alkyllithium, alkylsodium, potassium alkoxide, sodium alkoxide, calcium alkoxide, and barium alkoxide compounds and the like to maintain solubility and fluidity of the resulting magnesium alkoxides in the liquid hydrocarbon or chlorinated hydrocarbon solvent solutions.
  • organometallic compound, metallic alkoxide or other metal derivative can be varied in the range of 0.005 to 2 moles per mole of magnesium compound, but are preferably in the range of 0.01 to 1 mole per mole of magnesium compound, and most advantageously in the range of 0.02 to 0.1 mole of organometallic compound, metallic alkoxide, or metal derivative per mole of dialkylmagnesium compound.
  • Typical organometallic compounds employable are methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, phenylsodium, n-amylsodium, triethylboron, tri-n-butylboron, diethylzinc, di-n-butylzinc, and the like, and mixtures thereof.
  • Typical metallic alkoxides employable are lithium tert-butoxide, lithium
  • 2-ethyl-1-hexyloxide barium 2-methyl-1-pentyloxide, tri-n-butoxyboron, tri-2-methyl-1-pentyloxyboron, zinc di-2-methyl-1-pentyloxide, and the like, and mixtures thereof.
  • organometallic compounds or metallic alkoxides which are soluble in the liquid hydrocarbon or chlorinated hydrocarbon medium employed.
  • alkaline earth metal amides such as Ca(NH 2 ) 2 , Sr(NH 2 ) 2 and Ba(NH 2 ) 2 , can be reacted with said alcohols in a liquid hydrocarbon or chlorinated hydrocarbon medium.
  • the magnesium amide, barium amide, calcium amide and strontium amide can be produced by any convenient means, but are advantageously obtained in a finely-divided form.
  • One novel method for the preparation of the barium amide involves dissolution of barium metal in liquid ammonia, followed by addition of an aromatic solvent, such as toluene. This addition converts the dissolved barium metal to a slurry of barium amide, which can be filtered and dried, or the ammonia evaporated off, residual ammonia being removed by subsequent heating of the slurry to the boiling point of the aromatic solvent. A finely-divided slurry of barium amide in the aromatic solvent is obtained which can be used directly in the preparation of barium alkoxides.
  • an aromatic solvent such as toluene
  • the reaction of the aforesaid amides, particularly desirably barium and calcium amides, with the aforesaid alcohols to produce the desired hydrocarbon- or chlorinated hydrocarbon-soluble barium and calcium alkoxides can be carried out at any convenient temperature.
  • the reaction is carried out at room temperature; and the reaction mixture is then heated to reflux for a period of time (usually 1 to 4 hours) to complete the removal of by-product ammonia.
  • alkaline earth metal alkoxides include reaction of said alcohols with alkaline earth metal or alkaline earth metal hydrides, transalcoholysis of lower C 1 -C 3 alkaline earth metal alkoxides with said alcohols, or reaction of the alkali metal alkoxide derivatives of said alcohols with alkaline earth metal halide salts. It is, further, within the scope of my present invention to react Grignard reagents such as RMgX, RCaX, etc., with said alcohols to produce useful alkoxyalkaline earth metal compounds. Obviously, for optimal economy in the production of the resulting alkaline earth metal alkoxides, the lowest priced alkaline earth metal precursors (coupled with the simplest process parameters) will be most advantageous.
  • R 1 , R 2 and R 3 are the same or different alkyls, each containing from 1 to 4 carbon atoms, namely, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl;
  • X is a non-reactive group, such as or other divalent aliphatic hydrocarbon or alkylene radical, preferably containing from 2 to 4 carbon atoms; and w is 1 to 4.
  • Illustrative examples include, for instance, 2-dimethylaminoethylmethyl ether [ (CH 3 ) 2 N-CH 2 -CH 2 -OCH3], 2-diethylaminoethylmethyl ether [ (C 2 H 5 ) 2 N-CH 2 -CH 2 -OCH 3 ], and 2-dimethylaminopropylmethyl ether [ (CH 3 ) 2 N-CH 2 -CH 2 -CH 2 -OCH 3 ] .
  • TMEDA and generally functionally-equivalent aliphatic tertiary amines are disclosed in U.S. Patent No. 3,451,988.
  • Such aliphatic tertiary amines, as there disclosed, include, among others, those which are represented by the formulas:
  • R 1 , R 1 , R 1 and R 1 are the same or 2 3 4 different alkyl radicals of 1 to 5 carbon atoms, inclusive;
  • A is a non-reactive group;
  • R 11 , R 11 , R 11 and R 11 are the 1 2 3 4 same or different alkyl radicals of 1 to 3 carbon atoms, inclusive; and n is an integer between 1 and 4, inclusive.
  • the disclosure of said aliphatic tertiary amines in said patent is incorporated herein by reference.
  • the reaction of the aforementioned alcohols, used in accordance with my present invention, with dialkylmagnesium or other alkaline earth metal compounds, or other compounds disclosed and contemplated by the present invention can be carried out at any convenient temperature. Generally, it is preferred to carry out the reactions at lower temperatures, i.e., below the boiling point of the liquid hydrocarbon or chlorinated hydrocarbon solvent employed.
  • the said alcohols for instance, can be added to the dialkylmagnesium compound, or the dialkylalkaline earth metal compound, or vice versa. Addition is generally carried out incrementally.
  • liquid hydrocarbon and chlorinated hydrocarbon solvents can be employed in the practice of my invention.
  • Aliphatic or cycloaliphatic solvents such as, for example, isopentane, n-pentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, and the like, are preferred.
  • aromatic solvents can also be employed, such as, for example, benzene, toluene, xylene, mesitylene, and the like, or mixtures thereof with aliphatic or cylcoaliphatic solvents.
  • liquid chlorinated hydrocarbon solvents are 1,1,1-trichloroethane; 1,1-dichlorobutane; 1,4-dichlorobutane; 1-chlorohexane; chlorocyclohexane; mono- and polychlorobenzenes; 3 , 4-di-chlorotoluene; 1-chloropentane; 1,3-dichlorohexane; carbon tetrachloride; chloroform; and the like.
  • magnesium or other alkaline earth metal alkoxide solutions such as, for example, diethyl ether, THF, methyl tert-butyl ether, di-n-butyl ether and the like, or monofunctional tertiary amines, such as, for example, trimethylamine, triethylamine, N-methylpiperidine and the like.
  • co-solvents compatible with alkaline earth metal alkoxides, can also be employed, such as, for example, chlorobenzene, carbon tetrachloride, chloroform, dimethylacetamide, dimethylformamide, hexamethylphosphorus triamide, and the like.
  • organometal reagents may be admixed with the aforesaid metal alkoxides of this invention.
  • organolithium compounds generally soluble in hydrocarbon media, such as ethyllithium, isopropyllithium, n-hexyllithium, n-octyllithium and mixtures of these, such as n-butyllithium and ethyllithium, which form novel products soluble in hydrocarbon or chlorinated hydrocarbon solvents.
  • organoalkali compounds not normally soluble in liquid hydrocarbon or chlorinated hydrocarbon solvents can also be admixed with the magnesium alkoxides of my present invention, including, for example, n-butylsodium, n-butylpotassium, n-amylsodium, n-hexylsodium, n-hexylpotassium and the like, and mixtures of these with organolithium compounds in the range of 0.01 to 10 moles per mole of magnesium alkoxide, but more preferably in the range of 0.05 to 2 moles per mole of magnesium alkoxide.
  • organolithium or other organoalkali compounds In place of, or in admixture with, the organolithium or other organoalkali compounds, one can employ diorganomagnesium compounds soluble in liquid hydrocarbon or chlorinated hydrocarbon media for interaction with the alkaline earth metal alkoxides of my invention.
  • diorganomagnesium compounds are diethylmagnesium, n-butyl-ethylmagnesium, diisopropylmagnesium, n-butyl-sec-butylmagnesium, n-butyl-n-octylmagnesium, di-n-hexylmagnesium, di-sec-butyImagnesium, di-2-methylbutylmagnesium and di-n-octylmagnesium, and the like, and mixtures thereof.
  • alkylmagnesium alkoxides which also can be formed by adding only one-half the stoichiometric amount of the alcohol to a dialkylmagnesium compound, according to my invention.
  • triorganoaluminum compounds normally soluble in liquid hydrocarbon or chlorinated hydrocarbon media such as TIBAL, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum and the like, and mixtures thereof in the range of 0.01 to 10 moles per mole of magnesium alkoxide, but more preferably in the range of 0.05 to 2 moles per mole of alkaline earth metal alkoxide.
  • Barium, magnesium, lithium and aluminum are assayed in the presence of each other in the following Examples.
  • Aluminum is determined complexometrically by addition of an excess of either EDTA or CDTA at pH 5 to 6 and back titration of the excess with standard Zn ++ solution to a colored end point.
  • Magnesium is determined by precipitation of the Al as Al(OH) 3 , and Ba as Ba SO 4 , followed by complexometric titration with EDTA at pH 10; while barium is determined by subtracting the Mg value obtained from a separate determination of both Mg and Ba via back titration of an excess of EDTA with Zn ++ .
  • a 2 ml sample of the solution is treated with about 0.5 ml of neat titanium tetra-isopropylate, resulting in an immediate gelation, but no color change, indicating reaction of all alleyl groups with the alcohol.
  • the mixture is heated to reflux; but, again, no thinning or solution of the product occurs.
  • 50 ml of toluene is added, again with no effect.
  • two consecutive 15 ml (0.1 mole) additions of TMEDA is made, also with little or no effect.
  • the mix is decomposed by pouring the heavy, viscous, taffy-like mass into ice water.
  • Example 1(a) shows the beneficial effect of the addition of a very small amount of trialkylaluminum to the DBM prior to its reaction with 2-methyl-1-pentanol
  • ExampIes I(b) and (c) show the beneficial effects of the addition of a small amount of potass or lithium alkoxide during the reaction.
  • TMEDA 8.5 ml (0.056 moles) of TMEDA is added to the mixture.
  • the addition of TMEDA causes the mixture to become quite fluid, thus allowing the completion of the alcohol addition.
  • an additional 1 ml of TMEDA is added (total TMEDA present - 0.063 moles); and the mixture is heated overnight in an oil bath at about 80° (just below reflux point of the solution) . No discernable solids are present.
  • Mg(OEt) 2 magnesium ethoxide
  • "Cellosolve” 2-ethoxyethanol
  • the mix is heated to 50° for 1 hour, then allowed to cool and settle.
  • the dark, greyish-black liquid is analyzed for magnesium content and found to be 3.32 Molar in Mg.
  • the product is soluble in chlorobenzene and heptane.
  • this complex may be written as
  • TMEDA promotes solubility and reactivity of organometallics with calcium alkoxides of low solubility.

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EP19850900283 1983-11-15 1984-11-13 Preparation de composes organo-metalliques de metaux alcalino-terreux. Withdrawn EP0162908A4 (fr)

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US55191783A 1983-11-15 1983-11-15
US551917 1983-11-15
US655226 1984-09-27
US06/655,226 US4634786A (en) 1984-09-27 1984-09-27 Hydrocarbon and chlorinated hydrocarbon-soluble magnesium dialkoxides
US06/669,675 US4555498A (en) 1983-11-15 1984-11-08 Preparation of certain alkaline earth metal organometallic compounds
US669675 1984-11-08

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CA1328460C (fr) * 1988-09-30 1994-04-12 Conrad William Kamienski Traitement de masse de matieres cellulosiques
EP0369533A3 (fr) * 1988-11-14 1991-07-24 Akzo N.V. Alkoxydes métalliques solubilisés dans un solvant alkoxyalkanol
US6359088B1 (en) * 1998-10-01 2002-03-19 The Goodyear Tire & Rubber Company Calcium-based catalyst system
EP1582523A1 (fr) * 2004-04-02 2005-10-05 Ludwig-Maximilians-Universität München Procédé de préparation de composés organomagnésiens
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US9163097B2 (en) 2010-09-30 2015-10-20 Chemetall Gmbh Low-viscosity, concentrated solutions of magnesium complexes for producing polymerization catalysts and method for producing the same
ES2632062T3 (es) 2012-10-25 2017-09-08 Rockwood Lithium GmbH Soluciones concentradas y de baja viscosidad de alcóxidos de metales alcalino-térreos en disolventes apróticos y procedimiento para su fabricación
EP3619219B1 (fr) 2014-08-12 2023-11-01 Albemarle Germany GmbH Solutions faiblement visqueuses d'alcoolates métalliques alcalino-terreux dans des solvants aprotiques, procédé pour leur fabrication et utilisation pour la fabrication de catalyseurs de ziegler-natta
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US11986814B2 (en) 2021-03-16 2024-05-21 Shandong Jianzhu University Preparation method of embedded alkaline earth metal oxide solid alkali and application thereof in biodiesel production
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CA1244044A (fr) 1988-11-01
IT1199223B (it) 1988-12-30
AU3741185A (en) 1985-06-03
IT8449173A1 (it) 1986-05-15
WO1985002176A1 (fr) 1985-05-23
IT8449173A0 (it) 1984-11-15

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