WO1991005608A1 - Procede de fabrication de complexe de magnesium contenant de l'halogenure/alcoxy - Google Patents

Procede de fabrication de complexe de magnesium contenant de l'halogenure/alcoxy Download PDF

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Publication number
WO1991005608A1
WO1991005608A1 PCT/US1990/005894 US9005894W WO9105608A1 WO 1991005608 A1 WO1991005608 A1 WO 1991005608A1 US 9005894 W US9005894 W US 9005894W WO 9105608 A1 WO9105608 A1 WO 9105608A1
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WO
WIPO (PCT)
Prior art keywords
magnesium
alcohol
halide
grams
alkoxide
Prior art date
Application number
PCT/US1990/005894
Other languages
English (en)
Inventor
Bor-Ping Eric Wang
Elliot Isaac Band
Andrzej Mieczyslaw Piotrowski
Richard James Amata
Original Assignee
Akzo N.V.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US07/497,295 external-priority patent/US5023385A/en
Priority claimed from US07/497,294 external-priority patent/US5081320A/en
Application filed by Akzo N.V. filed Critical Akzo N.V.
Publication of WO1991005608A1 publication Critical patent/WO1991005608A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0212—Alkoxylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • Magnesium compositions containing halide and alkoxy moieties of the general formula X n Mg(OR) 2-n , where n is in the range of 0 ⁇ n ⁇ 2 , are known and have been found to be useful as olefin polymerization catalyst supports or components (see U.S. Patent No. 4,209,602).
  • U.S. Patent No. 4,792,640 to V. C. Mehta describes hydrocarbon-soluble compounds of the formula ROMgX, where R is a primary 2-alkyl substituted radical containing 5 to 18 carbon atoms and X is halide. These compounds are formed by reacting activated magnesium metal with an alkyl halide in an inert solvent to form a Grignard reagent which is then reacted with an oxygen-containing compound, including an alcohol, to produce the desired compound ROMgX.
  • U.S. Patent No. 4,820,879 describes preparation of hydrocarbyloxy magnesium halides by reacting activated magnesium metal with an oxygen-containing compound and an anhydrous hydrogen halide.
  • the present invention in its broadest sense, involves a process for forming hydrocarbon-soluble halide, alkoxy- containing magnesium complexes in a non-Grignard reaction (i.e., not involving reaction of a dialkylmagnesium compound and an alkyl halide as essential reactants to form a compound having the formula RMgX where X is halide and R is alkyl).
  • the present process relies upon the combination of appropriate sources of magnesium, halide, and alkoxide in the presence of a slight excess of the parent alcohol for the desired alkoxy group (OR) and an amount of a lower alkyl alcohol (e.g., an alcohol containing an alkyl group of from about one to about four carbon atoms) to effect solubilization of the resulting complex.
  • a lower alkyl alcohol e.g., an alcohol containing an alkyl group of from about one to about four carbon atoms
  • The. amount of "free" alcohol (combined amount of parent and lower alkyl alcohol) which should be used to achieve solubility needs to be no less than about 6 wt% of the
  • Free alcohol is the excess alcohol present as compared to the molar amount of magnesium present in the complex. As the “free” alcohol concentration is decreased below this amount (about 6 wt%), the complex formed tends to become insoluble.
  • the present invention in one embodiment, relates to a process for forming a hydrocarbon-soluble complex of a
  • magnesium haloalkoxide and an alcohol by combining a magnesium halide, a magnesium alkoxide and the aforesaid alcohol
  • hydrocarbon-soluble complex The combination may be any hydrocarbon-soluble complex.
  • the combination may be any hydrocarbon-soluble complex.
  • the combination may be any hydrocarbon-soluble complex.
  • the alkoxide and magnesium halide are first combined followed by addition of the mixture of alcohols.
  • the present invention in another embodiment of the invention, relates a process of preparing hydrocarbon-soluble complexes of a magnesium halohydrocarbyloxide and an alcohol by combining a magnesium halide with hydrocarbon solvent or solvents and alcohols followed by heating, if necessary, to dissolve the halide and form a solution, followed by addition of a magnesium metal source.
  • magnesium halide is inclusive of compounds of the formula MgX 2 where X is halogen, e.g., chlorine.
  • alcohol is inclusive of compounds of the formula ROH where R is a C 1 to C 12 straight or branched alkyl group, e.g., 2-ethylhexyl or an aralkyl group, e.g., benzyl alcohol.
  • hydrocarbon solvent is inclusive of such solvents as toluene, alkyl alcohols such as ethanol, or mixtures thereof, which can be used to enhance the
  • the present invention in accordance with yet another embodiment of the invention, relates a process of preparing hydrocarbon-soluble complexes of a magnesium haloalkoxide and an alcohol by forming a mixture of magnesium metal in
  • the present invention in its broadest sense, involves a process for forming hydrocarbon-soluble halide, alkoxy- containing magnesium complexes in a non-Grignard reaction
  • the present process relies upon the combination of appropriate sources of magnesium, halide, and alkoxide in the presence of a slight excess of the parent alcohol for the desired alkoxy group (R) and an amount of a lower alkyl alcohol (e.g., an alcohol containing an alkyl group of from about one to about four carbon atoms) to effect solubilization of the resulting complex.
  • a lower alkyl alcohol e.g., an alcohol containing an alkyl group of from about one to about four carbon atoms
  • One embodiment of the process of the instant invention comprises the initial step of dissolving a magnesium halide (such as magnesium dichloride) in an alcoholic solvent (such as a branched 2-alkyl substituted alcohol containing 5 to 12 carbon atoms as exemplified by 2-ethyl-1-hexanol) followed by heating (e.g., to about 100°C).
  • a magnesium C 1 -C 4 alkoxide such as magnesium ethoxide and an organic solvent, such as heptane.
  • the reaction medium is then heated and any added solvent is thereby removed.
  • magnesium halide preferred involves the initial combining of magnesium halide and magnesium alkoxide, in an appropriate solvent, followed by addition of the alcohol. This procedure will result in less alcohol being needed than the first procedure since in the first process embodiment the magnesium halide will tend to form an initial adduct with the alcohol thereby using more of that additive than in the second process embodiment.
  • the first step of yet another embodiment of the general the process of the instant invention comprises the formation of a solution by the admixture of magnesium halide
  • hydrocarbon solvent or solvents and alcohol.
  • This admixture can be brought about by first combining the solvent(s) (e.g., toluene and ethanol) and alcohol to form a solution to which the magnesium halide is added followed by appropriate heating to effect dissolution of the magnesium halide.
  • solvent(s) e.g., toluene and ethanol
  • alcohol e.g., toluene and ethanol
  • ethanol for example, if mixed with the alcohol first to form a solution can increase the solubility of the magnesium halide in forming the solution to which the
  • the second step involves the addition of a magnesium metal source (either magnesium metal itself or a dialkylmagnesium compound) to form the desired reaction product which is further described below. This particular embodiment of the general process described herein is economically more
  • the first step of yet another embodiment of the general process of the instant invention comprises the formation of a mixture of magnesium in an appropriate hydrocarbon solvent, e.g., heptane, and heating the solution.
  • an appropriate hydrocarbon solvent e.g., heptane
  • the magnesium metal can be suitably activated.
  • One preferred way is to also add a magnesium dialkyl (e.g., butyl ethyl
  • magnesium to the solvent containing the magnesium metal.
  • a magnesium halide preferably magnesium chloride.
  • alcohol preferably a mixture of a C 1 -C 4 alkyl alcohol, such as ethanol, and a branched (e.g., 2-alkyl substituted) C 5 -C 12 alcohol, such as 2-ethylhexanol. Heat is applied to achieve the desired production of the reaction product described below.
  • the relatively expensive magnesium alkoxide reagent has been replaced with magnesium metal and appropriate parent alcohol.
  • the resulting reaction product from any of the previously described embodiments of the general procedure first described above, which is soluble in hydrocarbon solvents, such as heptane, is a complex of a magnesium haloalkoxide and an alcohols. It may be represented by the formula X n Mg(OR) 2-n .mR'OH pR"OH where X is halogen, R, R' and R" are hydrocarbyl radicals (such as C 1 -C 12 alkyl) and can be the same or different, n is in the range of 0 ⁇ n ⁇ 2, and m+p is in the range of 0 ⁇ m+p ⁇ 4.
  • R' can be C 1 to C 4 alkyl and R" can be C 5 -C 12 branched alkyl.
  • Magnesium chloride (48.5 grams) was suspended in 210 grams of 2-ethyl-1-hexanol, and the suspension was heated to 100°C. At this point, 57 grams of magnesium ethoxide was added followed by 300 ml of heptane. The reaction mixture was stirred vigorously and was sparged with nitrogen to remove solvent. After 150 ml of solvent was evaporated, fresh heptane was added, and the reaction mixture was sparged with nitrogen until almost all solvent was removed. The reaction mixture temperature was 99°C at the beginning of the
  • Example 2 The solution from Example 1 was diluted with heptane to contain 1.82% Mg. This solution (100 grams) was then used to prepare 11.7 grams of supported catalyst.
  • the catalyst was prepared from a solution of chloromagnesium alkoxide containing 1.82% Mg, 2.54% Cl, 6.31%
  • the catalyst was tested in combination with triethyl aluminum and an external donor in hexane slurry to polymerize propylene. Hydrogen was added to control the MFI. The polymerization conditions were maintained at 100 psig and 70°C for two hours. The yield was 9070 grams polymer/grams
  • hydrocarbon-soluble chloromagnesiumalkoxide in accordance with the present invention.
  • the preparation was conducted under a nitrogen atmosphere.
  • the toluene, ethanol, and benzyl alcohol were dried over molecular sieve resin.
  • Magnesium chloride (22.3 grams, 0.234 mole, under 0.2% water content) was weighed and charged into a 500 ml round bottom flask equipped with stir bar coated with TEFLON fluoropolymer.
  • the vessel was purged with nitrogen.
  • a solution of pure toluene (84 grams), benzyl alcohol (70 grams, -0.647 mole), and absolute ethanol (24.46 grams, 0.532 mole) was then added to the vessel.
  • the vessel was heated to about 100°C for about 20 minutes with stirring until the MgCl 2 became dissolved.
  • Magnesium metal turnings (5.65 grams, 0.232 mole) were added to a separate three-neck flask equipped with a mechanical stirrer, dropping funnel, gas inlet, outlet, and solids addition port. Toluene (reagent grade, 43.7 grams) was then added followed by 1.0 gram of butyl ethyl magnesium (10.5% in heptane, 0.022 grams Mg, 9.1 x 10 -4 mole).
  • the vessel was heated to about 105°C for 15 minutes with stirring, and was then cooled.
  • the toluene solution which contains MgCl 2 /benzyl alcohol/ethanol was transferred into a dropping funnel through a tube of TEFLON fluoropolymer and then was added dropwise into the vessel with stirring.
  • the vessel's temperature was maintained at about 90°C for the addition of the remaining solution.
  • the vessel was heated to reflux (about 105°C) and was maintained at that temperature with stirring for one hour.
  • the vessel was cooled, and the liquid was slowly filtered through a 0.5 micron filter. The filtrate was a colorless mobile solution.
  • composition of the solution was: ciMgOc 7 H 7 78 grams
  • a 500 ml three-neck flask was equipped with a mechanical stirrer, condenser, gas inlet, outlet and solids addition port.
  • the vessel was purged with nitrogen for 30 minutes replacing the atmosphere with nitrogen.
  • a toluene/ethanol/MgCl 2 /benzyl alcohol solution was prepared in accordance with the procedure of Example 2 except less ethanol and benzyl alcohol was used. 57.2 grams of benzyl alcohol and 17.8 grams of ethanol were added. The final theoretical composition of this solution was:
  • Magnesium metal (0.28 gram 0.012 mole) and 1.13 gram (0.011 mole) of magnesium metal were placed in a 150 ml vial. Dry toluene (60 ml) was charged into the vial by syringe without ethanol being present as well. Then 6.65 gram of benzyl alcohol (0.06 mole) was added into the vial with stirring. After addition the vial was maintained at refluxing temperature for about 30 minutes. The final product was a white solid.
  • This Example illustrates the preparation of another hydrocarbon-soluble chloromagnesium hydrocarbyloxide.
  • the preparation was conducted under a nitrogen atmosphere.
  • the toluene, ethanol, and (for this Example) 2-octanol were dried over molecular sieves and degassed by purging with nitrogen.
  • Magnesium chloride (22.3 grams, 0.234 mole, under 0.2% water content), toluene (104 grams), 2-octanol (76.7 grams, 0.673 mole), and absolute ethanol (30.4 grams, 0.661 mole) were mixed in a three neck round bottom flask equipment with a mechanical stirrer, condenser, and solids addition port.
  • the vessel was heated to 111°C for about 15-20 minutes with stirring until the MgCl 2 dissolved. Then, magnesium metal turnings (5.65 grams, 0.232 mole) were added to the solution mixture slowly, with control of the gas and heat evolution. As the reaction subsided, the solution was heated to reflux for 2-3 hours. The solution was then diluted with toluene (about 74 grams) and filtered through a 0.5 micron
  • fluoropolymer TEFLON brand membrane in-line filter.
  • This Example illustrates the preparation of another hydrocarbon-soluble chloromagnesium alkoxide.
  • the preparation was conducted under a nitrogen atmosphere.
  • the toluene, ethanol, and (for this Example) 2-octanol were dried over molecular sieves and degassed by purging with nitrogen.
  • fluoropolymer TEFLON brand membrane in-line filter.
  • This Example illustrates the preparation of magnesium chloroalkoxide.
  • the process was conducted under a nitrogen, atmosphere.
  • the ethanol and 2-ethylhexanol used were dried over molecular sieve resin.
  • Magnesium metal turnings (5.40 grams, 0.222 mole) of over 98% purity were added to a 500 ml flask equipped with a mechanical stirrer, dropping funnel, gas inlet, outlet, and solids addition port.
  • the vessel was purged with nitrogen.
  • Heptane pure grade, 40 grams
  • the vessel was heated to about.100°C for about 15 minutes with stirring, and was then cooled .
  • Magnesium chloride 22 . 3 grams , 0.234 mole, under 0.2% water content
  • a solution of pure heptane (60 grams), 2-ethylhexanol (83.4 grams, 0.642 mole), and absolute ethanol (22.0 grams, 0.478 mole) were added dropwise to the vessel with stirring over 15 minutes.
  • the vessel heated up to about

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

On prépare des complexes solubles en hydrocarbures d'halo-alcoxydes de magnésium et d'alcools (XnMg(OR)2n.mR'OH pR''OH), dans une réaction non-Grignard, mettant en ÷uvre la combinaison de sources de magnésium, d'halogénure, et d'alcoxyde en présence d'un excédent de l'alcool du groupe alcoxy désiré, ainsi que d'une quantité d'alcool d'alkyle inférieur permettant de procéder à la solubilisation voulue du complexe.
PCT/US1990/005894 1989-10-16 1990-10-15 Procede de fabrication de complexe de magnesium contenant de l'halogenure/alcoxy WO1991005608A1 (fr)

Applications Claiming Priority (13)

Application Number Priority Date Filing Date Title
US42216489A 1989-10-16 1989-10-16
US42187389A 1989-10-16 1989-10-16
US421,873 1989-10-16
US422,164 1989-10-16
US43628389A 1989-11-13 1989-11-13
US436,283 1989-11-13
US49729390A 1990-03-22 1990-03-22
US497,293 1990-03-22
US497,294 1990-03-22
US07/497,295 US5023385A (en) 1990-03-22 1990-03-22 Novel halide-arylalkoxy-containing magnesium compounds
US07/497,294 US5081320A (en) 1990-03-22 1990-03-22 Novel halide/alkoxy-containing magnesium compounds
US497,295 1990-03-22
USNOTFURNISHED 1999-05-13

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0526941A1 (fr) * 1991-08-06 1993-02-10 Akzo Nobel N.V. Composition halomagnésium hydrocarbylosyde et procédé de préparation
EP1108730A1 (fr) * 1999-12-15 2001-06-20 Idemitsu Petrochemical Co., Ltd. Composée de magnésium, catalyseur pour la polymérisation d'oléfine, méthode pour la production de polymère d'oléfine
US6365540B1 (en) 1997-12-23 2002-04-02 Borealis Technology Oy Product containing magnesium, halogen and alkoxy
WO2007026016A1 (fr) * 2005-09-01 2007-03-08 Chemetall Gmbh Metal alcalino-terreux active, notamment magnesium, utilise pour produire des composes de metal organo-alcalino-terreux
EP3875503A1 (fr) 2020-03-02 2021-09-08 Borealis AG Catalyseur et sa préparation

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859231A (en) * 1972-10-13 1975-01-07 Gulf Research Development Co Simplified process for manufacture of catalyst component
US4105585A (en) * 1976-05-24 1978-08-08 Bp Chemicals Limited Polymerization catalyst
US4335016A (en) * 1981-02-23 1982-06-15 Chemplex Company Catalyst and method
US4727051A (en) * 1986-12-15 1988-02-23 Stauffer Chemical Company Production of halide-and alkoxy-containing magnesium compositions
US4792640A (en) * 1986-04-18 1988-12-20 Lithium Corporation Of America Hydrocarbyloxy magnesium halides
US4806696A (en) * 1986-06-18 1989-02-21 Shell Oil Company Process for stable preparation of alkoxymagnesium compounds

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859231A (en) * 1972-10-13 1975-01-07 Gulf Research Development Co Simplified process for manufacture of catalyst component
US4105585A (en) * 1976-05-24 1978-08-08 Bp Chemicals Limited Polymerization catalyst
US4335016A (en) * 1981-02-23 1982-06-15 Chemplex Company Catalyst and method
US4792640A (en) * 1986-04-18 1988-12-20 Lithium Corporation Of America Hydrocarbyloxy magnesium halides
US4806696A (en) * 1986-06-18 1989-02-21 Shell Oil Company Process for stable preparation of alkoxymagnesium compounds
US4727051A (en) * 1986-12-15 1988-02-23 Stauffer Chemical Company Production of halide-and alkoxy-containing magnesium compositions

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0526941A1 (fr) * 1991-08-06 1993-02-10 Akzo Nobel N.V. Composition halomagnésium hydrocarbylosyde et procédé de préparation
US6365540B1 (en) 1997-12-23 2002-04-02 Borealis Technology Oy Product containing magnesium, halogen and alkoxy
US6420499B1 (en) 1997-12-23 2002-07-16 Borealis Technology Oy Catalyst component comprising magnesium, titanium, a halogen and an election donor, its preparation and use
EP1108730A1 (fr) * 1999-12-15 2001-06-20 Idemitsu Petrochemical Co., Ltd. Composée de magnésium, catalyseur pour la polymérisation d'oléfine, méthode pour la production de polymère d'oléfine
WO2007026016A1 (fr) * 2005-09-01 2007-03-08 Chemetall Gmbh Metal alcalino-terreux active, notamment magnesium, utilise pour produire des composes de metal organo-alcalino-terreux
US8148286B2 (en) 2005-09-01 2012-04-03 Chemetall Gmbh Activated alkaline earth metal, in particular magnesium, for the preparation of organoalkaline earth metal compounds
EP3875503A1 (fr) 2020-03-02 2021-09-08 Borealis AG Catalyseur et sa préparation
WO2021175836A1 (fr) 2020-03-02 2021-09-10 Borealis Ag Catalyseur et son procédé de préparation

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