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GB2047708A - Butyloctylmagnesium compounds - Google Patents

Butyloctylmagnesium compounds Download PDF

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Publication number
GB2047708A
GB2047708A GB8006076A GB8006076A GB2047708A GB 2047708 A GB2047708 A GB 2047708A GB 8006076 A GB8006076 A GB 8006076A GB 8006076 A GB8006076 A GB 8006076A GB 2047708 A GB2047708 A GB 2047708A
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Prior art keywords
solution
octyl
butyl
reaction
compound
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GB2047708B (en
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Bayer Pharma AG
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Schering AG
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/02Magnesium compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides dialkyl magnesium compounds having n-butyl and n-octyl radicals, wherein the molar butyl : octyl ratio is from 1 : 1 to 9 : 1, and solutions of these compounds in hydrodcarbons. The compounds may be manufactured by reacting magnesium with butyl chloride and octyl chloride in the presence of an organoaluminium complex. They are useful as catalysts in polymerization reactions as they have a low crystallization tendency.

Description

SPECIFICATION Butyloctylmagnesium compounds Solutions of dialkylmagnesium compounds in hydrocarbons and the manufacture thereof are described in British Patent Specifications 955806 and 1 003 551, and also in German Patent Specification 2 027 237. The dialkylmagnesium compounds are manufactured by reacting magnesium and alkyl halides in the presence of aluminium compounds. Dialkylmagnesium compounds soluble in hydrocarbons are dialkylmagnesium compounds that are complexed with alkylaluminium compounds, the aluminium content being determined by the quantity used.
The present invention provides a dialkylmagnesium compound having n-butyl and n-octyl radicals with a molar butyl . octyl ratio of from 1:1 to 9:1, preferably 3: 1, and a solution thereof in a hydrocarbon.
These are useful as catalysts and catalyst constituents fdr polymerisation, e.g. of ethylene, propylene or butadiene.
A dialkylmagnesium compound of the invention, especially as a solution thereof in a hydrocarbon, may be prepared by reacting magnesium with suitable butyl and octyl compounds, e.g. halides, preferably butyl chloride and octyl chloride, in the appropriate proportions in the presence of an organoaluminate complex.
Suitable organoaluminate complexes are, for example, those of the general formula
in which Ml represents a metal of the 1st main group of the Mendeleev Periodic Table, M" represents a metal of the 2nd main group of the Mendeleev Periodic Table, R represents a straight-chain or branched alkyl radical having 1 to 18 carbon atoms, X represents a halogeno radical or hydride radical, a represents the number 1 or 2, b represents a number from 1 to (3a + 1), c represents the number (3a + 1) d represents a number from 1 to 4, e represents the number (6 + 2d) - f, and frepresentsthe number 0,1 to 2, and if b ore > 1,the radicals represented by R can be the same or different.
The organoaluminate complex is preferably added to the reaction mixture before the reaction in an amount of from 0.25 to 2 mole %, more especially 0.3 to 1.3 mole %, calculated on the magnesium used.
Especially good results are achieved if the magnesium used for the reaction is magnesium powder ground in the presence of the complex. If a sufficient quantity of the complex compound is added to the magnesium before grinding it is unnecessary to make another addition of the complex compound before the reaction itself. It is thought that the grinding has no influence, however, on the type and composition of the butyl-octyl-magnesium compound produced or the solutions produced therefrom.
The reaction may be carried out in the presence of an inert solvent, for example a hydrocarbon, preferably a saturated hydrocarbon, for example hexane, heptane, methylcyclohexane or petroleum benzine fractions.
The solvent is used usually in an amount of 2 to 30 times the quantity by weight of the magnesium to be reacted.
The reaction is usually carried out under normal pressure. However, it is also possible to use higher or lower pressures. The reaction temperature is preferably within the range of 80 to 1 50 C, more especially 90 to 1200C, depending interalia on the solvent used.
Uniform dialkylmagnesium compounds and the previously known mixed alkylmagnesium compounds such as, for example, butyl-sec.-butyl-magnesium have a tendency to crystallise, which interferes with technical processes. In contrast, the butyl-octyl-magnesium of the invention has a very low crystallisation tendency. Thus, a 30% (by weight) solution of butyl-sec.-butyl-magnesium in hexane precipitates the dialkylmagnesium in the form of cyrstals which spontaneously ignite in the air. A solution of butyloctylmagnesium of the invention in a hydrocarbon, even in a saturated non-cyclic hydrocarbon, is distinguished by particular stability, reduced tendency towards spontaneous ignition, and a high capacity for taking up the material to be dissolved.
Precipitation of butyloctylmagnesium from hexane solutions is generally not observed even with dialkylmagnesium contents of clearly above 30% by weight.
The preparation of the compound of the invention may be carried out for example by the following general procedure: The solvent is placed under an inert gas atmosphere (for example argon or nitrogen) in a reaction vessel equipped with external heating, stirring, reflux cooler, thermometer and inlet device. The magnesium to be reacted is introduced, while stirring, and the chosen complex then added. (Using this procedure the solids do not become lumpy.) If grinding is to be carried out it is advisable to transfer the suspension to a mill, grind it and then return it to the reaction vessel. After heating to at least 900C, the metered addition of the alkyl chlorides, for example as a mixture or, if desired, one after the other, is begun. The speed of the addition is dependent upon the scope of the heat supply.
After addition, the deposition of the solid portion can be accelerated, for example, by using a decanter or centrifuge; filtering is also suitable.
The following Examples illustrate the invention. Percentages given therein are percentages by weight.
Examples Compounds of the invention were prepared by the above-described general procedure. Unless otherwise stated and heating before the alkyl chloride addition was carried out at 105 to 115 C. The alkyl chloride was metered in over approximately 2 hours, for safety reasons approximately 1 hour being allowed in addition for subsequent reaction. In the final step the deposition of solid was accelerated by centrifuging, and the solid was washed twice. The main solution and the-combined washing.solutions were tested according to known methods for their content of magnesium, chloride and foreign elements. The results are given in the Table below.
The following abbreviations are used in the Table: MS = main solution WS = washing solutions R2Mg yield = total yield of dialkylmagnesium, calculated on the magnesium used.
Et = ethyl Bu = butyl Oc = octyl Example Substances used Reaction Products 1 1 mol Mg powder (smaller MS: 231 g than 150u) 3.20 % Mg 0.75 mol butyl chloride 0.14 % Cl 0.25 mol octyl chloride 0.09 % Al 225 g i-nonane (boiling WS: 334g point range 115 - 140 C) 0.56% Mg 4.68 mmoi Mg4[Al28u120c2] 0.01 % Al CI below detection limit R2Mg Yield: 76 % th. yield Bu1.5Oc0.5Mg Analysis: 71.68% C; 13.14% H; 13.91 % Mg; 0.87 % CI; 0.39 % Al 2 1 mol Mg chips (1 - 3 mm MS: 237 g x2mmx0.04mm) 3.19% Mg ground in 0.09 % Cl 225 g i-nonane 0.08% Al with WS:280 g 4.68 mmol Mg4[Al2Bu12Oc2i 0.60 % Mg ground product reacted with 0.01 % Al 0.75 mol butyl chloride Cl below detection limit and R2Mg yield: 0.25 mol octyl chloride 76 % th. yield Bu1.5Oc0.5Mg Analysis: 71.89%C; 13.18%H; 14.10% Mg; 0.45% Cl; 0.38 % Al Note: if Example 2 is carried out without grinding, the final solution contains no active magnesium Example Substances used Reaction Products 3 1 mol Mg powder (smaller MS: 224g than 150 ) 3.17 % Mg 0.5 mol octyl chloride 0.08% Cl 0.5 mol butyl chloride 0.09% Al 220 g i-nonane WS:315 g 4.68 mmol Mg[Al2Bu12Oc] 0.68 O/O Mg below 0.01 % Al Cl indetectable R2Mg yield: 76 % th. yield BuOcMg Analysis: 73.99%C; 12.93 % H; 12.37% Mg; 0.30% Cl; 0.35 % Al 4 as Example 3 but with MS: 232 9 0.20 mol octyl chloride 3.19% Mg and 0.05% Cl 0.80 mol butyl chloride 0.08 % Al WS: 321 g 0.57%Mg 0.01 %AI 0.01% Cl R2Mg yield: 76 % th. yield Bu1.6Oc0.4Mg Analysis: 71.72 % C; 13.19 % H; 15.08% Mg; 0.24% Cl; 0.36 % Al Example Substances used Reaction products 5 1 mol Mg powder (smaller MS: 221 g than 150 ) 3.27% Mg 0.75 mol butyl chloride 0.07 % CI 0.25 mol octyl chloride 0.08% 200 9 hexane WS: 290 9 4.68 mmol Mg4[Al2Bu12Oc2] 0.49 % Mg in autoclave under pressure 0.01 % Al maximum 2.8 atmospheres Cl not determined gauge R2Mg yields: 71 % th. yield Bu1.5Oc0.5Mg Analysis: 71.60% C; 13.17% H; 13.92 % Mg; 0.31 % Cl; 0.36%Al 6 1 mol Mg powder (smaller MS: 278 9 than 150 ) 2.60% Mg 0.75 mol butyl chloride 0.1% CI 0.25 mol octyl chloride 0.31 % Al 270 9 heptane WS: 280 g 20 mmol Mg4[Al2Bu12Oc2] 0.76 % Mg Al and Cl not determined R2Mg yield: 77 % th.yield Bu1.50c0.5Mg Analysis: 70.68 % C; 13.08 % H; 13.84% Mg; 0.56% Cl; 1.78 % Al Example Substances used Reaction products 7 as Example 6 but with MS: 550 g 2.5 mmol Mg4[Al2Bu12Oc2] 1.37 % Mg Afurther 270 g heptane 0.09% CI were additionally added 0.02% Al WS: 293 9 025% Mg Cl and Al below detection limit R2Mg yield: 68 % th. yield Bu1.5Oc0.5Mg Analysis: 72.08%C; 13.18%H; 13.79%Mg; 0.78%Cl; 0.27 % Al 8 as Example 6 but with MS: 278 9 8.75 mmol Na(AIEt4) 2.59%Mg 0.1 %Cl 0.08%AI WS: 320 9 0.68%Mg Al and Cl not determined R2Mg yield: 77 % th. yield Bu1.5Oc0.5Mg Analysis: 71.99%C; 13.12 % H; 13.82%Mg; 0.53%Cl; 0.11%Al 9 as Example 1 but with MS:230 g 4.38 mmol Mg2[AI2BugOc] 3.19 % Mg as complex 0.09% Cl 0.09 % Al WS: 290 g 0.61 % Mg below 0.01 %Al Cl below detection limit R2Mg yield: 75 % th. yield Bu1.5Oc0.5Mg 10 as Example 1 but with MS: 229 g 4.37 mmol Mg[Al2Bu7Oc] 3.035%Mg as complex 0.13% Cl 0.09 % Al WS: 334g 0.65% Mg 0.01% AL CI below detection limit R2Mg yield: 72.5 % th. yield 11 as Example 1 but with MS: 240 g 4.38 mmol Mg2[Al2Et6Bu3Oc] 3.04 % Mg as complex 0.11 %Cl 0.09 % Al WS: 349 g 0.56% Mg 0.01 % Al CI below detection limit R2Mg yield: 76 % th. yield Example Substances used Reaction products 12 as Example 1 but with MS:216g 8.75 mmol Na[AIH2Et21 3.03 % Mg as complex and 0.09 % Cl 180 9 heptane as solvent 0.10%Al WS: 306 9 0.65% Mg Al and Cl below detection limit R2Mg yield: 70.2 % th. yield 13 as Example 5 but with MS: 378 g 8.75 mmol Na(AlEt4) 1.60 % Mg as complex 0.1 % Cl 0.08 % Al WS: 3219 0.55%Mg < 0.01 %AI Cl below detection limit R2Mg yield: 74 % th. yield 14 as Example 1 but with MS: 237 g 8.5 mmol Li(AlEt3Bu) 2.96% Mg as complex 0.07% Cl 0.08% Al WS: 286 9 0.69% Mg 0.01 % Al Cl below detection limit R2Mg yield: 74 % th. yield 15 as Example 1 but with MS:214g 4.375 mmol Na[Al2Et6F] 3.12 /0 Mg as complex and 0.12% Cl 180 g n-octane as solvent 0.1 % Al WS: 284 9 0.71 % Mg Al and Cl below detection limit R2Mg yield: 71.4 % th. yield 16 as Example 1 but with MS: 231 9 8.75 mmol Li[Al(n-Oc)3n-Bul] 3.03 % Mg as complex 0.09 % CI 0.09 % Al WS: 309 9 0.65% Mg 0.01 % Al Cl below detection limit R2Mg yield: 74.1 % th. yield Example Substances used Reaction products 17 as Example 1 but with MS: 235.5 9 8.75 mmol Na[AlEtCl3] 2.75 % Mg as complex 0.11 %Cl 0.08 % Al WS:357 g 0.56 % Mg 0.01 % Al Cl below detection limit R2Mg yield: 69.5 % th. yield 18 as Example 1 but with MS:250g 4.375 mmol Na[AIEt4] 2.80 % Mg 4.375 mmol Li[Al(n-Oc)3n-Bu] 0.1 % Cl as complex mixture 0.09 % Al WS: 333 9 0.64% Mg Al and Cl below detection limit R2Mg yield: 75 % th. yield 19 as Example 1 but with MS: 234 g 4.3 mmol 3.09 % Mg MG2[Al2(i-Bu)4(n-Bu)3OcH2] 0.11%Cl as complex 0.08 % Al WS: 355 9 0.57 % Mg 0.01 %AI Cl below detection limit R2Mg yield: 76 % th. yield 20 as Example 1 but with MS: 210 g 4.37 mmol Ca(Al2Et8) 3.07 % Mg as complex 0.09 % Cl 0.08% Al WS:310g 0.67 % Mg Cl and Al below detection limit R2Mg yield: 70.1 %th.yield

Claims (22)

1. A dialkylmagnesium compound having n-butyl and n-octyl radicals, wherein the molar butyl : octyl ratio is from 1 : 1 to 9: 1.
2. A compound as claimed in claim 1, wherein the molar butyl : octyl ratio os 3 : 1.
3. A compound as claimed in claim 1, wherein the molar butyl : octyl ratio is 1 : 1.
4. A compound as claimed in claim 1, wherein the molar butyl : octyl ratio is 4 : 1.
5. A solution of a compound claimed in any one of claims 1 to 4 in a hydrocarbon.
6. A solution as claimed in claim 5, wherein the hydrocarbon is a saturated hydrocarbon.
7. A solution as claimed in claim 6, wherein the hydrocarbon is hexane, heptane, methylcyclohexane, a petroleum fraction, i-nonane or n-octane.
8. A solution as claimed in any one of claims 5 to 7, wherein the hydrocarbon is present in an amount of 2 to 30 times the weight of magesium in the compound.
9. A solution as claimed in any one of claims 5 to 7, which contains at least 30 % by weight of compound claimed in claim 1.
10. A solution of a dialkylmagnesium compound having n-butyl and n-octyl radicals, wherein the molar butyl : octyl ratio is from 1:1 to 9:1, in a hydrocarbon, manufactured by reacting magensium with butyl chloride and octyl chloride in the presence of an organoaluminate complex.
11. A solution as claimed in claim 10, wherein the organoaluminate complex has the general formula
in which Ml represents a metal of the 1st main group of the Mendeleev Periodic Table.
M" represents a metal of the 2nd main group of the Mendeleev Periodic Table.
R represents a straight-chain or branched alkyl radical having 1 to 18 carbon atoms.
D represents a halogeno radical or hydride radical.
a represents the number 1 or 2.
b represents a number from 1 to (3a + 1).
c represents the number (3a + 1) - b.
drepresentsa number from 1 to 4.
e represents the number (6 + 2d) - f, and frepresentsthe number 0,1 or 2.
and if b or e > 1,the radicals represented by R can be the same or different.
12. A solution as claimed in claim 10 or claim 11, wherein the organoaluminate complex is present in the reaction mixture in an amount of from 0.25 to 2 mole % calculated on the magnesium used.
13. A solution as claimed in claim 12, wherein the organoaluminate complex is present in the reaction mixture in an amount of from 0. to 1.3 mole % calculated on the magnesium used.
14. A solution as claimed in any one of claims 10 to 13, wherein the magnesium is ground with the complex before reaction.
15. A solution as claimed in any one of claims 10 to 14, wherein the reaction is carried out in a hydrocarbon solvent used in an amount 2 to 30 times the weight of magnesium to be reacted.
16. A solution as claimed in any one of claims 10 to 15, wherein the reaction is carried out in a saturated hydrocarbon solvent.
17. A solution as claimed in claim 16, wherein the hydrocarbon is hexane, heptane, methylcyclohexane, a petroleum fraction, i-nonane or n-octane.
18. A solution as claimed in any one of claims 10 to 17, wherein the reaction is carried out at a temperature in the range of from 80 to 150"C.
19. A solution as claimed in claim 18, wherein the reaction is carried out at a temperature in the range of from 90 to 120"C.
20. A solution as claimed in any one of claims 10 to 19, wherein the molar butyl : octyl ratio is 3:1.
21. A solution as claimed in claim 10, wherein the reaction is carried out substantially as described herein.
22. A solution as claimed in claim 10, wherein the reaction is carried out substantially as described in any one ofthe Examples 1 to 20 herein.
GB8006076A 1979-02-23 1980-02-22 Butyloctyl-magnesium compounds Expired GB2047708B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2907025 1979-02-23
DE2943357A DE2943357C2 (en) 1979-02-23 1979-10-12 ETHER-FREE SOLUTIONS OF N-BUTYL-N-OCTYL-MAGNESIUM COMPOUNDS

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GB2047708A true GB2047708A (en) 1980-12-03
GB2047708B GB2047708B (en) 1983-02-02

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DE (1) DE2943357C2 (en)
FR (1) FR2449695B1 (en)
GB (1) GB2047708B (en)
IT (1) IT1209300B (en)
NL (1) NL7909273A (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3104791A1 (en) * 1981-02-11 1982-09-02 Schering Ag, 1000 Berlin Und 4619 Bergkamen ORGANIC BARIUM-MAGNESIUM COMPLEXES AND METHOD FOR THEIR PRODUCTION
EP0422686B1 (en) * 1989-10-13 1997-04-16 Fuji Photo Film Co., Ltd. Image-forming material containing an aluminate complex
DE19757499A1 (en) * 1997-12-23 1999-06-24 Studiengesellschaft Kohle Mbh High yield production of Grignard compounds, for production of organomagnesium compounds
EP4153602A1 (en) 2020-05-20 2023-03-29 LANXESS Organometallics GmbH Novel organo-magnesium compounds and their use
EP4520722A1 (en) 2023-09-05 2025-03-12 LANXESS Organometallics GmbH Sustainable ziegler-natta catalysts

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB955806A (en) * 1959-04-29 1964-04-22 Nat Res Dev Preparation and use of organomagnesium materials
GB1003551A (en) * 1960-12-01 1965-09-08 Nat Res Dev Organomagnesium materials
NL139981B (en) * 1969-06-04 1973-10-15 Stamicarbon PROCESS FOR THE PREPARATION OF SOLUBLE COMPLEXES OF MAGNESIUM DIALKYLES AND ORGANO-ALUMINUM COMPOUNDS.
US4069267A (en) * 1976-10-27 1978-01-17 Lithium Corporation Of America Stable diorganomagnesium compositions
US4127507A (en) * 1977-06-29 1978-11-28 Texas Alkyls, Inc. Hydrocarbon soluble straight-chain di-(lower alkyl) magnesium compositions

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IT8019286A0 (en) 1980-01-18
FR2449695A1 (en) 1980-09-19
IT1209300B (en) 1989-07-16
DE2943357C2 (en) 1982-11-11
FR2449695B1 (en) 1985-07-26
NL7909273A (en) 1980-08-26
GB2047708B (en) 1983-02-02
DE2943357A1 (en) 1980-09-04

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Effective date: 20000221