Low-Viscosity Solutions of Alkaline-Earth Metal Alkoxides In Aprotic Solvents, Method for the Production of Same and Use for the Production of Ziegler-Natta Catalysts

Abstract

One or more concentrated low-viscosity solutions of alkaline earth alkoxide compounds M(OCH.sub.2R.sup.6).sub.2-a-b(OR.sup.7).sub.a[O(CHR.sup.8)OR.sup.9].sub.b in mixture with a metal alkyl compound M(R.sup.10R.sup.11) in an aprotic solvent and related methods are disclosed herein.

Claims

1-15. (canceled)

16. A solution of alkaline earth alkoxide compounds M(OCH.sub.2R.sup.6).sub.2-a-b(OR.sup.7).sub.a[O(CHR.sup.8).sub.nOR.sup.9].sub.b in mixture with a metal alkyl compound M(R.sup.10R.sup.11) with an alkaline earth metal concentration in the range of 0.2 to 1.8 mmol/g in an aprotic solvent, wherein M is an alkaline earth metal selected from the group consisting of Mg, Ca, Ba, and Sr; OCH.sub.2R.sup.6 is an alkoxide radical consisting of at least 3 and at most 40 carbon atoms with a branch in position 2 relative to the O function; R.sup.7 is an alkyl radical with 2-15 carbon atoms, which is either linear or has a branch in ≧position 3 relative to the O function; R.sup.8 is an alkyl radical with 1 to 6 carbon atoms, which is either linear or has a branch at ≧position 3 (relative to the O function; R.sup.9 is an alkyl radical with 2 to 15 carbon atoms, which is either linear or has a branch; R.sup.10 and R.sup.11 are any alkyl radicals with 1 to 15 carbon atoms; n is an integer from 1 to 4; a+b≦2 wherein a and b each have a value of 0 to 2; and the solution has a molar ratio of M(OCH.sub.2R.sup.6).sub.2-a-b(OR.sup.7).sub.a[O(CHR.sup.8).sub.nOR.sup.9].sub.b to M(R.sup.10R.sup.11) that is from 99.5:0.5 to 60:40.

17. The solution according to claim 16, characterized in that the alkaline earth metal concentration is in the range of 0.4 to 1.6 mmol/g.

18. The solution according to claim 16, characterized in that the solution, at Mg concentrations of ≧1 mmol/g to ≦1.6 mmol/g, has a viscosity, measured at room temperature, of ≦300 cP.

19. The solution according to claim 16, characterized in that the molar ratio of M(OCH.sub.2R.sup.6).sub.2-a-b(OR.sup.7).sub.a[O(CHR.sup.8).sub.nOR.sup.9].sub.b to M(R.sup.10R.sup.11) is from 99:1 to 70:30.

20. The solution according to claim 16, characterized in that an aluminum compound Al(OCH.sub.2R.sup.6).sub.3-c-d(OR.sup.7).sub.c[O(CHR.sup.8).sub.nOR.sup.9].sub.d is present, wherein OCH.sub.2R.sup.6 is an alkoxide radical consisting of at least 3 and at most 40 carbon atoms with a branch in position 2 relative to the O function; R.sup.7 is an alkyl radical with 2 to 15 carbon atoms, which is either linear or has a branch at ≧position 3 relative to the O function; R.sup.8 is an alkyl radical with 1 to 6 carbon atoms, which is either linear or has a branch at ≧position 3 relative to the O function; R.sup.9 is an alkyl radical with 2 to 15 carbon atoms, which is either linear or has a branch; n is an integer from 1 to 4; c+d≧3 and both c and d each have a value of 0 to 3, and wherein the amount of aluminum compound Al(OCH.sub.2R.sup.6).sub.3-c-d(OR.sup.7).sub.c[O(CHR.sup.8).sub.nOR.sup.9].sub.d, based on the dissolved alkaline earth metal, is in the range of 0 to about 20 mol %.

21. The solution according to claim 16, characterized in that it contains from 0.1 to 30 mol % active base R.sub.2Mg, determined by direct titration with sec-butanol and biquinoline as the indicator and based on the total alkaline earth metal M in solution and they are non-pyrophoric according to the UN test.

22. A method for synthesis of alkaline earth alkoxide compounds M(OCH.sub.2R.sup.6).sub.2-a-b(OR.sup.7).sub.a[O(CHR.sup.8).sub.nOR.sup.9].sub.b in mixture with a metal alkyl compound M(R.sup.10R.sup.11) the method comprising: mixing an alkaline earth metal or an alkaline earth metal mixture in an aprotic solvent with an alcohol HO(CHR.sup.8).sub.nOR.sup.9 under reaction conditions sufficient to produce a first reaction mixture, and adding a solution of a metal alkyl compound M(R.sup.10R.sup.11) to the first reaction mixture, wherein the molar ratio of M(OCH.sub.2R.sup.6).sub.2-a-b(OR.sup.7).sub.a[O(CHR.sup.8).sub.nOR.sup.9].sub.b to M(R.sup.10R.sup.11), is from 99.5:0.5 to 60:40.

23. The method according to claim 22 wherein the alkaline earth metal or an alkaline earth metal mixture in an aprotic solvent further comprises one or more alkyl aluminum compounds selected from trialkyl, alkylalkoxy and/or alkyl halide compounds, wherein the Al concentration based on the dissolved alkaline earth metal is in the range of 0 to about 20 mol %.

24. The method according to claim 23, characterized in that the aprotic solvent is either (i) an aliphatic solvent selected from the group consisting of cyclohexane, methyl cyclohexane, hexane, heptane, octane, nonane, decane, dodecane, decalin and gasoline fractions, or (ii) an aromatic solvent selected from the group consisting of benzene, toluene, ethylbenzene, xylenes and cumene.

25. The method according to claim 22, characterized in that the mixing of the alkaline earth metal or the alkaline earth metal mixture in the aprotic solvent with the takes place at a temperature in the range between about 0 and 180° C.

26. The method according to claim 22, characterized in that the alcohol HO(CHR.sup.8).sub.nOR.sup.9 is a C.sub.2-C.sub.4 glycol monoether selected from the group consisting of 2-ethoxyethanol, 3-ethoxy-1-propanol, 3-ethoxy-1-butanol, 2-(2-ethylhexoxy)ethanol, 2-butoxyethanol, 2-hexyloxyethanol, 1,3-propylene glycol monobutyl ether, or any mixture of at least two of the aforementioned alcohols.

27. A method for synthesis of alkaline earth alkoxide compounds M(OCH.sub.2R.sup.6).sub.2-a-b(OR.sup.7).sub.a[O(CHR.sup.8).sub.nOR.sup.9].sub.b in mixture with a metal alkyl compound M(R.sup.10R.sup.11), the method comprising: mixing a solution of the metal alkyl compound M(R.sup.10R.sup.11) in an aprotic solvent with one or more alcohols selected from the group of HOCH.sub.2R.sup.6, HOR.sup.7, HO(CHR.sup.8).sub.nOR.sup.9, and any mixture thereof, wherein half of the molar ratio of the total number of moles of all alcohols to the metal alkyl compound is from 99.5:0.5 to 60:40.

28. A use of a solution according to claim 16 to produce one or more polymerization catalysts.

29. A use of a solution according to claim 16 in mixture with a metal alkyl compound M(R.sup.10R.sup.11) in organic synthesis as a base.

30. The solution according to claim 16, characterized in that the alkaline earth metal concentration is in the range of 0.7 to 1.4 mmol/g.

31. The solution according to claim 16, characterized in that the solution, at Mg concentrations of >1 mmol/g to <1.6 mmol/g, has a viscosity, measured at room temperature, of <100 cP.

32. The solution according to claim 16, characterized in that the molar ratio of M(OCH.sub.2R.sup.6).sub.2-a-b(OR.sup.7).sub.a[O(CHR.sup.8).sub.nOR.sup.9].sub.b to M(R.sup.10R.sup.11) is from 95:5 to 80:20.

33. The solution according to claim 20, characterized in that the amount of aluminum compound Al(OCH.sub.2R.sup.6).sub.3-c-d(OR.sup.7).sub.c[O(CHR.sup.8).sub.nOR.sup.9].sub.d, based on the dissolved alkaline earth metal, is in the range of 0.2 mol %. to 15 mol %.

34. The solution according to claim 20, characterized in that the amount of aluminum compound Al(OCH.sub.2R.sup.6).sub.3-c-d(OR.sup.7).sub.c[O(CHR.sup.8).sub.nOR.sup.9].sub.d, based on the dissolved alkaline earth metal, is in the range of 0.5 mol %. to 4 mol %.

35. The method according to claim 22, characterized in that the mixing of the alkaline earth metal or the alkaline earth metal mixture in the aprotic solvent with the alcohol HO(CHR.sup.8).sub.nOR.sup.9 takes place at a temperature in the range between about 40 and 140° C.

36. The method according to claim 22, characterized in that the mixing of the alkaline earth metal or the alkaline earth metal mixture in the aprotic solvent with the alcohol HO(CHR.sup.8).sub.nOR.sup.9 takes place at a temperature that is the boiling point of the aprotic solvent.

37. The method according claim 23, wherein the amount of aluminum compound Al(OCH.sub.2R.sup.6).sub.3-c-d(OR.sup.7).sub.c[O(CHR.sup.8).sub.nOR.sup.9].sub.d, based on the dissolved alkaline earth metal, is in the range of 0.2 mol%. to 15 mol%.

38. The solution according to claim 23, wherein the amount of aluminum compound Al(OCH.sub.2R.sup.6).sub.3-c-d(OR.sup.7).sub.c[O(CHR.sup.8).sub.nOR.sup.9].sub.d, based on the dissolved alkaline earth metal, is in the range of 0.5 mol %. to 4 mol %.

Description

EXAMPLES

[0048] All the reactions were carried out in dry glass equipment inertized with argon. Commercial magnesium shavings were used. The concentrations of Mg and Al were measured by means of ICP (inductively-coupled plasma).

[0049] The active base is determined by direct titration with 1M 2-butanol solution in hexane against 2,2-biguinoline as the indicator. Color change from red to gray.

Example 1

Preparation of a 35% Solution of Magnesium Bis(2-Ethylhexoxide) in Mixture with 6 Mol % Bibutyl Magnesium in Heptane

[0050] Using a 0.5 L double-jacketed glass reactor with a reflux condenser and a dropping funnel, 32.0 g magnesium shavings and 352 g heptane were placed as starting materials. Then 11.3 g of a 20 wt % solution of triethyl aluminum in heptane, 1.8 g ethanol and 171.9 g 2-ethylhexanol were added and heated to the boiling point, then refluxed for 4 hours, whereupon 14.6 L gas was formed and a viscous solution of magnesium bis(2-ethylhexoxide) was obtained. A sample was taken and its viscosity was determined (1025 cP at 25° C.).

[0051] The reaction mixture was then cooled to approx. 80° C. and 54.6 g of a dibutyl magnesium solution in hexane (Mg=1.08 mmol/g) was added. After this addition, the resulting solution had a low viscosity and was easy to handle. The light gray suspension was syphoned off and filtered, yielding 579 g of a non-viscous liquid with a magnesium content of 1.22 mmol/g. The product solution in turn contained 0.030 mmol/g aluminum and had an active base content of 0.15 mmol/g (corresponding to 0.075 mmol/g Bu.sub.2Mg, approx. 6 mol %).

[0052] Yield: 98% of the theoretical

[0053] Viscosity (Brookfield, 25° C.): 33 cP

[0054] In the UN test N.2, N.3, the product solution was found to be non-pyrophoric.

Example 2

Preparation of a 29% Magnesium Decanolate Solution in Hexane in Mixture with 14 Mol % Dibutyl Magnesium

[0055] Using a 0.5 liter double-jacketed glass reactor with a reflux condenser and dropping funnel, 82.0 g of a dibutyl magnesium solution in hexane (Mg=1.11 mmol/g, 91 mmol) was added as the starting mixture. Then 23.6 g n-decanol (149 mmol) was added while stirring vigorously. A gelatinous reaction product was formed temporarily at the addition point, but it completely dissolved as stirring was continued. After the end of dosing, a non-viscous colorless and clear solution was obtained.

[0056] Yield: 104 g solution

[0057] Total magnesium content: 0.88 mmol/g

[0058] Active base unit: 0.24 mmol/g

[0059] Viscosity (Brookfield, 25° C.): 4.8 cP

[0060] In the UN test N.2, N.3, the product solution was found to be non-pyrophoric.

[0061] Comparative Example 1: Preparation of an approx. 30% magnesium decanolate solution in hexane

[0062] Using a 0.5 liter double-jacketed glass reactor with a reflux condenser and dropping funnel, 85.0 g of a dibutyl magnesium solution in hexane (Mg=1.11 mmol/g, 94 mmol) was added. Then 31.2 g n-decanol (197 mmol) was added while stirring vigorously. After adding approx. 90% of the total amount of alcohol, the gelatinous phase formed at the addition point would always dissolve more slowly and then would no longer dissolve at all. After the end of dosing, a stiff gel was formed and could not be liquefied even by heating (approx. 80° C.).

[0063] No sample could be taken by syringe due to the gelatinous consistency.

Example 3

Preparation of a 35% Solution of Magnesium Bis(2-Ethylhexoxide)/Magnesium Decanolate (75:25) in Mixture with Approx. 5 Mol % Butylethyl Magnesium in Heptane

[0064] Using a 0.5 liter double-jacketed glass reactor with a reflux condenser and a dropping funnel, 32.0 g magnesium shavings and 352 g heptane were placed as starting materials. Then 11.3 g of a 20 wt % solution of triethyl aluminum in heptane, 1.8 g ethanol and a mixture of 128.9 g 2-ethylhexanol and 52.2 g 1-decanol were added and heated to the boiling point. Refluxing was continued for 3.5 hours, whereupon 16.0 L gas had formed and the viscous solution of the mixed magnesium alkoxide was obtained. A sample was taken and its viscosity was determined (3800 cP at 25° C.).

[0065] The solution was cooled to 100° C. and 55.1 g of a butylethyl magnesium solution in heptane (Mg=1.09 mmol/g) was added. After the addition, a low viscosity solution that could be handled easily was obtained. The light gray suspension was syphoned and filtered, and 534 g of a non-viscous liquid with a magnesium content of 1.19 mmol/g was isolated. The product solution still contained 0.033 mmol/g aluminum and had an active base content of 0.11 mmol/g (corresponding to 0.055 mmol/g BuMgEt, 4.6 mol %).

[0066] Yield: 88% of theoretical

[0067] Viscosity (Brookfield, 25° C.): 16 cP

[0068] In the UN test N.2, N.3, the product solution was found to be non-pyrophoric.

Example 4

Preparation of a 34% Solution of Magnesium Bis(2-Ethylhexoxide in Mixture with 5 mol % Butylethyl Magnesium in Toluene

[0069] Using a 0.5 liter double-jacketed glass reactor with a reflux condenser and a dropping funnel, 32.0 g magnesium shavings and 352 g toluene were placed as starting materials. The 9.0 g of a 25 wt % solution of triethyl aluminum in toluene, 1.8 g ethanol and 171.9 g 2-ethylhexanol were added and the mixture was heated to the boiling point. Refluxing was continued for just 4 hours, whereupon 16.4 L gas had formed and a viscous solution of the magnesium alkoxide was obtained.

[0070] Then the mixture was cooled to 100° C. and 56.5 g of a dibutyl magnesium solution in heptane (Mg=1.08 mmol/g) was added. After this addition, a low viscosity solution that could be handled easily was obtained. The light gray suspension was syphoned off and filtered, and 576 g of a non-viscous liquid with a magnesium content of 1.21 mmol/g was isolated. The product solution again contained 0.030 mmol/g aluminum and had an active base content of 0.13 mmol/g (corresponding to 0.065 mmol/g BuMgEt, 5.4 mol %).

[0071] Yield: 97% of the theoretical

[0072] Viscosity (Brookfield, 25° C.): 94 cP

[0073] In the UN test N.2, N.3, the product solution was found to be non-pyrophoric.

[0074] Comparative Example 1 and a comparison of the viscosity data before and after addition of dialkyl magnesium solution in Examples 1 and 3 show the positive effect achieved by adding dialkyl magnesium solution to magnesium alkoxide solutions (Examples 1 and 3) and/or using a substoichiometric amount of alcohol in the reaction with dialkyl magnesium solution (Example 2 and Comparative Example 1).

[0075] Whereas all the product solution prepared according to the invention with Mg concentrations between 0.88 and 1.22 mmol/g and Al concentrations of ≦3 mol % could be handled very well and had a low viscosity (viscosity at 25° C. <100 cP), the product solutions containing dialkyl magnesium were extremely viscous: the viscosities of the liquid products were between >1000 cP and 3800 cP. If no alcohol branched in position 2 (HOCH.sub.2R.sup.6 consisting of at least 3 carbon atoms and at most 40 carbon atoms with a branch in position 2 relative to the ) function, i.e., R.sup.6=—CHR.sup.12R.sup.13 where R.sup.12, R.sup.13=independently of one another alkyl radicals C.sub.1-C.sub.18) is used but instead only unbranched alcohols are used, the result of a complete reaction and/or use of a slight excess of alcohol (Comparative Example 1) is a gelatinous product that is not comparable or transferable in any other way. However, in the presence of approx. 14 mol % dibutyl magnesium, a watery, low-viscosity product is obtained. Such a product cannot be produced according to U.S. Pat. No. 4,634,786 because, according to this prior art document, “(a) aliphatic 2-alkyl-substituted primary monoalcohols; or (b) mixtures of the aforementioned (a) alcohols with C.sub.3-C.sub.12 aliphatic secondary or tertiary alcohols; or (c) mixtures of said (a) alcohols with C.sub.1-C.sub.12 aliphatic primary linear unsubstituted alcohols; wherein the molecular ratios of said (a) alcohols to said (b) alcohols and of said (a) alcohols to said (c) alcohols (amounts to) 1 for said (a) alcohols to 0.1 to 2 of said (b) alcohols and said (c) alcohols,” i.e., in each case, (a) alcohols branched in position 2 are needed.

[0076] All the product solutions according to the invention are non-pyrophoric.