NOVEL ORGANO-MAGNESIUM COMPOUNDS AND THEIR USE

Abstract

The present invention relates to novel organo-magnesium compounds obtained by reaction of dialkyl-magnesium compounds and carbodiimides and their use as precursors for the preparation of further magnesium compounds and catalysts.

Claims

1. Organo-magnesium compounds obtainable by reacting compounds of formula (I) with compounds of formula (II) ##STR00008## ##STR00009## wherein R.sup.1 each independently of the other residue R.sup.1 present in the compound of formula (I) denotes alkyl which is either not or once substituted by phenyl and R.sup.2 each independently of the other residue R.sup.2 present in the compound of formula (II) denotes alkyl which is either not or once substituted either by optionally substituted phenyl or N(R.sup.3).sub.2, or denotes optionally substituted phenyl or denotes Si(R.sup.3).sub.3, wherein in the aforementioned formulae R.sup.3 is alkyl or optionally substituted phenyl.

2. The organo-magnesium compounds according to claim 1, wherein the compounds of formula (I) are selected from the group consisting of n-butyl-n-octyl-magnesium, n-butyl-ethyl-magnesium, n-butyl-sec-butyl-magnesium, di-n-butyl-magnesium, di-n-hexyl-magnesium and di-n-octyl-magnesium.

3. The organo-magnesium compounds according to claim 1, wherein the compounds of formula (II) are selected from the group consisting of N,N′-dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1,3-bis(trimethylsilyl)carbodiimide, bis(4-methylphenyl)carbodiimide and N,N′-bis(2-methylphenyl)carbodiimide.

4. The organo-magnesium compounds according to claim 1, wherein the reaction is performed in non-coordinating solvents.

5. The organo-magnesium compounds according to claim 4, wherein the non-coordinating solvents are selected from the group consisting of pentanes, hexanes, heptanes, octanes, nonanes, decanes, undecanes, dodecanes, each of the aforementioned in any possible isomeric pure form or in isomeric mixtures, mineral oils or any mixture of the aforementioned aliphatic solvents.

6. The organo-magnesium compounds according to claim 1, wherein the reaction is performed batchwise or continuously .

7. The organo-magnesium compounds according to claim 1, wherein the molar ratio between compounds of formula (I) and compounds of formula (II) is from 1.0 to 200.0 .

8. The organo-magnesium compounds according to claim 1, comprising at least a structural unit of formula (III) or formula (IV) ##STR00010## ##STR00011## wherein R.sup.1 and R.sup.2 have the meaning as set forth in the preceding claims, the arrows denote coordinative bonds from magnesium to nitrogen or the amidinate group the other solid, bold or dashed bonds denote covalent bonds or, where magnesium and alkyl residues R.sup.1 are involved a three center two electron bond and wherein at least one of the solid bonds for each magnesium showing no bound element or group is linking to a residue R.sup.1 or both solid bonds are linking to a further chain element MgR.sup.1.sub.2.

9. Solutions of organo-magnesium compounds according to claim 1 in non-coordinating solvents.

10. The solutions according to claim 9, wherein the concentration of the organo-magnesium compounds in the non-coordinating solvents is from 5 to 60 wt.% .

11. A process for the preparation of organo-magnesium compounds or their solutions according as defined in claim 1 by reacting compounds of formula (I) with compounds of formula (II) ##STR00012## ##STR00013## in a non-coordinating solvent and optionally removal of such non-coordinating solvent.

12. A process for the preparation of magnesium alcoholates of formulae (III) and (IV) ##STR00014## ##STR00015## wherein R.sup.4 each independently of the other residue R.sup.4 present in the compounds of formulae (III) and (IV) denotes alkyl which is either not or once substituted by phenyl the process comprising at least the step of a) reacting the organo-magnesium compounds or their solutions according to claim 1 with an alcohol, an alcohol of formula (V) ##STR00016## wherein R.sup.4 has the same meaning as defined for formulae (III) and (IV) above.

13. A process for the preparation of magnesium chloride comprising the steps of a) reacting the organo-magnesium compounds or their solutions according to claim 1 with an alcohol, an alcohol of formula (V) to obtain the respective magnesium alcoholates, those of formulae (III) or (IV) and b) reacting the magnesium alcoholates obtained according to step a) with a chloride source to magnesium dichloride, or alternatively the step of A) reacting the organo-magnesium compounds or their solutions according to claim 1 with a chloride source to magnesium dichloride.

14. Use of compounds of formula (II) according to claim 1 as viscosity modifier of compounds of formula (I) according to claim 1 or magnesium alcoholates, those of formulae (III) and (IV) as defined in claim 12, each of the aforementioned in non-coordinating solvents.

15. Use of organo-magnesium compounds or their solutions according to claim 1 for the preparation of magnesium alcoholates, those of formulae (III) and (IV) or magnesium dichloride.

Description

EXPERIMENTAL

General

[0058] All syntheses were performed under argon or nitrogen and water exclusion. The chemicals used were: dicyclohexylcarbodiimide, (≥ 99 %, Sigma-Aldrich); ethylaluminiumdichloride (EADC, 25.3 wt-% in heptane, LANXESS Organometallics GmbH); butyl-octylmagnesium (BOMAG, 20 wt-% in heptanes, LANXESS Organometallics GmbH), 2- ethylhexanol (≥ 99 %, Merck); n-Heptane (≥ 99 %, Roth); Mol sieve (3 Å, type 562 C, Roth); titanium(IV)chloride (1 mol 1.sup.-1 in toluene; Acros Organics); hydrochloric acid (36 wt-%, Analpure), nitric acid (≥ 69.0%; Honeywell) and hydrofluoric acid (48 wt-%, Analpure).

Viscosity Measurement

[0059] The viscosity measurement according to DIN 53019 was slightly adapted to be applicable to pyrophoric compounds.

[0060] A LVDV2T* EXTRA Viscosimeter from Brookfield AMATEK including the SSA-K Small Sample Adapter (EZ), the SC4-13T sample chamber , the SX-V80 spindle extension and SC4-18 spindle were used for measuring the viscosity.

[0061] Spindle, probe chamber, spindle extension and the Small Sample Adapter were dried and completely free of moisture. The spindle, probe chamber and adapter were placed in the viscosimeter and tempered to 20° C. The probe chamber was removed and completely covered and cleaned with argon for min. 2 minutes. Under argon 7.3 mL of the sample liquid were filled into the probe chamber and the probe chamber with sample placed in the Small Sample adapter. The spindle was completely covered with sample. The probe chamber was closed and constantly covered with a blanket of argon. The measurement was started with app. 10 rpm and the desired measurement range adjusted. The viscosity data was collected after 60 s of constant measurement.

General Experimental Procedure

[0062] A magnesium-dialkyl compound solution was distilled or diluted to the desired concentration and a carbodiimide added. Subsequent stirring at the indicated temperature completed the reaction.

EXAMPLES

Example 1

1A) BOMAG-DCC 20

[0063] To 105.5 g of a 20 wt.-% solution of n-butyl-n-octyl magnesium (BOMAG) in heptanes ( Mg-content = 2.97 wt.-%, Al content = 780 ppm) 0.67 g dicyclohexylcarbodiimide (2.5 mol %) were added at room temperature. An increase of 3° C. was observed and the mixture heated to 50° C. and stirred for 1 hour at this temperature.

1B) BOMAG-DCC 25

[0064] To 98.18 g of a 25 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg content 3.64 wt.-%, Al content 1017 ppm) 0.78 g dicyclohexylcarbodiimide were added (2.5 mol %) at room temperature. An increase of 3° C. was observed. The reaction was stirred at 50° C. for 1 hour.

1C) BOMAG-DCC 30

[0065] 1278.6 g of a 30 wt.-% solution of n-butyl-n-octyl magnesium in heptanes ( Mg-content 2.97 wt.-%,) were concentrated by distillation of heptanes to 842.4 g to yield a 30.19 % solution of n-butyl-n-octyl magnesium in heptanes. To this solution a solution of 8.06 g dicyclohexylcarbodiimide in 9.0 g heptanes was added and the reaction mixture stirred for 60 minutes at room temperature. The solution remains clear and colorless.

1D) BOMAG-DCC 35

[0066] To 84.97 g of a 35 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg content 5.25 wt.-%, Al content 1374 ppm) 0.95 g dicyclohexylcarbodiimide were added (2.5 mol %) at room temperature. An increase of 3° C. was observed. The reaction was stirred at 50° C. for 1 hour.

[0067] The viscosities were measured according to the method indicated above and the results are given in table 1.

TABLE-US-00001 Viscosities of BOMAG-DCC-solutions Example Mg-content [m/m] BOMAG content* [m/m] Viscosity at 20° C. [mPa*s] 1a) 3.02 20.7 12.6 1b) 3.62 24.8 21.5 1c) 4.37 29.9 48.9 1d) 5.22 35.8 95.3 *BOMAG content is calculated from measured Mg-content.** DCC was used 2.5 mol% calculated on measured Mg-content

Example 2

2A) BEM-DCC 20

[0068] To 105.9 g of a 20 wt.-% solution of n-butyl-ethyl-magnesium (BEM) in heptanes (Mg-content = 4.48 wt.-%, Al content = 956 ppm) 1.01 g dicyclohexylcarbodiimide (2.5 mol %) were added at room temperature. An increase of 3° C. was observed and the mixture heated to 50° C. and stirred for 1 hour at this temperature.

2B) BEM-DCC 30

[0069] To 793.4 g of an 32 wt.-% solution of n-butyl-ethyl-magnesium in heptanes (Mg content 6.99 wt.-%) 14.12 g dicyclohexylcarbodiimide (3 mol %) dissolved in 27.5 g heptanes were added at room temperature and stirred for 60 minutes.

2C) BEM-DCC 30

[0070] To 1207.5 g of a 20 wt.-% solution of n-butyl-ethyl-magnesium in heptanes (Mg content 4.48) a solution of 11.48 g dicyclohexylcarbodiimide (2.5 mol %) dissolved in 7.0 g heptanes were added at room temperature. The temperature increased by 6° C. and the reaction mixture was concentrated to 30 wt.-% by distillation in vacuum.

[0071] The viscosities were measured according to the method indicated above and the results are given in table 2.

TABLE-US-00002 Viscosities of BEM-DCC-solutions Example Mg-content [m/m] BEM content* [m/m] Viscosity [mPa*s] 2a) 4.48 20.4 26.9 2b) 6.62 30.1 66.9 2c) 6.67 30.3 109.0 *BEM content is calculated from measured Mg-content.** DCC was used 2.5 or 3 mol% calculated on measured Mg-content

Example 3

3A) BOMAG-DCC Stock Solution (1:1)

[0072] To 43.3 g of a 32 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg content 4.66 wt.-%, 0.083 mol) 17.12 g dicyclohexylcarbodiimide ( 0.083 mol) in 1 g heptanes were added and stirred at 50° C. for 60 minutes. The solution was clear and yellowish. 1.63 g of this solution and 1 g heptanes was added to 46.0 g of an 32 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg content 4.66 wt.-%, 0.088 mol) and stirred at 50° C. for 60 minutes.

3B) BOMAG-DCC Stock Solution (2:1)

[0073] To 45.4 g of a 32 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg content 4.66 wt.-%, 0.087 mol) 8.97 g dicyclohexylcarbodiimide ( 0.043 mol) in 1 g heptanes were added and stirred at 50° C. for 60 minutes. The solution was clear and yellowish. 3.62 g of this solution was added to 59.4 g of a 32 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg content 4.66 wt.-%, 0.1138 mol) and stirred at 50° C. for 60 minutes.

[0074] The viscosities were measured according to the method indicated above and the results are given in table 3.

TABLE-US-00003 Viscosities of stock solutions of BOMAG-DCC Example Mg-content [m/m] BOMAG content* [m/m] Viscosity [mPa*s] 3a) 5.02 34.4 60.0 3b) 4.96 34.0 62.7 *BOMAG content is calculated from Mg-content.

Comparative Examples 4a) to 4f)

[0075] Standard solutions of n-butyl-n-octyl magnesium in heptanes were prepared as comparison by dilution of a 20 wt.-% solution of n-butyl-n-octyl magnesium with heptanes or removal of heptane by distillation.

[0076] The viscosities were measured according to the method indicated above and the results are given in table 4.

TABLE-US-00004 Viscosities of BOMAG-solutions Example Mg-content [m/m] BOMAG content* [m/m] Viscosity [mPa*s] 4a) 5.25 36.1 305.3 4b) 4.32 29.7 142.6 4c) 3.64 25.0 72.4 4d) 2.97 20.4 40.2 4e) 2.22 15.3 17.1 4f) 1.50 10.3 8.3 *BOMAG content is calculated from Mg-content.

[0077] It is apparent that the examples according to the invention exhibit a far lower viscosity at the same concentration of diorganomagnesium compound compared to the standard material or a much higher concentration at the same viscosity level even though only a small amount of carbodiimide was added.

Examples 5a) and 5b): Synthesis of Magnesiumdichloride - MgCl.SUB.2

[0078] The a solution of BOMAG-DCC 20 according to example 1a) (example 5a) or BOMAG (example 5b) in an amount that it comprised 8.55 mmol of BOMAG or the modified organomagnesium compounds BOMAG-DCC were introduced into a 25 ml two neck round bottom flask and 2-ethylhexanol (17.2 mmol) was added dropwise within 30 min with stirring in the glovebox. Due to the exothermic nature of the reaction, the mixture was cooled and kept at a temperature of about 10° C. During reaction the viscosity decreased and after approx. 75 % of conversion the viscosity of the mixture started to increase again. After full addition, the reaction mixture was stirred for 40 min at room temperature.

[0079] To convert the resulting alcoholate into the desired magnesium chloride EADC (8.55 mmol) was heated to 60° C. The addition of the alcoholate solution to EADC was done dropwise within 30 minutes and a white precipitate was formed. After 1 h stabilization time the MgCl.sub.2 was separated by centrifugation (Thermo Megafuge 1.0R, 1500 rpm, 5 min). The carrier was washed twice with 3 ml n-heptane at room temperature and diluted at the end with 5 ml n-heptane to form a suspension of Magnesium chloride.

[0080] The magnesium chlorides obtained according to examples 5a) and 5b) were employed as carrier materials for Ziegler-Natta-catalysts which themselves were used as catalyst in ethylene polymerization. Both magnesium chlorides showed similar results proving that the carbodiimide addition has no negative effect on magnesium chloride quality and applicability.

Example 6

6A) BOMAG-BTMSCD 20

[0081] To 20.32 g of a 20.4 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg-content = 2.97 wt.-%, Al-content = 780 ppm) 0.066 g bis(trimethylsilyl)-carbodiimide (1.4 mol %) were added at room temperature and the mixture heated to 50° C. and stirred for 0.5 hours at this temperature.

6B) BOMAG-BTMSCD 20

[0082] To 28.01 g of a 20 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg-content = 2.97 wt.-%, Al-content = 780 ppm) 0.139 g bis(trimethylsilyl)-carbodiimide (2.1 mol %) were added at room temperature. An increase of 1° C. was observed, the mixture heated to 50° C. and stirred for 0.5 hour at this temperature.

6C) BOMAG-BTMSCD 20

[0083] To 26.4 g of a 20 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg-content = 2.97 wt.-%, Al-content = 780 ppm) 0.155 g bis(trimethylsilyl)-carbodiimide (2.5 mol %) were added at room temperature. An increase of 1° C. was observed, the mixture heated to 50° C. and stirred for 0.5 hour at this temperature.

6D) BOMAG-BTMSCD 20

[0084] To 19.4 g of a 20 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg-content = 2.97 wt.-%, Al-content = 780 ppm) 0.147 g bis(trimethylsilyl)-carbodiimide (3.3 mol %) were added at room temperature. An increase of 1° C. was observed, the mixture heated to 50° C. and stirred for 0.5 hour at this temperature.

6E) BOMAG-BTMSCD 35

[0085] To 19.1 g of a 35 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg-content = 5.13 wt.-%, Al-content = 1300 ppm) 0.184 g bis(trimethylsilyl)-carbodiimide (2.4 mol %) were added at room temperature. An increase of 1° C. was observed, the mixture heated to 50° C. and stirred for 0.5 hour at this temperature.

6F) BOMAG-BTMSCD 35

[0086] To 19.03 g of a 35 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg-content = 5.13 wt.-%, Al-content = 1300 ppm) 0.093 g bis(trimethylsilyl)-carbodiimide (1.2 mol %) were added at room temperature. An increase of 1° C. was observed and the mixture heated to 50° C. and stirred for 0.5 hour at this temperature.

[0087] For comparison, the viscosities of the 20 and 35 wt.-% solution of n-butyl-n-octyl magnesium in heptanes employed for examples 6a) to 6f were measured as well (see entries for examples 6g and 6h).

[0088] The viscosities were measured according to the method indicated above and the results are given in table 5.

TABLE-US-00005 Viscosities of BOMAG-BTMSCD-solutions Example Mg-content [m/m] BOMAG content* [m/m] Viscosity at 20° C. [mPa*s] 6a) 2.97 20.4 14.0 6b) 2.97 20.4 16.2 6c) 2.97 20.4 7.6 6d) 2.97 20.4 5.9 6e) 5.13 35.1 48.0 6f) 5.13 35.1 100.4 6g)** 5.13 35.1 326 6h)** 2.97 20.4 40.2 *BOMAG content is calculated from Mg-content. ** for comparison

Example 7

7A) BEM-BTMSCD 30

[0089] To 20.13 g of a 33.2 wt.-% solution of n-butyl-ethyl magnesium in heptanes ( Mg-content = 7.3 wt.-%, Al content = 700 ppm) 0.29 g bis(trimethylsilyl)-carbodiimide 2.5 mol %) were added at room temperature, the mixture heated to 50° C. and stirred for 0.5 hour at this temperature. For comparison, the viscosity of the 33.2 wt.-% solution of n-butyl-ethyl magnesium in heptanes employed for example 7a) was measured as well (see entry for example 7b).

[0090] The viscosities was measured according to the method indicated above and the results are given in table 6.

TABLE-US-00006 Viscosity of BEM-BTMSCD-solution Example Mg-content [m/m] BEM content* [m/m] Viscosity at 20° C. [mPa*s] 7a) 7.3 20.4 47.1 7b)** 7.3 20.4 509.0 *BEM content is calculated from Mg-content. ** for comparison

Example 8

BOMAG-DCC Solution (1.4 Mol-%)

[0091] To 21.11 g of a 35.1 wt.-% solution of n-butyl-n-octyl magnesium in heptanes (Mg content 5.13 wt.-%, 44.6 mmol) 0.129 g dicyclohexylcarbodiimide ( 0.625 mmol) were added and stirred at room temperature for 60 minutes. The solution thus contained 1.4 mol-% calculated on Magnesium.

Example 9

[0092] To 5.706 g (12.04 mmol) of the BOMAG-DCC Solution (1.4 mol-%) prepared according to example 8 in a 50 ml Schlenk-flask, 2.937 g 2-ethylhexanol (22.55 mmol) were added dropwise at 0° C. and thereafter stirred at room temperature for 60 minutes. Thereafter, further 0.0335 g (0.162 mmol) of dicyclohexylcarbodiimide (DCC) were added to increase the total amount of DCC added to 2.74 mol-% calculated on magnesium. The viscosity was measured as indicated above and found to be 61.5 mPa*s at 20° C.

Example 10

[0093] To 5.445 g (11.49 mmol) of the BOMAG-DCC Solution (1.4 mol-%) prepared according to example 8 in a 50 ml Schlenk-flask, 2.878 g 2-ethylhexanol (22.10 mmol) were added dropwise at 0° C. and thereafter stirred at room temperature for 60 minutes. Thereafter, further 0.0234 g (0.113 mmol) of dicyclohexylcarbodiimide (DCC) were added to increase the total amount of DCC added to 2.39 mol-% calculated on magnesium. The viscosity was measured as indicated above and found to be 340.2 mPa*s at 20° C.

Example 11

[0094] To 5.451 g (11.51 mmol) of the (unmodified) BOMAG solution employed to prepare the solution according to example 8 in a 50 ml Schlenk-flask, 2.880 g 2-ethylhexanol (22.12 mmol) were added dropwise at 0° C. and thereafter stirred at room temperature for 60 minutes. Thereafter, 0.0238 g (0.115 mmol) of dicyclohexylcarbodiimide (DCC) or 0.99 mol-% calculated on magnesium were added. The viscosity was measured as indicated above and found to be 504.0 mPa*s at 20° C.

[0095] From examples 9 to 11 it is apparent that the addition of compounds of formula (II) are suitable to significantly decrease not only the viscosity of diorganomagnesium compounds but also those of magnesium alcoholates in non-coordinating solvents.