JPS5953279B2 - Production method of organomagnesium complex - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing organomagnesium complexes.

An organic magnesium compound obtained by reacting an organic halide and metallic magnesium in the presence of an ether is known as a so-called Grignard reagent, and is widely used as a raw material for organic synthesis or as a raw material for a catalyst.

This compound can also be synthesized by reacting in a hydrocarbon medium in the absence of ether, and further modified compounds can be synthesized depending on the purpose of use. For example, British Patent No. 1003551 discloses a complex of organomagnesium with a metal derivative of an organic compound having a hydroxyl group or an enolizable keto group, and states that it can be used in place of an organolithium catalyst. There is. As a result of research into organomagnesium compounds useful as catalyst raw materials for producing polyolefins using the Ziegler method, the present inventors discovered a novel method for producing organomagnesium complexes and led to the present invention. That is, the present invention provides general formula RゝM
g
General formula Al(0R2)Br2 or Ai(0R2)I,
(in the formula, R2 represents a hydrocarbon group having 2 to 20 carbon atoms) is reacted with an aluminum compound B of the general formula MgaAIlβRb(0R2)q (in the formula, R1
, R2 have the above meanings, α, β, p, q are numbers larger than o, Vβ=0.5 to 2.0, 2α+3β=p+
This is a method for producing an organomagnesium complex soluble in an inert hydrocarbon-based medium, which has the relational expression q.

The complex represented by the above general formula will be explained in detail below.

In the formula, the hydrocarbon groups represented by R1 and R2 can be aliphatic, aromatic, or alicyclic hydrocarbon groups. These are, for example, the methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, hexadecyl, benzyl, phenyl, cyclohexyl group. α/β is important for obtaining a soluble complex, and a range of 0.5 to 20 is preferable for obtaining a stable complex.

This complex is obtained in the form of a hydrocarbon solution, and is presumed to be a single complex or a mixture of multiple types of complexes.

The composition of the complex can be determined by analyzing the solution, and the average composition can be determined by measuring the molecular weight. The complexes of the present invention are characterized firstly by being easy to handle since they are dissolved in an inert hydrocarbon medium and obtained in the form of a solution, making them extremely suitable for use on an industrial scale.

Furthermore, since it contains an alkoxy group that is stable in water, oxygen, etc., it is safer to handle than those that do not contain this group. Furthermore, this complex is extremely useful as a catalyst for olefin polymerization, and has various Wl properties such as high activity and easy control of reefs by changing the content of alkoxy groups. I have Prayer I. MgX, ? to the general formula R used in the above reaction? Compound a is synthesized from a halogenated hydrocarbon and metallic magnesium according to the known Grignard reagent synthesis method.

As the synthesis solvent, either ether or an inert hydrocarbon can be used, but ether lowers the yield of the desired organomagnesium complex and is not a preferred component when this complex is used as a catalyst component. Therefore, when it is synthesized in a ether, it is desirable to deetherify it. If it's a hitomimono again (B>Fl)
The general formula Al(0R2)Br or At[0R! ) The aluminum compound represented by I can be synthesized by various known methods, for example, by reacting an alkyl aluminum bromide or an alkyl aluminum iodide with an alcohol. Alternatively, it is synthesized by reacting trialkoxyaluminum and aluminum trihalide. Aluminum Ibi? Examples include Al(0C,H5)Br,
,Al(0C,H,)Br,,Al(0C4H,)Br
,,Al(0C,H,,)Bt,,Aj(0C.H1,
)Br,,Al(0C,H1,)Br,,Al(0C8
H,,)Br2,Al(0C,H,1riBr2,Al(
0C10H21)Br2,A2(0C,1H,,)Br
,,Ae(0C12H2,)Br2,A2(0C1,H
,7) Br2,Al(0C2H5)12,A1(0C,
H7)12,,”・Al(0′C4H,)12,Ae(
0c,H,,)12,A1(0c6H,3)12,A1
(0C,H,7)12 etc. are mentioned. Ae (0R2)
Zn(
It is possible to make complexes of this type using 0R)Br, Be(0R)Br, B(0R)Br, or Zn(0R)I, Be(0R)I, B(0R)12. The starting material has the general formula RhMgX2-. The organomagnesium compound represented by is insoluble or sparingly soluble in an inert hydrocarbon medium, but due to the above reaction, the organomagnesium component forms a complex with the aluminum compound component and becomes soluble in the solvent. There is a partitioning of alkoxy groups between the organomagnesium component and the aluminum compound, which is observed from the nuclear magnetic resonance spectrum. (4) and (3)
The reaction is carried out at 20-200°C, particularly preferably at 50-150°C.
C. for 0.5 to 20 hours.

When carrying out this reaction, (the reaction concentration of A component is 0.
Although the reaction can be carried out in a concentration range of 1 to 2.5 mol/2, in order to obtain a highly concentrated solution of the organomagnesium complex, it is advantageous to increase the reaction concentration of component (4) within a range that does not interfere with the reaction operation. . Component (8) can be used at a concentration of 0.005 to 5 mol/l. The inert hydrocarbon medium soluble organomagnesium complex obtained by the reaction of (4) and (8) is M
It has a composition with a g/Al molar ratio of 0.5 to 20, and this composition can be arbitrarily changed within the above range by changing the amount of evacuation added to the reaction system for component (A). . The reaction medium for carrying out the reactions (4) and (13) includes aliphatic hydrocarbons such as hexane and hebutane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Hydrocarbons can be used.

Also, as a known method, All(0R),,A2Br3
Alternatively, it is possible to obtain similar complexes using A213, but Al(0R)3, A2Br, or A21, is poorly soluble in hydrocarbon media and reduces the reaction yield of the complex.

Ae(0R)Br2,A2(0R)I? of the method of the present invention?
When used, it is particularly preferred because it easily dissolves in the hydrocarbon medium and improves the reaction yield of the complex.

In order to further clarify the effects of the present invention, a comparison with known methods is shown in Table 1. As is clear from Table 1, the yield of the method of the present invention is higher than that of the known method.

Further, when AeBr3 is used as the component (8) (Comparative Example 2), the complex does not contain an (0Bu) group and is different from the complex of the present invention. The present invention will be explained in more detail below with reference to Examples.

Example 1 Aluminum tribromide 169 (0.06 mol), tri-n-butoxyaluminum 7.49 (0.03 mol) and dry heptane 90- are introduced into a flask with a capacity of 200 ml under a nitrogen atmosphere.

The reaction was carried out at 98° C. for 5 hours, and the solid components were completely dissolved to obtain a transparent solution.

As a result of analysis, it was an Ae(0nBU)Br, 1M/e solution. , then the capacity is 50
A 0d flask under a nitrogen atmosphere was charged with 7.69g of magnesium powder (0.32 gram atom) and added with a dry hebutane solution containing 0.30 moles of n-butyl chloride.
Of the 00d, 30d was added. The flask was heated to the boiling point while stirring, and after the reaction started, the remaining n-butyl chloride was added over 30 minutes, and after the addition was complete, the mixture was heated under reflux for an additional hour. To the resulting reaction mixture, 0.0% of the n-butoxyaluminum dipromide obtained in the above reaction was added.
010 mol was added with 50T1Lt of heptane, 80
The reaction was carried out at ℃ for 3 hours.

A solution containing magnesium at a concentration of 0.35 mol/l was obtained. As a result of analysis, the composition of the obtained complex was found to be MgAeO. ，
3(NC4H,)2. ,,(0nc4H,)0.16. Comparative Example 1 The reaction was carried out in exactly the same manner as in Example 1, except that tri-n-butoxyaluminum was used instead of n-butoxyaluminum dipromide.

A solution containing magnesium at a concentration of 0.18 mol/2 was obtained. As a result of analysis, the composition of the obtained complex was found to be MgAeO. 2
, (Nc4H,), . 23 (0nc4H,). ．． It was 64. Comparative Example 2 The reaction was carried out in exactly the same manner as in Example 1, except that aluminum tribromide was used instead of n-butoxyaluminum dipromide.

A solution containing magnesium at a concentration of 0.06 mol/l was obtained. As a result of analysis, the composition of the obtained complex was found to be MgAeO. ，
6 (NC4H,). ．． It was 4S. Examples 2 to 10
Organomagnesium compound (4) synthesized from magnesium powder and alkyl halide in exactly the same manner as in Example 1
was reacted with an aluminum compound under the conditions shown in Table 2, and the results shown in the table were obtained.

Claims (1)

[Claims] 1 General formula R_a^1MgX_2_-_a (in the formula, R^
1 is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and a is a number greater than 0 and less than or equal to 2);
2) Br_2 or Al(OR^2)I_2 (in the formula, R
^2 represents a hydrocarbon group having 2 to 20 carbon atoms).
)_q (In the formula, R^1 and R^2 have the above meanings, and α
, β, p, q are numbers larger than 0, α/β = 0.5 to 2
0,2α+3β=p+q) A method for producing an organomagnesium complex soluble in an inert hydrocarbon medium.