JPS62148491A - Production of almino-oxane - Google Patents

Abstract

PURPOSE:The reaction of a specific compound containing crystal water with an organic Al compound gives the titled compound of large oligomerization degree in high yield under mild conditions and additionally makes it possible to effect practical-scale production, because the reaction temperature is readily controlled. CONSTITUTION:The reaction of (A) a compound containing crystal water selected from magnesium, nickel and lanthanide compounds containing crystal compounds, preferably magnesium chloride hexahydride or the like with (B) an organic aluminum compound, preferably trialkylaluminum is carried out, preferably at 1-3 molar ratio of component A to component B to give the objective compound. The reaction is preferably conducted in an aromatic hydrocarbon such as benzene at 40-80 deg.C for 10-200hr.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing aluminoxanes. In general, in detail, the present invention relates to a method for producing aluminoxanes with a high degree of oligomerization in a good yield through a relatively mild reaction.

[Conventional technology]

By using aluminoxanes as a catalyst for olefin polymerization in combination with transition metal compounds such as titanium compounds and zirconium compounds, it is possible to achieve highly active and unique polymerization compared to conventional Ziegler-type polymerization catalysts. Are known.

Conventionally, as a method for producing aluminoxanes, for example, a method in which a benzene solution of an organoaluminum compound is reacted with water vapor (J, Am, Chem.

Soc, 90.5173 (1968)), Method of oxidizing organoaluminum compounds with lead dioxide (J, Orgn.
omet.

Ohem, 45, 81 (1971)), a method for reacting trialkylaluminium with copper sulfate containing water of crystallization (Jqv, Akad, N1uh, 5SSR, Se
r, (!him,, 11°2547 (1975)')-
Process for reacting organoaluminum compounds with salts containing water of crystallization [Soviet Patent No. 566.844]; Process for gradually adding water to inorganic aluminum compounds [US Pat. No. 32]
No. 42099], etc. are known. In all of these methods, short-chain aluminoxanes with a low degree of oligomerization can only be obtained in low yields.

Further, JP-A-59-95292 proposes a method in which organic aluminium compound 1 is reacted with an aluminum compound containing water of crystallization. This method has the characteristic that aluminoxanes with a high degree of oligomerization can be obtained in a higher yield than the method proposed in the prior art document, but the heat of reaction is particularly large due to the large amount of heat generated at the initial stage of the reaction. There were drawbacks that needed to be overcome for implementation on an industrial scale, such as difficulty in removal and, as a result, difficulty in controlling the temperature of the reaction system. Furthermore, the degree of oligomerization of the aluminoxanes obtained by this method is much higher than that of the method proposed in the prior art document, but
When the aluminoxanes are used as cocatalyst components for olefin polymerization, aluminoxanes with a higher degree of oligomerization are desired from the viewpoint of polymerization activity and polymerization specificity.

[Problem that the invention seeks to solve]

The present inventors recognized that the conventional technology related to the production method of aluminoxane is in the above situation, and furthermore, it is easy to control the reaction temperature due to a mild exothermic reaction, and it is easy to implement on an industrial scale. Yes.

Moreover, as a result of investigating a method for producing aluminoxanes with a high degree of oligomerization in high yield, it was discovered that the above object could be achieved by reacting a specific crystal water-containing compound and an organoaluminum compound, and the present invention was realized. Reached.

[Means for Solving the Problems] and [Operation] According to the present invention, (A) a compound containing water of crystallization selected from the group consisting of a magnesium compound, a nickel compound, and a lanthanide compound containing water of crystallization, and CB. ) A method for producing aluminoxanes is provided, which comprises reacting an organoaluminum compound.

Crystal water-containing compound (A
) is a magnesium compound containing water of crystallization.

It is a crystal water-containing compound selected from the group consisting of nickel compounds and lanthanide compounds. Specifically, as a magnesium compound containing water of crystallization.

For example, magnesium chloride hexahydrate, magnesium chloride tetrahydrate, magnesium bromide hexahydrate, magnesium sulfate heptahydrate, magnesium citrate nonahydrate, magnesium acetate tetrahydrate. Specific examples of nickel compounds containing water of crystallization include nickel sulfate filtrate, nickel chloride, and nickel chloride.
Hexahydrate.

I would like to give an example of nickel acetate tetrahydrate.
Specifically, as a lanthanide compound containing water of crystallization,
For example, lanthanum chloride heptahydrate, cerous sulfate,
octahydrate, ceric chloride heptahydrate, neodymium chloride heptahydrate, samarium chloride filtrate, europium chloride hexahydrate-gatrium chloride heptahydrate, terbium chloride heptahydrate hexahydrate, dysprosium chloride hexahydrate,
Examples include holmium chloride hexahydrate, erbium chloride hexahydrate, and ytterbium chloride filtrate.

In the method of the present invention, it is preferable to use a crystalline water-containing magnesium compound as the crystalline water-containing compound (A), since aluminoxanes having a particularly high degree of oligomerization can be obtained.

Specifically, the organoaluminum compound (E) used in the method of the present invention has the general formula 8% (wherein R represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, or a halogen atom). and O< n
All elRs representing numbers of ≦6 may be the same or different. ) can be exemplified by organoaluminum compounds represented by: More specifically, examples include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-5ec-butylaluminum, tri-6rt-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum. Aluminum, trialkylaluminum such as tridecylaluminum, tricyclohexylaluminum, tricyclooctylaluminum, dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminium bromide, diisobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride chloride, alkylaluminum sesquihalides such as inbutylaluminum sesquichloride, partially halogenated alkylaluminums such as alkylaluminum cybarides such as methylaluminum dichloride, ethylaluminum dichloride, alkylaluminum hydride, diisobutylaluminum hydride, etc. Examples include hydride. Among these organoaluminum compounds, those in which R is an alkyl group and X is a chlorine atom in the general formula are preferred, and trialkylaluminum is particularly preferred.

In the method of the present invention, the ratio of the crystal water-containing compound (A) to be used is usually 0.02 molar as the number of moles of crystal water in the crystal water-containing compound (A) to 1 mole of the organoaluminum compound.
The amount ranges from 5 to 5 mol, preferably from 0.772 to 4 mol, particularly preferably from 1 to 6 mol.

In the method of the present invention, the reaction of the crystal water-containing compound (A) and the organoaluminum compound (B) is generally carried out in an organic solvent. Examples of organic solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, and decane, alicyclic hydrocarbons such as methylcyclopentane, cyclopentane, cyclooctane, cyclodecane, and cyclododecane, benzene, toluene, and xylene. , aromatic hydrocarbons such as cumene and cymene, gasoline, kerosene,
Examples include petroleum fractions such as light oil.

Among the organic solvents, organic solvents that can dissolve aluminoxane under reaction conditions are preferred.

Aromatic hydrocarbons are particularly preferred. The proportion of these organic solvents used is usually 300 to 6000 parts by weight, preferably 4 parts by weight, per 100 parts by weight of the organoaluminum compound.
00 to 3000 parts by weight. The concentration of the organoaluminum compound in the reaction system is 0.2 to 4 g atoms/l, preferably 0.4 in terms of aluminum atoms.
The concentration of water of crystallization in one reaction system is usually maintained in the range of 0.5 to 5 mol/l, preferably 0.8 to 4 mol/l.

In the method of the present invention, the method of reacting the crystal water-containing compound (A) and the organoaluminum compound (B) includes, for example, a suspension of the crystal water-containing compound in the organic solvent and the organoaluminum compound in the organic solvent. A method of bringing the two into contact with each other under heating and stirring conditions.

More specifically, a method can be exemplified in which the organic solvent suspension of the crystal water-containing compound is brought into contact with the organic solvent solution of the organoaluminum compound under heating and stirring conditions. The temperature during the reaction is usually 20 to 100°C, preferably 20 to 90°C.

The temperature is more preferably 40 to 80°C, and the time required for one reaction is usually 5 hours or more, preferably 10 to 200 hours.

In the method of the present invention, after removing unreacted crystal water-containing compounds and/or crystal water-eliminating compounds present in the reaction mixture after completion of one reaction by a conventional method such as door-to-door visits, the solvent is removed from the P solution. tilminoxanes can be separated.

〔Example〕

Next, the method of the present invention will be specifically explained using examples.

Example 1 3.0 g of magnesium chloride hexahydrate and 2 toluene were placed in a 100 m glass flask that had been sufficiently purged with nitrogen argon.
After cooling to 0° C., 5 Q mmol of trimethylaluminum diluted with 25 J of toluene was added dropwise. During the dropwise addition, the temperature inside the flask was maintained at 0°C. After finishing dropping,
The temperature was raised to 70°C, and the reaction was carried out for 4 days at that humidity. After the reaction, solid-liquid separation was performed by filtration, and toluene was further removed from the separated liquid. In this way, 1.5 g of methylaluminoxane as a white solid was obtained. The molecular weight determined by freezing point depression in benzene was 1860, and the degree of oligomerization (m) of the aluminoxane was 30. In addition,
The degree of oligomerization represents the m value of the following formula.

RQ A l + O-A i+mQ -A (? R
2hi Example 2 The same procedure as in Example 1 was repeated except that the reaction time in Example 1 was changed to 30 hours, and 1.7 g of methylaluminoxane having a total molecular weight of 1390 and an m value of 22 was obtained.

Example 3 The procedure was carried out in exactly the same manner as in Example 1, except that 5.4 units of magnesium chloride hexahydrate and 100 mmol of trimethylaluminum were used in Example 1, and the molecular weight was 1450. 2.5 g of methylaluminoxane having an m value of 23 was obtained.

Example 4 The procedure was carried out in exactly the same manner as in Example 1 except that 50 mmol of diethylaluminum chloride was used instead of trimethylaluminum in Example 1, and the reaction temperature was 40°C for 24 hours. 1
2.1 g of chloroaluminoxane of 0.0 was obtained.

Example 5 Example 1 except that 5.9 ct of nickel sulfate hexahydrate was used instead of magnesium chloride hexahydrate in Example 1, and the reaction temperature and reaction time were 40°C and 24 hours.
In the same manner as above, 1.4 g of methylaluminoxane having a molecular weight of 870 and an m value of 16 was obtained.

Example 6 Example 1 except that 5.2 g of ceric chloride heptahydrate was used instead of magnesium chloride hexahydrate, 55 mmol of alimethylaluminum was used, and the reaction temperature and time were 40° C. and 24 hours, respectively. was carried out in the same manner as in Example 1, and the molecular weight was 1040. 1.6 g of methylaminooxane with an rn value of 16 was obtained.

Claims (1)

[Claims] (1) Aluminoxanes characterized by reacting (A) a crystal water-containing compound selected from the group consisting of crystal water-containing magnesium compounds, nickel compounds, and lanthanide compounds, and (B) an organoaluminum compound. manufacturing method.