JPH0745546B2 - Olefin Polymerization Method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for polymerizing olefins. Specifically, it relates to a method for polymerizing olefins using a catalyst having a magnesium halide obtained by a specific method as a carrier.

[Conventional technology]

For the polymerization of olefins, it is recommended to use a catalyst composed of a transition metal catalyst component in which a titanium halide is supported on a carrier such as magnesium halide and an organometallic compound.
Since its disclosure in No. -12105, various improved methods have been proposed, and fairly excellent performances have been obtained.

[Problems to be solved by the invention]

The above improving method is mainly to add a crusher to obtain a carrier and grind it, or to dissolve a magnesium halide used as a carrier in a solvent and then precipitate it, thereby carrying a transition metal and a catalyst for olefin polymerization. At this time, the carrier is treated so that the diffraction line measured by X-ray diffraction does not have a clear peak and is observed as a halo so that the carrier has excellent performance. In particular, the method of dissolving and then depositing is excellent,
Highly active catalysts can be produced (see, for example, JP
56-11908). However, this method has a problem that a large amount of a precipitant is required and that a product having good activity cannot be obtained unless it is repeatedly treated with titanium halide.
Further, it is difficult to provide a catalyst with excellent reproducibility and excellent performance by the method of adding additives and pulverizing.

[Means for solving problems]

The present inventors diligently studied a method for solving the above problems, found that magnesium halide which can be produced by a specific method is suitable as a carrier, and completed the present invention.

That is, the present invention has the general formula R ¹ MgX ¹ _L X ² _1-L (wherein R ¹ is a hydrocarbon residue, X ¹ is bromine or iodine, X ² is chlorine, L
Is 0 <L ≦ 1. ) Is treated with a chlorinating agent selected from chlorinated hydrocarbons, metal chlorides, thionyl chloride, and phosphorus chloride to obtain MgX ¹ _L X ² _2-L (where X ¹ is Bromine or iodine, X ² is chlorine, L is 0
<L ≦ 1. After treating the carrier represented by) with water,
A method for polymerizing an olefin, which comprises using a catalyst comprising a transition metal catalyst component obtained by supporting titanium chloride and an organometallic compound of Groups 1 to 3 of the periodic table.

In the present invention, MgX ¹ _L X ² _2-L as a carrier (wherein X ¹ is bromine or iodine, X ² is chlorine, and L is 0 <L ≦ 1).
Is characterized in that the carrier is treated with water prior to supporting titanium chloride, and there is no particular limitation on the method of supporting titanium chloride on the carrier treated with water,
Various methods can be adopted. For example, a method of contact-treating a carrier with an oxygen-containing organic compound such as a carboxylic acid ester, an ether, an orthoester, an alkoxy silicon, a phosphoric acid ester, and a ketone before treating the carrier with titanium chloride, and then contact-treating with titanium chloride, or Examples include a mixture of an oxygen-containing compound and titanium chloride, or a method of further diluting titanium chloride with an inert solvent and subjecting it to contact treatment. The temperature at the time of the contact treatment is not particularly limited and may be carried out under optimum conditions depending on the combination, but usually from room temperature to
The temperature is about 200 ° C., and the time is generally several minutes to several hours.

Liquid titanium chloride is preferable as titanium chloride, and specific examples thereof include titanium tetrachloride and titanium trichloride complexed with an electron-donating compound and solubilized in a hydrocarbon compound.

R ¹ MgX ¹ _L X used in producing magnesium halide represented by MgX ¹ _L X ² _2-L which is important in the present invention
^The Grignard reagent represented by 21 _-L (wherein R ¹ is a hydrocarbon residue, X ¹ is bromine or iodine, X ² is chlorine, and L is 0 <L ≦ 1) is known. The halogenated hydrocarbon generally represented by R ¹ X ¹ and metallic magnesium are first reacted with a halogenated hydrocarbon in an amount of 1 mol or less with respect to metallic magnesium, and then metallic magnesium is produced. The sum of halogenated hydrocarbons for
R ¹ X ² (in the formula; R ¹ is a hydrocarbon residue which may be the same as or different from R ¹ above, X ² is chlorine) is reacted in a molar manner,
It is fully aged and synthesized. In the synthesis, ether is usually used as a solvent. The hydrocarbon residue may be any of aliphatic, alicyclic, aromatic hydrocarbon residues and the like, and is not particularly limited, but those having 1 to 20 carbon atoms are generally used. Is.

In the present invention, the Grignard reagent obtained by the above method is treated with a chlorinating agent to form MgX ¹ _L X ² _2-L (wherein, X ¹ is bromine or iodine, X ² is chlorine, L is 0 <L ≦ 1
Is. ) Is a carrier represented by. As the chlorinating agent used here, chlorinated hydrocarbons, chlorides of metals such as aluminum chloride, silicon chloride, tin chloride and boron chloride, or chlorides such as thionyl chloride and phosphorus chloride can be used.
As these compounds, those which are usually used on an industrial level can be used as they are.

The MgX ¹ _L X ² _2-L thus obtained (wherein X ¹ is bromine or iodine, X ² is chlorine, and L is 0 <L ≦ 1).
The carrier represented by is then contact-treated with water. The contact treatment is preferably carried out in a solvent inert to a carrier such as a hydrocarbon compound in a state where water is dissolved in the solvent, in which water is 0.3 mol or less per 1 mol of the carrier, Preferably about 0.2 to 0.01 mol is used.

Here, the solvent used for the contact treatment is, for example, a hydrocarbon compound such as pentane, hexane, heptane, nonane, decane, benzene, toluene, xylene, ethylbenzene, cumene, or a mixture thereof, or hydrogen of the above-mentioned hydrocarbon compound is a halogen. The halogenated hydrocarbon substituted with is exemplified.

Examples of the organic metal compound of the metals of Groups 1 to 3 of the periodic table used in the present invention include organic lithium, organic sodium, organic magnesium, organic beryllium, organic aluminum and the like, among which organic aluminum is preferably used.

Examples of the olefin used in the present invention include ethylene, propylene, butene-1, pentene-1, hexene-1, octene-1, styrene and vinylnaphthalene, and their homopolymerization or mutual copolymerization and further with diene. It is used for copolymerization.

In the present invention, conventional olefin polymerization methods can be applied to the polymerization of olefins other than using the magnesium halide carrier produced by the above-mentioned method, such as solution polymerization using a solvent, bulk polymerization using the olefin itself as a medium, or substantial solvent polymerization. Vapor-phase polymerization or the like, which does not contain a specific amount, can be performed.

〔Example〕

 Hereinafter, the present invention will be described with reference to examples.

Example 1 13.1 g of magnesium and 240 ml of diethyl ether were placed in a 500 ml round bottom flask, and methyl bromide was introduced under reflux of ether until the magnesium disappeared. 40 ml of the homogeneous solution thus obtained and 80 ml of di-n-butyl ether were prepared separately.
Put in a 500 ml round bottom flask, then 5 ml of carbon tetrachloride was added dropwise to precipitate MgBrCl, then the solid content was separated from this slurry, the solid content was toluene containing 0.03 ml of water.
It was dispersed in 100 ml and stirred for 30 minutes. When a part of this solid content was taken out and analyzed, it was found that the ratio of Br and Cl was almost 1: 1 and that the content of water was 0.8 wt%.

The solid content obtained by the above operation was filtered and dried, and then 5 g was added to 200 ml.
Into a round bottom flask was added 10 ml of toluene, 0.8 ml of diisobutyl phthalate and 70 ml of titanium tetrachloride, and the mixture was stirred at 120 ° C for 1 hour. Then, the mixture was left standing to remove the supernatant, 80 ml of titanium tetrachloride was further added, and the mixture was stirred at 130 ° C. for 2 hours. Similarly, the mixture was allowed to stand still to remove the supernatant, and then the solid content was washed with n-heptane until titanium was not detected in the washing liquid to obtain a transition metal catalyst component. Analysis revealed that titanium was 2.3 wt% and Br: Cl was abbreviated.
It was 1: 1.

Ethylene was polymerized using the transition metal catalyst component obtained by the above operation. N-heptane 1 in autoclave with internal volume 2
Placed, the transition metal catalyst component 20 mg, triethylaluminum 0.5ml added Hydrogenation until 2Kg / cm ² gauge, the temperature was further raised to ethylene 75 ° C. After the addition is-out 6 Kg / cm ² gauge, 10 Kg / cm ² Polymerization was carried out at 75 ° C. for 2 hours while adding ethylene so as to make a gauge. After cooling, the unreacted ethylene was purged and then filtered to obtain polyethylene powder. The dry weight was 340 g. This powder had an intrinsic viscosity of 2.42 (measured with a tetralin solution at 135 ° C.) and a bulk specific gravity of 0.40. The yield per transition metal catalyst component was 17,000 g / g-cat.

Example 2 The polymerization reaction was carried out by using 20 mg of a transition metal catalyst component, 0.2 ml of triethylaluminum and 0.05 ml of diphenyldimethoxysilane in an autoclave having an internal volume of 5 l, and using 1.5 kg of propylene,
1.4Nl of hydrogen was introduced and the reaction was carried out at 75 ° C for 3 hours. Then, unreacted propylene was purged, polypropylene was taken out and dried and analyzed to obtain 720 g of polypropylene. The intrinsic viscosity was 1.72, the boiling n-heptane extraction residual ratio (using a Soxhlet extractor for 6 hours in boiling n-heptane). Extraction, below
(Abbreviated as II) was 98.1% and the bulk specific gravity was 0.43.

Example 3 The same procedure as in Example 1 was carried out except that methyl iodide was used instead of methyl bromide. As a result, the polymer obtained was 291 g, and the physical properties of the powder were an intrinsic viscosity of 2.41 and a bulk specific gravity of 0.40.

Example 4 The same as Example 2 except that the amount of water used was 0.1. The polymer obtained was 620 g, and the physical properties of the powder were an intrinsic viscosity of 1.
49, boiling n-heptane extraction residual rate (abbreviated as II below) 98.3
%, And the bulk specific gravity was 0.42.

Example 5 A polymer was obtained in the same manner as in Example 2 except that 1000 l of n-heptane containing 50 ppm of water was used for treatment, and the polymer obtained was 595 g. The physical properties of the powder were an intrinsic viscosity number of 1.56 and boiling n. -Heptane extraction residual rate (abbreviated as II below) was 98.5%, and the bulk specific gravity was 0.42.

Example 6 Magnesium halide having a Br: Cl ratio of about 3: 7 in the same manner as in Example 1 except that a mixture of methylmagnesium bromide and butylmagnecyclolide in a 1: 1 molar ratio was used instead of methylmagnesium bromide. Which was used to obtain a transition metal catalyst component. The polymer obtained by polymerizing propylene in the same manner as in Example 2 except that this catalyst component was used was 485 g, the physical properties of the powder were an intrinsic viscosity of 1.69, and the boiling n-heptane extraction residual rate (abbreviated as II below) was 97.8%. The bulk specific gravity was 0.41.

〔The invention's effect〕

By carrying out the method of the present invention, it is possible to produce a polyolefin with high yield, which is industrially valuable.

[Brief description of drawings]

 FIG. 1 is a flow chart for helping understanding of the present invention.

Claims (1)

[Claims] 1. A general formula R ¹ MgX ¹ _L X ² _1-L (wherein R ¹ is a hydrocarbon residue, X ¹ is bromine or iodine, X ² is chlorine, and L is 0 <L. MgX ¹ _L X ² _2-L (formula ≦ 1) obtained by treating a Grignard reagent represented by (1) with a chlorinating agent selected from chlorinated hydrocarbons, metal chlorides, thionyl chloride and phosphorus chloride. Wherein X ¹ is bromine or iodine, X ² is chlorine, and L is 0.
<L ≦ 1. After treating the carrier represented by) with water,
A method for polymerizing olefins, which comprises using a catalyst comprising a transition metal catalyst component obtained by supporting titanium chloride and an organometallic compound of Groups 1 to 3 of the periodic table.