JP2537221B2 - Method for producing catalyst component for olefin polymerization - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a catalyst component for olefin polymerization. More specifically, it relates to a method for producing a catalyst component for olefin polymerization using a magnesium halide obtained by a specific method as a carrier.

[Conventional technology]

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 for the polymerization of olefins
Since its disclosure in 39-12105, various improved methods have been proposed, and fairly excellent performances have been obtained.

[Problems to be solved by the invention]

The above improvement method is carried out mainly by adding additives to obtain a carrier and crushing, or by dissolving magnesium halide used as a carrier in a solvent and then precipitating it, thereby carrying a transition metal and carrying a catalyst component for olefin polymerization. In order to obtain excellent performance, the carrier is treated so that the diffraction line measured by X-ray diffraction has no clear peak and is observed as a halo. . In particular, the method of dissolving and then precipitating is excellent, and a highly active catalyst can be produced (for example, JP-A-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 a number that is not 0 and is 1 or less. ) And a general formula R ² _n SiX ² _4-n (wherein R ² is a hydrocarbon residue, X ² is a chlorine atom, and n is an integer of 0 to 3). Mg X ¹ _L X ² _2-L (wherein X ¹ is bromine or iodine, X ² is chlorine and L is 0)
Not a number less than or equal to 1. The method for producing a catalyst component for olefin polymerization is characterized in that a titanium halide is supported on (1).

The present invention is characterized by a method for producing MgX ¹ _L X ² _2-L (wherein X ¹ is bromine or iodine, X ² is chlorine, and L is a number not greater than 1 and not greater than ¹⁾ used as a carrier. There is no particular limitation on the method of supporting titanium halide on the obtained carrier, and various methods can be adopted. For example, the carrier may be a carboxylic acid ester, an ether, an orthoester, an alkoxy silicon, a phosphoric acid ester, an alcohol,
Contact or co-pulverize with oxygen-containing organic compounds such as ketones,
Then, a method of contact treatment with titanium halide or co-pulverization, a method of contact treatment at the same time, and the like can be mentioned.

Here, as the titanium halide, titanium chloride can be preferably exemplified, and titanium tetrachloride and titanium trichloride can be mentioned as specific examples.

R ₁ Mgx ¹ used in the production of magnesium halide represented by MgX ¹ _L X ² _2-L which is important in the present invention
Grignard represented by _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 a number not greater than 1 and not greater than 1). The reagent can be produced by a known method. Generally, the halogenated hydrocarbon represented by R ¹ X ¹ and the metal magnesium are first reacted with an amount of 1 mol or less of the halogenated hydrocarbon based on the metal magnesium and then reacted. , R ¹ X ² (wherein R ¹ is the above R ¹ so that the total amount of halogenated hydrocarbons relative to magnesium metal is 1 mol).
It may be the same or different and may be synthesized by reacting a hydrocarbon residue, X ² is chlorine) and aging sufficiently. As the solvent used here, ethers are usually used. 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. MgX ¹ _L X
R ² _n SnX ² which is one of the components used in the production of ² _2-L
4-n (In the formula, R ² is a hydrocarbon residue, X ² is a chlorine atom, and n is 0.
Is an integer of ˜3. Examples of the tin chlorinated compound R ² represented by) are the above-mentioned hydrocarbon residues or hydrogen, and tin tetrachloride is also exemplified in addition to monochlorotin, dichlorotin and trichlorotin.

The reaction is carried out simply by adding the tin chlorinated compound to the Grignard reagent described above, and the reaction proceeds relatively easily.

Examples of the organometallic compound of a metal of Groups 1 to 3 of the periodic table used for polymerizing an olefin using the catalyst component produced by the present invention include organolithium, organosodium, organomagnesium, organoberium, organoaluminum, etc. Are exemplified, and among them, organoaluminum 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.

As a method for polymerizing an olefin using the catalyst component produced in the present invention, a conventional olefin polymerization method can be applied other than using the magnesium halide carrier produced by the above method, a solution polymerization using a solvent, an olefin. Bulk polymerization using itself as a medium or gas-phase polymerization substantially containing no solvent may be performed.

〔Example〕

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

Example 1 A 300 ml round bottom flask was charged with 7.4 g of magnesium and 20 ml of diethyl ether, and a mixture of 25 g of cyclohexane bromide and 50 ml of diethyl ether was added dropwise over 1 hour under reflux of ether. Then, 18 g of cyclohexane chloride was added over 1 hour, and the mixture was stirred under reflux for 2 hours, and C ₆ H ₁₁ MgBr
_A solution of _0.5 Cl _0.5 in ethyl ether was prepared.

Then 50 ml of tin tetrachloride (20 g) under the reflux of ethyl ether.
What was melt | dissolved in the ethyl ether of 3 was dripped over 3 hours, and also it stirred under reflux for 4 hours.

Then, the mixture was filtered at room temperature, the solid content was washed with ethyl ether, and dried with a nitrogen stream to obtain a solid content of 40 g. The obtained solid content was Mg: Cl: Br was approximately 1: 0.5: 0.5, and MgBr _0.5 Cl
It was _1.5 .

10 g of the above solid content was placed in a 200 ml round bottom flask, 50 ml of titanium tetrachloride and 50 ml of toluene were placed therein, and the mixture was stirred at 90 ° C. for 1 hour and then left to stand to remove the supernatant. Further, 50 ml of titanium tetrachloride and 50 ml of toluene were added, and the mixture was stirred at 90 ° C. for 1 hour, then left standing to remove the supernatant, and the obtained solid content was washed 7 times with toluene to obtain a transition metal catalyst component. . As a result of the analysis, the titanium content was 1.5 wt%.

Ethylene was polymerized using the transition metal catalyst component obtained by the above operation. The autoclave 2 n-heptane 1 placed, the transition metal catalyst component 20 mg, was added triethylaluminum 0.5 ml, hydrogen 2Kg / cm ² placed to gauge, ethylene was 6Kg / cm ² 75 ℃ after adding a-out gauge The mixture was heated to 75 ° C. and polymerized at 75 ° C. for 2 hours while adding ethylene to a pressure of 10 kg / cm ² gauge. Then, the mixture was cooled, unreacted ethylene was purged, and then filtered to obtain polyethylene powder. The dry weight was 235 g. This powder had an intrinsic viscosity of 2.24 (measured with a tetralin solution at 135 ° C.), a bulk specific gravity of 0.41, a viscosity of fine powder of 200 mesh or less 1.2%, and coarse particles of 10 mesh or more 0.0%. The yield per Ti was 783 Kg / g-Ti, the bulk specific gravity was good, and the particle size distribution was relatively sharp.

Example 2 Propylene was polymerized using the transition metal catalyst component obtained in Example 1. N-heptane 1 in 2 autoclave
Placed, the transition metal catalyst component 30mg, diethylaluminum chloride 0.32 ml, p-toluic acid methyl 0.12 ml, triethylaluminum 0.20ml addition, hydrogen 0.1 Kg / cm ² gauge, propylene 2Kg / cm ² gauge was placed, then the internal temperature 70 ℃
And polymerized for 2 hours at a total pressure of 6 kg / cm ² gauge. After the completion of the polymerization, unreacted propylene was purged, and the slurry was filtered to obtain 138 g of polypropylene powder, and 3.4 g of active polypropylene was obtained from the filtrate.

The polypropylene powder had a boiling n-heptane extraction residual rate of 95.5% (using a Soxhlet extractor for 6 hours with boiling n-heptane), an intrinsic viscosity number of 2.21, and a bulk specific gravity of 0.41.

Example 3 The amount of cyclohexane bromide and the amount of cyclohexane chloride were changed, and 20 g of tin tetrachloride was used instead of 17 g of dimethyldichlorotin to synthesize magnesium halide having a composition of MgBr _0.5 Cl _1.7. The mixture was placed in a 200 ml round bottom flask, 1.5 g of dibutyl phthalate, 50 ml of titanium tetrachloride and 10 ml of toluene were added, and the mixture was stirred at 120 ° C. for 1 hour to remove the supernatant. Next, 100 ml of titanium tetrachloride was added, and the mixture was stirred at 130 ° C. for 1 hour and left to stand to remove the supernatant, and the resulting solid content was n-
It was washed 9 times with hexane to obtain a transition metal catalyst component. As a result of the analysis, the titanium content was 2.9 wt%. Polypropylene powder 285 g, a component soluble in n-heptane in the same manner as in Example 2 except that 30 mg of this titanium catalyst component, 0.15 ml of triethylaluminum, and 0.03 ml of diphenyldimethoxysilane were used.
3.3 g was obtained. The boiling n-heptane extraction residual rate of polypropylene powder was 98.5% (extracted with boiling n-heptane for 6 hours using a Soxhlet extractor), and the intrinsic viscosity number was
The bulk specific gravity was 1.88 and 0.45.

〔The invention's effect〕

By carrying out the method of the present invention, it becomes possible to efficiently produce a catalyst component for olefin polymerization having good performance, which is industrially valuable.

[Brief description of drawings]

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

Claims (1)

(57) [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 not 0 1 The following numbers are used) and a Grignard reagent represented by the general formula R ² _n SnX ² _4-n (wherein R ² is a hydrocarbon residue, X ²
Is a chlorine atom, and n is an integer of 0 to 3. ) MgX ¹ _L X ² _2-L (in the formula, X ¹
Is bromine or iodine, X ² is chlorine, and L is a number not greater than 0 and not greater than 1. A method for producing a catalyst component for olefin polymerization, comprising: