JPS63168412A - Transition metal catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain a transition metal catalyst useful as a catalyst ingredient for the polymerization of an olefin, by treating a crystalline magnesium halide having a specified X-ray diffraction pattern with a liquid titanium halide. CONSTITUTION:Crystalline MgBrCl having a maximum intensity at about 7.38Angstrom and having a relatively intense diffractions at about 7.89, 5.32, 3.57, 3.47, 3.26 and 2.90Angstrom in its X-ray diffraction pattern is treated with a liquid titanium halide to give a transition metal catalyst for the polymerizatiom of an olefin, which does not show a sharp diffraction at about 7.38Angstrom at least.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a catalyst for the polymerization of olefins. Specifically, the present invention relates to a transition metal catalyst for olefin polymerization obtained using crystalline magnesium halide having a specific X-ray diffraction line.

[Conventional technology]

The use of a transition metal catalyst consisting of a titanium halide supported on a carrier such as magnesium halide and a catalyst consisting of an organometallic compound for the polymerization of olefins was disclosed in Japanese Patent Publication No. 39-1989.
Since the disclosure in No. 12105, various improved methods have been proposed, and some with excellent performance are known.

[Problem that the invention seeks to solve]

The improved method described above mainly involves adding additives and pulverizing the carrier, or dissolving the magnesium halide used as the carrier in a solvent and then precipitating it to support the transition metal and use it as a catalyst for olefin polymerization. In order to obtain excellent performance when carrying out this process, 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. In particular, the method of dissolving and then precipitating is excellent and can produce highly active catalysts (e.g., JP-A-56-11908).However, this method requires a large amount of precipitate. Moreover, there is a problem in that good activity cannot be obtained unless it is repeatedly treated with titanium halide. Furthermore, the method of adding additives and pulverization makes it difficult to provide a catalyst with excellent performance with good reproducibility.

The inventors of the present invention have conducted extensive studies on ways to solve these problems, and have found that by using magnesium halide, which gives a specific crystalline diffraction line, crystalline particles, which have conventionally been said to be unusable as a support, can be used. The present invention was completed by discovering that even a carrier having a diffraction line can surprisingly provide an excellent performance catalyst for olefin polymerization.

[Means for solving problems]

That is, the present invention has a maximum intensity near 7.38 as a diffraction line measured by X-ray diffraction, and has a maximum intensity of 7.98.5°32.
．． 3.57.3.47.3.26.2.A sharp diffraction line near 7.38 obtained by treating crystalline MgBrCl with liquid titanium halide, which gives a relatively strong diffraction line near 90. This is a transition metal catalyst for olefin polymerization that has no lines.

In the present invention, as MgBrCl used as a carrier, the XS! Where the diffraction spectrum is specific, i.e.
The maximum intensity is around 7.38 people, 7.98.5°32
．． There is no particular restriction on the manufacturing method as long as it has a relatively strong diffraction line around 3.57.3.26.2.90, but the following manufacturing method can be exemplified.

-a formula R'MgBr (wherein R1 is a hydrocarbon residue);

) (as is well known, it is obtained by reacting a brominated hydrocarbon compound represented by R'Br with metallic magnesium in the presence of ether etc.) and the general formula R''CI (wherein R1 is a hydrocarbon residue), the crystalline MgBrCl as defined above can be easily obtained by reacting the chlorinated hydrocarbon compound, wherein R1 is a hydrocarbon residue. The hydrocarbon residue of the compound or chlorinated hydrocarbon compound may be any aliphatic, alicyclic, aromatic hydrocarbon residue, etc., and there is no particular restriction, but it may have about 1 to 20 carbon atoms. It is common to use

The reaction between the Grignard reagent and the chlorinated hydrocarbon is normally carried out at the boiling point of the ether used as the medium, and the reaction proceeds sufficiently.When the reaction proceeds, MgBrCl becomes insolubilized in the medium and precipitates, so filtration or static separation is performed. You can easily take it out by doing so.

The MgBrCl thus obtained is then treated with liquid titanium halide to be used as a transition metal catalyst for olefin polymerization. The titanium halide used here is preferably titanium tetrachloride, titanium trichloride solubilized in a hydrocarbon solvent with ether, or titanium compounds in which part of the chlorine in the above titanium compound is converted into an alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, etc.).

Here, the contact treatment is performed under mild conditions that do not apply strong force to the MgBrCl particles, and is performed, for example, by simply dispersing MgBrCl in liquid titanium halide and stirring. The temperature during the contact treatment is usually room temperature to 200°C.

Further, during the contact treatment, an electron-donating compound such as an oxygen-containing organic compound such as ether, ester, or alkoxysilane may be present.

The transition metal catalyst of the present invention polymerizes olefins by using in combination metal compounds of metals from Group 1 to Group 3 of the periodic table, such as organolithium, organosodium, organomagnesium, organoberyllum, organoaluminium, etc. be able to.

Examples of olefins that can be polymerized using the catalyst of the present invention include ethylene, propylene, butene-11pentene-1, hexene-1, octene-1, styrene, and vinylnaphthalene. is used for copolymerization with dienes, etc.

In the present invention, olefin polymerization can be carried out by conventionally known olefin polymerization methods, such as solution polymerization using a solvent, bulk polymerization using the olefin itself as a medium, or gas phase polymerization substantially free of solvent.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 7.4 g of magnesium and 2 On+1 diethyl ether were placed in a 300 ml round bottom flask, and a mixture of 50 g of cyclohexane bromide and 50 ml of diethyl ether was added dropwise over 2 hours while the ether was being refluxed. Thereafter, the mixture was further stirred under reflux for 1 hour to prepare an ethyl ethyl solution of CJ8MgBr.

Then, 15 g of carbon tetrachloride was added to 4 ml of ethyl ether under reflux.
The mixture was added over time and further stirred under reflux for 2 hours.

Then, it was filtered at room temperature, and the solid content was washed with ethyl ether and dried with a nitrogen stream to obtain 40 g of solid content. The obtained solid content has a ratio of Mg:C1:Br of approximately 1:1:1, and Mg:C1:Br is approximately 1:1:1.
gBrCl. Moreover, the measurement results of X-ray diffraction are shown in FIG.

Put 10g of the above solid content into a 200ml round bottom flask,
Titanium tetrachloride 50a+1. ) Add 5 hl of luene, 9
The mixture was stirred with 1'BIPA at 0° C. for 1 hour, then allowed to stand and the supernatant was removed. Furthermore, 51) ml of titanium tetrachloride and 50 ml of toluene were added, stirred at 90°C for 1 hour, then allowed to stand, the supernatant was removed, and the resulting solid content was washed 7 times with toluene to convert it into a transition metal catalyst. The result of the 0 analysis was that titanium was 1
．． It contained 9wtχ.

Ethylene was polymerized using the transition metal catalyst obtained in the above operation. n-hebutane li in an autoclave with an internal volume of 2 It
Add 20 figs of the above transition metal catalyst, 0.5a+1 triethyl aluminum, and add 2 kg/cn of hydrogen.
After adding ethylene at a rate of 6 kg/cnl gauge, the temperature was raised to 75°C, and polymerization was carried out at 75°C for 2 hours while adding ethylene to 10 kg/cnl gauge. Thereafter, it was cooled, unreacted ethylene was purged, and then filtered to obtain polyethylene powder. The dry weight was 360 g. The intrinsic viscosity of this powder was 2.56 (measured using a tetralin solution at 135°C).

), the bulk specific gravity was 0.48, the particle size was 4.5% fine powder of 200 mesh or less, and 0.3% coarse particle of 10 mesh or more. The yield per Ti was 947 Kg/g-Ti, the bulk specific gravity was also good, and the particle size distribution was also relatively sharp.

Example 2 10 g of MgBrCl obtained in Example 1 was placed in a 2001 Il round bottom flask, and 1.5 g of dibutyl phthalate and 50 ml of titanium tetrachloride were added. ) Add 10 liters of luene and bring to 120°C.
After stirring for 1 hour and removing the supernatant, 100 ml of titanium tetrachloride was added and stirred for 1 hour at 130°C, left to stand and the supernatant was removed.
As a result of analysis, titanium was washed twice and used as a transition metal catalyst.
．． It contained 5wtχ.

30 mg of the above transition metal catalyst, 0.151111 triethyl aluminum, 0.
Polymerization was carried out using 03+*I in a 51 autoclave using propylene itself as a solvent. At this time, propylene 1
5 kg of hydrogen and 3.2 NL of hydrogen were added, and polymerization was carried out at 756C for 2 hours.

After 2 hours of polymerization, unreacted propylene was purged to obtain 670 g of polypropylene powder. (Transition metal catalyst light: 22,333 g/g) The intrinsic viscosity of this powder is 1.
56, the bulk specific gravity was 0.42g/a+1, and the ratio of boiling 11-" butane extraction residue was 98.2χ.

(Effects of the Invention) The catalyst of the present invention is excellent as a polyolefin polymerization catalyst and has industrial value.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an X-ray diffraction spectrum of magnesium halide used in producing the catalyst of the present invention.

Claims (1)

[Claims] Diffraction lines measured by X-ray diffraction have maximum intensity around 7.38 Å, and 7.98, 5.32, 3.57, 3
．． Transition for olefin polymerization that does not have sharp diffraction lines at least around 7.38 Å obtained by treating crystalline MgBrCl that gives relatively strong diffraction lines around 47, 3.26, and 2.90 Å with liquid titanium halide. metal catalyst.