JPS59174601A - Preparation of transition metal catalyst supported on carrier - Google Patents

Abstract

PURPOSE:To prepare the titled catalyst free from coarse particles liable to cause the blocking of polymerizer pipings, by crushing magnesium halide together with an organic compound having C-O bond, etc., mixing the crushed product with liquid titanium halide, and irradiating ultrasonic radiation to the obtained slurry. CONSTITUTION:The objective catalyst is obtained by crushing magnesium halide (e.g. magnesium chloride) together with an organic compound having C-O and/ or C-N bond (e.g. ethyl orthoacetate) using e.g. a ball mill, adding a liquid titanium halide (e.g. titanium tetrachloride) to the crushed product, and irradiating ultrasonic radiation to the mixture containing the solid material in a slurry form. An autoclave is charged with the catalyst, and then with diethyl aluminum chloride, methyl p-toluylate, and trialkyl aluminum, and propylene is polymerized in the autoclave.

Description

[Detailed Description of the Invention] Specifically, the present invention relates to an improved method when the manufacturing process includes a co-pulverization step.

7゛1 Carrier of transition metal, which is one component of Chigara-Natsuta catalyst,
In particular, a method of improving catalyst activity by supporting on magnesium halide is known.

Among them, the method of co-pulverizing magnesium halide and a compound containing a C-0 or C-N bond and then contacting it with liquid titanium halide is not only easy to operate but also improves the performance of the resulting catalyst. This is a good and excellent method. However, since this method co-pulverizes an organic compound and a magnesium halide, it contains relatively large particles, and when used for polymerization of the olefin, it becomes large polymer particles, which settle to the bottom of the polymerization tank. Otherwise, there was a risk that the pump, piping, valves, etc. would be blocked during polymer transfer, or that the pump would stop in some cases.

The inventors of the present invention have conducted various studies on methods for solving the above-mentioned problems, and have found that the problems can be solved by using a specific method, and have completed the present invention.
41 The present invention relates to a method for producing a supported transition metal catalyst for olefin polymerization.

An object of the present invention is to provide a method for producing a supported transition metal catalyst free of relatively coarse particles.

The magnesium halide used in the present invention may be magnesium chloride (including anhydride). Also, C
Examples of organic compounds containing -O or C-N bonds include ethers, esters, ketones, orthoesters, amines, amides, phosphoric esters, phosphorous esters, etc. First, the magnesium halide and an organic compound containing a C-0 or C-N bond are co-pulverized.

The ratio during co-pulverization does not particularly affect the implementation of the present invention, but usually the latter is 5 to 1 mole times the former, and aromatic hydrocarbons or halogenated hydrocarbons are added at the same time. Co-pulverization is also practiced. A ball mill or a vibration mill is used as a pulverizer for co-pulverization. The grinding time is from several minutes to several tens of hours.

Next, the co-pulverized product obtained in the above operation is brought into contact with liquid titanium chloride, so that titanium chloride is supported on the solid carrier.

As the titanium halide, titanium chloride is preferably used, and particularly preferably titanium tetrachloride, a mixture of titanium tetrachloride and a hydrocarbon or a halogenated hydrocarbon, or titanium trichloride prepared in a liquid state with a complexing agent such as ether is used. It is being The contacting process is usually carried out at room temperature to 150°C.

It is also possible to perform ultrasonic irradiation, which is a feature of the present invention, simultaneously with this contact treatment.

Following the contact treatment, excess titanium halide is removed by filtration or static separation or evaporation, and the solid portion is washed with an inert hydrocarbon compound to remove free titanium halide. Ultrasonic irradiation can also be carried out during this cleaning, 9 or after free titanium halide has been removed, ultrasonic irradiation can be carried out in the form of a slurry dispersed in an inert hydrocarbon compound.

commonly used. The irradiation time should be set appropriately depending on the frequency and the output of the device; however, excessive irradiation will cause the catalyst particles to become too fine, which is not preferable.

By carrying out the method of the present invention, it becomes possible to produce a carrier-type transition metal catalyst that does not produce coarse particles that pose a problem in the operation of the polymerization process, and is of great industrial significance.

The method of the present invention will be explained in more detail with reference to Examples below.

Comparative Example I A) Production of Supported Transition Metal Catalyst A vibratory mill equipped with two grinding pots each having an internal volume of 600 m containing 80 steel balls each having a diameter of 121 m was prepared. In this pot under nitrogen atmosphere, 1 piece of magnesium chloride 302
, orthoethyl acetate 3-11,2-dichloroethane 6-
was added and ground for 40 hours. One 10f portion of the above pulverized product and 50% titanium chloride were added to a 200° round bottom flask, and the mixture was stirred at 80°C for 2 hours, and then the supernatant liquid was removed by decantation. Next, 100m7 of n-hebutane! After stirring at room temperature for 15 minutes, the washing operation of removing the supernatant liquid by decantation was repeated 7 times.
00- was added to prepare carrier-type transition metal catalyst slurry A.

When a portion of this slurry was sampled and Ti was measured, the amount of Ti was 1.82 wt per carrier-type transition metal catalyst 11.
It contained.

B) Polymerization 5US-32 with an internal volume of 5 tons that was sufficiently dried and purged with nitrogen.
In a prepared autoclave, in 50 d of n-hebutane was added 3 o of the above supported transition metal catalyst, wry, 0.24 d of diethylaluminium chloride, and 0.14 d of P=) methyl ruylate.
A catalyst slurry containing 0.20% of trialkylaluminium is charged, and then 1.0% of liquid propylene is charged. ．． 5 to 9
was loaded. Next, 16 Nt of hydrogen was charged and the autoclave was heated with hot water to raise the internal temperature to 75°C, and polymerization was carried out at 75°C for 3 hours.

After the polymerization was completed, unreacted propylene was discharged to obtain white polypropylene. The obtained polypropylene was dried under reduced pressure at 60°C and weighed to determine the yield of polypropylene, the yield per supported transition metal catalyst, the proportion of the boiling n-heptane extraction residual polymer in the powder (hereinafter abbreviated as powder 1 process), and the yield per supported transition metal catalyst. The bulk specific gravity and intrinsic viscosity number (measured with a tetralin solution at 135° C.) were calculated, and the powder was further sieved using a sieve and the particle size distribution expressed by American Tyler mesh was measured. The results are shown in the table.

Example 1 The carrier-attached transition metal catalyst slurry prepared in Comparative Example 1 was irradiated with ultrasonic waves. Polymerization was carried out in the same manner as in Comparative Example 1 except that a transition metal catalyst with a carrier thus obtained was used, and the results are shown in the table.

Example 2 Comparative Example 1 was carried out in the same manner as in Comparative Example 1, except that after the contact treatment of TiCt* and the pulverized material, ultrasonic waves were irradiated for 30 seconds using the apparatus of Example 1. The results are shown in the table.

Example 3 An experiment was conducted in the same manner as in Example 1 except that the ultrasonic irradiation time was 2 minutes. The results are shown in the table.

Comparative Example 2 A supported transition metal catalyst was manufactured on a scale 2 times that of Comparative Example 1, and then, after stopping stirring, the lower layer was taken out into another container to remove the portion containing relatively large particles, and a supported transition metal catalyst was produced. The results of polymerization in the same manner as in Comparative Example 1 are shown in the table.

Example 4 The catalyst slurry obtained in Comparative Example 2 was irradiated with ultrasonic waves for 1 minute in the same manner as in Example 1 to obtain a supported transition metal catalyst slurry, except that polymerization was carried out in the same manner as in Comparative Example 1F. The results are shown in the table. .

Claims (1)

[Claims] ・・Magnesium rogenide and at least C-0 or C-
In the method of producing a supported transition metal catalyst by contacting a liquid titanium halide with a co-pulverized product with an organic compound containing an N bond, it is recommended that the ultrasonic irradiation treatment be carried out while at least the solid material is in the form of a slurry. How to characterize it.