JPS6079016A - Production of supported transition metal catalyst - Google Patents

Abstract

PURPOSE:To produce the titled catalyst free of coarse particles in good efficiency, by classifying a specified copulverizate, allowing the fine particles as such to support a titanium halide and, after adding a halohydrocarbon and copulverizing the mixture, allowing the product to support a titanium halide. CONSTITUTION:A magnesium halide (e.g., MgCl2) and an organic compound (e.g., ethyl benzoate) are classified, the undersize as such is allowed to support a titanium halide (e.g., TiCl4), and the oversize is mixed and copulverized with a halohydrocarbon (e.g., trichloroethane), and then allowed to support a titanium halide. The titted catalyst is produced in this way. When the coarse particles are copulverized in the presence of a halohydrocarbon, the ultrafine partile fraction does not substantially increases, and the activity can be improved. Therefore, when it is used in the polymerization of an alpha-olefin, a polyolefin of improved stereoregularity can be obtained.

Description

[Detailed description of the invention] The present invention relates to a method for producing a supported transition metal catalyst.

Details≦ relate to a method for producing a supported transition metal catalyst suitable for polymerizing α-olefins.

Various methods have been used to increase the yield of polyolefin per transition metal since the invention of catalysts by Ziegler and Natsuta.
The method proposed in No. 5 to obtain a catalyst by supporting titanium halide on a metal halide can greatly increase the yield of polyolefin per transition metal, and many improved methods have been proposed.

In particular, the improvement in catalyst performance over the past thousand years has been remarkable, and not only the yield of polyolefin per transition metal, but also the yield per transition metal catalyst (catalyst color including carrier) has improved, and the yield per transition metal catalyst has improved. It is a high performance y-transition metal catalyst.

Polyolefin polymerization is generally carried out in a slurry state in a liquid medium or a gaseous medium due to problems with solution viscosity and removal of polymerization heat. During polymerization in a slurry state, polyolefin exists in the form of particles, so it is better not to have large or fine particles.If large particles are present, they will accumulate in narrow parts of equipment such as polymerization tanks and piping. In some cases, there was a problem that the parts would close. This clogging problem is a serious problem in continuous production methods such as polyolefin polymerization, which can lead to the shutdown of the entire plant. To deal with this problem, since the size of the transition metal catalyst and the size of the polyolefin particles are correlated, the transition metal catalyst may be classified to remove particles larger than a certain level. Among these, it is preferable to classify the carrier at the carrier stage because it is relatively easy to operate. However, when classified, carriers larger than a certain size are wasted, and since the carriers contain various organic substances, they must be disposed of as industrial waste, which is not preferable.

As a result of intensive study on the above problem, the present inventors discovered that a transition metal catalyst could be obtained without wasting the carrier by carrying out a specific method, and completed the present invention.

An object of the present invention is to provide a method for efficiently producing a phased transition metal catalyst.

The present invention is a method for producing a phased transition metal catalyst by supporting a titanium halide on a phase obtained by co-pulverizing a red sea bream sium halide and an organic compound, in which the co-pulverized product is classified as a carrier. The fine particles directly support titanium halide,
The present invention relates to a method for producing a supported transition metal catalyst, characterized in that the coarse particles are co-pulverized with the addition of a halogenated hydrocarbon and then supported on a titanium halide.

In the present invention, magnesium chloride may include magnesium chloride and magnesium bromide, with magnesium chloride being preferred.

In addition, as organic compounds, various compounds used in the production of carriers of magnesium rogenide (known in the art) can be used, and among them, C--O bond-containing compounds are preferably used. For the co-pulverization method, various known devices and methods can be employed, but co-pulverization using a ball mill or a vibration mill is particularly preferred.

In the present invention, the co-pulverized product obtained by the above operation is classified to separate coarse particles. The particle size of the co-pulverized material to be removed in this classification is usually about 5 + ms, which is the coarse particle size of polyolefin which is undesirable in the polymerization process. The yield corresponds to a particle size of approximately 01□ of supported transition metal catalyst. Therefore, if the yield per supported transition metal catalyst is, for example, W2/2, the particle size R of the co-pulverized material to be classified and removed can be determined by many known classification methods. Examples include a method of classification using a sieve, or a classification method using a classification knife using an air flow transport process.

The co-pulverized product separated by classification and free of coarse particles carries titanium halide. On the other hand, the classified coarse particles are further pulverized using the aforementioned ball mill or vibration mill, etc. to make the coarse particles fine. At this time, if only coarse co-pulverized particles are pulverized and polymerized using a catalyst obtained by supporting titanium halide, the number of ultrafine particles will increase, which is undesirable.
When used in the polymerization of olefins, the stereoregularity of the resulting polyolefin is reduced. On the other hand, when coarse particles are co-pulverized in the coexistence of a halogenated hydrocarbon, the number of ultrafine particles hardly increases, the activity is improved, and the stereoregularity of the polyolefin obtained when used in the polymerization of α-olefins is also improved. Improves sex. The amount of halogenated hydrocarbon added when co-pulverizing the coarse particles is 0.01 to 0.05, preferably 0.01 to 1 of the coarse particles, in terms of weight ratio.
It is about 05 to o2. The time required for co-pulverization varies depending on the shape of the crusher and cannot be specified, but a time of 1/3 to 1/1 of the time required for the initial co-pulverization is sufficient.

The halogenated hydrocarbons used include methylene chloride, ethylene dichloride, trichloroethane, furopane chloride,
Dichloropropane, trichloropropane, α, α, α-
Trichlorotoluene, nathoaliphatic and aromatic halogenated hydrocarbons are used, preferably those which are liquid at room temperature.

By applying the method of the present invention, a supported transition metal catalyst free of coarse particles can be obtained in higher yield than VC, and it is of high industrial value.

EXAMPLES The present invention will be explained in more detail with reference to Examples below.

Experimental Example 1 a) Production of catalyst Magnesium chloride 3Or containing 0.4 wt% water,
4.5 ml of orthoethyl acetate and 1,2-dichloroethane/3- were placed in a pot containing 80 stainless steel balls with a diameter of 12 mm and ground for 40 hours. This operation was repeated to obtain 1 co-pulverized product. The co-pulverized product 5002 was placed on the open-mouth gold eyes of 0074 strawberries, and the co-pulverized product was stirred to separate the top and bottom parts of the whole egg. I got 57 as Kinnejo.

Using the crusher used above, the whole egg was co-pulverized with 3 m7B of 1,2-dichloroethane (201) and the wire mesh (202) for 5 hours, respectively.

Co-pulverized product obtained above, bottom of wire mesh (a), top of wire mesh +1.
2-dichloroethane co-pulverization (bl, gold-based grinding (C),
For the four types on the gold line (d), 107 and 200 respectively
Put it in a round bottom flask and add 50% of titanium tetrachloride.
Treated under stirring for 1 hour at 0°C and then treated with n-
After washing the solid portion with hebutane five times and extracting n-hebutane, titanium tetrachloride 50+++1! Add 80
℃ for 1 hour under stirring, then the solid portion was
Wash 7 times with n-hebutane 6, and then wash with n-hebutane 5
0ml was added to prepare a supported transition metal catalyst.

1) Polymerization reaction Prepare an autoclave with an internal volume of 5 tons that is sufficiently dried and purged with nitrogen. N-heptane, which was dried and purged with nitrogen, was placed in a 200-ml flask that had been thoroughly dried and purged with nitrogen.
The catalyst slurry obtained by adding 50 cm of the catalyst obtained in step 1) was placed in the above autoclave, and then 1 part of propylene was added to the mixed catalyst slurry.
．． 511Ji and 0.6 Nt of hydrogen were heated in an autoclave to conduct polymerization at an internal temperature of 75° C. for 2 hours. Next, unreacted propylene was discharged, and the resulting polypropylene powder was taken out, dried under reduced pressure at 60° C. for 10 hours, and weighed. In addition, the intrinsic viscosity number of the powder (hereinafter abbreviated as η13
(measured with a tetralin solution at 5°C) boiling n-hebutane extraction residue (hereinafter abbreviated as II, calculated using boiling n-hebutane in a Soxhlet extractor), bulk specific gravity and particle size distribution (Tyler mesh, USA)'ff: Measured, The results are shown in the table.

Experimental Example 2 Co-pulverization of magnicium chloride 30F and ethyl benzoate 3M
l! The procedure was the same as Experiment 1, except that gold 4!
The upper limit was about 10%.

Experimental Examples 3-, b, 4-b Experimental Example 1 except that 1,3-dichloroethane was used instead of 3rnl of 1,2-dichloroethane in Actual M Example 1-'b
, the same as in -b (3-b), 1.2 in Experimental Example 2-b
-Dichloroethane 37! The procedure was the same as in Experimental Example 2-b except that 1,1.1-) dichloroethane was used instead of (4-
b) Results are shown in the table.

Claims (1)

[Claims] In the method of manufacturing a supported transition metal catalyst by supporting titanium halide on a phase obtained by co-pulverizing magnesium halide and an organic compound, the co-pulverized product is classified as a carrier, and the fine particles are left as they are... 1. A method for producing a supported transition metal catalyst, characterized in that the coarse particles are co-pulverized with the addition of a halogenated hydrocarbon and then supported on the titanium halide.