JPS6088010A - Polymerization of olefin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for polymerizing olefins using specific titanium catalysts. More specifically, the present invention relates to an olefin polymerization method that does not cause process troubles due to coarse particles.

Various methods have been used to increase the yield of polyolefin using catalysts since the invention of the Ziegler-Natsuta catalyst, and among them, the method of supporting titanium halide on a metal halide proposed in Japanese Patent Publication No. 39-12105 A method using a catalyst made of a catalyst obtained by the above method and an organoaluminum compound is effective. In addition, many improvements have been proposed regarding this method, and catalyst performance has improved significantly over the past thousand years, with catalysts boasting high performance of tens of thousands of grams per titanium catalyst/11-titanium catalyst being reported. 1. When polymerizing olefins in a homogeneous solution state, the solution viscosity becomes extremely high, making it difficult to remove the polymerization heat and transfer the solution, so it is generally polymerized in a slurry state in a liquid or gas phase medium. .

In polymerization in this slurry state, 1? Liolefin exists in granular form, but it is better not to have huge or fine particles. However, if there are large particles, there is a problem that they can accumulate in narrow parts of equipment such as polymerization tanks and smelting tubes, and in some cases they can become clogged. This clogging problem is a serious problem in continuous production methods such as olefin polymerization, which can lead to the shutdown of the entire plant.

The present inventors have conducted various studies to solve the above problem, and have discovered that this problem can be solved by using a titanium catalyst with special consideration given to the shape of the carrier used, and have developed the present invention. completed.

An object of the present invention is to provide a method for polymerizing olefins that is free from troubles caused by coarse polyolefin particles.

That is, the method for polymerizing olefin/ of the present invention involves adding / to a carrier obtained by co-pulverizing magnesium 710gnide and an organic compound.
- In a method of polymerizing olefin using a catalyst consisting of a titanium catalyst obtained by supporting titanium rogonide and an organoaluminum compound, the support is formed into a mesh whose opening is smaller than R represented by the following formula [1]. This method is characterized by using a titanium catalyst obtained by passing through a sieve and then contacting liquid nologonized titanium.

In the formula, the critical slurry particle size of the RO7' process, the density of d1 polyolefin, the density of d2 titanium catalyst, and the amount of polyolefin produced per W titanium catalyst are represented.

Magnesium 710 chloride used in the present invention includes magnesium chloride b, magnesium bromide, etc., but magnesium chloride 75 is particularly preferred.

Further, as the organic compound, known compounds such as ttn used in producing a non-rodanized magnesium carrier can be used, and among them, a C-O bond-containing compound is preferably used. Various known methods can be used as the co-grinding method, among which yl? - Co-pulverization using a vibratory mill or a vibratory mill is preferred.

In the present invention, the rhodanized magnesium carrier obtained by co-pulverization is passed through a mesh sieve with small openings (R in formula [1]). , indicates the minimum diameter of coarse particles when the various process troubles mentioned above occur due to the presence of coarse particles. That is,
This is the minimum diameter of the coarse particles that caused the problem. Although this cannot be specified depending on the details of the process, when polymerization is carried out using a liquid medium slurry, 10t
Particles larger than nm should not be present. Preferably 5
It is better that there are no particles that exceed the throat. 1. In the gas phase medium three-way method, the allowable particle size of coarse particles is generally large, but it is still better not to have particles larger than 10 mm. Preferably, the RO is less than or equal to 5 ttm.

Passing through the mesh sieve may be done by applying appropriate vibrations so that the carrier passes under the action of gravity, but since many carriers will not pass, it is also possible to use a method of forcing the carrier to pass through a brush or the like. .

The support thus obtained is then brought into contact with liquid titanium halide to produce a titanium catalyst. As the titanium halide to be used, titanium tetrachloride, which is itself liquid, is preferred and often used, but it can also be diluted with hydrocarbons, etc., and solid titanium halide, such as titanium trichloride, can also be used in an appropriate medium. It is also possible to dissolve it and use it in liquid form. The contact is carried out in close contact using an appropriate stirring means, usually under heating at room temperature or higher, preferably at a temperature of 40 to 13
It is best to do this at 5°C. Many conditions for these contact conditions are already known.

The titanium catalyst thus obtained is combined with an organoaluminum compound and subjected to olefin polymerization. The organoaluminum compounds used in the present invention include trialkylaluminum, dialkylaluminum chloride, alkylaluminum sesquichloride, alkylaluminum dichloride, and other commercially available organoaluminum compounds. Examples include various organoaluminum compounds available at

Examples of olefins used in the present invention include ethylene, propylene, butene-1, hexene-1, etc., and homopolymerization or mutual copolymerization of these is carried out. In olefins, the effect is dog. That is, the polymerization method of the present invention does not reduce the disfigurement performance, especially the stereoregularity of the polyolefin obtained.

The method of the present invention makes it possible to produce polyolefins in high yields using catalysts without causing troubles due to coarse particles, and is therefore extremely valuable industrially.

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

[Example/Comparative example]

Predicted value of R The critical slurry particle size of the zolopyrene polymerization process is set to the normal value of 5.
w, and the predetermined density of the titanium catalyst (actual value 2
．． 2), and using a density of polypropylene of 0.9,
Furthermore, the normal value of W in this catalyst system is about 20,000,
By substituting each into the above formula, an approximate value of R was determined.

Using this R value as a standard, using a mesh sieve with a smaller opening (wire mesh with an opening of 0.074 m) and a mesh sieve with a larger opening (wire mesh with an opening of 0.147 w + t),
The inventive method and comparative polymerization method were carried out.

Example 1, Comparative Example 1 a) Production of titanium catalyst 80 stainless steel balls with a diameter of 12II+++1 were placed in 30 g of magnesium chloride containing water Q and 4 wt%, 4.5 ml of ethyl orthoacetate, and 3 ml of 1,2-dichloroethane. The mixture was placed in a pulverizing pot with an internal volume of 600 mA1 and pulverized for 40 hours. Next, the co-pulverized material 15F was
．． When the co-pulverized material was placed on a 074Nn open mesh sieve and stirred with a brush to pass through, a 13p co-pulverized material passed through. 10 g of each of those passed through a mesh sieve (Example 1) and/or) (Comparative Example 1) was placed in a 200 mJ round bottom flask, 50 ml of titanium tetrachloride was added to each, and the mixture was heated at 80°C. The solid portion was washed with 100 ml of re-hebutane five times, and after removing the n-hebutane, 50 ml of titanium tetrachloride was added and the solid portion was stirred at 80°C for 1 hour. The portion was washed 7 times with 10 ml of n-hegetane, and 50 ml of n-hegetane was added to prepare a titanium catalyst slurry.

1) Polymerization reaction Prepare an autoclave with an internal volume of 51 cm, which is sufficiently dried and purged with nitrogen. 200 mAt fully dried and replaced with nitrogen
n-Hesothane 50II dried to 72 sco and replaced with nitrogen
Added Il, diethyl aluminum chloride 0.128
0.06 mA'% triethylaluminum o, 30 m9 of the titanium catalyst obtained from osmIt (a) was added to the mixture, and the mixed catalyst slurry was placed in the above autoclave, and then propylene 1. sky, water t.

After polymerizing for 2 hours at an internal temperature of 75°C by heating the autoclave with 0.6 N/ml, the unreacted 7″ Robile was discharged and the resulting polyno Robilene powder was taken out.
The procedure of drying at ℃ for 10 hours and then weighing is performed in step (a) above.
The experiment was carried out on titanium catalyst 2'81 obtained in . Regarding the powder obtained in each case, the intrinsic viscosity (hereinafter abbreviated as η, measured in a tetralin solution at 135°C) and the residual rate of boiling n-hebutane extraction (hereinafter abbreviated as 11, 6 in boiling n-hebutane using a Soxhlet extractor) The table shows the results of measuring the weight of the residual polymer (calculated as extraction m!!li, v-M amount x 100 h), bulk specific gravity, and particle size distribution (Tyler mesh).

From the table, it can be seen that in the example using a carrier that passes through a wire mesh with an opening of 0.074 mm, an opening of 4.76y++m (ASTM standard sieve Φ
4) It can be seen that there are no coarse polyolefin particles at all.

Example 2, Comparative Example 2 Additives during co-grinding were 76 m/1.2-dichloroethane 31 rLl, half of which was a wire mesh with a 0.074 mm opening (Example 2), and half with a wire mesh of 0.147 mm. (Comparative example 2
) was passed in the same manner as in Example 1.

It can be seen that there are polyolefin coarse particles of 4.7 m or more in the wire mesh of 0.147 m.

Comparative Example 3 The same procedure as Comparative Example 1 was carried out except that the co-pulverization time was 40 hours. The results are shown in the table.

Comparative Example 4 The same procedure as Comparative Example 1 was carried out except that a glass stirrer chip was placed in the titanium catalyst slurry and the slurry was vigorously stirred for 2 hours with a stirrer. The results are shown in the table.

Claims (1)

[Claims] Using a catalyst consisting of a titanium catalyst obtained by contacting -titanium rogonide (liquid with a carrier obtained by co-pulverizing magnesium rehalodanide and an organic compound) and an organoaluminum compound. A method for polymerizing an olefin, characterized in that a titanium catalyst obtained by passing the carrier through a mesh sieve whose autoclosing rate is smaller than R expressed by the following formula and then contacting it with liquid titanium halide is used. polymerization method. In the formula, RO represents the critical slurry particle size of the process, dl represents the density of the polyolefin, d2 represents the density of the titanium catalyst, and W represents the amount of polyolefin produced per titanium catalyst. (2) The method for polymerizing an olefin according to claim (1), wherein the olefin is an α-olefin having 3 or more carbon atoms.