JPS6189210A - Preparation of catalytic component - Google Patents

Abstract

PURPOSE:To obtain a novel polymerization catalyst having high polymerization activity and useful for the production of a polymer having low crystallinity, by treating a Mg halide with a hydrocarbon solution of an addition product of an electron donor and a Ti or V halide. CONSTITUTION:(A) A solid Mg halide is dissolved in (B) a solution prepared by dissolving (i) preferably 10<-5>-1mol/l of a Ti and/or V halide and (ii) an electron donor (e.g. ethyl ether) in a (halogenated) hydrocarbon at a molar ratio of 2-1,000, at a ratio of the component (i) to the component A of preferably >=10<-6>mol/g, and the mixture is treated e.g. at -50-+200 deg.C for 1sec-2hr, to obtain the objective catalyst component. USE:A soft copolymer of ethylene and an alpha-olefin can be prepared at a relatively low temperature by combining the above catalyst with an organometallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides
j Concerning the manufacturing method. For more details, see Olefin (co)
This invention relates to a novel method for producing catalyst components used in polymerization.

It has been well known that a titanium or vanadium halide is supported on magnesium halide as a method for obtaining the above-mentioned catalyst component.

However, unless the polymerization activity per halide of titanium or vanadium is high, corrosion caused by the halogen remaining in the resulting polyolefin becomes a problem.

Furthermore, the harder and rougher the particle shape of the obtained polyolefin powder, the easier it is to handle during manufacturing processes such as transportation and storage.

The high polymerization activity per halide of titanium or vanadium and the good shape of the powder particles are particularly important when preparing a polymer with a low degree of crystallinity.

Polymer powders with low crystallinity tend to stick to each other, and it is important to have a good powder shape to avoid agglomeration.Generally, when trying to avoid agglomeration at a low temperature, catalyst activity is reduced. Therefore, it is important that the polymerization activity is high.

As a result of intensive studies in view of the above circumstances, the present inventors have determined that a trapped material (A) mainly consisting of magnesium halide, an electron donor capable of forming an adduct with the magnesium halide, and a halogen of titanium and/or vanadium. Hydrocarbon or halogenated hydrocarbon solutions of adducts with compounds (
By using the catalyst component obtained by the treatment in B),
The present invention was completed by discovering that it is possible to obtain a polymer with good powder properties, and in this case, the polymerization activity per titanium or vanadium atom is also increased.

The magnesium halide used in the present invention includes magnesium chloride, magnesium bromide, magnesium iodide, magnesium hydroxychloride, magnesium hydroxychloride, etc. Magnesium chloride is particularly preferred.

Examples of the solid material mainly composed of magnesium halides include the above-mentioned magnesium halides or complexes of these with electron donors, inert organic compounds, or inert inorganic compounds.

Complexes with electron donors can be particularly effective because of their high polymerization activity. Preferred electron donors include ether compounds such as ethyl ether, dioxane, and tetrahydrofuran, alkoxysilanes such as tetraethoxysilane, diphenyljethoxysilane, and I.liphenylethoxysilane, and siloxanes such as hexamethyldisiloxane and dimethylpolysiloxane. alkoxytitaniums such as tetrabutoxytitanium, phosphoric acid esters such as tributyl phosphate and triphenyl phosphate, phosphines such as triptylph A-sphine and triphenylphosphine, esters such as ethyl benzoate and butyl phthalate. I'll give you something.

Methods for obtaining the above composite include co-pulverization;
Contact treatment with an electron donor liquid or solution, precipitation from a mixed solution of an electron donor and magnesium halide, or washing of the solid material obtained by these methods,
Alternatively, it can be obtained by Lewis awakening treatment.

Examples of titanium halides include titanium tetrachloride, titanium trichloride, titanium dichloride, titanium tetrabromide, and titanium tribromide. Examples of vanadium halides include vanadium oxychloride, vanadium tetrachloride, vanadium trichloride, vanadium tetrabromide, and vanadium tribromide.

Titanium halides, especially titanium trichloride, are preferred in order to obtain high catalytic activity. On the other hand, in order to control the degree of copolymerization, it is generally preferred to use vanadium halides, but from the viewpoint of catalytic activity, vanadium trichloride or vanadium tetrachloride, especially vanadium trichloride, is preferred. Vanadium is preferred. In particular, the activity of a catalyst using a vanadium compound as a solid catalyst component is much lower than that of a catalyst using a titanium compound, but according to the method of the present invention, the activity can be improved by as much as 1J.

The electron donor that can form an adduct with magnesium halide may be selected from among the electron donors listed above, but it must have a solubility that allows the solid material to be treated with a practical solution, and Ethers are preferred because the activity of the catalyst component is high. Specifically, aliphatic ethers such as diethyl ether, di-n-propyl ether, di-1SO-propyl ether, moro-butyl ether, di-1SO-amyl ether, and dioctyl ether, cyclic ethers such as dioxane, tetrahydrofuran, and furan, and anisole; Aromatic ethers such as diphenyl ether can be mentioned. In order to maintain good powder properties of the polymer, aliphatic ethers and cyclic ethers are preferred, and tetrahydrofuran is particularly preferred.

Examples of hydrocarbons include saturated aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatic hydrocarbons, but aromatic hydrocarbons are preferred from the viewpoint of showing a solubility that is sufficient to process the solid materials in a practical solution. It is preferable to include hydrogen, and specific examples include benzene, ]-toluene, xylene, tetralin, and styrene.

In addition, halogenated hydrocarbons are preferable because they dissolve the adducts well, but from the viewpoint of preventing the solid catalyst component from dissolving and reducing the activity, it is preferable to use halogen atoms like carbon tetrachloride. Fatty LX halogenated hydrocarbons such as butyl chloride, octyl chloride, etc. contained in the molecule are preferred.

Moreover, it is also preferable to measure the solubility using a mixed solvent of these aromatic hydrocarbons, halogenated hydrocarbons, and aliphatic hydrocarbons.

The processing conditions include titanium and/or vanadium (hereinafter T
i (sometimes expressed as 10V) has a concentration of 10 to 111
0ρ/fJ, preferably 10-4 to 10-1 mof)/
It is J. If it is too thin, the polymerization activity will be low, and if it is too thin, the powder properties will deteriorate. Ti+■ and solid matter (A>
The ratio is 10-6ioρ/g or more, preferably 10-5m
olt g or higher. If it is too small, the polymerization activity will be low. If it is too high, the unsupported Ti + 17 minutes will be wasted and it will be uneconomical, so 10 moρ/g is set as the upper limit for practical purposes. It is usually necessary to use a larger amount of electron donor than that observed in complexes that can be separated and identified, and specifically, the molar ratio of electron donor/(Ti + V) is between 2 and 1000, more preferably 5 to 200.

If this ratio is too small, the solubility of titanium or vanadium is low, so the amount of supported m is small, and the polymerization activity B is low (if it is too large, the powder becomes bamboo-like).
10-” to 5moJ/J, preferably 10-3
~3mol/fl. If it is too little or too much, the powder properties will deteriorate. The temperature is -50-4200°C, preferably -20 to -1-120°C.

If it's too low, dissolve titanium or vanadium lol? ,lf
If f1 is low, loading operation becomes uneconomical. When the temperature is too high, the polymerization activity decreases, probably because some of the catalyst decomposes.

The treatment time is usually 1 second to 2 hours, more preferably 1 minute to 2 hours. Supporting is usually carried out quickly, so it is sufficient to allow the time necessary for uniform stirring in the system.
There is no advantage to processing for longer than that. It is desirable to perform washing after the treatment using the same solvent used during the treatment or the above-mentioned solvents. In general, hydrocarbons are preferred in order to avoid dissolution and swelling of catalyst components.

This catalyst component can be used in combination with known organometallic compounds to polymerize olefins as described below. Deep metal 1 is AIRY (R is an alkyl group, 3-n Y is a halogen atom or an alkoxy group, n is 3
to 1.5) or alkylalumoxanes, especially trialkylaluminum or tetraalkylalumoxanes are preferred for high activation, specifically triethylaluminum, triisobutylaluminum, trihexyl Aluminum, trioctylaluminum, and tetraethyldialumoxane may be mentioned. These organic metals are usually used in an amount of 1 DImOjI to 1 m01 per 1tj of the above catalyst components.

Furthermore, a known electron donor can also be used as the third catalyst component.

The method for polymerizing olefins using these catalyst systems is not particularly limited, and any known ordinary method may be used, but the feature of this catalyst system in particular stands out is the copolymerization of ethylene and α-olefin. . That is, good powder properties and high polymerization activity per halide of titanium and/or vanadium are suitable for polymerizing soft copolymers at relatively low temperatures.

α-olefins copolymerized or copolymerized with ethylene include α-olefins having 20 or less carbon atoms and α-unsaturated diolefins; α-monoolefins are preferred, specifically propylene, butene-1, hexene-1,
List 4-methylpentene-1 and octene-1's.

Example 1 [Preparation of solid catalyst component] 30.309 (1,97 FL mol) of H-type TiC and 1.59 (21 mmol) of tetrahydrofuran were placed in 100 mmol of xylene and heated to 70°C to form a homogeneous solution. did. Into this solution, 5 g of a co-pulverized mixture of magnesium chloride and tetrahydrofuran with a fit ratio of 110.3 was added.
After 10 min bl J'r at <RTIgt;C,</RTI> the solids were filtered off and washed with 50 ml of xylene and then 100 ml of hexane. This solid was dried at 20° C. under reduced pressure to obtain a solid catalyst component. As a result of analysis, this solid catalyst component contained 4.5% TiC.
It included three officials.

[Polymerization] Add 1:1 of the above solid catalyst component to a 1.5-liter autoclave.
ly, propylene 360 ONd and hydrogen 170ONd
Add and stir. This contains 0.0% triethylaluminum.
A mixture of 349 and 0.11 J of tetrahydrofuran was injected under pressure with ethylene gas to initiate polymerization. Temperature 30℃
The pressure inside the system was maintained at 18 Ky/ciG by introducing ethylene gas. After 60 minutes, methanol was injected under pressure to terminate polymerization, and the gas was purged. Table 1 shows the composition and properties of the obtained polymer.

Comparative Example 1 230 g of MjIC, H-type Ti C132,0, and 50% of the apparent amount of stainless steel balls were placed in 11 containers and ground in a vibrating mill with a double swing width of 9 for 30 hours to obtain a light brown solid powder. Ta. 3.5 g of the above solid material and 2.7 g of tetrahydrofuran were placed in 100 d of xylene, and after stirring at 50°C for 10 minutes, the solid material was taken from door to door, washed in the same manner as in Example 1, and dried to obtain a solid catalyst component.

Comparative example 2 MgC cross 23.5 SF and H type TiC cross 30.30g 5
It was dissolved in tetrahydrofuran at 0°C. Tetrahydrofuran required approximately 200 d. In this, xylene 500
d was added and the resulting precipitate was separated, washed and dried in the same manner as in Example 1.

Example 2 AA type T! C10 (composition is TiC 吏3 ・1/3 AI
Ci3) 0.409 (2.0 mmol) in H type 1”1cj
The same procedure as in Example 1 was carried out, except that L3 was replaced with a co-pulverized mixture of magnesium chloride and tetrabutoxytitanium with an ff1ffl ratio of 110.3 as a carrier, and the treatment temperature was changed to room temperature.

Example 3 [Preparation of solid catalyst component] V C130.9 g (5,7 TrL-E) and tetrahydrofuran 203 were mixed with xylene, 100- and hexane 50-
It was dissolved in a mixed solvent of m at 50°C. Example 1
Add the same solid carrier as used in step 3 and incubate at 50°C for 30 minutes.
After stirring, the precipitate was separated, washed with 100 d of xylene, then 200 d of hexane, and dried under reduced pressure at 30°C. This solid contained 324% VCu.

[Polymerization] 40 μm of the above solid catalyst component was placed in a 1.5 μm autoclave.
Then, 360 g of propylene and 100 ONd of hydrogen were added and stirred. In this, 1°2-dichloroethane (1,
30g, then 0.85 tri-n-hexylaluminum
SF was pressurized with ethylene gas to initiate polymerization. The temperature was maintained at 20° C., and the pressure within the system was maintained at 16 Ny/cIAG by introducing ethylene gas. After 60 minutes, methanol was injected under pressure to terminate polymerization, and the gas was purged.

Comparative example 3 MQ C1225! F and VCJL310g, Lt, comparison N
Solid powder 49 obtained by crushing under the same conditions as in Example 2 and 2 (l) of tetrahydrofuran were added to a mixed solvent of 100 m of xylene and 50 m of hexane, and after stirring at 50°C for 10 minutes, the solid was separated. Washed and dried in the same manner.

(Margin below)

Claims (1)

[Scope of Claims] (A) A solid mainly consisting of magnesium halide, (B) I) an electron donor capable of forming an adduct with the magnesium halide, and II) a halide of titanium and/or vanadium. 1. A method for producing a catalyst component for olefin polymerization, which comprises treating with an adduct hydrocarbon or halogenated hydrocarbon solution.