JPS5911306A - Production of catalytic component for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain a high-polymerization activity catalyst component for the stereospecific polymerization of a 3C or higher alpha-olefin, by contacting and reacting a magnesium alcoholate with a titanium tetrachloride in the presence of an electron-donating compound. CONSTITUTION:A magnesium compound of the formula: Mg(OR')2 (wherein R' is a hydrocarbon group), e.g., magnesium diethylate or magnesium di-n-propylate, is contacted and reacted with a titanium halide (e.g., titanium tetrachloride or titanium tetrabromide) in the presence of an electron-donating compound (e.g., triphenylphosphine oxide or triethylamine) and preferably a halosilane (e.g., tetrachlorosilane). Thus, a catalyst component for the stereospecific polymerization of a 3C or higher olefin or a mixture of this olefin with other olefins is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a catalyst component for olefin polymerization, and more specifically, a method for stereospecific polymerization of an α-olefin having 3 or more carbon atoms or a mixture of the olefin and an olefin. This relates to a method for producing catalyst components.

Conventionally, catalysts for the polymerization of α-olefins include solids obtained by reducing titanium tetrachloride with hydrogen gas at high temperatures, or by heating the reduction product of titanium tetrachloride with metal aluminum to 710°C or higher. Titanium trichloride and titanium trichloride/aluminum trichloride solid eutectic are known.

However, these catalysts have low polymerization activity as α-olefin polymerization catalysts, and the stereospecificity of the resulting polymers is insufficient, meaning that only polymers containing a large amount of amorphous polymer can be obtained. There is a problem with the commission.

Other methods for obtaining α-olefin/polymerization catalysts include treating solid β-type titanium trichloride with a complexing agent and converting it into purple titanium trichloride by heating in titanium tetrachloride; Proposed methods include crushing titanium trichloride obtained by various known methods such as pulverizing titanium trichloride, and reducing titanium tetrachloride with an organoaluminum compound in the presence of an electron-donating compound such as an ether to obtain solid titanium trichloride. has been done. However, an excellent 93-braided titanium catalyst that has high polymerization activity and produces a polymer with high stereospecificity for the polymerization of α-olefins having 3 or more carbon atoms has not been developed.

A method in which a product obtained by contacting a dihalide, a halogen-containing titanium compound, and an electron-donating compound is used for stereospecific polymerization of α-olefins (e.g., % Kaishog 2
- Toni No. 222), magnesium halide,
silicon compounds, organic acid esters and titanium tetrano)
A method has been proposed in which a product obtained by contacting a compound with a compound is used as a catalyst (see, for example, Japanese Patent Application Laid-open No. 1983/0fjjrj).

However, these 'I'EI No. 1 catalysts use halogenated magnesium or manganese as a carrier, which is the main component, so a large amount of halogen is inevitably contained in the polymer. This causes undesirable phenomena such as destabilization of the polymer due to halogen contamination and corrosion of equipment. Therefore, when a halogen-containing carrier is frozen, a step of removing or stabilizing the halogen from the 1-mer is required after the 1-mer. The inventors of the present invention have conducted extensive research to solve the above-mentioned problems regarding supported catalysts for polymerizing α-olefins having 3 or more carbon atoms, and have completed the present invention.

That is, the present invention provides a catalyst component for the production of polyolefins that reduces the undesirable influence of the produced polymer by M harmful substances such as halogen, increases the polymerization activity, and improves the stereoregularity of the polymer. - The purpose is to provide a method for producing a magnesium compound of the general formula Mg(OR')t (wherein R' represents a hydrocarbon group) and titanium tetrahalide according to the invention. Achieved by a method for producing a catalyst component for stereospecific polymerization of an α-olefin having 3 or more carbon atoms or a mixture of this olefin and other olefins, which is characterized by carrying out a catalytic reaction in the presence of an electron-donating compound. Ru.

The specific components used in preparing the catalyst system used in the method of the present invention are as follows.

First, the magnesium compound [component (a)] represented by the general formula Mg(OR'')s (in the formula, R1 represents a hydrocarbon group) used in the present invention, specifically, R1 is aralyl, Examples include aryl, aralkyl, and alkyl groups, and more specific compounds include magnesium dimethylate Mg (OM
θ)3, magnesium diethylate Mg(oEt)2,
Magnesium di-n-propyl 4-) Mg(O2nPr)1, Mg(0-@
)t, Mg(Os)Me). Among them, magnesium diethylate and magnesium di-n-propylade are preferred. It is necessary to sufficiently remove moisture, air, etc. from these magnesium compounds before use.

Further, titanium tetrahalide (component (b)) used in the present invention includes titanium tetrachloride, titanium tetrabromide/titanium tetraiodide, and titanium tetrachloride is preferred.

Examples of the electron donating compound [component (0)] include phosphorus-containing compounds, oxygen-containing compounds, sulfur-containing compounds, and nitrogen-containing compounds.

Among these, the phosphorus-containing compound has the following general formula % formula %) (In the formula, R8 represents hydrogen, a hydrocarbon group, an amine group, an alkylamino group, and represents 5YFi, Wl, or sulfur, and m is the number of θ to 3. Specific examples thereof include triphenylphosphine oxyto, trimethylphosphine, triphenyl phosphate, triphenyl phosphite, hexamethyl phosphoric acid triamide, triphenyl thiophosphite, and the like.

As the Mamiai oxygen compound, the following general formula (in the formula R', R
' represents a hydrocarbon group, which may be bonded to each other to form a cyclic group. Further, examples include compounds represented by the following (k represents a number from 7 to 3). Specifically, diethyl ether,
Ethers such as dipropyl ether, diethylene glycol, phoriflobylene glycol, ethylene oxide, propylene oxide, furan; ketones such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, phenylpropyl ketone; ethyl acetate, methyl propionate, Ethyl acrylate, ethyl oleate, ethyl stearate, ethyl phenylacetate,
Esters of carboxylic acids such as methyl benzoate, ethyl benzoate, methyl p-tolylate, ethyl p-ethylbenzoate, lP-methoxybenzo@e-butyl, ethyl cinnamate or cyclic acids such as γ-butyrolactone. Examples include esters.

Examples of nitrogen-containing compounds include amines such as triethylamine, ethylenediamine, piperazine, pyridine, and piperidine or their derivatives, urethanes,
Examples include fatty acid amides, lactams, imides, carbamate esters, glycine esters, and alanine esters.

Examples of the di-sulfur-containing compound include thioethers such as diptyl thioether and diptyl thioether, and metal salts of sulfonic acids such as sodium benzenesulfonate and sodium toluenesulfonate.

Among these, preferred are trialkyl, trialkoxy, triaryl or triarylotoxyphosphine, carboxylic ester diN-substituted phosphoric acid amide; N-substituted diamine; trialkylamine; triarylphosphine oxyto.

In the method of the present invention, when the above-mentioned (a) component and (1)) component are brought into contact, the above-mentioned Cc,) component is present. A halogenated silane (component (d)) represented by a halogen, t is a hydrocarbon group, and t is the number of /--g (component (d)) may coexist, and this coexistence brings about more favorable results. Specific examples of this halogenated silane include:
Tetrachlorosilane, tetrabromosilane, tetraiodosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane.

dipropyldichlorosilane, trimethylchlorosilane,
triethylchlorosilane, tripropylchlorosilane,
Other compounds similar to these may be mentioned, and among them, tetrachlorosilane, methyl 8-trichlorosilane, and diethyldichlorosilane are preferred.

In the present invention, as described above, in the presence of component (c),
When components (a) and (b) are brought into contact with each other, it is preferable that component (d) is further present when the contact force is K. Usually it is as follows.

Mg(OR')! Electron-donating compound /θ~θ, θ/, preferably /~
θ, 0/titanium tetrahalide jθ~0.0/, preferably 10-0. /halogenated silane /~θ
, preferably 7 to θ, θ/ and usually the amount of each of the above components used is adjusted so that the amount of titanium in the product is 0.7 to 30% by weight.

Although there are various methods of contacting these components and the order of addition, examples thereof are as follows.

(1) ``g(0R1)*s The 7rane halide and the electron-donating compound are mechanically pulverized or brought into contact with each other by suspension in an inert hydrocarbon solvent, and then reacted with titanium tetrahalide.

(2) After mechanically grinding Mg(OR')l and the halogenated silane or contacting them in suspension in an inert hydrocarbon solvent, an electron-donating compound is added, and mechanically grinding or in a solvent, Suspension contacting is carried out followed by reaction with titanium tetrahalide.

t3) Mg(OR')! After mechanically grinding, halogenated silane and an electron-donating compound are added, mechanical grinding or suspension contact is carried out in a solvent, and then reaction with titanium halide is performed.

f4) Mixing Mg (○Ut) and halogenated silane mechanically crushed or suspended in a solvent and a reaction (addition) product of an electron donating compound and titanium tetrahalide. and then mechanically crushed.

(5) Mg('')t, halogenated silane, and electron-donating compound are mechanically crushed or suspended in a solvent, titanium tetrahalide is added, and further mechanically crushed. .

Among these methods (1) to (5), methods (1) to (3) are particularly preferred.

Mechanical pulverization in each of the above methods is performed using a ball mill.

Any conventionally commonly used method such as an impact mill or a vibration mill may be used. The pulverization temperature may normally be around room temperature, and heating and cooling are not particularly required.

The pulverization treatment time depends on the type of pulverizer used, but is usually from several hours to 200 hours.

In the above method, when each component is mechanically pulverized and then reacted with titanium tetrahalide, it is not necessary to use an inert hydrocarbon solvent, but it may be used. The reaction temperature at this time is usually θ~/, tO'Q, preferably 10~/00'Q.

When titanium tetrahalide is added, heat is generated, so it is preferable to cool the mixture appropriately. A reaction time of about θ,j−1 hour is sufficient.

In the present invention, the reaction product obtained above is then washed with an inert hydrocarbon solvent to remove components soluble in the solvent.

What is thus obtained is a catalyst component according to the method of the present invention, which is hereinafter referred to as catalyst component A.

In order to obtain a polymer with high stereospecificity by polymerizing an α-11-olefin having 3 or more carbon atoms or a mixture of this olefin and other olefins using this catalyst component A, the above-mentioned catalyst component island becomes a cocatalyst. Stereospecific polymerization is carried out using a catalyst system in which an organoaluminum compound (hereinafter referred to as component B) is added and, if necessary, an electron donating compound (hereinafter referred to as component C) is added.

Examples of the organoaluminum compound of component B include compounds represented by the general formula AtX3□.

In the above formula, R1 is a hydrocarbon group having 7 to 20 carbon atoms, especially an aliphatic hydrocarbon group, X is a halogen, and n is λ~!
Indicates the number of Specific examples of the organoaluminum compound include triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, monovinyldiethylaluminum, diethylaluminium monochloride, etc., but trialkylaluminium is preferred. is used.

12- As the electron-donating compound of component C, those listed above as the electron-donating compounds used in the production of catalyst component A are used.

There is no particular restriction on the order in which the above components A%B and C are added.

The proportions of components A, B, and O are titanium in catalyst component A, aluminum compound in component B, and α'α in component C.
Electron-donating compound mono: 30~/: within! The olefin to be polymerized is selected to be propylene,
Examples include α-olefins having 3 or more carbon atoms such as buteno, and propylene is particularly preferred. The polymerization can be applied not only to homopolymerization but also to random or block copolymerization.

The polymerization reaction is carried out by slurry polymerization using an inert hydrocarbon such as hexane, heptane, hexane, benzene, toluene, pentane, butane, or a mixture thereof, or a liquefied α-olefin to be polymerized. Although preferred, it is also possible to carry out the polymerization in the gas phase.

The temperature is 10-700℃, preferably θ~? θ゛0, and the pressure is not particularly limited, but is usually selected from within the range of atmospheric pressure to /θθ atmospheric pressure.

Hydrogen can also be present as a molecular weight regulator in the 1st reaction system, which results in a melt flow index (MF
engineering, measured according to ASTM-D I237) / 0-O
, / can be easily produced. It is also possible to apply other means commonly used for polymerization and copolymerization of each α-olefin.

The polyolefin obtained by the above polymerization does not use a metal halide such as magnesium halide, which is found in the catalyst system of the conventionally known highly stereospecific polymerization method using a supported catalyst, and therefore there are disadvantages caused by this halide. This provides usefulness in that the stereospecificity of the resulting polymer is reduced and the stereospecificity of the obtained polymer is high.

Next, examples of the present invention, usage examples in which polymerization was carried out using the obtained catalyst components, and comparative examples will be described, but the present invention is not limited by these examples as long as it does not depart from the gist thereof.

In addition, in the following examples, the polymerization activity (denoted as K) is the amount of polymer produced (g) per α-olefin pressure/su/cnt per 7 hours, per titanium/g, and the catalyst efficiency (
am) is the amount of polymer produced per gram of titanium/g of the catalyst component (9). Isotactic index (denoted as AE) is the residue (% by weight) after 6 hours of extraction with boiling n-hebutane in a modified Soxhlet extractor. Since amorphous polymer is soluble in boiling n-hebutane, AE indicates the yield of crystalline polymer. Bulk density (expressed as ρB).

The position (g/cc) was measured according to J-Engineering S-672/. Melt flow index (denoted as MP) was measured according to ASTM-DI23F.

Examples/Preparation of Catalyst Component A In an argon dry box, EIUS! Pot made of # (Contents: Ond, inner diameter 10g, diameter/6! IIa SUS 3/l% balls 910 pieces 1
5- containing 7oy of magnesium diethylate,
27 mmol of ethyl benzoate and 73 mmol of tetrachlorosilane were charged, and pulverization was carried out in a vibrating mill at a low temperature for 7 hours. The white powder obtained is then passed through an argon dry box, then the solid components are separated and washed with n-hebutane. Light brown titanium content 742
% by weight of catalyst component A'i was obtained.

Usage example: A stirred autoclave with a capacity of 2 tons is used, and after replacing the inside with sufficiently dry argon, the temperature is %7jθ-0n.
-hexane, O1/mmol ethyl benzoate, /
, θ mmol of triethylaluminum and catalyst component A obtained by the above treatment/g 6iy (titanium is 24.
Contains 4 pieces).

Next, 9/crll of hydrogen gas was charged at θ, / and heated to 70°C.
The temperature was raised at 50° C., and propylene was charged to initiate condensation polymerization.

pyrene pressure f: maintained at /2 J/ci/l and 1 at 7θ°0
Continue step 16- and 3. After j hours, the excess propylene was quickly discharged and cooled, and the contents were taken out and dried to obtain 3Fg of white powdered polypropylene.

This is the total amount of product, including amorphous materials.

The physical properties and 1st grade results of this product are as follows.

All units are as explained above.

OE=//♂90 K -ko♂3 MF Knead, 3 ■Knee 7g,! ρB−θ, 2? Amount of titanium remaining in polypropylene = ♂＠ppm (
Weight)〃Chlor amount = 330 ppm (weight) Comparative example/Experimental example when magnesium chloride gold is used as the magnesium compound (1) Preparation of catalyst components 6 ml of magnesium chloride λθJ1 ethyl benzoate and tetrachlorosilane, ? The tnt was vibrated milled for 79 hours at room temperature. Then, take out the contents and Ti06.
/ j Suspend in Oml,! All treatments for λ time were performed at O°0. Next, washing with n-hebutane was performed to reduce the titanium content to 7% by weight and the chlorine content to M. A catalyst component of 313M% was obtained.

(2) Polymerization Using the above example, the catalyst component obtained in (1) of the above comparative example was used in place of catalyst component A, and the waiting time was 2 hours. Polymerization was carried out in the same manner as above to obtain polypropylene in the form of chestnut powder with c'ri,;voθ.As a result, the amount of titanium remaining in the polypropylene was 7 J' ppm (yli amount), and the amount of titanium remaining in the polypropylene was 7 J' ppm (yli amount). θOppm (weight).

It can be seen that the amount of chlorine remaining in lipropylene is extremely small.

Example Preparation of co-catalyst component A In Example 1, magnesium diethylate was replaced with 10/j of magnesium di-n-propylade, and the other operations were the same, and the light brown titanium content/7.3N amount % was prepared. Catalyst component A was obtained.

Application Example 2 Polymerization was carried out in the same manner as in Application Example 1 using the catalyst component At- obtained in Example λ above.

The results are as follows.

C]l! i = /7 and Zθ K = 2j MF Aero, +2 AE, = 76, / ρB = θ, 26 ・Example 3 and
), triphenylphosphine oxide (@), PO (TPPO) (Example 3) or hexamethylene (Example G) is substituted in place 9 of ethylbenzoate. Catalyst component A was prepared in the same manner as above except that it was used, and polymerization was carried out in the same manner as in Example 1 using each catalyst component. the result? 1st below
Shown in the table.

Examples j below in Table 1, ? is still necessary for the preparation of catalyst component A. In these examples, the same preparation equipment as in Example/1 was used, and the operations were conducted in accordance with the same.

Example j and usage example! This example shows the case where no silane compound was used.

70 g of magnesium diethylate and 27 mmol of ethyl benzoate were placed in a pot containing stainless steel balls, ground in a vibratory mill for 75 hours at room temperature, taken out into a four-eye flask, and mixed with 3θ titanium tetrachloride. Preparation? After stirring for 2 hours at θ°O, the solid component was separated and washed with n-hebutane. Using the thus obtained catalyst component A, polymerization was carried out in the same manner as in Use Example. The results are shown in Table 2.

In Example B and Usage Example, 10 fl of magnesium diethylate and 73 mmol of tetrachlorosilane were placed in a pot and kept at room temperature! Grind on a timed mill, then add 2θ mmol of ethyl benzoate and grind on a vibratory mill for an additional 70 hours at room temperature, remove the product to a fourth flask, and remove the product into a fourth flask. Add titanium tetrachloride of O-, and θ°
0 for 2 hours. The solid component was separated from the product and washed with n-hebutane.

Using the scented catalyst component, kf, the following usage example/
Polymerization was carried out according to . The results are shown in Table 4.

Examples and Usage Example 2 Magnesium diethylate of IOIl was dissolved at room temperature for 5
The product was ground in a vibrating mill for an hour, then 3 mmol of tetrachlorosilane and 3 mmol of ethyl benzoate were added, and the product was further ground in a vibrating mill at room temperature for 70 hours, and the product was taken out into a fourth flask. 3θd titanium tetrachloride was added and treated at /θ°C for 2 hours. The solid component was separated from the product and washed with n-hebutane. Using the catalyst component A thus obtained, a reaction was carried out in the same manner as in Example 1, and the results shown in Table 4 were obtained.

Example! and usage examples tiog magnesium diethylate and/! Millimole of tetrachloride t7 was ground in a vibratory mill for 5 hours at room temperature, then 2 (complex consisting of 17 mmol of titanium tetrachloride and 20 mmol of ethyl benzoate) was added and ground in a vibratory mill for another 20 hours at room temperature. From this, the solid component was separated and n
- Washed with hebutane. Using the thus obtained catalyst component A, polymerization was carried out in the same manner as in Use Example. The results are shown in Table 4.

EXAMPLES AND USE EXAMPLES / θI of magnesium diethylate, 7549 moles of tetrachlorosilane and λθ mmoles of ethyl benzoate - ground in a vibratory mill for 5 hours at room temperature;
To this was added 2θ mmol of titanium tetrachloride, and the mixture was further ground for 20 hours at room temperature in a vibrating mill, and the solid component was separated from the product and washed with n-hebutane. Polymerization was carried out in the same manner as in Example 1 using catalyst component A obtained by smelting. The results are shown in Table 2 below.

23 - Table λ Example 10 and/or Usage Examples 10 and 7) Example/
The catalyst was prepared in the same manner except that p-)methyl lylate (PMBM) (Example 10) or ethyl p-ethylbenzoate (InBE) (Example //) was used instead of ethylbenzoate. A component was prepared and polymerization was carried out using it in the same manner as in the usage example. The results are shown in Table 3.24-Table 3 Applicant Mitsubishi Chemical Industries, Ltd.

Claims (2)

[Claims] (1) A magnesium compound represented by the general formula Mg('')t (in the formula, R' represents a hydrocarbon group) and titanium tetrahalide are catalytically reacted in the presence of an electron-donating compound. A method for producing a catalyst component for stereospecific polymerization of an α-olefin having 3 or more carbon atoms or a mixture of this olefin and other olefins. (2) When causing a contact reaction between a magnesium compound and titanium tetrahalide in the presence of an electron-donating compound,
A method for producing a catalyst component for stereospecific polymerization of an α-olefin having 3 or more carbon atoms or a mixture of this olefin and other olefins according to claim 7, in which a halogenated silane is present.