JPH0429685B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a catalyst component for α-olefin polymerization, and more specifically, in producing a solid component of a catalyst for α-olefin polymerization consisting of a reaction product of a magnesium compound and a titanium compound, a titanium compound is recycled and recycled. It relates to a method for efficiently producing the catalyst component by using the present invention. It has been known to use a polymerization catalyst in which a solid catalyst component, which is a reaction product of a magnesium compound, a titanium compound, and an electron-donating compound, and an organoaluminum compound are combined in homopolymerization of α-olefin or copolymerization with a comonomer. ing. Furthermore, a method is known in which a titanium compound is added in two or more portions and reacted during the preparation of the solid catalyst component (Japanese Patent Laid-Open No. 57-63309). Although this preparation method can improve catalyst performance,
The problem was that the consumption of titanium compounds increased. Unreacted substances discharged during the preparation of catalyst components need to be introduced into waste treatment equipment and treated, so it is desirable to reduce such emissions as much as possible, and from the standpoint of resource conservation, emissions should also be minimized. Less is better. The object of the present invention is to reduce the consumption of catalyst preparation raw materials as much as possible, reduce waste treatment costs at the same time, and develop an efficient catalyst preparation method. The present invention, which was completed to achieve this object, is based on the general formula
^Mg ₍ ^{OR 1 )} _o It is a real number satisfying ≦n≦2. ] In producing a catalyst component for α-olefin polymerization by contacting a magnesium compound represented by This is a method for producing a catalyst component for α-olefin polymerization, characterized in that titanium tetrahalide in the filtrate obtained in the subsequent reactions is reused in the first reaction. The magnesium compound used in the present invention has the general formula
It is expressed as Mg(OR ¹ ) _o X ¹ _2-o . here
R ¹ represents an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms.
In addition, X ¹ represents a halogen atom such as chlorine or bromine,
n represents a real number satisfying ≦n≦2. Specific examples of these magnesium compounds include magnesium dialkoxides such as magnesium methoxide, magnesium diethoxide, magnesium dipropoxide, and magnesium dibutoxide, or magnesium monochloromonomethoxide, magnesium monochloromonoethoxide, and magnesium monochloromonopropoxide. Examples include magnesium monohalogenated monoalkoxides, and further magnesium dihalides such as magnesium dicyclohexoxide, magnesium diphenoxide, and magnesium dichloride and magnesium dibromide. Although these magnesium compounds may be used alone, they can also be used in an appropriate mixture. On the other hand, the electron-donating compound brought into contact with the magnesium compound is usually an organic compound containing oxygen, nitrogen, phosphorus, or sulfur. Specifically, amines, amides, ketones, nitriles,
Phosphines, phosphoramides, esters,
thioethers, thioesters, acid anhydrides,
Examples include acid halides, aldehydes, and organic acids. More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid; acid anhydrides such as succinic anhydride, benzoic anhydride, and p-toluic anhydride; acetone, methyl ethyl ketone, and methyl Ketones with 3 to 15 carbon atoms such as isobutyl ketone, acetophenone, benzophenone, and benzoquinone; aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde naphthaldehyde; methyl formate, methyl acetate, Ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl bivalate, dimethyl maleate, Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate,
Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate,
Esters with 2 to 18 carbon atoms such as ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate, ethyl naphthoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; acetyl Acid halides having 2 to 15 carbon atoms such as chloride, benzyl chloride, toluyl chloride, anisyl chloride; methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether,
Ethers with 2 to 20 carbon atoms such as tetrahydrofuran, anisole, diphenyl ether, and ethylene glycol butyl ether; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; Tributylamine, N,N'-dimethylpiperazine, and Examples include amines such as livenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; nitrites such as acetonitrile, benzonitrile, and tolnitrile; tetramethylurea, nitrobenzene, and lithium butyrate. Among these, preferred are esters, ethers, ketones,
These include acid anhydrides. In particular, alkyl esters of aromatic carboxylic acids, such as benzoic acid, p-
Alkyl esters of aromatic carboxylic acids having 1 to 4 carbon atoms such as methoxybenzoic acid, p-ethoxybenzoic acid and toluic acid are preferable, and aromatic ketones such as benzoquinone and aromatic carboxylic acid anhydrides such as benzoic anhydride are preferred. Also preferred are esters, ethers such as ethylene glycol butyl ether, and the like. The conditions under which the above-mentioned magnesium compound is brought into contact with the electron-donating compound are not particularly limited and may be appropriately determined depending on various circumstances. Usually, 0.01 electron donating compound is used per 1 mole of magnesium compound.
Add ~10 mol, preferably 0.05-5 mol, 0-10 mol, preferably 0.05-5 mol,
The contact reaction may be carried out at 200°C for 5 minutes to 10 hours, preferably at 30 to 150°C for 30 minutes to 3 hours. Note that an inert hydrocarbon such as pentane, hexane, heptane, octane, etc. can also be added to this reaction system as a solvent. The catalyst component of the present invention is prepared by carrying out the above catalytic reaction and then reacting the resulting product with titanium tetrahalide two or more times. The titanium tetrahalides include TiCl ₄ , TiBr ₄ , TiI ₄
Among them, it is particularly preferable to use titanium tetrachloride (TiCl ₄ ). The conditions for reacting the product obtained by the above-mentioned contact reaction with the titanium tetrahalide are not particularly limited, but usually magnesium 1 in the product is
1 to 50 moles of titanium tetrahalide per mole,
Preferably added in a range of 2 to 20 mol and at a temperature of 0 to 200°C
for 5 minutes to 10 hours, preferably at 30 to 150℃ for 30 minutes.
Allow to react for minutes to 5 hours. This reaction can also be carried out using an inert solvent such as pentane, hexane, heptane, etc., if necessary. In the method of the present invention, the above-mentioned reaction using titanium tetrahalide is repeated two or more times, and at this time, the titanium tetrahalide used in the second and subsequent reactions is reused in the first reaction. . The flow of the treatment steps in the method of the present invention is shown in FIG. 1, taking as an example the case of two-time treatment. The method of the present invention will be explained based on FIG. 1. First, the above-mentioned magnesium compound and an electron-donating compound are reacted.
Next, the obtained product is reacted with titanium tetrahalide (first reaction), and the generated reaction product is reacted again with titanium tetrahalide (second reaction) to remove the catalyst component. obtain. Here, the titanium tetrahalide used in the first reaction may be partially or entirely equal to the titanium tetrahalide used in the second reaction. That is, in the second reaction, unreacted titanium tetrahalide is recovered together with the liquid and used in the first reaction.
Of the titanium tetrahalide subjected to the first reaction, components that are not incorporated into the reaction product are led to a waste treatment process as spent titanium compounds. Therefore, in the second and subsequent reactions, new titanium tetrahalide is used, but in the first reaction, it is sufficient to use the titanium tetrahalide that has already been used in the second and subsequent reactions, and as a result, titanium The amount of compound used and the amount of waste can be reduced, and the activity of the resulting catalyst component is almost comparable to that when fresh titanium tetrahalide is used in the first reaction. In addition, in the method of the present invention, only the titanium compound used in the second and subsequent reactions may be used as the titanium tetrahalide used in the first reaction, but if necessary, new titanium compounds may be used together with this used titanium compound. Other titanium compounds can also be used. As mentioned above, in the method of the present invention, the titanium tetrahalide used in the second and subsequent reactions is used in the first reaction, but vice versa, that is, the titanium tetrahalide used in the first reaction is used in the first reaction. The second titanium chloride
If it is used in subsequent reactions, the activity of the resulting catalyst component will not be sufficient, which is undesirable. According to the method of the present invention, the consumption of titanium compounds is small, the processing equipment and costs for used titanium compounds can be reduced, and a highly active catalyst component for α-olefin polymerization can be obtained. The catalyst component produced by the method of the present invention constitutes an α-olefin polymerization catalyst together with an organometallic compound, and contains ethylene, propylene, and butene.
1, hexene-1, octene-1,4-methyl-
It can be effectively used in the polymerization and copolymerization of α-olefins such as pentene-1. Examples of metals contained in the organometallic compound include metals of Groups 1 to 3 of the periodic table, such as lithium, sodium, potassium, zinc, cadmium, and aluminum, with aluminum being particularly preferred. Specific examples of these compounds include alkyllithiums such as methyllithium, ethyllithium, propyllithium, and butyllithium, and dialkylzincs such as dimethylzinc, diethylzinc, dipropylzinc, and dibutylzinc. is the general formula AlR ³
The expression kX ³ _3-k is widely used. R ³ is an alkyl group, cycloalkyl group, or aryl group having 1 to 10 carbon atoms, k is a real number between 1 to 3, and X ₃ represents a halogen atom such as chlorine or bromine. Specifically, trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, and trioctylaluminum, and dialkyl compounds such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, and dioctylaluminum monochloride. Aluminum monohalides are preferred, and mixtures thereof are also preferred. When α-olefin is polymerized using the catalyst component obtained by the method of the present invention and the above-mentioned organometallic compound, the catalytic activity is extremely high.
Furthermore, the resulting polymer has great stereoregularity, making it extremely valuable as a product. Next, the present invention will be explained in more detail using Examples and Comparative Examples. Comparative example 1 Magnesium diethoxide 10g (88 mmol)
Add to 150ml of n-heptane to make a slurry,
2.64 g (17.6 mmol) of ethyl benzoate under stirring
added. Next, after raising the temperature to about 40°C, 28.8 ml (264 mmol) of titanium tetrachloride was added dropwise over several minutes.
The reaction was carried out under reflux for 2 hours. Then increase the temperature to 80℃
The temperature was raised to
Washed twice. Next, 150 ml of fresh n-heptane was added to the reaction product to form a slurry, and while stirring, 28.8 ml (264 mmol) of titanium tetrachloride was added dropwise over several minutes, and the reaction was carried out under reflux for 1 hour. Ta. Finally, the supernatant liquid was extracted at 80°C and thoroughly washed with n-heptane to obtain a catalyst component. Subsequently, 400 ml of dehydrated n-heptane, 2 mmol of triethylaluminum (TEA), 0.5 mmol of methyl p-toluate, and 0.02 mmol of the above catalyst component as titanium were added to a 1 liter stainless steel autoclave, and the temperature was raised to 70°C. Next, 0.2Kg/cm ² of hydrogen was added and propylene was continuously introduced to bring the total pressure to 8Kg/cm ^{2 .}
-G and polymerization was carried out for 2 hours. The results of the polymerization reaction are shown in Table 1. Comparative Example 2 In Comparative Example 1, 48 ml of titanium tetrachloride used in preparing the catalyst component was used for both the first and second times.
The preparation of the catalyst component and the polymerization of propylene were carried out under the same conditions as in Comparative Example 1, except that the amount was changed to (440 mmol). The results are shown in Table 1. Comparative Example 3 In Comparative Example 1, 96 ml of titanium tetrachloride used in preparing the catalyst component was used for both the first and second times.
The preparation of the catalyst component and the polymerization of propylene were carried out under the same conditions as in Comparative Example 1, except that the amount was changed to (880 mmol). The results are shown in Table 1. Comparative Example 4 In a stainless steel container with an internal volume of 400 ml and a diameter of 80 mm, containing 50 stainless steel balls with a diameter of 15 mm,
20 g of anhydrous magnesium chloride in an argon atmosphere
(210 mmol) and ethyl benzoate 6.3 g (42
Millimoles) were charged and pulverized at 200 rpm for 20 hours. Next, 11 g of the obtained co-pulverized product (MgCl ₂ 88
millimole equivalent) was made into a slurry with 150 ml of n-heptane. For the subsequent operations, use 48 ml (440 mmol) of titanium tetrachloride for both the first and second times.
The preparation of catalyst components and the polymerization of propylene were carried out under the same conditions as in Comparative Example 1, except for the following.
The results are shown in Table 1. Example 1 Except that used titanium tetrachloride obtained by over-separating the slurry after the second reaction of titanium tetrachloride was used as the first titanium tetrachloride in the preparation of the catalyst component of Comparative Example 1. The catalyst components were prepared and propylene was polymerized under the same conditions as in Comparative Example 1. The results are shown in Table 1. Example 2 Except that used titanium tetrachloride obtained by over-separating the slurry after the second reaction of titanium tetrachloride was used as the first titanium tetrachloride in the preparation of the catalyst component of Comparative Example 2. The catalyst components were prepared and propylene was polymerized under the same conditions as in Comparative Example 2. The results are shown in Table 1. Example 3 Except that used titanium tetrachloride obtained by over-separating the slurry after the second reaction of titanium tetrachloride was used as the first titanium tetrachloride in the preparation of the catalyst component of Comparative Example 3. The catalyst components were prepared and propylene was polymerized under the same conditions as in Comparative Example 3. The results are shown in Table 1. Example 4 Except that used titanium tetrachloride obtained by over-separating the slurry after the second titanium tetrachloride reaction was used as the first titanium tetrachloride in the preparation of the catalyst component of Comparative Example 4. The catalyst components were prepared and propylene was polymerized under the same conditions as in Comparative Example 4. The results are shown in Table 1.

【represent.
Boiling n-heptane insoluble polymer weight
*2 IY＝

Claims (1)

[Claims] 1 General formula Mg (OR ¹ ) _o X ¹ _2-o [In the formula, R ¹ is carbon number 1
~20 alkyl, cycloalkyl, aryl, or aralkyl groups, X ¹ represents a halogen atom, and n is a real number satisfying 0≦n≦2. ] When producing a catalyst component for α-olefin polymerization by contacting a magnesium compound represented by an electron-donating compound with an electron-donating compound and then reacting it with titanium tetrahalide two or more times, the second reaction of the titanium tetrahalide is carried out. A method for producing a catalyst component for α-olefin polymerization, characterized in that titanium tetrahalide in the filtrate obtained in the subsequent reactions is reused in the first reaction. 2. The method according to claim 1, wherein the electron donating compound is an aromatic carboxylic acid ester.