JPS6346764B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a catalyst component for olefin polymerization, and more particularly, to 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. It is something. Conventionally, as a catalyst for polymerization of α-olefin,
For example, titanium tetrachloride is reduced at high temperature with hydrogen gas, titanium tetrachloride is reduced at high temperature with metal aluminum, titanium tetrachloride is reduced with an organoaluminum compound, or the reduction product is further heated at 150°C or higher. Solid titanium trichloride and titanium trichloride/aluminum trichloride solid eutectic obtained by heating are known. However, these catalysts have low polymerization activity as α-olefin polymerization catalysts, and the stereospecificity of the resulting polymers is insufficient, and only polymers containing a large amount of amorphous polymer can be obtained. There is a drawback. Other methods for obtaining a catalyst for α-olefin polymerization include a method in which solid β-type titanium trichloride is treated with a complexing agent and converted into purple titanium trichloride by heating in titanium tetrachloride; A method of further treating various titanium trichlorides obtained by known methods, a method of grinding with a ball mill in the presence or absence of various complexing agents, a method of grinding with a ball mill, an electron-donating method such as ethers, etc. A method for obtaining solid titanium trichloride by reducing titanium tetrachloride with an organoaluminum compound in the presence of a compound has been proposed.
However, an excellent titanium trichloride catalyst that has high polymerization activity and produces a polymer with high stereospecificity for polymerizing α-olefins having 3 or more carbon atoms has not been developed. In addition, as a recently relatively improved method for supported catalysts, a product obtained by contacting a magnesium or manganese dihalide, a halogen-containing titanium compound, and an electron donating compound is used.
- A method used for stereospecific polymerization of olefins (for example, see JP-A-49-86482), a method using a product obtained by contacting magnesium halide, a silicon compound, an organic acid ester, and titanium tetrahalide as a catalyst. (For example, Japanese Patent Application Publication No. 1973-
(See Publication No. 108385) have been proposed. However, since these supported catalysts use magnesium or manganese halides as their main component carriers, they inevitably contain a large amount of halogen in the polymer. Unfavorable phenomena such as instability due to contamination and corrosion of equipment occur. Therefore, when a halogen-containing carrier is used, a step of removing or stabilizing the halogen from the polymer is required after polymerization. The present inventors 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 method for producing a catalyst component for polyolefin production that reduces the undesirable effects of harmful substances such as halogens on the produced polymer, increases polymerization activity, and improves the stereoregularity of the polymer. The purpose of this invention is to combine a magnesium compound represented by the general formula Mg(OR ¹ ) ₂ (wherein R ¹ represents a hydrocarbon group) and titanium tetrahalide into an electron-donating compound according to the present invention. A method for producing a solid component that can be used as 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, characterized by carrying out a catalytic reaction in the presence of It is achieved by doing so. The specific components used in preparing the catalyst system used in the method of the present invention are as follows. First, the general formula Mg(OR ¹ ) ₂ used in the present invention
Specifically, the magnesium compound [component (a)] represented by (in the formula, R ¹ represents a hydrocarbon group) is
Examples include those in which R ¹ is an aralyl, aryl, aralkyl, or alkyl group, and more specific examples include magnesium dimethylate.
Mg (OMe) ₂ , magnesium diethylate Mg
(OEt) ₂ , magnesium di-n-propylate Mg
(O−nPr) ₂ ,

【formula】

Examples include compounds such as [Formula]. Among them, magnesium diethylate and magnesium di-n-propylate are preferred. It is necessary to sufficiently remove moisture, air, etc. from these magnesium compounds before use. The titanium tetrahalide [component (b)] used in the present invention includes titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, with titanium tetrachloride being preferred. Examples of the electron-donating compound [component (c)] include phosphorus-containing compounds, oxygen-containing compounds, sulfur-containing compounds, and nitrogen-containing compounds. Among these, phosphorus-containing compounds have the following general formula: P(R ³ ) _n (YR ³ ) _3-n , O=P(R ³ ) _n (YR ³ ) _3-n (where R ³ is hydrogen, hydrocarbon group, amino group, alkylamino group, Y represents oxygen or sulfur, m represents a number from 0 to 3), specifically triphenylphosphine oxide, trimethylphosphine , triphenyl phosphate, triphenyl phosphite, hexamethyl phosphoric acid triamide, triphenyl thiophosphite, and the like. In addition, as an oxygen-containing compound, the following general formula

【formula】

[Formula] R ⁴ (COOR ⁵ ) _k (In the formula, R ⁴ and R ⁵ represent a hydrocarbon group, and may be bonded to each other to form a cyclic group. Also, k represents a number from 1 to 3. Examples include compounds represented by: Specifically, ethers such as diethyl ether, dipropyl ether, diethylene glycol, polyprobylene glycol, ethylene oxide, propylene oxide, and furan; acetone;
Ketones such as diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, phenylpropyl ketone; ethyl acetate, methyl propionate,
Ethyl acrylate, ethyl oleate, ethyl stearate, ethyl phenyl acetate, methyl benzoate, ethyl benzoate, methyl p-tolylate, p-
Examples include esters of carboxylic acids such as ethyl ethylbenzoate, butyl p-methoxybenzoate, and ethyl cinnamate, and cyclic esters such as γ-butyrolactone. In addition, nitrogen-containing compounds include triethylamine, ethylenediamine, piperazine, pyridine,
Amines such as piperidine or their derivatives; tertiary amines, pyridines, nitroso compounds such as N-oxides of quinolines; urea or its derivatives, urethanes, fatty acid amides, lactams, imides, carbamate esters , glycine ester, alanine ester, and the like. Examples of the sulfur-containing compound include thioethers such as diethyl thioether and dibutyl thioether, and metal salts of sulfonic acids such as sodium benzenesulfonate and sodium toluenesulfonate. And among them, trialkyl, trialkoxy, triaryl or triaryloxyphosphine, carboxylic acid ester; N-substituted phosphoric acid amide; N-substituted diamine; trialkylamine;
Triarylphosphine oxide is preferred. In the method of the present invention, the component (c) is present when the components (a) and ⁽ b) are brought into contact with _each other. ⁶ is a hydrocarbon group, l is a number from 1 to 4)
A halogenated silane represented by [component (d)] may also be present, and this coexistence brings about more favorable results. Specific examples of the halogenated silane include tetrachlorosilane, tetrabromosilane, tetraiodosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, Examples include trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane, and other similar compounds thereof, and among these, tetrachlorosilane, methyltrichlorosilane, and dimethyldichlorosilane are preferred. In the present invention, as described above, components (a) and (b) are brought into contact in the presence of component (c), and during this contact,
Furthermore, it is preferable to have component (d) present, and the ratio of the amounts used of each component in this case, expressed in molar ratio, is usually as follows. Mg (OR ¹ ) _2- electron donating compound 10~0.01, preferably 1~
0.01 Tetrahalogenated silane 50~0.01, preferably 10~
0.1 Halogenated silane 1-0, preferably 1-0
0.01 and usually the amount of titanium in the product is between 0.1 and 30
The amount of each of the above components used is adjusted so that the weight % is achieved. Although there are various methods of contacting these components and the order of addition, examples thereof are as follows. (1) Mg(OR ¹ ) ₂ , a halogenated silane, and an 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) Mg(OR ¹ ) ₂ and the halogenated silane are mechanically pulverized or brought into contact with each other in suspension in an inert hydrocarbon solvent, and then an electron-donating compound is added, followed by mechanical pulverization or in a solvent. Suspension contacting is carried out followed by reaction with titanium tetrahalide. (3) After mechanically pulverizing Mg(OR ¹ ) ₂ , a halogenated silane and an electron-donating compound are added, mechanical pulverization or suspension contact is performed in a solvent, and then it is reacted with a titanium halide. (4) Mg (OR ¹ ) ₂ and halogenated silane are mechanically crushed or suspended in a solvent and brought into contact with each other, and a reaction (addition) product of an electron donating compound and titanium tetrahalide. Mix and mechanically grind. (5) Mg (OR ¹ ) ₂ , halogenated silane, and electron-donating compound are mechanically pulverized or suspended in a solvent, titanium tetrahalide is added, and further mechanically pulverized. . Among these methods (1) to (5), methods (1) to (3) are particularly preferred. Mechanical pulverization in each of the above methods includes a ball mill,
Any conventional 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 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,
An inert hydrocarbon solvent need not be used, but may be used. The reaction temperature at this time is usually 0 to 150℃,
Preferably it is 20-100°C. When titanium tetrahalide is added, heat is generated, so it is preferable to cool the mixture appropriately. A reaction time of about 0.5 to 2 hours 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 solid component that can be used as a catalyst component according to the method of the present invention, and is hereinafter referred to as catalyst component A. In order to obtain a polymer with high stereospecificity by polymerizing an α-olefin having 3 or more carbon atoms or a mixture of this olefin and other olefins using this catalyst component A, the above catalyst component A is combined with an organic Stereospecific polymerization is also carried out using a catalyst system comprising an aluminum compound (hereinafter referred to as component B) and, if necessary, an electron-donating compound (hereinafter referred to as component C). Examples of the organoaluminum compound of component B include compounds represented by the general formula AlR ² _o X _3-o . In the above formula, ^R2 is a hydrocarbon group having 1 to 20 carbon atoms, particularly an aliphatic hydrocarbon group, X is a halogen, and n is a number of 2 to 3. Specific examples of the organoaluminum compound include triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, monovinyldiethylaluminum, diethylaluminium monochloride, etc., but trialkylaluminum is preferably used. It will be done. 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 ratio of components A, B, and C used is such that the molar ratio of titanium in catalyst component A to aluminum compound in component B to electron donating compound in component C is 1:100 to 1:0 to 10, preferably 1: 30-1:
It is chosen to be between 0.1 and 5. FIG. 1 of the accompanying drawings is a flowchart showing an embodiment of a method for producing a solid component that can be used as a catalyst component of the present invention. Examples of the olefin to be polymerized include α-olefins having 3 or more carbon atoms such as propylene and 1-butene, with propylene being particularly preferred. The polymerization can be applied not only to homopolymerization but also to random or block copolymerization. The polymerization reaction is carried out using an inert hydrocarbon, such as hexane,
Slurry polymerization is preferably carried out using heptane, cyclohexane, benzene, toluene, pentane, butane, or a mixture thereof, or a liquefied product of α-olefin undergoing polymerization as a solvent, but polymerization can also be carried out in a gas phase. . The temperature is
The temperature is 50 to 100°C, preferably 60 to 90°C, and the pressure is not particularly limited, but is usually selected from within the range of atmospheric pressure to 100 atm. Hydrogen can also be present as a molecular weight regulator in the polymerization system, resulting in a melt flow index (measured with MFI.ASTM-D1238) of 10 to
0.1 polymer can be easily produced.
Other means commonly used for polymerization and copolymerization of each α-olefin can also be applied. The polyolefin obtained by the above polymerization is
Since metal halides such as magnesium halides, which are found in the catalyst systems of conventionally known highly stereospecific polymerization methods using supported catalysts, are not used,
The inconveniences caused by this halide are reduced,
Moreover, the resulting polymer has high stereospecificity, which brings about its usefulness. Next, examples of the present invention, use examples of polymerization using the obtained catalyst components, and comparative examples will be explained, but the present invention is not limited by these examples unless it deviates from the gist of the present invention. . In addition, in the following examples, the polymerization activity (indicated as K) is expressed as α-olefin pressure of 1 Kg/cm ² per hour.
catalytic efficiency (denoted as CE) is the amount of polymer produced (g) per gram of titanium as a catalyst component. The isotactic index (denoted as II) is the residual amount (% by weight) after 6 hours of extraction with boiling n-heptane in a modified Soxhlet extractor.
It is. Since amorphous polymer is soluble in boiling n-heptane, II indicates the yield of crystalline polymer. The bulk density (shown as ρB, unit: g/cc) is
Measured according to JIS-K-6721. The melt flow index (denoted as MFI) is an ASTM-
Measured according to D1238. Example 1 Preparation of catalyst component A In an argon dry box, a pot made of SUS316 (inner volume 650 ml, inner diameter 106 mm cylinder with a diameter 16 mm
10 g of magnesium diethylate, 21 mmol of ethyl benzoate, and 13 mmol of tetrachlorosilane were placed in a 40 SUS316 pole (accommodating 40 poles made of SUS316) and pulverized in a vibrating mill at room temperature for 15 hours. Then, the obtained white powder was taken out into a 300 ml four-necked flask in an argon dry box.
Add 30ml of titanium tetrachloride. Stir at 80 DEG C. for 2 hours, then separate the solid component and wash with n-heptane. In this way, a light brown catalyst component A having a titanium content of 18.2% by weight was obtained. Usage example 1 Using an induction stirring autoclave with a capacity of 2,
After purging the inside of this with sufficiently dry argon, 750 ml of n-hexane, 0.1 mmol of ethylpenzoate, 1.0 mmol of triethylaluminum, and 146 mg of catalyst component A obtained in the above treatment were added.
(Contains 26.6 mg of titanium). Next, 0.1 kg/cm ² of hydrogen gas was charged, the temperature was raised to 70°C, and propylene was charged to start polymerization. Propylene pressure 12
The polymerization was continued at 70° C. while keeping the temperature at Kg/cm ² , and after 3.5 hours, the excess propylene was rapidly discharged, the mixture was cooled, and the contents were taken out and dried to obtain 316 g of white powdery polypropylene. This is the total amount of product, including amorphous materials. The physical properties and polymerization results of this product are as follows. All units are as explained above. CH=11890 K=283 MFI=4.3 II=74.8 ρB=0.28 Amount of titanium remaining in polypropylene
=84ppm (weight) Chlor amount
=330ppm (weight) Comparative example 1 Experimental example using magnesium chloride as the magnesium compound (1) Preparation of catalyst components Magnesium chloride 20g, ethyl benzoate 6
ml and 3 ml of tetrachlorosilane were vibrated milled at room temperature for 19 hours. Then take out the contents,
It was suspended in 150 ml of TiCl ₄ and treated at 80° C. for 2 hours. After washing with n-heptane, the titanium content was 4.7% by weight and the chloride content was 55.3%.
% by weight of catalyst component was obtained. (2) Polymerization In the above Usage Example 1, the same procedure as Usage Example 1 was carried out except that the catalyst component obtained in (1) of Comparative Example 1 above was used in place of catalyst component A, and the polymerization time was changed to 2 hours. Polymerization was carried out to obtain powdered polypropylene with CE12700. As a result, the amount of titanium remaining in the polypropylene was 78 ppm (by weight), and the amount of chlorine was 900 ppm (by weight). From this, it can be seen that in the case of Use Example 1 using catalyst component A of Example 1, the amount of chlorine remaining in the polypropylene obtained was significantly smaller than in Comparative Example 1. Example 2 Preparation of catalyst component A In Example 1, 10 g of magnesium di-n-propylate was used instead of magnesium diethylate.
The other operations were the same, and the light brown titanium content
17.3% by weight of catalyst component A was obtained. Application Example 2 Polymerization was carried out in the same manner as in Application Example 1 using catalyst component A obtained in Example 2 above. The results are as follows. CE=17840 K=425 MFI=6.2 II=76.1 ρB=0.26 Examples 3 and 4 and Usage Examples 3 and 4 In (1) of Example 1, triphenylphosphine oxide was used instead of ethylbenzoate.

[Formula] (Example 3) or hexamethylphosphoric acid triamide [(CH ₃ ) ₂ N] ₃ PO
Catalyst component A was prepared in the same manner except that (HMPTA) (Example 4) was used, and polymerization was carried out in the same manner as in Use Example 1 using each of these components. The results are shown in Table 1 below.

[Table] Examples 5 to 9 below show that similar effects can be obtained when the order of addition of each component in the preparation of catalyst component A is varied. In these examples, the same preparation equipment as in Example 1 was used, and the operations were conducted accordingly. Example 5 and Usage Example 5 This example shows the case where no silane compound was used. 10 g of magnesium diethylate and 21 mmol of ethyl benzoate were placed in a pot containing a stainless steel ball, ground in a vibrating mill for 15 hours at room temperature, taken out into a four-necked flask, and charged with 30 ml of titanium tetrachloride. The mixture was stirred at 80° C. for 2 hours, and the solid components were separated and washed with n-heptane. Using the thus obtained catalyst component A, polymerization was carried out in the same manner as in Use Example 1. The results are shown in Table 2. Example 6 and Usage Example 6 10 g of magnesium diethylate and 13 mmol of tetrachlorosilane were placed in a pot, ground in a vibrating mill for 5 hours at room temperature, and then
Add 20 mmol ethyl benzoate and add 10
The product was ground in a vibratory mill at room temperature for an hour and the product was taken into a four-necked flask, 30 ml of titanium tetrachloride was added and treated at 80° C. for 2 hours. The solid component was separated from the product and washed with n-heptane. Using the thus obtained catalyst component A, polymerization was carried out according to Usage Example 1 below.
The results are shown in Table 2. Example 7 and Use Example 7 10 g of magnesium diethylate were ground in a vibratory mill for 5 hours at room temperature, then 13 mmol of tetrachlorosilane and 20 mmol of ethylbenzoate were added and milled in a vibratory mill for a further 10 hours at room temperature. After pulverization, the product was taken out into a four-necked flask, and 30 ml of titanium tetrachloride was added thereto and treated at 80°C for 2 hours. The solid component was separated from the product and washed with n-heptane. Using the thus obtained catalyst component A, polymerization was carried out in the same manner as in Use Example 1, and the results shown in Table 2 were obtained. Example 8 and Application Example 8 10 g of magnesium diethylate and 15 mmol of tetrachlorosilane are ground in a vibrating mill for 5 hours at room temperature, and then a complex consisting of 20 mmol of titanium tetrachloride and 20 mmol of ethyl benzoate is prepared. was added thereto, and the mixture was further pulverized using a vibrating mill at room temperature for 20 hours. The solid component was separated from this and washed with n-heptane. Using the thus obtained catalyst component A, polymerization was carried out in the same manner as in Use Example 1. The results are shown in Table 2. Example 9 and Usage Example 9 10 g of magnesium diethylate, 15 mmol of tetrachlorosilane and 20 mmol of ethylbenzoate were ground in a vibratory mill for 5 hours at room temperature, and further mixed with 20 mmol of titanium tetrachloride. The solid components were separated from the product by milling in a vibratory mill for 20 hours at room temperature and washed with n-heptane. Polymerization was carried out in the same manner as in Use Example 1 using the catalyst component A thus obtained. The results are shown in Table 2 below.

[Table] Examples 10 and 11 and Usage Examples 10 and 11 In Example 1, methyl P-tolylate (PMBM) (Example 10) or ethyl P-ethylbenzoate (PEBE) (Example) was used instead of ethylbenzoate.
Catalyst component A was prepared in the same manner as in Use Example 1, except that 11) was used, and polymerization was carried out in the same manner as in Use Example 1. The results are shown in Table 3.

【table】 [Brief explanation of the drawing]

FIG. 1 is a flowchart showing an embodiment of a method for producing a solid component that can be used as a catalyst component of the present invention.

Claims (1)

[Claims] 1. A magnesium compound represented by the general formula Mg(OR ¹ ) ₂ (in the formula, R ¹ represents a hydrocarbon group) and titanium tetrahalide are catalytically reacted in the presence of an electron-donating compound. α− having 3 or more carbon atoms, characterized by
A method for producing a solid component that can be used as a catalyst component for stereospecific polymerization of olefins or mixtures of said olefins and other olefins. 2. A magnesium compound represented by the general formula Mg(OR ¹ ) ₂ (in which R ¹ represents a hydrocarbon group) and titanium tetrahalide are catalytically reacted in the presence of an electron donating compound and a halogenated silane. A method for producing a solid component that can be used as a catalyst component for stereospecific polymerization of a characterized α-olefin having 3 or more carbon atoms or a mixture of this olefin and other olefins.