JPH0128050B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an olefin polymer. More specifically, the present invention relates to the production of ethylene in the presence of a catalyst system comprising a combination of a supported catalyst component having high polymerization activity and an organoaluminum compound.
The present invention relates to a method for producing an olefin polymer by polymerizing olefins such as propylene and butene-1. Conventionally, various methods have been proposed for using Grignard compounds for producing supported catalyst components for olefin polymerization. For example, JP-A-53-24378 discloses a method using a reaction product of a Grignard compound and silanol as a starting material.
Furthermore, JP-A-53-117083 discloses a method of using polysilanol instead of the silanol.
53-40093 and JP-A-54-53182 disclose a method using polysiloxane,
Furthermore, JP-A-52-147688 and JP-A-53-
Publication No. 85877 discloses a method using alcohol. However, the activity of the catalysts obtained by these methods is still not sufficiently high, and improvements are desired. Furthermore, since these methods require operations such as production and separation of the Grignard compound, they are disadvantageous not only in terms of the process but also in that they increase the production cost of the catalyst. As a method that does not use Grignard compounds, JP-A-51-
No. 64586 discloses metal magnesium, halogenated hydrocarbons, alcohols, ketones, aldehydes,
Although a method for obtaining a halogen-containing magnesium compound by catalytic reaction with amines, esters, etc. has been disclosed, the activity of the catalyst obtained by this method is still not sufficiently high. Therefore, as a result of extensive research in order to solve these drawbacks, the present inventors have developed a magnesium compound with a low halogen content obtained by contacting silanol or polysilanol, metallic magnesium, and a halogenated hydrocarbon with a tetrahydrogen compound. The present inventors have discovered that a catalyst component that provides a highly active and highly stereoregular polymer can be obtained by contacting a titanium halide with an electron-donating compound such as a carboxylic acid ester, leading to the completion of the present invention. That is, the gist of the present invention is that (a) silanol or polysilanol, (b) metallic magnesium, (c) halogenated hydrocarbon, (d) titanium tetrahalide, and (e) amine, amide, phosphine, phosphate ester, Olefin is polymerized using a titanium-containing solid catalyst component obtained by catalytically reacting one or more electron-donating compounds selected from phosphoric acid amide, ketone, and carboxylic acid ester, and a catalyst system containing an organoaluminium compound. A method for producing an olefin polymer is provided. Each of these components used in the present invention will be explained. (a) Silanol or polysilanol Silanol has the general formula RnSi(OH) _4-o , where:
R represents a hydrocarbon group, and n represents 1, 2 or 3). Silanol is, for example,
As shown in the following formula, it can be easily synthesized by hydrolyzing the corresponding organic halosilane. (C ₆ H ₅ ) ₃ SiCl+H ₂ O→(C ₆ H ₅ ) ₃ SiOH+HCl Polysilanol has the general formula (R′Si) _x
(OH) _y O _z (where R' is a hydrocarbon group, x, y, z
represents the number of x, y≧2, z≧1. ) or HO(R′ ₂ SiO) _n H (where R′ is a hydrocarbon group, m
represents a number of 2 or more. ) or a mixture of these polysiloxanes having at least one hydroxyl group per molecule. Polysilanols, for example, have the general formula
One or more organic trihalosilanes and/or organic dihalosilanes represented by R′SiX ₃ or R′ ₂ SiX ₂ (in the formula, R′ represents a hydrocarbon group and X represents a halogen atom). , in an inert hydrocarbon solvent, preferably at a temperature around -50°C to 20°C,
It can be easily synthesized by reacting the halogen in the organic halosilane with water or aqueous alkaline solution in an amount equivalent to or more, then washing the resulting solution with water until the washing liquid becomes neutral, and drying. In addition, one or more silanols represented by the general formula R′ ₂ Si(CH) ₂ (in the formula, R′ represents a hydrocarbon group) are heated preferably at 50° C. or higher in the presence of an alkali in alcohol. It can be easily synthesized by heating. R and R' in these general formulas are:
Specific examples include alkyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl, and cycloaralkyl groups having up to 20 carbon atoms. In particular, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl,
Preferred are alkyl groups such as octyl and decyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. (b) Magnesium metal Used in the form of powder, flakes, etc., and preferably highly purified. Further, it is preferable to use it after activation in order to cause the reaction with the halogenated hydrocarbon to occur rapidly. Examples of activation methods include treatment with iodine. (c) Halogenated hydrocarbon Generally, aliphatic, alicyclic or aromatic monohalogenated hydrocarbons can be used. Monohalogenated aliphatic hydrocarbons usually have up to 12 carbon atoms, and specifically include methyl chloride, ethyl chloride, propyl chloride, butyl chloride, amyl chloride,
In place of chlorides such as hexyl chloride, octyl chloride, vinyl chloride, and allyl chloride, or chlorides, similar fluorides, bromides, and iodides may be used. The monohalogenated alicyclic hydrocarbon usually has up to 10 carbon atoms, and specifically includes chlorides such as cyclohexyl chloride and methylcyclohexyl chloride, or similar fluorides, bromides, and iodides. Monohalogenated aromatic hydrocarbons usually have up to 12 carbon atoms, and specific examples include chlorides such as benzene chloride, benzyl chloride, toluene chloride, and xylene chloride, as well as similar fluorides, bromides, and iodides. It will be done. (d) Titanium tetrahalide Examples include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium tetrachloride is particularly preferred. (e) Electron-donating compound A nitrogen-containing compound selected from amines and amides, a phosphorus-containing compound selected from phosphines, phosphoric esters and phosphoric acid amides, and an oxygen-containing compound selected from ketones and carboxylic esters. Can be used. Specifically, nitrogen-containing compounds such as tetramethylethylenediamine, tetraethylethylenediamine, acetamide, phosphorus-containing compounds such as triphenylphosphine, triphenylphosphite, tris-nonylphenylphosphite, hexamethylphosphoric acid triamide, and benzoic acid. Methyl, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl benzoate, p-methyl methyl benzoate, p
-ethyl methylbenzoate, methyl p-methoxybenzoate, ethyl p-methoxybenzoate, p-
Propyl methoxybenzoate, butyl m-methoxybenzoate, phenyl o-methoxybenzoate,
Methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, phenyl acetate, phenyl propionate, ethyl crotonate, propyl crotonate, butyl crotonate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethylglycine Examples include oxygen-containing compounds such as ethyl ester, dimethylglycine propyl ester, dimethylglycine butyl ester, diphenylglycine ethyl ester, diphenylglycine propyl ester, and diphenylglycine butyl ester. In particular, phosphoric acid esters and carboxylic acid esters are preferred. In the present invention, the above-mentioned (a), (b), (c), (d) and
The five components (e) are subjected to a contact reaction in an appropriate order to obtain a titanium-containing solid catalyst component. For example, in the presence of (a) (e) an electron-donating compound, (a) a silanol or polysilanol, (b) metallic magnesium, and (c) a halogenated hydrocarbon are catalytically reacted, and then (d) a tetrahalogenated hydrocarbon is reacted. A method of catalytically reacting titanium. (b) Adding (e) an electron-donating compound to the product obtained by catalytically reacting (a) silanol or polysilanol, (b) metallic magnesium, and (c) halogenated hydrocarbon; , and then (d) a method of catalytic reaction with titanium tetrahalide. (c) The product obtained by catalytically reacting (a) silanol or polysilanol, (b) metallic magnesium, and (c) halogenated hydrocarbon is catalytically reacted with (d) titanium tetrahalide, and then ( e) Method of catalytic reaction with electron-donating compounds. etc., can be obtained by various methods. Before the catalytic reaction with titanium tetrahalide, that is, (a) silanol or polysilanol (b) metallic magnesium and (c) halogenated hydrocarbon are catalytically reacted first, or (a), (b), (c) ) In addition to (e), the magnesium compound obtained by adding an electron-donating compound and carrying out a catalytic reaction first has a catalyst component with high polymerization activity when the molar ratio of halogen to magnesium is 1 or less. This is preferable because it allows In these methods, the contact reaction is carried out in the presence or absence of a diluent. As a diluent, aromatic hydrocarbons such as benzene and toluene, n
-pentane, n-hexane, n-heptane, n-
Examples include saturated aliphatic hydrocarbons such as octane, n-dodecane, and liquid paraffin, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and ethers such as diethyl ether and dibutyl ether. More specifically, the method of contacting the titanium-containing solid catalyst will be described for cases (a) to (c) above. (b) Add silanol or polysilanol, metallic magnesium, and halogenated hydrocarbon to the electron-donating compound at room temperature to around 100°C, and heat to 50 to 200°C;
Preferably, the reaction is carried out at 80 to 150°C for several hours. Next, titanium tetrahalide is added to this product as it is or to a powder obtained by drying under reduced pressure, etc., and heated at 60 to 150°C, preferably 80 to 150°C for 0.1 hour or more. Preferably, the contact reaction is carried out for 0.5 to 2 hours. It is then thoroughly washed with a hydrocarbon solvent. Examples of hydrocarbon solvents include aromatic hydrocarbons such as benzene and toluene, saturated aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, n-dodecane, and liquid paraffin, cyclohexane, and methylcyclohexane. Alicyclic hydrocarbons such as, etc. can be used. (b) Silanol or polysilanol, metal magnesium, and halogenated hydrocarbon are brought into contact at room temperature to around 100°C, and then reacted at 50 to 200°C, preferably 80 to 150°C for several hours. Next, an electron donating compound is added and the contact reaction is carried out at 60 to 200°C for an additional 0.1 hour or more, preferably several hours. Next, this product is subjected to a catalytic reaction with titanium tetrahalide in the same manner as in (a) above, and washed with a hydrocarbon solvent. (c) The product obtained by catalytically reacting silanol or polysilanol, metallic magnesium, and a halogenated hydrocarbon in the same manner as in (b) above,
Catalytic reaction is carried out with titanium tetrahalide in the same manner as above. Next, in the same manner as in (b) above, a contact reaction is carried out with an electron-donating compound, followed by washing with a hydrocarbon solvent. The amounts of each component used in these methods are selected from the following ranges: 0.1 to 20 moles of hydroxyl groups in silanol or polysilanol per gram atom of magnesium metal,
Preferably 0.5 to 5 mol, 0.1 halogenated hydrocarbon
~20 mol, preferably 0.5-3 mol, titanium tetrahalide 0.1-50 mol, preferably 1-30 mol,
Electron donating compound 0.01-10 mol, preferably 0.05
~5 moles. Thus, by catalytically reacting each component of an electron-donating compound selected from silanol or polysilanol, metallic magnesium, halogenated hydrocarbon, titanium tetrahalide, and a specific compound, a titanium content of 0.1 to 20% by weight, Preferably 0.1
~10% by weight of a tan solid can be obtained,
This is used in the polymerization of olefin. Olefin polymerization is carried out using a catalyst system that combines the titanium-containing solid catalyst component and an organoaluminum compound. As an organoaluminum compound, for example, the general formula AlR _' ' _k k is a number from 1 to 3,
X′ represents a halogen atom. ) is used. Particularly preferred are trialkylaluminums such as triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum. The amount of organic aluminum compound used is
Usually, it is selected from the range of 1 to 100 mol per Ti atom. Furthermore, the above-mentioned electron-donating compound can also be added as a third component during polymerization. In that case, the amount used is usually selected from the range of 1 to 20 mol per Ti atom. Examples of the olefins used include α-olefins such as ethylene, propylene, butene-1, etc., and using the catalyst system of the present invention, homopolymerization, random copolymerization of two or more types, or block copolymerization of these can be carried out. These olefin polymers can be advantageously obtained by carrying out the following steps. In the case of copolymerization,
Preferably, the content of comonomer is below 20% by weight. The catalyst system according to the invention is particularly suitable for the homopolymerization of propylene or the copolymerization of propylene with other α-olefins, but is not limited to the polymerization of propylene. In the method of the present invention, the polymerization or copolymerization reaction is
Various polymerization methods can be used, such as solution polymerization or slurry polymerization in the presence of an inert hydrocarbon or liquefied monomer, and gas phase polymerization in the absence of a solvent. The temperature during polymerization is 50 to 100°C, preferably 50°C.
The temperature is selected from the range of ~80℃, and the pressure is selected from the range of atmospheric pressure ~100 atm. Further, by allowing hydrogen to exist in the polymerization zone, the molecular weight of the produced polymer can be easily controlled. As detailed above, according to the method of the present invention, a titanium-containing solid catalyst component having a high olefin polymerization activity not seen in the past can be obtained with industrial advantage. Furthermore, when used in the polymerization of propylene, polypropylene with good stereoregularity can be easily obtained. Next, the present invention will be explained by giving examples and comparative examples. In the Examples and Comparative Examples, the isotactic index (II) is the amount of solids remaining after extraction with boiling n-heptane for 6 hours using an improved Soxhlet extractor, expressed in weight percent. Further, FIG. 1 is a flowchart diagram to help understand the technical content included in the present invention, and the present invention is not limited in any way by the flowchart diagram as long as it does not deviate from the gist thereof. Example 1 [] Preparation of titanium-containing solid catalyst component A 200 ml flask purged with dry nitrogen was charged with 40 mmol of magnesium metal powder, 70 ml of toluene, and trace amounts of ethyl iodide and iodine, and the temperature was raised to 80°C. While stirring at the same temperature, 50 ml of a toluene solution containing 45 mmol of triphenylsilanol and 45 mmol of n-butyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was raised to 110°C and the reaction was continued at the same temperature for 2.5 hours, whereby most of the metallic magnesium disappeared and a gray solid precipitate was formed. Gray solid precipitate (B) using a glass filter under nitrogen after cooling to room temperature.
was separated and removed to obtain a completely homogeneous colorless toluene solution (A). The Cl/Mg mol ratio of the magnesium compound contained in this toluene solution (A) was 0.8. On the other hand, Cl/Mg of gray solid precipitate (B)
The molar ratio was 1.5. The toluene solution obtained above was charged with 2 mmol of magnesium, 0.6 mmol of ethyl benzoate, and 20 ml of toluene into a 100 ml flask purged with dry nitrogen, heated to 110°C with stirring, reacted at the same temperature for 1 hour, and then added toluene. was distilled off under reduced pressure and dried to obtain a white powder. Next, 60 mmol of titanium tetrachloride was added to the white powder, heated to 130°C, reacted at the same temperature for 2 hours, and then cooled to room temperature.
The supernatant was separated and the precipitate was diluted with 50 ml of n-heptane.
After washing twice, a pale yellowish brown solid was obtained. The titanium content of the obtained solid was 3.1% by weight. [] Polymerization of olefin Olefin was polymerized using the catalyst component prepared in [] above in the following manner. Place the flask to a volume of 0.5 n with dry nitrogen.
- 200ml heptane, triethylaluminum
0.09 mmol, ethyl benzoate 0.014 mmol, and 11.3 mg of the titanium-containing solid catalyst prepared in [] above.
I prepared it. While stirring, the temperature was raised to 70°C, propylene gas was supplied at normal pressure, and polymerization was carried out at the same temperature for 2 hours. Next, a small amount of methanol was added to stop the polymerization, and the contents were added to a large amount of methanol, and the product was separated and dried to obtain 8.7 g of white powdery polypropylene. The polymerization activity Kcat (polymer (g)/catalyst component (g), time (hr), propylene pressure (Kg/cm ² )) was 642, and II was 88.7%. Example 21 In [] of Example 1, 2 mmol of solid precipitate (B) was used as magnesium instead of toluene solution (A).
A titanium-containing solid catalyst component was obtained in exactly the same manner except for using the same method. The titanium content of this thing is 3.3
It was in weight%. Next, propylene was polymerized in the same manner as [ ] in Example 1, and Kcat was
It dropped dramatically to 260. On the other hand, II was 83.2%.
The results are shown in Table 1. Examples 2 to 6 Titanium-containing solid catalyst components were prepared in [ ] of Example 1 by changing the types of silanol and halogenated hydrocarbon. The halogen content of the magnesium reaction product used in all Examples was 1 or less in molar ratio to magnesium. Polymerization of propylene was carried out in the same manner as in Example 1 using the catalyst component thus obtained. Table 1 shows the results.
Shown below. Examples 22 and 23 Catalyst components were prepared in the same manner as in Examples 5 and 6, except that a solid precipitate that was insoluble in toluene and had a halogen content of 1 or more in molar ratio to magnesium was used as the magnesium reaction product. Then, propylene was polymerized. The results are shown in Table 1.

[Table] Examples 7 to 15 Titanium-containing solid catalyst components were prepared in [ ] of Example 1 by changing the type and amount of the electron-donating compound. Polymerization of propylene was carried out in the same manner as in Example 1 using the catalyst component thus obtained. The results are shown in Table 2. Comparative Example 1 A titanium-containing solid catalyst component was prepared in [ ] of Example 1 without adding an electron-donating compound, and then propylene was polymerized in the same manner as in [ ] of Example 1. The results are shown in Table 2, and II was significantly lower. Examples 16 to 18 Titanium-containing solid catalyst components were prepared by changing the amounts of silanol and halogenated hydrocarbon in [] of Example 1, and then propylene was polymerized in the same manner as in [] of Example 1. The results are shown in Table 3.

【table】

【table】

[Table] Example 19 3.2g of pure water and 170ml of toluene in a 500ml flask
was added and kept cool at -20°C while stirring. 25g of phenyltriclosilane in this toluene suspension
(0.118 mol) was added dropwise over 1 hour using a dropping funnel. After the dropwise addition was completed, the reaction mixture was heated to 0° C., and stirring was continued for an additional 30 minutes.
Next, it was washed with ice water until the washing solution became neutral. The obtained toluene solution was dehydrated and dried over anhydrous sodium sulfate, filtered, and the resulting solution was used as a raw material for preparing a carrier. The hydroxyl group concentration of this toluene solution was determined to be 0.4 mmol/ml. A titanium-containing solid catalyst component was prepared in exactly the same manner as in Example 1 [], except that 100 ml of the toluene solution of the polysilanol thus obtained was used, and propylene polymerization was carried out in the same manner as in Example 1 []. As a result, 8.2 g of polypropylene was obtained for a catalyst amount of 13.5 mg. Kcat was 506 and II was 91.3%. Example 20 2 mmol of the toluene solution (A) of the magnesium reaction product used in [] of Example 1 as magnesium and 60 mmol of titanium tetrachloride were charged into a 100 ml flask purged with dry nitrogen, and heated to 110°C with stirring. The mixture was heated and reacted at the same temperature for 0.5 hour. Next, add 0.6 mmol of methyl p-methylbenzoate.
After reacting at 110° C. for 1 hour, the reaction mixture was cooled to room temperature, the supernatant liquid was separated, and the precipitate was washed with 50 ml of n-heptane seven times to obtain a pale yellow-green solid. The titanium content was 3.2% by weight. Using the catalyst component thus obtained, propylene was polymerized in the same manner as [ ] in Example 1.
11.0g was obtained. Kcat was 610 and II was 90%. Comparative Example 2 40 mmol of triphenylsilanol and toluene were placed in a 500 ml four-necked flask purged with dry nitrogen.
Pour 100ml and add 3.2mmol/ml chloride-n-
12.5 ml of a di-n-butyl ether solution of butylmagnesium was slowly added at 25° C. with thorough stirring. After the addition was complete, stir at 25°C for 1 hour, then at 70°C.
The temperature was raised to 0.degree. C., and stirring was continued for an additional hour. After cooling to 25° C., 12 ml of a 1.0 mmol/ml toluene solution of ethyl benzoate was added with thorough stirring. After addition,
The temperature was raised to 110°C and stirring was continued for 1.5 hours. Then,
Toluene and di-n-butyl ether were distilled off under reduced pressure and dried to obtain a white powder. 1.2 mol of titanium tetrachloride was added to the obtained white powder, and the temperature was raised to 130°C. During the temperature rise, it became a blackish brown viscous semi-dissolved state. Stirring treatment was carried out at 130°C for 1.0 hour, and then 200 ml of n-heptane was added, resulting in the formation of a large amount of precipitate. The supernatant was separated, and the precipitate was washed five times with 200 ml of n-heptane to obtain a tan solid. The titanium content of the obtained solid was 3.0% by weight. Polymerization of propylene was carried out in the same manner as in Example 1 using the catalyst component thus obtained, and 5.0 g of polypropylene was obtained for 15 mg of catalyst. Kcat was 278 and II was 90%.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing one embodiment of the present invention.

Claims (1)

[Claims] 1 (a) silanol or polysilanol, (b) metallic magnesium, (c) halogenated hydrocarbon, (d) titanium tetrahalide, and (e) amine, amide, phosphine, phosphate ester, Olefin is polymerized using a titanium-containing solid catalyst component obtained by catalytically reacting one or more electron-donating compounds selected from phosphoric acid amide, ketone, and carboxylic acid ester, and a catalyst system containing an organoaluminium compound. A method for producing an olefin polymer, characterized by: 2. A magnesium compound in which the titanium-containing solid catalyst component has a molar ratio of halogen to magnesium of 1 or less, which is obtained by catalytically reacting (a) silanol or polysilanol, (b) metallic magnesium, and (c) halogenated hydrocarbon; Obtained by catalytic reaction of (d) titanium tetrahalide and (e) one or more electron-donating compounds selected from amines, amides, phosphine, phosphoric acid esters, phosphoric acid amides, ketones, and carboxylic acid esters. 2. The method according to claim 1, wherein the solid catalyst component is a titanium-containing solid catalyst component.