JPS648005B2 - - Google Patents

Description

[Detailed description of the invention]

In the present invention, ethylene (co-polymerized) is produced by polymerizing ethylene or ethylene and α-olefin in the presence of a highly active catalyst obtained from a solid catalyst component obtained by special treatment and trialkylaluminium. ) A method for producing a polymer. Many proposals have been made regarding methods for polymerizing ethylene in the presence of a highly active polymerization catalyst obtained from a solid component in which a transition metal compound is supported on magnesium chloride and trialkyl aluminum.
In the proposed method, as a solid component, for example, a co-pulverized ether complex of titanium tetrachloride, magnesium chloride and aluminum chloride (Japanese Patent Publication No. 10916/1983), a co-pulverized product of magnesium chloride and trialkoxyaluminum, etc. A material supported with titanium tetrachloride (Special Publication No. 15111 of 1983) is used. Catalysts obtained from these solid components and trialkylaluminium have considerably high polymerization activity per unit weight of titanium in the solid component, but the polymerization activity per unit weight of the solid component is still insufficient, and the resulting ethylene polymer contains large amounts of catalyst residues, it is necessary to remove catalyst residues from the ethylene polymer before use. An object of the present invention is to provide a method for producing an ethylene (co)polymer using a catalyst having high polymerization activity per solid component. That is, in this invention, after dissolving magnesium chloride in a saturated aliphatic alcohol, the alcohol is distilled off and the precipitated magnesium chloride is dried to prepare activated magnesium chloride, and the activated magnesium chloride is dissolved in aluminum halide. The co-pulverized product was treated with saturated aliphatic ether, the ether-treated solid was reacted with titanium tetrachloride, and the reaction product solid was converted to a compound with the formula AlRnX _3-o (where R is a carbon number of 1 to 20). is an alkyl group, X is a halogen atom, and n is a number from 1 to ₂ . In the formula, R is an alkyl group having 1 to 20 carbon atoms.) In the presence of a catalyst obtained from a trialkylaluminum () represented by This is a method for producing an ethylene (co)polymer, which is characterized by polymerization. According to this invention, the yield of polymer per solid catalyst component () used for catalyst preparation is extremely large, and the catalyst residue content of the produced polymer is small, so there is no need to remove catalyst residue from the polymer. ,
Furthermore, the density of the resulting polymer can be adjusted over a wide range by varying the proportion of α-olefin copolymerized with ethylene. A method for preparing the solid catalyst component () used in this invention will be explained. The method for producing the ethylene polymer or copolymer of the present invention and the process for preparing the catalyst used in the polymerization are shown in FIG. Process After dissolving magnesium chloride in a saturated aliphatic alcohol, the alcohol is distilled off and the precipitated magnesium chloride is dried to prepare activated magnesium chloride. The raw material magnesium chloride is preferably anhydrous. As the saturated aliphatic alcohol, methanol, ethanol, propanol, butanol, etc. are used. These alcohols may be used in an amount sufficient to dissolve magnesium chloride. Alcohol is distilled off from an alcoholic solution of magnesium chloride to precipitate magnesium chloride as white crystals. Activated magnesium chloride is obtained by drying the magnesium chloride thus obtained. Drying is preferably carried out at a temperature of 100 to 300°C under reduced pressure. Process The activated magnesium chloride obtained in the process is co-milled with aluminum halide. As the aluminum halide, aluminum chloride, aluminum bromide, and aluminum iodide can be used, and among them, aluminum chloride is preferred. The amount of aluminum halide used is usually 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, per 1 part by weight of activated magnesium chloride.
Parts by weight. Co-milling can be carried out using a known mill, such as a ball mill, vibratory ball mill, tower mill, or jet mill. There are no particular restrictions on the temperature during co-pulverization, but it is usually -30 to 150°C, and the co-pulverization time is usually 1 to 100 hours. Operations in this step and subsequent steps must be carried out under an inert gas atmosphere from which moisture, oxygen, etc. are almost completely removed. Process The co-ground product obtained in the process is treated with saturated aliphatic ether. As a saturated aliphatic ether, the number of carbon atoms is 2 to 10.
Saturated aliphatic ethers such as ethyl ether, isopropyl ether, isobutyl ether, isoamyl ether are used. The amount of these ethers used is usually 0.1 to 100 mol, preferably 0.5 to 50 mol, per mol of aluminum halide in the co-pulverized product. The ether can be used neat (if liquid) or as a solution in an inert hydrocarbon solvent such as n-hexane, n-heptane, cyclohexane. Ether treatment is carried out by suspending the co-milled product in ether or a solution of ether and an inert hydrocarbon solvent. The ether treatment temperature is generally 20 to 100°C, and the ether treatment time is generally 30 minutes to 10 hours. After the ether treatment, the ether treated solid is filtered,
Separate by decanting or other method and wash thoroughly with an inert hydrocarbon solvent. It is thought that by the ether treatment, the aluminum halide in the co-pulverized material forms a soluble complex with ether and is eluted from the co-pulverized material. Step The ether treated solid obtained in step is reacted with titanium tetrachloride. The reaction of titanium tetrachloride with an ether treated solid is generally carried out by adding the ether treated solid or a suspension thereof in an inert hydrocarbon solvent to a solution of titanium tetrachloride or an inert hydrocarbon solvent. . There are no particular restrictions on the amount of titanium tetrachloride used, but generally 10
~1000 mmol. The reaction temperature is usually from 20°C to the boiling point of titanium tetrachloride, and the reaction time is usually 0.5 to 10 hours. The reaction product solid obtained in this way is separated from unreacted titanium tetrachloride by a method such as filtration or decanting.
Wash thoroughly with an inert hydrocarbon solvent. 0.5 to 5% by weight of titanium in the solid produced by the reaction
Contains. Step The reaction product solid obtained in the step is reacted with an organoaluminum halide to obtain a solid catalyst component (). As the organic aluminum halide, a compound represented by the aforementioned formula AlRnX _3-o is used.
Examples of organoaluminum halides include diethylaluminum chloride, diethylaluminium bromide, diethylaluminium iodide, ethylaluminum sesquichloride,
Ethylaluminum dichloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride, di-n-laurylaluminum chloride, distearylaluminum chloride, etc. are used. Among these organoaluminum halides, diethylaluminum chloride, diisobutylaluminum chloride and ethylaluminum sesquichloride are preferred. The amount of organoaluminum halide used is usually 1 gram atom of titanium in the reaction solid.
The amount is 0.1 to 100 mol, preferably 0.5 to 50 mol. The reaction is generally carried out by suspending the reaction product solid in an inert hydrocarbon solvent and adding to this suspension an inert hydrocarbon solution of the organoaluminum halide. The reaction temperature and reaction time are generally 20-100°C and 0.5-10 hours, respectively. Solid catalyst component obtained after the reaction ()
is separated from unreacted organoaluminium halide by a method such as filtration or decanting, and thoroughly washed with an inert hydrocarbon solvent. The solid catalyst component () obtained in this way has the following properties:
Titanium is contained in an amount of 0.5 to 5% by weight. It is necessary to prepare the solid catalyst component () in this invention in the above order, and the catalyst obtained from the solid component and trialkylaluminium prepared by changing this order has a significantly low ethylene polymerization activity. . In the present invention, ethylene or ethylene and α-olefin are prepared in an inert solvent in the presence of a catalyst obtained from a solid catalyst component () and a trialkylaluminium () represented by the formula _AlR'3 described above. Polymerize. As the trialkyl aluminum (), trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trilaurylaluminum, tristearylaluminum, etc. are used. , among these, triethylaluminum,
Triisobutylaluminum is preferred. The amount of trialkyl aluminum () used is
The amount is usually 1 to 1000 mol per gram atom of titanium in the solid catalyst component. The polymerization reaction is carried out in an inert solvent. As the inert solvent, aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane and cyclopentane, and aromatic hydrocarbons such as benzene and toluene are used. There is no particular limit to the concentration of the solid catalyst component () and trialkyl aluminum () in these inert solvents during the polymerization reaction, but
In general, for the solid catalyst component (), the amount is 0.001 to 1000 milligram atoms of titanium in the solid catalyst component () per inert solvent, and for the trialkylaluminium (), the amount is 0.001 to 1000 milligram atoms per inert solvent.
0.01 to 1000 mmol per unit. As the α-olefin to be copolymerized with ethylene, an ethylenically unsaturated hydrocarbon having 3 or more carbon atoms, such as propylene, 1-butene, and 1-hexene, is used. In the present invention, the polymerization reaction is carried out in a state substantially free from moisture, oxygen, etc., as in the case of a typical ethylene polymerization reaction using a Ziegler type catalyst. The polymerization reaction temperature is usually 30 to 180°C, and the polymerization reaction pressure is usually 1 to 70 kg/cm ² . Next, Examples and Comparative Examples will be shown. In Examples and Comparative Examples, "polymerization activity" refers to the yield (g) of polymer per 1 g of solid catalyst component used and 1 hour of polymerization time. Example 1 Preparation of solid catalyst component () 10 g of anhydrous magnesium chloride was added to 100 ml of ethanol.
Then, the ethanol was distilled off to precipitate white crystals of magnesium chloride. The crystals were heated at 120° C. for 3 hours under a pressure of 1-2 mmHg (absolute). Next, this crystal is powdered in a mortar, and this powder is placed under a pressure of 1 to 2 mmHg (absolute pressure).
The mixture was dried by heating at 200°C for 4 hours to obtain activated magnesium chloride. 10 g of activated magnesium chloride and 2 g of aluminum chloride were placed in a vibrating ball mill with an inner diameter of 10 cm and a length of 5.7 cm containing 60 steel balls with a diameter of 1.59 cm.
Co-milling was carried out at 20°C for 5 hours. 5 g of the co-pulverized material was suspended in 100 ml of n-heptane containing 7.5 mmol of isoamyl ether, and the mixture was heated at 90°C.
The mixture was treated with ether for 1 hour. Then, increase the temperature to 90℃
The supernatant was removed by decanting at a constant temperature. Add 60 ml of n-heptane to the remaining suspension to suspend it,
After raising the temperature to 90°C, the ether treated solid was washed by removing the supernatant liquid by decanting. This washing operation was repeated 5 times. Add 60 ml of n-heptane to the ether-treated solid to suspend it, and add 20 ml of titanium tetrachloride to this suspension.
(182 mmol) was added, and the mixture was reacted at 90° C. for 1 hour with stirring. The reaction solids were washed with n-heptane in the same manner as the ether-treated solids. The titanium content of the reaction product solid was 2.0% by weight. 60 ml of n-heptane was added to the reaction product solid to suspend it, 20 ml of n-heptane containing 40 mmol of diethylaluminium chloride was added to this suspension, and the mixture was reacted at 90° C. for 1 hour. 4.78 g of the obtained solid catalyst component was added to n
- Washed with heptane. The titanium content of the solid catalyst component was 2.0% by weight. 100 ml of n-heptane was added to the solid catalyst component to prepare a slurry of the solid catalyst component. Polymerization Slurry of solid catalyst component (10 mg as solid catalyst component) in an autoclave with internal volume 1 equipped with a stirrer
After attaching the glass ampoule filled with the autoclave, the inside of the autoclave was purged with nitrogen. 400 ml of n-heptane followed by an n-heptane solution containing 0.93 mmol of triethylaluminum.
11.8ml was charged into an autoclave. Heat the autoclave to 90℃ and release hydrogen under pressure.
The pressure was introduced until the pressure reached 2.4Kg/cm ² (gauge pressure, the same applies hereinafter), and then ethylene was introduced until the total pressure reached 12.4Kg/cm ² (ethylene partial pressure: 10Kg/cm ² ). Stirring was started, the glass ampoule was crushed, and a polymerization reaction was carried out at 90°C for 1 hour. Ethylene was continuously fed during the polymerization to maintain the total pressure at 12.4 Kg/cm ² . After the polymerization reaction was completed, the reaction mixture was taken out from the autoclave, and isopropanol was added thereto to bring the total volume to 1. Separate the polymer and vacuum dry at 50°C for 20 hours.
122 g of white polyethylene was obtained. This polyethylene had a density of 0.961 g/cm ³ and a bulk specific gravity of 0.33. The polymerization activity was 12,200. Example 2 The same procedure as in Example 1 was carried out except that the amount of solid catalyst component used was changed to 5 mg and the ethylene partial pressure was changed to 5.7 Kg/cm ² . The polymerization activity was 6830. Example 3 The same procedure as in Example 2 was carried out except that the amount of trialkylaluminium used was changed to 1.41 mmol. The polymerization activity was 6710. Examples 4 to 7 The same procedure as in Example 1 was carried out except that the hydrogen pressure and ethylene pressure were changed as shown in Table 1. Table 1 shows the melt flow index (unit: g/10 min) (hereinafter referred to as MI) and polymerization activity of the polyethylene obtained.

[Table] Example 8 A glass ampoule filled with the solid catalyst component slurry prepared in Example 1 (4.8 mg as solid catalyst component) was attached to an autoclave with an internal volume of 1 equipped with a stirrer, and the inside of the autoclave was then flushed with nitrogen. Replaced. 600 ml of n-heptane followed by 11.8 ml of n-heptane solution containing 0.95 mmol of triethylaluminum.
ml was placed in an autoclave. The autoclave was heated to 90° C. and ethylene was introduced until the pressure reached 10 Kg/cm ² . Thereafter, ethylene polymerization was carried out in the same manner as in Example 1. The polymerization activity was 21,340. Example 9 The same procedure as Example 8 was carried out except that the amount of triethylaluminum used was changed to 1.17 mmol. The polymerization activity was 27,670. Example 10 The same procedure as Example 8 was carried out except that the amount of triethylaluminum used was changed to 1.39 mmol. The polymerization activity was 27350. When the polyethylene obtained in each of the above Examples was extracted with boiling n-hexane for 15 hours, the proportion of extraction residue was 99.5% by weight or more. Example 11 A glass ampoule containing the slurry of the solid catalyst component prepared in Example 1 (10 mg as the solid catalyst component) was attached to an autoclave with an internal volume of 1 and equipped with a stirrer, and then the inside of the autoclave was purged with nitrogen. n-heptane 400ml, triethylaluminum
11.8 ml of n-heptane solution containing 0.93 mmol and 30 ml (360 mmol) of 1-butene were charged in this order into the autoclave. Heat the autoclave to 90℃ and release hydrogen under pressure.
The pressure was introduced until the pressure reached 0.5Kg/cm ² , and then ethylene was introduced until the total pressure reached 7.4Kg/cm ² . Stirring was started, the glass ampoule was crushed, and a copolymerization reaction was carried out at 90°C for 1 hour. During the polymerization, ethylene was continuously supplied to maintain the total pressure at 7.4 Kg/cm ² . After the copolymerization reaction was completed, the reaction mixture was taken out from the autoclave, and isopropanol was added thereto to bring the total volume to 1. After separating the copolymer and washing with methanol,
Vacuum drying at 50℃ for 20 hours yields white ethylene 1-
81.6 g of a random copolymer with butene was obtained. The 1-butene unit content of this copolymer was 14.7% by weight.
The density was 0.910 g/cm ³ . The polymerization activity was 8160. Example 12 The same procedure as in Example 11 was carried out except that the amount of 1-butene used was changed to 20 ml (240 mmol). The obtained copolymer of 1-butene and ethylene contains 7.4% by weight of 1-butene units,
Its density was 0.933 g/cm ³ . The polymerization activity was 8390.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing a method for producing the polymer or copolymer of the present invention.

Claims (1)

[Claims] 1. After dissolving magnesium chloride in a saturated aliphatic alcohol, the alcohol is distilled off and the precipitated magnesium chloride is dried to prepare activated magnesium chloride, and the activated magnesium chloride is dissolved in aluminum halide. The co-pulverized product was treated with saturated aliphatic ether, the ether-treated solid was reacted with titanium tetrachloride, and the reaction product solid was converted to a compound with the formula AlRnX _3-o (where R is a carbon number of 1 to 20). is an alkyl group, X is a halogen atom, and n is a number from 1 to ₂ . In the formula, R' is an alkyl group having 1 to 20 carbon atoms.) In an inert solvent, ethylene or ethylene and α-olefin are combined in the presence of a catalyst obtained from a trialkylaluminium () represented by A method for producing an ethylene (co)polymer, which comprises polymerizing ethylene (co)polymer. 2 0.05 to 1 part by weight of activated magnesium chloride
The manufacturing method according to claim 1, characterized in that 5 parts by weight of aluminum halide is used. 3. The production method according to claim 1, characterized in that 0.1 to 100 moles of saturated aliphatic ether are used per mole of aluminum halide in the co-pulverized product. 4 per gram atom of titanium in the solid produced by the reaction
The method according to claim 1, characterized in that 0.1 to 100 moles of organoaluminum halide are used. 5. Process according to claim 1, characterized in that from 1 to 1000 moles of trialkylaluminium () are used per gram atom of titanium in the solid catalyst component ().