JPH0446287B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an ethylene polymerization method suitable for producing an ethylene polymer or a copolymer of ethylene and α-olefin with high catalytic efficiency and having a narrow molecular weight distribution or composition distribution. In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and similarly, the term "polymer" may be used to include not only homopolymers but also copolymers. There is. Olefin polymers are used after being processed into a large number of molded products such as films, tapes, sheets, fibers, blow molded products, and injection molded products. In order to obtain products with excellent transparency, impact resistance, etc., it is preferable to use polymers with narrow molecular weight distribution and composition distribution in each of these products. In particular, in copolymers, as the content of a small proportion of olefin comonomer to be copolymerized increased, the influence of the width and narrowness of the composition distribution on the physical properties of the copolymer tended to increase. As a method for obtaining an olefin polymer with a narrow distribution, it is effective to polymerize olefin using a catalyst formed from a vanadium-based catalyst component and an organoaluminum compound catalyst component. The disadvantage is that the polymer yield is low. If a catalyst formed from a highly active titanium catalyst component containing magnesium, titanium, and halogen as essential components and a typical organoaluminum compound catalyst component, such as trialkyl aluminum, is used instead of the vanadium-based catalyst, the Although it is possible to dramatically increase the polymer yield, for example, in copolymerization of ethylene and α-olefin having 3 or more carbon atoms, it is difficult to obtain a copolymer with a sufficiently narrow composition distribution; The melting point of the resulting copolymer is high. If an alkyl aluminum halide is used in place of the above trialkylaluminum and high-temperature melt polymerization is carried out under conditions such that the copolymer dissolves in the polymerization medium, it is possible to obtain a copolymer with a fairly narrow composition distribution, but it is not suitable for the intended use. Therefore, it cannot be said that it is still satisfactory. As a result of intensive study on improving the polymerization method using such a highly active titanium catalyst component, the present inventors have discovered that an organoaluminum compound catalyst component obtained by treating a specific organoaluminum compound with a specific oxygen-containing compound. It has been discovered that by using a catalyst formed from the highly active titanium catalyst component, it is possible to further improve the catalytic activity and to produce a polymer with an even narrower distribution. That is, according to the present invention, (A) a highly active titanium catalyst component containing magnesium, titanium, and a halogen as essential components; and (B) a halogen-containing organoaluminum compound in which the halogen/aluminum (atomic ratio) is 1 or more and less than 2. Using a catalyst formed from an organoaluminum compound catalyst component obtained by reacting at least a portion of (b-1) with an organic compound (b-2) containing active hydrogen bonded to water and/or oxygen, A method for polymerizing ethylene is provided, which comprises polymerizing ethylene or copolymerizing ethylene and α-olefin. The highly active titanium catalyst component (A) used in the present invention contains magnesium, titanium and halogen as essential components, for example, the magnesium/titanium (atomic ratio) is preferably 2 to 100, particularly preferably 4 to 100, particularly Preferably it is in the range of 10 to 70. Further, when the component (A) is solid, its specific surface area is, for example, 3 m ² /g or more, preferably
40m ² /g or more, more preferably 100 to 800
m ² /g. The titanium catalyst component usually does not release the titanium component contained therein by simple means such as washing with hexane at room temperature. And usually, the x-ray spectrum exhibits low crystallinity for the magnesium compound, regardless of the magnesium compound used in the catalyst preparation, or is very low crystallinity compared to that of common commercially available magnesium halides. It is desirable that The highly active titanium catalyst component (A) may also contain other elements, metals, functional groups, electron donors, etc. in addition to the above-mentioned essential components. For example, elements or metals such as silicon, aluminum, zirconium, and hafnium, functional groups such as alkoxy groups and aryloxy groups, and electron donors such as esters, amines, ethers, ketones, acid anhydrides, acid amides, and acid chlorides. It may be contained. Such a highly active titanium catalyst component (A) contacts or reacts a magnesium compound (or magnesium metal) and a titanium compound, either directly or in the coexistence of one or more compounds such as an electron donor and the above-mentioned other elements and metals. Alternatively, for example, one or both of the magnesium compound (or magnesium metal) and the titanium compound may be subjected to preliminary contact treatment with an electron donor, other element, metal, etc. It can be obtained by contacting or reacting the two. Methods for producing such highly active titanium catalyst components are already known in the art from numerous proposals. For example, Tokuko Sho 46-34092
No. 47-41676, No. 50-32270, No. 53-
Examples of manufacturing methods disclosed in Japanese Patent Application Laid-open No. 46799, No. 54-25517, No. 57-19122, and Japanese Patent Application Laid-open No. 56-811 and No. 56-11908 can be cited. Examples of compounds of other metals or elements mentioned above include:
Examples include organoaluminum compounds and halogen-containing silicon compounds. The organoaluminum compound is, for example, trialkylaluminum,
You can choose from various alkyl aluminum halides, various alkyl aluminum alkoxides, etc. Moreover, the halogen-containing silicon compound is
For example, it can be selected from silicon tetrachloride, alkoxy silicon halide, allyloxy silicon halide, halopolysiloxane, and the like. Magnesium compounds that can be used to prepare the highly active titanium catalyst component (A) include magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium Examples include reaction products of organic magnesium compounds such as magnesium halide, magnesium dihalide, alkylmagnesium halide, arylmagnesium halide, dialkylmagnesium, or alkylmagnesium halide with silanol or siloxane. There are no particular restrictions on the manufacturing method of these magnesium compounds, and they can be selected as appropriate. Examples of titanium compounds that can be used to prepare the highly active titanium catalyst component (A) include titanium tetrahalides, alkoxytitanium halides,
Examples include allyloxytitanium halide, tetraalkoxytitanium, and tetraallyloxytitanium. Furthermore, examples of electron donors that can be used in the preparation of the highly active titanium catalyst component (A) include alcohol,
Phenols, ketones, aldehydes, carboxylic acids, esters, ethers, acid amides, acid anhydrides,
Examples include oxygen-containing electron donors such as alkoxysilane compounds, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc. Alcohols having 1 to 18 carbon atoms; Phenols having 6 to 15 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, naphthol; acetone, methyl ethyl ketone, methyl Ketones with 3 to 15 carbon atoms such as isobutyl ketone, acetonephenone, and benzophenone; aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and 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 cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, toluyl Methyl acid, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, diisobutyl phthalate, diisobutyl malonate, γ-butyrolactone, δ-vallerolactone , organic acid esters having 2 to 18 carbon atoms, such as coumarin, phthalide, and ethylene carbonate; inorganic acid esters, such as ethyl silicate; 15 acid halides; ethers with 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acetic acid amide, benzoic acid amide, toluic acid amide, etc. Acid amides; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile, tolnitrile; etc. can. Two or more types of these electron donors can be used. In the present invention, the organoaluminum compound catalyst component (B) used together with the titanium catalyst component (A) is
The average composition is in the range of halogen/aluminum (atomic ratio) of 1 or more and less than 2, particularly preferably
A component obtained by reacting at least a part of a halogen-containing organoaluminum compound (b-1) expressed in the range of 1.25 to 1.75 with an organic compound (b-2) containing active hydrogen bonded to water and/or oxygen. It is. When an organoaluminum compound with a halogen/aluminum (atomic ratio) of less than 1 is used instead of the halogen-containing organoaluminum compound (b-1) specified above, ethylene copolymerization is carried out in a high temperature melted state. In this case, it is not possible to produce a copolymer with a sufficiently narrow composition distribution. Further, when an organoaluminum compound having the above-mentioned ratio of 2 or more is used, it is not preferable because the polymerization activity cannot be said to be sufficiently satisfactory. The organoaluminum compound catalyst component (b-
1) includes diethylaluminium chloride,
dialkylaluminum halides such as diisobutylaluminum chloride, di-n-hexylaluminum chloride, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, isobutylaluminum sesquichloride, isobutylaluminum sesquichloride, ethylaluminum sesquibromide, or mixtures thereof. This can be shown as a representative example.
Further, some of the alkyl groups of these alkyl aluminum halides may be substituted with hydrogen or the like. Furthermore, materials that can be converted into halogen-containing organic aluminum by mixing may be used, such as any mixture of trialkylaluminum, alkylaluminium halide, aluminum trihalide, etc., and halogen and aluminum are combined with the above halogen/aluminum ( For example, 2 ethylaluminum sesquichloride to triethylaluminum (atomic ratio).
It can also be used in the form of a mixture of more than double the molar amount, or a mixture of the aluminum compound described above and a compound other than the aluminum compound that can react with the aluminum compound to form a halogen-containing organoaluminum compound, satisfying the above ratio. can. Examples of the latter include, for example, a mixture of triethylaluminum and silicon tetrachloride in a molar ratio of 4:1 to 2:1, a mixture of diethylaluminum chloride and n-butyl chloride in an amount of 1.5 times the mole or less, di-n- Examples include a mixture of hexylmagnesium and aluminum trichloride in a ratio of 1.5/1 to 3/1. An organic compound containing active hydrogen bonded to water and/or oxygen (b-
In 2), the organic compound is a compound containing a hydroxyl group, a carboxyl group, etc., and examples thereof include alcohols, phenols, and carboxylic acids. More specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, n-octanol, 2-
Ethylhexanol, n-decanol, n-decyl alcohol, oleyl alcohol, ethoxyethanol, n-butoxyethanol, 1-butoxy-2-propanol, 2-chloroethanol,
Monohydric or polyhydric C ₁ to _{C 18} aliphatic alcohols such as ethylene glycol and propylene glycol; C ₅ to C ₁₂ alicyclic alcohols such as cyclopentanol and cyclohexanol; benzyl alcohol, phenyl Ethyl alcohol,
_C7 such as α,α-dimethylbenzyl alcohol
Alcohols represented by ~ _C15 aromatic alcohols, and _C6 ~ _C16 phenols such as phenol, cresol, xylenol, ethylphenol, isopropylphenol, t-butylphenol, hydroquinone, and bisphenol A. ; _C2 to _C18 aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caprylic acid, caproic acid, stearic acid, oleic acid, succinic acid, and adipic acid; Alicyclic carboxylic acids such as cyclohexanecarboxylic acid Acids; benzoic acid, toluic acid,
Representative examples include carboxylic acids represented by _C7 to _C15 aromatic carboxylic acids such as salicylic acid and phthalic acid. Among these, alcohols, particularly aliphatic alcohols having 1 to 12 carbon atoms, are preferred, and ethanol is particularly preferred. Organoaluminum compound (b-1) and water and/or
or oxygen-containing compounds such as the above organic compounds (b-
The reaction with 2) is preferably carried out in an inert hydrocarbon medium. Examples of inert hydrocarbons that can be used for this purpose include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, kerosene, and alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane. ,
Examples include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, halogenated hydrocarbons such as ethylene chloride, ethyl chloride, and chlorobenzene, and mixtures thereof. When the reaction is carried out in an inert hydrocarbon medium, the concentration of the organoaluminum compound (b-1) can be changed and selected as appropriate, for example, from 0.001 to 5 mol/,
In particular, it is preferable to use a concentration of 0.01 to 2 mol/ml. As the organoaluminum compound catalyst component (B),
It is also possible to use a compound reacted with the oxygen-containing compound (b-2) in the presence of the entire amount of the halogen-containing organoaluminum compound (b-1) used,
A part of the organoaluminum compound (b-1) used is reacted with the oxygen-containing compound (b-2), and the remaining organoaluminum compound (b-2) is reacted with the oxygen-containing compound (b-2).
-2) may be used in combination. The amount of the oxygen-containing compound (b-2) used is, for example, 0.05 to 1 mole of the organoaluminum compound used.
An example is 1.0 mol, preferably 0.1 to 0.8 mol. A part of the organoaluminum compound (b-1) used and an oxygen-containing compound (b-2)
When reacting, the oxygen-containing compound (b-2)
per mole of organoaluminum compound (b-
1) is preferably used in a proportion of at least 0.5 mole. Further, when two or more kinds of compounds are used in combination as the organoaluminum compound (b-1) as described above, the order of mixing these two or more kinds of compounds and the above-mentioned oxygen-containing organic compound may be arbitrary. However, it is preferable to adopt an embodiment in which the two or more types of compounds are mixed in advance, and then all or part of the mixture is mixed with the oxygen-containing organic compound. Organoaluminum compound (b-1) and water and/or
Alternatively, the reaction temperature of the oxygen-containing organic compound (b-2) can be selected as appropriate, for example, -20°C to +100°C,
In particular, a range of -20°C to 70°C is preferred. If this reaction temperature becomes too high, it becomes difficult to obtain the desired effect. The reaction time is arbitrary, for example from 1 minute to several tens of hours, preferably from about 2 minutes to 10 hours. Although it is not clear what compounds are produced by the above reaction, diethylaluminium chloride,
Halogen-containing organoaluminum compound (b-1) such as ethylaluminum sesquichloride and water, ethanol, n-butanol, butyl cellosolve,
When the reaction product with the active hydrogen-containing compound (b-2) bonded to oxygen such as propionic acid was analyzed by IR, it was found that the active hydrogen-containing compound (b-2) was )
When the amount of the active hydrogen-containing compound was equal to or less than equimolar, the absorption peak based on the stretching vibration of -OH of the active hydrogen-containing compound completely disappeared. Moreover, when the temperature of the reaction is changed,
It is assumed that the IR absorption pattern changes accordingly, and that the structure of the product differs depending on the reaction temperature. Furthermore, when the above reaction ratio is an equimolar excess of the halogen-containing organoaluminum compound (b-1), it was confirmed by ¹³ C-NMR that free alkylaluminum exists in proportion to the excess amount. Ta. In either case, the compound (b-2) containing active hydrogen bonded to oxygen reacts with the organoaluminum compound (b-1) component to form a bulky, for example, a quantifier with a membered ring structure. However, it is estimated that the reactivity is significantly weakened. In the present invention, it is important to react the organoaluminum compound (b-1) and the oxygen-containing compound (b-2) in advance; for example, the titanium catalyst component (A) and the organoaluminum compound (b-2) are added to the polymerization system. b
Even if polymerization is carried out by directly supplying -1) and the oxygen-containing compound (b-2), the effect of producing a polymer with a narrower distribution by adding the oxygen-containing compound cannot be found. In the method of the present invention, in the presence of a catalyst formed from the highly active titanium catalyst component (A) and the organoaluminum compound catalyst component (B) described in detail above,
Polymerize ethylene or copolymerize ethylene and α-olefin. Examples of the α-olefin used in polymerization include propylene, 1-butene, 4-methyl-1-pentene, and 1-octene. Ethylene can be subjected not only to homopolymerization but also to random copolymerization and block copolymerization with the above α-olefin. In copolymerization, polyunsaturated compounds such as conjugated dienes and non-difunctional dienes can be selected as copolymerization components. The present invention is particularly suitable as a method for producing resinous polymers by homopolymerization of ethylene or copolymerization of ethylene and a small proportion of α-olefin. Polymerization can be carried out in either liquid phase or gas phase. When carrying out liquid phase polymerization, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, but the olefin itself may also be used as the reaction medium. The amount of catalyst to be used is approximately 0.0001 to approximately 1.0 mmol of titanium catalyst component (A) in terms of titanium atoms per 1 reaction volume, and the amount of organoaluminum compound catalyst component (B) in terms of 1 mole of titanium atoms in component (A). On the other hand, it is preferred that component (B) contains about 1 to about 2,000 moles of metal atoms, preferably about 5 to about 500 moles. During polymerization, hydrogen can be allowed to coexist for the purpose of controlling the molecular weight. The polymerization temperature is preferably about 20° to about 300°C,
More preferably it is about 50° to about 230°C. In particular, homopolymerization of ethylene or ethylene and a small amount of α
- When copolymerizing olefins, it is preferable to carry out solution polymerization under conditions such that the resulting polymer or copolymer is dissolved in an inert hydrocarbon medium, such as at about 100°C to about 230°C. Temperature is particularly recommended. Polymerization pressure is atmospheric pressure to about 200Kg/cm ² ,
Preferably, a range of about 2 to about 50 kg/cm ² is adopted. Although the polymerization can be carried out in any of the batch, semi-continuous and continuous methods, it is industrially advantageous to use the continuous polymerization method. Furthermore, the polymerization may be carried out in two or more polymerization zones having different polymerization conditions. According to the present invention, a polymer with high polymerization activity and narrow distribution can be produced. In particular, in the above-mentioned ethylene copolymer, it is possible to produce a copolymer with a narrow composition distribution. Next, examples will be shown. In the examples shown below, a parameter U expressed by the following formula (1) was used to express the composition distribution of the produced copolymer. U=100×(Cw/Cn-1)...(1) However, in the formula, Cw represents the weight average degree of branching, and Cn represents the number average degree of branching. The U is a parameter indicating the distribution of the composition components of the copolymer, which is unrelated to the molecular weight, and the smaller the value, the narrower the composition distribution. For example, if the U is too large, the composition distribution will be too wide, and when formed into a film, the transparency, tear resistance, impact resistance, blocking resistance, and low-temperature heat sealability will be poor, and the copolymer of the present invention will have poor transparency, tear resistance, impact resistance, blocking resistance, and low-temperature heat sealability. It is difficult to exhibit the excellent properties of and properties that combine these excellent properties in a well-balanced manner. In addition, in formula (1) for calculating U above, Cw and Cn
is a value determined by the following method. In order to perform compositional fractionation of the ethylene copolymer, the copolymer was added to a mixed solvent of p-xylene and butyl cellosolve (volume ratio: 80/20), and heat stabilizers 3 and 5 were added.
- di-tert-butyl-4-methylphenol was dissolved in the coexistence of diatomaceous earth (trade name: Celite 560 manufactured by John Manville (USA)), which was coated and packed into a cylindrical column, and the mixture had the same composition as the above-mentioned mixed solvent. While transferring and flowing out the solvent into the column, the temperature inside the column was raised stepwise from 30℃ to 120℃ in 5℃ increments, and the coated ethylene copolymer was fractionated, reprecipitated with methanol, and then separated and dried. and obtain the fractionated material. Next, the number of branches C per 1000 carbons of each fraction was determined by the 13C-NMR method, and the number of branches C and the cumulative weight fraction I(w) of each fraction were calculated according to the lognormal distribution according to the following equation (2). Assuming that, Cw and Cn are found by the least squares method. However, in the formula, β ² is expressed as β ² =2ln(Cw/Cn) (3), and Co ² is expressed as Co ² =Cw·Cn (4). Example 1 <Preparation of titanium catalyst component> Commercially available anhydrous magnesium chloride 3 under nitrogen atmosphere
A mole was suspended in dehydrated and purified hexane 6, and 18 moles of ethanol was added dropwise over 1 hour with stirring, followed by reaction at room temperature for 1 hour. 7.8 mol of diethylaluminum chloride was added dropwise to this at room temperature,
Stirring was continued for 2 hours. Next, after adding 18 mol of titanium tetrachloride, the system was heated to 80°C and the reaction was carried out with stirring for 3 hours. After the reaction, the solid part was separated, washed repeatedly with purified hexane, and then made into a hexane suspension. In this way, the titanium catalyst component (A)
I got it. <Preparation of organoaluminium compound catalyst component> Dehydrated and purified hexane 1 in a nitrogen atmosphere
500 mmol of ethylaluminum sesquichloride was added and stirred. Next, add 1mol/hexane
375 milliliters of ethanol diluted with 375 ml of ethanol was added dropwise at room temperature, the temperature was raised to 40°C, and the mixture was reacted for 1 hour. After the reaction, the mixture was allowed to cool to room temperature. In this way, an organoaluminum compound catalyst component (B) was obtained. <Polymerization> Using a continuous polymerization reactor with an internal volume of 200, dehydrated and purified hexane was used at 100/hr, and the organoaluminum compound catalyst component (B) obtained above was converted to Al at 18
mmol/hr, titanium catalyst component (A) obtained above
Continuously supplied at a rate of 0.66 mmol/hr in terms of Ti, 13 kg/hr of ethylene was simultaneously supplied in the polymerization vessel.
hr, 4-methyl-pentene 13Kg/hr, hydrogen 70/
Continuous copolymerization was carried out under conditions such as a polymerization temperature of 165° C., a total pressure of 30 Kg/cm ² , an average residence time of 1 hour, and a copolymer concentration of 130 g/h to the solvent hexane. The results are shown in Table 3. A copolymer with very narrow molecular weight distribution and composition distribution was obtained. Next, the copolymer was formed into a film having a width of 350 mm and a thickness of 30 μm using a commercially available tubular film molding machine for high-pressure polyethylene (manufactured by Modern Machinery).
Molding conditions are resin temperature 180℃, screw rotation speed
100rpm, die diameter 100mm, die slit width 0.7mm
It is. Next, the film was evaluated by the following method. Haze (%): ASTM D 1003 Impact strength (Kg-cm/cm): Measured using a film impact tester manufactured by Toyobo. The spherical surface of the impact head was 1″φ. Elmendorf tear strength (Kg/cm): ASTM D 1922 blocking value (g); According to ASTM D 1893, the peeling bar was made of glass and the peeling strength was 20 cm/min. Heat Sealing start temperature (°C): Using a heat sealer manufactured by Toyo Tester, heat sealing was performed at the specified temperature at a pressure of 2 Kg/cm ² and a sealing time of 1 second. The specimen width was 15 mm, and the peel test speed was 300 mm/min. The sealing start temperature was set at the temperature at which the test piece began to break in the peel test, not due to peeling on the sealing surface, but instead on the thick section.The results are shown in Table 4.Example 2 <Preparation of organoaluminum compound catalyst component> Same as Example 1 except that the molar ratio of ethylaluminum sesquichloride and ethanol was changed to 1:1 instead of 4:3 in Example 1. (B) component was obtained. <Polymerization> Using the same continuous polymerization apparatus as in Example 1, ethyl aluminum sesquichloride was added at 10 mmol/hr, and the (B) component obtained above was converted into Al at 10 mmol/hr. The titanium catalyst component (A) obtained in Example 1 was continuously supplied at a rate of 0.62 mmol/hr, and copolymerization of ethylene and 4-methyl-1-pentene was carried out under the conditions shown in Table 2. The results are shown in Tables 3 and 4. As in Example 1, a copolymer with very narrow molecular weight distribution and composition distribution was obtained. Correspondingly, transparency, impact strength, and heat sealability were improved.This heat seal initiation temperature is comparable to that of a commercially available ethylene-vinyl acetate copolymer film with a vinyl acetate content of 5 wt%. Comparative Example 1 In Example 1, instead of using component (B) obtained in Example 1 as the organoaluminum compound catalyst component, 15 m
Continuous copolymerization was carried out in the same manner as in Example 1, except that the supply rates of 4-methyl-1-pentene and hydrogen were changed as shown in Table 2. The results are shown in Tables 3 and 4. Since the obtained copolymer had a somewhat wide compositional distribution, the blocking resistance of the formed film was insufficient. Examples 3 and 4 <Preparation of organoaluminium compound catalyst component> Component (B) was prepared in the same manner as in Example 1, except that the type of organoaluminum compound and the molar ratio to ethanol were changed as shown in Table 1. At this time, in each case, an organoaluminum compound diluted to 1 mol/mole with hexane was mixed in advance at room temperature, and ethanol diluted to 1 mol/mole/mole with hexane was added dropwise into the mixture. <Polymerization> Using component (B) obtained above as the organoaluminum compound catalyst component and component (A) obtained in Example 1 as the titanium catalyst component, ethylene and α-olefin were combined under the conditions shown in Table 2. Continuous copolymerization was carried out. The results are shown in Table 3. Regarding Example 4, the evaluation results of the molded film are shown in Table 4. Even at such a low density, the pellets could be easily formed without blocking. Due to its low density, the film is extremely transparent and has excellent heat sealability. Comparative Examples 2 and 3 <Preparation of Organoaluminium Compound Catalyst Component> Component (B) was prepared under the conditions shown in Table 1 by changing the type of organoaluminum compound and the molar ratio to ethanol as shown in Table 1. <Polymerization> Copolymerization was carried out under the conditions shown in Table 2 using component (B) obtained above as the organoaluminum compound catalyst component and component (A) obtained in Example 1 as the titanium catalyst component. The results are shown in Tables 3 and 4. In the case of Comparative Example 2, the composition distribution of the obtained copolymer was wide, and the blocking resistance and heat sealability were insufficient. In the case of Comparative Example 3, the polymerization activity was extremely low;
The polymer contained a large amount of catalyst residue and could not be molded due to foaming. Examples 5 to 10 <Preparation of organoaluminum compound catalyst component> The types and molar ratios of the organoaluminum compound, halogen compound other than the organoaluminum compound, and active hydrogen-containing compound bonded to water or oxygen were changed as shown in Table 1. Component (B) was prepared under the conditions shown in 1. <Polymerization> Using component (B) obtained above as the organoaluminum compound catalyst component and component (A) obtained in Example 1 as the titanium catalyst component, ethylene and α-olefin were combined under the conditions shown in Table 2. Continuous copolymerization was carried out. The results are shown in Table 3. In both cases, the molecular weight distribution,
A copolymer with a very narrow composition distribution was obtained. Example 11 <Preparation of Ti catalyst component> Commercially available anhydrous magnesium chloride 1 under nitrogen atmosphere
mol is suspended in dehydrated and purified n-decane 2,
3 mol of 2-ethylhexanol was added with stirring and kept at 120°C for 3 hours. After the reaction, the solid disappeared and became a colorless and transparent solution. In this way, a solution of magnesium chloride-2-ethylhexanol complex in n-decane was obtained. This product remained a colorless and transparent solution even at room temperature. Next, in a separate reactor, add n-decane under nitrogen.
1.5, 2.4 mol of titanium tetrachloride was added, and the mixture was cooled to 0°C. Then, magnesium chloride-2 obtained above
-N-decane solution of ethylhexanol complex
0℃ while stirring 400 mmol in terms of Mg.
It was dripped at. After the dropwise addition, the temperature was raised to 80°C and the mixture was reacted for 1 hour. After the reaction, the solid portion was washed repeatedly with n-decane to form an n-decane suspension. In this way, titanium catalyst component (A) was obtained. <Polymerization> Using ethylaluminum sesquichloride and the component (B) obtained in Example 2 as the organoaluminum compound catalyst component, and the component (A) obtained above as the titanium catalyst component, ethylene was added under the conditions shown in Table 2. and 4-
Copolymerization with methyl-1-pentene was carried out. The results are shown in Table 2. Example 12 <Preparation of titanium catalyst component> 400 mmol of the n-decane solution of the magnesium chloride-2-ethylhexanol complex obtained in Example 11 was taken in terms of Mg, and 80 mmol of ethyl benzoate was added to it at room temperature. It was added and stirred. The system remained a homogeneous liquid. Next, this homogeneous solution is −
The mixture was added dropwise to 3.6 mol of titanium tetrachloride cooled to 20° C. over 1 hour with stirring under a nitrogen atmosphere. Then, the temperature was raised to 90°C and the mixture was reacted for 2 hours. After the reaction, the liquid part was removed, and 2 mol of titanium tetrachloride was added again to react for 2 hours. After the reaction, the solid portion was washed repeatedly with n-decane to obtain an n-decane suspension. In this way, titanium catalyst component (A) was obtained. <Polymerization> Using ethylaluminum sesquichloride and the component (B) obtained in Example 2 as the organoaluminum compound catalyst component, and the component (A) obtained above as the titanium catalyst component, ethylene was added under the conditions shown in Table 2. and 4-
Copolymerization with methyl-1-pentene was carried out. The results are shown in Table 3. Example 13 <Preparation of titanium catalyst component> Using component (A) obtained in Example 1, 400 mmol of ethanol was added to 40 mmol of Ti in terms of Ti at room temperature under a nitrogen atmosphere with stirring. Ta. Then, the temperature was raised to 80°C and the mixture was reacted for 1 hour. After the reaction, cool to room temperature and add triethylaluminum.
125 mmol was gradually added dropwise and reacted for 1.5 hours at room temperature. After the reaction, the solid portion was washed repeatedly with purified hexane and then made into a hexane suspension. In this way, titanium catalyst component (A) was obtained. <Polymerization> Using ethylaluminum sesquichloride and the component (B) obtained in Example 2 as the organoaluminum compound catalyst component, and the component (A) obtained above as the titanium catalyst component, ethylene was added under the conditions shown in Table 2. and 4-
Copolymerization with methyl-1-pentene was carried out. The results are shown in Tables 3 and 4. Comparative Example 4 <Polymerization> In Example 1, ethylaluminum sesquichloride and ethanol were reacted in advance outside the polymerization system instead of using ethylaluminum sesquichloride and ethanol as the organoaluminum compound catalyst component. Continuous polymerization was carried out in exactly the same manner as in Example 1, except that ethanol and ethanol were separately supplied to the polymerization system at the same molar ratio as in Example 1. The results are shown in Tables 3 and 4. The obtained copolymer had a wider molecular weight distribution and a wider composition distribution than that of Example 1, and the performance of the formed film was inferior. Example 14 Using a continuous polymerization reactor with an internal volume of 200, the dehydrated and purified hexane was heated at 100/hr, the organoaluminum compound catalyst component (B) obtained in Example 1 was converted to Al, and the amount was 18 mmol/hr. titanium catalyst component
(A) was continuously supplied at a rate of 0.52 mmol/hr in terms of Ti, and at the same time, ethylene 13
Kg/hr, hydrogen is continuously supplied at a rate of 130/hr,
Polymerization temperature 165℃, total pressure 30Kg/cm ² , average residence time 1
130 h, polymer concentration relative to solvent hexane
Continuous polymerization was carried out under conditions such that g/g/. The MFR of the obtained polymer is 1.77g/10min, Mw/Mn is
2.7, and the density was 0.967 g/cm ³ . Comparative Example 5 Using a continuous polymerization reactor with an internal volume of 100, dehydrated and purified hexane was used at 40/hr, and the organoaluminum compound catalyst component (B) obtained in Example 1 was converted into Al.
The titanium catalyst component (A) obtained in Example 1 was continuously fed at a rate of 5 mmol/hr in terms of Ti, and at the same time, ethylene 13
Kg/hr, 4-methyl-1-pentene 2Kg/hr, hydrogen was supplied so that the hydrogen/ethylene molar ratio in the polymerization vessel was 0.7, polymerization temperature was 60°C, total pressure was 5Kg/hr.
cm ² , copolymer concentration relative to solvent hexane 250
Continuous copolymerization was carried out under conditions such that g/g/. Note that an ethanol tank was connected to the polymerization vessel to remove catalyst residues. The obtained copolymer was evaluated in the same manner as in Example 1. As a result, the NFR was 2.22g/10min, and the density was
0.92g/cm ³ , Mw/Mn is 4.1, U value is 97, HaZe is
18.8%, impact strength was 3100 kg cm/cm, blocking was 10.3 g, and heat sealing start temperature was 135°C.

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【table】 [Brief explanation of drawings]

FIG. 1 is a flowchart showing the steps for preparing a catalyst used in the method of the present invention.

Claims (1)

[Scope of Claims] 1 (A) a highly active titanium catalyst component containing magnesium, titanium, and halogen as essential components; and (B) a halogen-containing organoaluminum compound in which the halogen/aluminum (atomic ratio) is 1 or more and less than 2. Using a catalyst formed from an organoaluminum compound catalyst component obtained by reacting at least a portion of (b-1) with an organic compound (b-2) containing active hydrogen bonded to water and/or oxygen, The polymerization of ethylene or the copolymerization of ethylene and α-olefin is carried out at a polymerization temperature of 100 to 230°C under conditions such that the polymer is soluble in an inert hydrocarbon medium, and at least 90 mol% of repeating units derived from ethylene are present. A method for polymerizing ethylene, the method comprising producing a polymer containing ethylene.