JPS6353203B2 - - Google Patents

Description

[Detailed description of the invention]

[] Object of the Invention The present invention relates to an improved method for producing ethylene polymers. Specifically, the present invention relates to a method for producing an ethylene polymer, which comprises homopolymerizing ethylene or copolymerizing ethylene with other α-olefins using a novel catalyst system with excellent polymerization activity. . More specifically, a solid catalyst component obtained by contacting a tetravalent titanium compound with a pretreated carrier and a catalyst system obtained from an organoaluminum compound have excellent polymerization activity, and have excellent polymerization activity with respect to ethylene and other α-olefins. Homopolymerization of ethylene or copolymerization of ethylene and other olefins using a catalyst system that yields a copolymer with a relatively homogeneous distribution of short chain branches relative to molecular weight (branching degree distribution) during copolymerization. The present invention relates to an improved method for producing an ethylene copolymer, which is characterized by: [] Background of the Invention Conventionally, transition metal halides (for example,
Many proposals have been made to improve the catalytic activity per transition metal by supporting titanium tetrachloride. However, these catalyst systems
Polymerization activity per solid catalyst component is very low. Therefore, there is a problem that a large amount of catalyst residue is contained in the produced polymer, which tends to cause coloring and deterioration of the polymer. In addition, unless the amount of the molecular weight regulator (for example, hydrogen) is increased during polymerization, a polymer having a molecular weight with good moldability cannot be obtained, which causes problems such as reduced productivity. be. On the other hand, many catalyst systems for olefin polymerization using magnesium halides, magnesium alcoholates, and the like as carrier components have also been proposed. These catalyst systems can be catalyst systems with significantly improved polymerization activity compared to catalyst systems using the above-mentioned oxides, but
The copolymerization performance may be low, the halogen content in the catalyst residue of the resulting polymer may be high, and problems may occur in terms of poor color of the polymer and corrosion of the polymerization vessel and molding machine. In order to solve these problems, the present inventors have previously proposed a catalyst system with excellent copolymerizability and high activity (Japanese Patent Application No.
No. 154218, No. 52-46780, No. 52-85684, No. 52
-141487 and 52-148780). However, when catalyst particles are stirred or rolled in a slurry state during polymerization, changes occur over time and the catalyst particles become finer and finer. Average particle size decreases. Therefore, a large amount of finely powdered polymer is produced, which may interfere with continuous polymerization. Furthermore, when producing a relatively high molecular weight polymer, a small amount of lumpy polymer may adhere to the stirring blades or walls of the polymerization vessel, making continuous operation unstable. [] Structure of the Invention Based on the above, the present inventors have conducted various searches to solve these problems (A) (1) "Silicon oxide, aluminum oxide, magnesium oxide, boron oxide and calcium oxide" at least one inorganic oxide selected from the group consisting of
(hereinafter referred to as "inorganic oxide"), (2) aluminum halide, (3) the general formula is Si (OR ¹ ) _n R ² _4-n [in the formula, R ¹ and
R ² may be the same or different, and may be an alkyl group, a cycloalkyl group, or a cycloalkyl group having at most 20 carbon atoms.
A hydrocarbon group selected from the group consisting of an aryl group and an aralkyl group, m
is an integer from 1 to 4. ] (hereinafter referred to as "silicon compound") and (4) a reaction product insoluble in a hydrocarbon solvent obtained by reacting magnesium alcoholate with (5) "the general formula is A solid catalyst component obtained by reacting a titanium compound represented by TiX ₄ (X is a halogen atom) (hereinafter referred to as a titanium compound) and (B) a catalyst system obtained from an organoaluminum compound. The inventors have discovered that an ethylene-based polymer with high polymerization activity can be obtained by homopolymerizing ethylene or copolymerizing ethylene with a small amount of other olefins in the presence of olefins, and has arrived at the present invention. [] Effects of the Invention The effects (characteristics) of homopolymerizing ethylene or copolymerizing ethylene and other olefins in the presence of the catalyst system used in the present invention are as follows. (1) The catalyst system has high activity. Therefore, since the content of catalyst residues in the polymer produced after completion of polymerization is extremely small, the step of removing catalyst residues from the polymer can be substantially omitted. (2) Since the bulk specific gravity (density) of the obtained polymer is relatively high, the productivity of the polymerization process, the drying process of the obtained polymer, and the transfer process is excellent. (3) Due to the low deactivation of the catalyst system used, it is possible to use the catalyst system for a fairly long time. (4) Since the soluble content in the polymerization solvent is small, there are relatively few deposits in the equipment during the polymerization process, so it is possible to produce the polymer without difficulty. (5) Even when the catalyst component (solid catalyst component) is supplied into the reactor in the form of a dilute slurry, the particles of the solid component are relatively hard to be destroyed by stirring or rolling with a centrifugal pump. It is therefore possible to keep the particles relatively large. (6) For example, the high load melt index (melt flow index at a temperature of 190°C and a load of 21.6 kg, hereinafter referred to as "HLMI") is 1.0 g/
Even when producing a high molecular weight polymer in 10 minutes or less, the polymer does not adhere to the blades of the stirrer or the walls of the reactor, thus ensuring stable and long-term operation. Furthermore, the characteristics of copolymerizing ethylene and other olefins are as follows. (1) Since the branching degree distribution of the obtained copolymer is relatively homogeneous regardless of the molecular weight of the polymer, the environmental stress cracking resistance of this copolymer is good. (2) Since the copolymerizability of other olefins (comonomers) is excellent, the polymerization conversion rate of comonomers is higher than that of other catalyst systems. (3) Ethylene polymers with relatively low density (approximately 0.920 g/cc) are heated at relatively low temperatures (generally,
Slurry polymerization is possible at temperatures below 100℃. Therefore, the resulting polymer can be easily recovered. [] Detailed Description of the Invention (A) Hydrocarbon-insoluble products The hydrocarbon-insoluble products used to produce the solid catalyst component used in the present invention include inorganic oxides, aluminum halides, silicon-based compounds, and It is obtained by reacting magnesium alcoholate. (1) Inorganic oxides The inorganic oxides used to produce the hydrocarbon-insoluble products are silicon oxide, aluminum oxide, boron oxide, magnesium oxide and calcium oxide. Moreover, double oxides of these inorganic oxides can also be used. These inorganic oxides have hydroxyl groups on their surface (generally, 1 g of inorganic oxide contains at most 0.1 mole of hydroxyl groups). Among these inorganic oxides, their specific surface area (BET method)
is preferably 10 to 700 m ² /g,
Moreover, those having an average particle size of 1 to 1000 microns are suitable. Among these inorganic oxides, silicon oxide,
Aluminum oxide, silica-alumina, magnesium oxide, boron oxide and magnesium silicate are preferred. (2) Aluminum halides Additionally, the aluminum halides used to produce hydrocarbon-insoluble products are anhydrous, typical examples of which include aluminum chloride, aluminum fluoride, and aluminum bromide, especially aluminum halides. , aluminum chloride is preferred. (3) Silicon-based compounds Furthermore, the silicon-based compounds used to produce hydrocarbon-insoluble products are organic compounds having a Si-OR bond, and their general formula is shown by [formula ()]. be. Si(OR ¹ )mR ² _4-n () In the formula, R ¹ and R ² may be the same or different, and are an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group having at most 20 carbon atoms. It is a hydrocarbon group selected from the group consisting of, m is an integer of 1 to 4. Typical silicon-based compounds represented by formula () include tetramethoxysilane,
Dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydimethylsilane, ethoxytriethylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetra-isopropoxysilane, di-isopropoxy-di-isopropylsilane, dimethoxydiethyl silane,
Diethoxydibutylsilane, tetra-n-butoxysilane, di-n-butoxy-di-n-
Butylsilane, tetra-secondary-butoxysilane, tetrahexoxysilane, tetraoctoxysilane, tetraphenoxysilane,
Mention may be made of tetracresylsilane, diethoxydiphenylsilane, dimethoxydibencylsilane and tri-n-propylaryloxysilane. Among these silicon-based compounds, in the above formula (), R ¹ and R ² are an alkyl group having at most 8 carbon atoms, a phenyl group, or a 5-carbon group.
Those represented by an alkyl group having at most 6 carbon atoms are preferred. Among these silicon compounds, representative examples of preferred ones include dimethyldiethoxysilane, dimethoxydiphenylsilane, tetraethylsilicate, and diethoxydiphenylsilane. (4) Magnesium Alcoholate Additionally, among the magnesium compounds used to produce hydrocarbon-insoluble products,
A typical general formula is shown by the following formula [formula ()]. In the formula Mg(OR ⁷ ) ₂ () (), R ⁷ is a group consisting of an alkyl group having at most 8 carbon atoms, a cycloalkyl group, a cycloalkyl group having an alkyl group, an aryl group, and an aralkyl group. This is a hydrocarbon group selected from Representative examples of these magnesium alcoholates include magnesium methylate, magnesium ethylate, magnesium (n-propylate), (isopropylate) magnesium butyrate, magnesium hexylate, magnesium phenolate, and magnesium cyclohexanolate. , magnesium benzyl alcoholate and magnesium cresolate. Among these magnesium alcoholates, those in which R ⁷ in the formula () represents an alkyl group or a phenyl group having at most 3 carbon atoms are desirable. These suitable magnesium alcoholates include magnesium ethylate, magnesium methylate and magnesium phenolate. (5) Reaction ratio In producing a hydrocarbon-insoluble product, the reaction ratio of inorganic oxide to 1 part by weight of magnesium alcoholate is generally as follows:
It is preferably 0.3 to 10 parts by weight, particularly preferably 0.65 to 4 parts by weight. The reaction ratio of aluminum halide to 1 mol of magnesium alcoholate is generally 0.1 to 10 mol, particularly preferably 0.2 to 2 mol. If the reaction ratio of aluminum halide to 1 mole of magnesium alcoholate is less than 0.1 mole, the polymerization activity of the resulting catalyst system will be low, while if it is more than 10 moles, the bulk specific gravity of the ethylene polymer produced will be low, and As a result, productivity decreases. Furthermore, the reaction ratio of the silicon-based compound to 1 mol of magnesium alcoholate is generally 0.05 to 5 mol, particularly,
0.1-2 mol is desirable. A particularly important factor in this reaction is the reaction ratio of aluminum halide and silicon compound, and the reaction ratio of aluminum halide to 1 mole of silicon compound is usually 0.10 to 10 moles. The optimum molar ratio of this reaction ratio is determined depending on the mode of reaction (for example, simultaneous mixing reaction method or sequential reaction method). This reaction ratio is important because it changes the ease of preparation of the catalyst and the effectiveness of the molecular weight regulator, as well as the polymerization activity. (6) Reaction conditions and post-treatment In order to produce a hydrocarbon-insoluble reaction product, it is preferable to remove the adsorbed water of the inorganic oxide used before production. This removal method (drying method) generally uses 100
A method is used in which the inorganic oxide is dried using dry air at a temperature of .degree. C. to 200.degree. C. while it is allowed to stand still or is allowed to flow. However, if necessary, a method of firing at a higher temperature of 650° C. or lower can also be used. Depending on the drying temperature, the drying time is generally 1 to 12
It's time. The hydrocarbon-insoluble reaction product can be produced by simultaneously mixing and reacting a dried inorganic oxide, aluminum halide, a silicon-based compound, and a magnesium alcoholate, or by adding a silicon-based compound to a dried inorganic oxide. In addition, there is a sequential reaction method in which these are reacted in advance and then the resulting reaction product is reacted with magnesium alcoholate and aluminum halide. All reactions are carried out under a dry (moisture-free) inert gas (eg, nitrogen, argon) atmosphere. Additionally, this reaction is usually carried out in an inert hydrocarbon solvent that is liquid at room temperature. This inert hydrocarbon solvent is an aliphatic, alicyclic or aromatic hydrocarbon, typical examples of which are:
Mention may be made of n-hexane, n-heptane, cyclohexane, methylcyclohexane, benzene and toluene. These inert hydrocarbon solvents may be used alone or in combination of two or more. The amount of inert hydrocarbon solvent used is generally 1 to 50 ml, preferably 2 to 20 ml, per 1 g of magnesium alcoholate. The reaction temperature is generally room temperature (20°C) to 150°C when reacting an inorganic oxide and a silicon-based compound in a sequential reaction method and when reacting the reactant with magnesium alcoholate and aluminum halide, 50°C to 100°C is preferred. Also,
In the simultaneous reaction method as well, the temperature is generally room temperature to 150°C, preferably 50 to 100°C. From the above, in any of the methods, it is possible to
It is preferable to carry out the reaction at a temperature of 50 to 100C for 20 minutes to 5 hours, and it is particularly preferable to carry out the reaction at a temperature of 50 to 100C for 1 to 2 hours at each stage. The hydrocarbon-insoluble product obtained as described above is obtained by removing the supernatant liquid using the inert hydrogen solvent used in the reaction or another hydrocarbon solvent.
The hydrocarbon-insoluble product can then be purified by adding a new hydrocarbon solvent (or even a different type of hydrocarbon), stirring, washing, and removing the supernatant (so-called decanting method) several times. . The color of the solid product (composite carrier) purified in this way varies depending on the type of silicon compound used in the reaction, but it is often white to ocher in color and in powder form. It is a composite carrier containing the elements constituting an inorganic oxide, magnesium, aluminum, and silicon, as determined by atomic absorption spectrometry. (B) Solid catalyst component The solid catalyst component used in the present invention can be produced by reacting the purified hydrocarbon-insoluble product obtained by the above method with the titanium-based compound described below. can. (1) Titanium-based compound The titanium-based compound used to produce the solid catalyst component is represented by the following formula [formula ()]. In the TiX ₄ () () formula, X is a chlorine atom, a bromine atom or an iodine atom. Typical examples of titanium-based compounds include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, with titanium tetrachloride being particularly preferred. (2) Reaction ratio The reaction ratio between the hydrocarbon-insoluble product and the titanium-based compound varies depending on the content of magnesium in the hydrocarbon-insoluble product, but in general, the reaction ratio between the hydrocarbon-insoluble product and the titanium-based compound differs depending on the content of magnesium in the hydrocarbon-insoluble product. The minimum amount required to support the compound as much as possible is sufficient, and the reaction ratio of titanium-based compound per atom of magnesium in the hydrocarbon-insoluble product is usually from 0.1 to 200 mol (preferably from 0.2 to 100 mol). It can be selected from a range, but can vary depending on reaction temperature, concentration and time. The amount of titanium atoms supported on the hydrocarbon-insoluble product (composite support) is generally
Appropriate conditions may be selected such that 1 to 10% by weight is supported. (3) Reaction conditions and purification (post-treatment) In order to produce the solid catalyst component, the hydrocarbon-insoluble product and the titanium-based compound are subjected to inert carbonization, which is used in the production of the hydrocarbon-insoluble product (composite carrier). It can be obtained by reacting in a hydrogen solvent or in the absence of a solvent. The reaction temperature in this reaction varies depending on reaction conditions such as the reaction ratio of titanium-based compound to magnesium in the hydrocarbon-insoluble product and the type of hydrocarbon-insoluble product and titanium-based compound, but in the presence of a solvent. When reacting, the temperature is generally room temperature to 150°C, and particularly preferably 40 to 120°C. If the reaction occurs below room temperature, the reaction will be insufficient. On the other hand, although the desired product can be obtained even if the reaction is carried out at a reaction temperature of 150° C. or higher, it is not necessary. on the other hand,
When performing a reaction in the absence of a solvent, it is desirable to conduct the reaction at a higher temperature than in the presence of a solvent, and the preferred reaction temperature range is 40°C.
~140℃. Although the reaction time varies depending on the reaction conditions and reaction temperature, it is generally 10 minutes to 3 hours, but from the viewpoint of activity it is usually desirable to react for 30 minutes to 2 hours.
If the reaction time is less than 10 minutes, the reaction is insufficient. Moreover, even if the reaction is allowed to take place for more than 3 hours,
Further, the reaction may not proceed and the resulting catalyst system may be deactivated. The solid catalyst component obtained by the above method is generally purified by the following method. That is, the mixture of solid catalyst components and unreacted substances is obtained by decanting the supernatant using the hydrocarbon solvent used during the reaction or another hydrocarbon solvent (preferably one with a relatively low boiling point). Alternatively, it is preferable to remove the titanium-based compound by a filtration method and repeat the washing until the presence of the titanium-based compound is no longer recognized in the washing solution. It is also possible to supply a slurry (substantially free of unreacted titanium compounds) to the polymerization vessel described later. Alternatively, after the hydrocarbon solvent used for washing is removed under reduced pressure, it can be fed as a solid component into a polymerization reactor. (C) Organoaluminum compound The catalyst system used in the present invention is obtained from the solid catalyst component obtained as described above and an organoaluminum compound. The organoaluminum compounds used in the present invention have general formulas represented by the following formulas [formula (), formula () and formula ()]. AlR ⁹ R ¹⁰ R ¹¹ () AlR _1.5 ¹² X _1.5 () In formula (), formula () and formula (),
R ⁹ , R ¹⁰ and R ¹¹ , R ¹² and R ¹³ , R ¹⁴ ,
R ¹⁵ and R ¹⁶ may be the same or different, R ⁹ ,
R ¹⁰ and R ¹¹ are a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group having at most 8 carbon atoms, R ¹² is an alkyl group having at most 8 carbon atoms, and R ¹³ , R ¹⁴ and ^R15
is an alkyl group having at most 8 carbon atoms,
R ¹⁶ is a halogen atom or has at most 8 carbon atoms
X is a halogen atom. At least one of R ⁹ , R ¹⁰ and R ¹¹ is an alkyl group. Representative examples of these include trialkylaluminums such as triethylaluminum, triisobutylaluminum and trihexylaluminum, alkylaluminum halides such as diethylaluminum chloride, ethylaluminum sekischloride and dibutylaluminum chloride, and dialkylaluminums such as diethylaluminum hydride. Mention may be made of hydrides, alkyl aluminum alkoxides such as diethylaluminum ethoxide and dibutyl aluminum methoxide, and alkyl aluminum amides such as diethylaluminium diethyl alumide. Among these organoaluminum compounds, trialkylaluminums are preferred, and trialkylaluminums in which the alkyl group has at most 6 carbon atoms (eg, triethylaluminum, triisobutylaluminum) are particularly preferred. In obtaining the catalyst system used in the present invention, the metal oxides, aluminum halides, silicon-based compounds and magnesium alcoholates used to produce the hydrocarbon-insoluble products, the solid catalyst components used to produce the solid catalyst components, The hydrocarbon-insoluble product, the titanium compound, and the organoaluminum compound may each be used alone or in combination of two or more. (D) Polymerization When carrying out the present invention, the solid catalyst component and organoaluminum compound obtained above may be introduced into the polymerization vessel separately, but they may be mixed in advance. , or may be used after being diluted in advance with an inert organic solvent such as a hydrocarbon. (1) Amount of solid catalyst component and organoaluminum compound used In carrying out the present invention, there is no restriction on the amount of the solid catalyst component and organoaluminum compound obtained as described above, but 1 mg to 1 g of solid component and 0.1 to 10
A proportion of millimoles of organoaluminum compounds used is preferred. In addition, the amount of the organoaluminum compound used is generally 1 to 1000 per atomic equivalent of titanium metal contained in the solid catalyst component.
It is in the molar range. (2) Comonomer In carrying out the present invention, ethylene may be polymerized alone, or ethylene and a comonomer may be copolymerized. The comonomer is a hydrocarbon with a double bond at the end, and the number of carbon atoms is at most 12. Representative examples include propylene, butene-1,
Mention may be made of 4-methylpentene-1, hexene-1, octene-1, butadiene and isoprene. The copolymerization ratio of the above comonomer (olefin) in the obtained ethylene polymer is generally at most 30 mol%,
The content is preferably 20 mol% or less, particularly preferably 10 mol% or less. (3) Other polymerization conditions Polymerization is carried out by dissolving ethylene or ethylene and olefin in an inert solvent, and if necessary, a molecular weight regulator (generally,
(hydrogen) may coexist. Polymerization temperature is generally -10℃ to 200℃
In practical terms, the temperature is above room temperature and below 170°C. In addition, the type of polymerization solvent and the ratio of ethylene or ethylene to olefin are known for the production of ethylene polymers (ethylene homopolymers, ethylene copolymers). Furthermore, the configuration of the polymerization reactor, the method of controlling polymerization,
Regarding the post-treatment method, the ratio of monomer (ethylene or ethylene and comonomer) and organic aluminum to the inert organic solvent used in polymerization, the type of inert organic solvent, and the post-treatment method after completion of polymerization, etc. There are no limitations inherent to this catalyst system, and all known methods can be applied. [] Examples and Comparative Examples The present invention will be explained in more detail below using Examples. In addition, in the examples and comparative examples, the melt index (hereinafter referred to as "MI") is based on JIS K-
Measured by 6760. Also, the true density is JIS K-
Measured by 6760. Furthermore, the bulk density is JIS
Measured by K-6721. In each Example and Comparative Example, each compound used in the production and polymerization of the solid catalyst component (inert organic solvent, ethylene, other olefins, inorganic oxides, aluminum halides, titanium compounds, organoaluminum compounds, silicon compounds,
Hydrogen, etc.) were all substantially free of moisture, and the production and polymerization of each catalyst component were conducted in the absence of substantial moisture and under a nitrogen atmosphere. Examples 1 to 6, Comparative Example 1 [Production of (A) solid catalyst components (A) to (G)] Silicon oxide [manufactured by Dawison, trade name 952, specific surface area 300 m ² /g, average particle size 54 to 65 micron, hereinafter referred to as "SiO ₂ (1)"], silicon oxide aluminum monoxide (manufactured by Dawison, trade name silica alumina, aluminum oxide content 13% by weight, specific surface area)
500m ² /g, average particle size 65 microns, hereinafter referred to as “SiO ₂ −
Al ₂ O ₃ ], silicon oxide [manufactured by Dawison,
Product name Silica 56, specific surface area 300m ² /g, average particle size
65 microns, hereinafter referred to as "SiO ₂ (2)"], magnesium oxide [manufactured by Kyowa Chemical Industry Co., Ltd., trade name Kiyowa Mag 20, specific surface area 20 m ² /g, average particle size 74 microns,
Magnesium oxide (manufactured by Kyowa Kagaku Kogyo Co., Ltd., trade name Kiyowa Mag 150, specific surface area 150 m ² /g, average particle size 74 microns or less, hereinafter referred to as "MgO(2)"); Activated aluminum oxide (manufactured by Wako Pure Chemical Industries, Ltd., for column chromatography, average particle size
70 microns, hereinafter referred to as "Al ₂ O ₃ "
It was dried for 8 hours using a hot air dryer at 140°C. The above dried inorganic oxide and toluene were added to a 200 ml three-necked flask in the amounts shown in Table 1-1. Subsequently, aluminum chloride (granules of 2 to 16 meshes), dimethyldiethoxysilane (as a silicon compound) and magnesium ethylate [as magnesium alcoholate]
Mg(OC ₂ H ₅ ) ₂ ] was added and mixed at a molar ratio of 2:2:1, and the reaction was carried out at a temperature of 90° C. for 90 minutes with stirring. The solid product obtained was washed several times by decanting method, each time using about 50 ml of n-hexane. Each solid product obtained has a first
Titanium tetrachloride shown in Table 1 was added, and each reaction was carried out at a temperature of 90°C for 90 minutes. Approximately 60 ml of the supernatant liquid of each solid catalyst component obtained was
- Washed several times using hexane until substantially unreacted titanium tetrachloride was no longer detected, and then dried under reduced pressure for 1 hour. The solid catalyst component obtained had an ocher to gray color. Their yields are shown in Table 1-1.

[Table] [(B) Copolymerization of ethylene and butene-1] The solid catalyst components obtained in Examples 1 to 6 and Comparative Example 1 (A) were sufficiently added in the amounts shown in Table 1-2. The mixture was placed in a dry 1.2 autoclave under nitrogen flow. After injecting 0.7 mmol of triisobutylaluminum (as a 0.5 molar solution in n-heptane), an additional 346 g of isobutane (as solvent) was added and the polymerization system was sealed. 150% hydrogen under standard conditions using a micro cylinder
An amount equivalent to 1 ml was injected under pressure, and the temperature of the polymerization system was raised. The hydrogen partial pressure at the polymerization temperature of 85°C was 0.23Kg/cm ² . While maintaining this temperature, ethylene was immediately injected continuously to maintain an ethylene partial pressure of 5 kg/cm ² . In addition, butene-
1 at the feed ratio to ethylene (first
Copolymerization of ethylene and butene-1 was carried out (as shown in Table 1-2), and ethylene and butene-1 were copolymerized (copolymerization times are shown in Table 1-2).
After the copolymerization was completed, the solvent and monomer were discharged from the relief line, and the pressure was removed. Each of the obtained powdered ethylene and butene-1 copolymers was dried for 3 hours using vacuum drying at 80°C. The yield and calculated specific activity of each copolymer are shown in Table 1-2. The powder of each copolymer is sieved as it is,
Table 1-2 shows the average particle size (in microns) that is plotted on log probability paper and corresponds to an integral amount of 50%. The powders of each copolymer obtained in Examples 1 to 6 and Comparative Example 1 both showed a lognormal distribution, which means that the powder with a larger average particle size has less fine powder. Each of the copolymers obtained in Examples 1 to 6 exhibited the effect of reducing the cyclohexane soluble content and increasing the copolymer particle size compared to the copolymer obtained in Comparative Example 1. It is clear that For these examples, copolymerization in an autoclave was repeated in 4 or 5 batches, but no lumps were observed to adhere to the vessel wall.

[Table] Example 7 [(A) Production of solid catalyst component] As in (A) of Example 1, 3.13 as an inorganic oxide
g of boron oxide (B ₂ O ₃ ), aluminum chloride 7.30
g (54.7 mmol) and 51.0 ml of toluene.
The reaction was carried out in a 200 c.c. flask with stirring.
Next, 8.14 g of dimethyldiethoxysilane (54.8 mmol) was gradually added dropwise, and an additional 3.13 g
of magnesium ethylate (27.4 mmol) was added and the reaction was carried out at a temperature of 90° C. for 90 minutes. After the reaction system was cooled to about 40°C, 54 ml of the supernatant was taken out to obtain a pale reddish brown precipitated product. An additional 39 ml of n-hexane was added to this product (composite carrier) for washing. This washing was performed three times. 14.2 ml of titanium tetrachloride was added to this washed composite carrier, and a reaction was carried out at a temperature of 90° C. for 90 minutes. After the completion of this supporting reaction, washing was performed using 60 ml of n-hexane, and the solid catalyst component was washed by a declination method until substantially no titanium tetrachloride could be detected in the washing solution, and then the solid catalyst component was washed under reduced pressure at a temperature of 50°C. It was dried for 1 hour. As a result, 7.12 g of ocher solid catalyst component was obtained. [(B) Copolymerization of ethylene and butene-1] Instead of the solid catalyst component (A) used in (B) of Example 1, the solid catalyst component obtained in (A) above was used.
Example 1 except that 32.6 ml was used and the feed ratio of butene-1 to ethylene was changed to 2.90% by weight.
Copolymerization of ethylene and butene-1 was carried out for 90 minutes in the same manner as in (B). As a result, 258 g of a white powdery copolymer was obtained. That is, the specific activity is 1054
g/g - solid catalyst component, time, and ethylene partial pressure (atmospheric pressure). The bulk density of the obtained copolymer was 0.28
g/cc, and the true density was 0.9288 g/cc.
Furthermore, the HLMI of this copolymer was 1.22 g/10 min, and the average particle size was 800 microns. Also,
No adhesion was observed inside the reactor. Examples 8 to 10 [Production of (A) solid catalyst components (H) to (K)] SiO ₂ (2) used as the inorganic oxide in the production of the solid catalyst component (A) of Example 3 was 3.00% each. g
The molar ratios of aluminum chloride (AlCl ₃ ), dimethyldiethoxysilane [(CH ₃ ) ₂ Si(OC ₂ H ₅ ) ₂ ] and magnesium ethylate [Mg(OC ₂ H ₅ ) ₂ ] were The reactions were carried out in the same manner as in Example 2 (A), except that the reactions were changed as shown in Table 1. The obtained solid product was washed in the same manner as in Example 2 (A). 13.6 ml of titanium tetrachloride was added to each of the obtained solid products to conduct a reaction. Each of the obtained reaction products was washed and dried in the same manner as in Example 2 (A). The yield of each solid catalyst component is shown in Table 2-1. [(B) Copolymerization of ethylene and butene-1] The amounts of each solid catalyst component obtained in (A) above were used as shown in Table 2-2, and the feed ratio of butene-1 to ethylene was determined as shown in Table 2-2. Copolymerization of ethylene and butene-1 was carried out under the same conditions as in Example 3 (B), except that the conditions were changed as shown in Table 2-2 and the copolymerization time was changed to 90 minutes for each. .
The yield of each copolymer obtained, the specific activity determined from it, and the bulk density of each copolymer,
The true density, MI, HLMI/MI and average particle size are shown in Table 2-2.

【table】

[Table] Examples 11 to 13, Comparative Example 2 Solid catalyst components (B), (C) and (F) produced in (A) of Examples 2, 3 and 6 and produced with (A) of Comparative Example 1 Take out 1 g of each solid catalyst component (G),
Weigh it under a nitrogen stream, add it to n-paraffin,
The slurry was adjusted so that each concentration was 2% by weight. Each was continued to be stirred using a magnetic stirrer. After a certain period of time (shown in Table 3) had passed, the slurry of each solid catalyst component was extracted with a syringe and injected into the autoclave as a slurry. Furthermore, a copolymer of ethylene and butene-1 was produced under the same conditions as in Example 2 (B) except that the feed ratio of butene-1 to ethylene was changed as shown in Table 3. The specific activities of each are shown in Table 3. of each copolymer obtained
HLMI, true density and average particle size are shown in Table 3. Table 3 shows that in Comparative Example 2, the average particle size of the copolymer obtained in Examples 11 to 13 decreases to 250 microns when using the slurry that has been stirred for one day. The average particle size of the aggregate is relatively large, indicating that the solid catalyst component is unlikely to become fine.

[Table] Example 14 [(A) Production of solid catalyst component (L)] 3.00 g of MgO(2) and
0.60 g of tetraethyl silicate (2.88 mmol) was charged and 22.5 ml of toluene was added as a solvent. After reacting at a temperature of 90℃ for 60 minutes with stirring, the supernatant liquid was removed, and the mixture was diluted with 15 ml of toluene.
The supernatant was washed twice. Then 3.00 g of magnesium ethylate (26.2 mmol) and 40 ml of toluene were added. Then, 3.50 g of aluminum chloride (26.2 mmol) was added, and the reaction was carried out for 90 minutes with stirring at a temperature of 90°C. The solid product obtained was diluted with 38 ml of n-hexane each.
Washed twice. Add 23 ml of titanium tetrachloride to this solid product and add 90 ml of titanium tetrachloride to this solid product while stirring at a temperature of 90°C.
The reaction was carried out for minutes. After completion of the reaction, (A) of Example 1
Washing and drying were carried out in the same manner as above. the result,
8.5 g of a light cream-colored solid catalyst [hereinafter referred to as "solid catalyst component (L)"] was obtained. [(B) Copolymerization of ethylene and butene-1] The polymerization time was changed to 60 minutes, and the solid catalyst component (A)
Same conditions as Example 1 (B) except that the amount of solid catalyst component (L) used instead, the hydrogen partial pressure, and the feed ratio of butene-1 to ethylene were changed as shown in Table 4. Copolymerization of ethylene and butene-1 was carried out. After each copolymerization, (B) of Example 1
Post-processing was performed in the same manner. Specific activity of each catalyst system and MI, HLMI of each copolymer,
Table 4 shows the ratio of HLMI to MI and the true density. Table 4 shows that when ethylene and butene-1 are copolymerized using the solid catalyst component obtained by this sequential reaction method, the amount of copolymerization obtained is higher than that obtained by the simultaneous mixing reaction method. It can be seen that the molecular weight distribution (HLMI/MI) of the polymer has become broader.

[Table] Examples 15 to 20 The solid catalyst components (A) to (F) obtained in Examples 1 to 6 (A) were used in the amounts shown in Table 5, and butyn-1 was not used. Otherwise, ethylene was independently polymerized under the same conditions as in Example 2 (B). After the polymerization was completed, post-treatment was carried out in the same manner as in Example 1 (B). The yield of each ethylene monopolymer obtained, the specific activity of each catalyst system determined from them, and the bulk density, true density, and
The HLMI is shown in Table 5.

[Table] Comparative Example 3 A solid catalyst was prepared in the same manner as in (A) of Example 1, except that the aluminum chloride used in producing the solid catalyst component (A) in (A) of Example 1 was not used. produced the ingredients. Then, washing and drying were performed in the same manner as in Example 1 (A). In place of the solid catalyst component (A) used to produce the copolymer of ethylene and butene-1 in (B) of Example 1, 25.4 mg of the solid catalyst component obtained as described above was used. Copolymerization of ethylene and butene-1 was otherwise carried out under the same conditions as in Example 1 (B). Then, post-treatment was carried out in the same manner as in Example 1 (B). As a result, 138.5 g of copolymer was obtained.
That is, the specific activity is 1091 g/solid catalyst component (g), time, and ethylene partial pressure (atmospheric pressure). The bulk density of this copolymer is 0.23 g/cc, and the HLMI is 1.09.
g/10 minutes. Comparative Example 4 A solid catalyst component was produced in the same manner as in (A) of Example 1, except that the magnesium ethylate used in producing the solid catalyst component (A) in (A) of Example 1 was not used. Manufactured. Then, washing and drying were performed in the same manner as in Example 1 (A). In place of the solid catalyst component (A) used to produce the copolymer of ethylene and butene-1 in (B) of Example 1, 90.3 mg of the solid catalyst component obtained as described above was used. Copolymerization of ethylene and butene-1 was otherwise carried out under the same conditions as in Example 1 (B). Then, post-treatment was carried out in the same manner as in Example 1 (B). As a result, 14.2 g of copolymer was obtained.
That is, the specific activity is 31.4 g/solid catalyst component (g), time, and ethylene partial pressure (atmospheric pressure). The bulk density of this copolymer is 0.18 g/cc, and the HLMI is 0.075 g/cc.
It was hot in 10 minutes. From Comparative Examples 3 and 4, when producing a solid catalyst component, ethylene and butene-1 were copolymerized using a solid catalyst component produced without using either aluminum halide or magnesium alcoholate. , the bulk density of the copolymer obtained is lower than that of the above examples. moreover,
It is clear that not only the effect of molecular weight adjustment by hydrogen is poor, but also the activity is low.

[Brief explanation of the drawing]

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

Claims (1)

[Scope of Claims] 1 (A)(1) At least one inorganic oxide or double oxide selected from the group consisting of silicon oxide, aluminum oxide, magnesium oxide, boron oxide, and calcium oxide; (2) halogen; aluminum oxide, (3) whose general formula is Si(OR ¹ ) _n R ² _4-n [wherein R ¹ and
R ² may be the same or different, and may be an alkyl group, a cycloalkyl group, or a cycloalkyl group having at most 20 carbon atoms.
A hydrocarbon group selected from the group consisting of an aryl group and an aralkyl group, m
is an integer from 1 to 4] and (4) a reaction product insoluble in a hydrocarbon solvent obtained by reacting magnesium alcoholate (5) with the general formula TiX ₄ (X is a halogen It is an atom.)
(B) Homopolymerization of ethylene or copolymerization of ethylene with a small amount of other olefins in the presence of a solid catalyst component obtained by reacting a titanium-based compound represented by An improved method for producing an ethylene polymer, comprising polymerization.