JPS6254325B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing ethylene using a catalyst comprising a special solid catalyst component containing a titanium or vanadium compound and an organoaluminum compound, in which the bulk specific gravity of the polyethylene powder is extremely high;
The object of the present invention is to provide a method for producing a polymer with uniform particle size at a good yield. In recent years, various techniques have been proposed for the purpose of increasing the catalyst efficiency and omitting the catalyst removal step in so-called Ziegler-type olefin polymerization catalysts comprising a transition metal compound and an organometallic compound.

In other words, a group of catalysts using a reaction product of an inorganic magnesium compound and a titanium or vanadium compound has been proposed as a highly active catalyst, and the polymer yield per transition metal and per solid catalyst component has reached a sufficiently high level. There are some.

However, there is an ever-increasing need to reduce construction and manufacturing costs by simplifying the process, and to this end, it is necessary to improve the catalyst components to increase the activity per transition metal and solid catalyst component, and to use such catalysts. When carrying out continuous slurry polymerization, it is necessary to enable efficient long-term continuous operation. To achieve this, it is necessary to obtain a polymer with a high bulk specific gravity with a uniform particle size and less formation of fine polymers.This will increase the slurry concentration, reduce the amount of solvent used, and further increase the It becomes possible to reduce construction costs and manufacturing costs.

The present inventors have been conducting various studies on polymerization catalysts for some time, and have developed a method for polymerizing ethylene with high catalytic activity and producing polyethylene with good powder properties using specific organosilicon compounds and organomagnesium compounds. He invented a method using a catalyst consisting of an organometallic compound and a solid catalyst component insoluble in an inert hydrocarbon solvent obtained by reacting the reaction product with a halogen-containing compound of titanium or vanadium. A patent application was filed as No.

According to this method, the polyethylene yield per unit weight of the transition metal and solid catalyst component is high, and even if the resulting polyethylene is omitted from the purification step after polymerization, it can be easily processed by the molding process caused by the catalyst residue. This was extremely preferable as it did not cause rusting of the machine or coloring or deterioration of the molded product. It was also excellent in terms of powder properties such as a narrow particle size distribution of polyethylene and a relatively high bulk specific gravity.

In particular, the higher the bulk specific gravity is, the more likely it is that (1) during polymerization operation;
Since the concentration of the polymer slurry can be maintained high, the production capacity of the polymerization vessel can be improved. (2) The amount of solvent used relative to the amount of unit polymer produced can be reduced. (3) Since the solvent content in the obtained wet cake is reduced, the amount of heat required for drying the polymer can be saved. (4) The silo for storing dried polymers can be small. (5) When pelletizing, the pelletizer has good bite and capacity is improved. For the following reasons, it is desired that it be as high as possible.

An object of the present invention is to provide a method for producing polyethylene having a uniform particle size and particularly high bulk specific gravity using a highly active catalyst.

The present invention comprises (a) a reaction product [A] of a hydropolysiloxane or a silicon compound in which an organic group and a hydroxyl group are bonded to a silicon atom, and an organomagnesium compound, and (b) a halogen-containing compound of titanium or vanadium. , magnesium 1 in the reaction product [A]
The reaction is carried out at a ratio of 0.05 to 0.5 mol per gram atom, and then (c) aluminum alkoxide, and (d) general formula SiXnY _4-o (where X: Cl or
Br, Y: hydrogen, alkyl group, or alkoxy group n: represents an integer from 1 to 4, respectively. ) to the reaction product [B] obtained by reacting the halogen-containing silicon compound represented by (d)
Solid catalyst component [C] obtained by reacting a halogen-containing compound of titanium or vanadium,
and An improved method for polymerizing ethylene, characterized in that ethylene is polymerized using a catalyst comprising an organoaluminum compound.

In the ethylene polymerization method using the catalyst of the present invention, the activity per transition metal and per solid catalyst component is extremely high, so it is not only excellent as a catalyst for use in processes that omit the catalyst removal step, but also has fine particles. It has extremely excellent particle properties, such as less generation of coarse particles that interfere with polymer production and continuous polymerization, and a polymer with uniform particle size and high bulk specific gravity can be obtained.

The hydrobolysiloxane used in the production of the reaction product [A] in the present invention has the following general formula R'aHbSiO4-ab/2...(1) (where R' is an alkyl group, an aryl group, A monovalent organic group selected from the group consisting of an aralkyl group, an alkoxy group, and an alloxy group, a represents 0, 1 or 2, b represents 1, 2 or 3, and a+b≦3
It is. ) or a mixture thereof with a structural unit shown in
Examples include those in the form of grease or wax with various degrees of polymerization up to centistokes, and those in the form of solids. Since the structure of the terminal group of this hydropolysiloxane does not significantly affect the activity, it may be capped with any inert group such as a trialkylsilyl group. Specific examples include tetramethyldisiloxane, diphenyldisiloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, ethoxyhydropolysiloxane, cyclooctylhydropolysiloxane, and chlorophenyl. Examples include hydropolysiloxane.

Another group of silicon compounds used in the production of the reaction product [A] in the present invention are those in which an organic group and a hydroxyl group are bonded to a silicon atom, and have the following general formula R ² _o Si (OH ) _4-o ...() (However, R ² represents a monovalent hydrocarbon residue having 1 to 18 carbon atoms, and n represents a number of 1, 2 or 3, and R ² in one molecule. When a plurality of compounds exist, they may be the same or different.) and polysiloxane compounds corresponding to condensates thereof. Examples of R ² in formula () include alkyl groups, cycloalkyl groups, aralkyl groups, aryl groups, alkaryl groups, etc., which are linear, branched, saturated, unsaturated, Any cyclic type may be used. Examples of the silane type compound represented by the above formula () where n is 3 include trimethylhydroxysilane, triethylhydroxysilane, triphenylhydroxysilane,
Examples include methyldiphenylhydroxysilane and benzyldiphenylhydroxysilane. Also n
Examples of compounds where is 2 include diethyldihydroxysilane, dipropyldihydroxysilane, diallyldihydroxysilane, dicyclohexyldihydroxysilane and diphenyldihydroxysilane. Furthermore, examples of compounds where n is 1 include butyltrihydroxysilane,
Examples include phenyltrihydroxysilane.

As a polysiloxane type compound corresponding to the bond of the compound represented by the above formula (), Si-O-
Those with a linear, branched or three-dimensional network structure having Si siloxane condensation are used, and there is no particular restriction on the degree of polymerization, ranging from a low degree of polymerization with a viscosity of several centistokes at 25°C. Examples include those in the form of grease or wax with a density of 1,000,000 centistokes, and those in the form of a complete solid.
As shown in formula (), any polysiloxane type compound can be used as long as it contains one or more hydroxyl groups per molecule, but compounds with too few hydroxyl groups are not practical. The content of hydroxyl groups in the polysiloxane type compound is preferably 0.1% by weight or more. Examples of the polysiloxane type compounds used in the present invention include HO[Si(CH ₃ ) ₂ O]
α,ω-dihydroxydimethylpolysiloxane represented by nH (where n represents an integer of 2 or more), HO[Si(CH ₃ ) (C ₆ H ₅ )O] nH (where n
represents an integer greater than or equal to 2. ) denoted by α, ω-
Examples include dihydroxymethylphenylpolysiloxane. Of course, a mixture of two or more of the silicon compounds represented by the above general formulas () and () can be used in producing the reaction product [A] in the present invention, and also has high catalytic efficiency. It does not necessarily have to be pure as long as it can be obtained.

The organomagnesium compound used in the production of the reaction product [A] in the present invention has the general formula (MgR ³ ₂ ) _p・(R ³ MgX) _q ……( ) (However, R ³ represents a hydrocarbon group, X represents a halogen atom, and p and q represent numbers from 0 to 1,
It has the relationship p+q=1. ), its ether complex compound, or a mixture thereof; for example, a so-called Grignard reagent in the narrow sense, represented by R ³ MgX where p is 0 and q is 1, p
is 1 and q is 0. Dihydrocarbylmagnesium represented by R ³ ₂ Mg, other (MgR ³ ₂ ) _p .
(R ³ MgX) Various organic magnesium halides represented by _q , their ether complexes, or mixtures thereof. These organomagnesium compounds are prepared by a conventionally known method, for example, in an ether solvent such as diethyl ether, dibutyl ether, or tetrahydrofuran, or in a hydrocarbon solvent such as heptane, octane, benzene, toluene, etc., using an appropriate amount of a complexing agent such as an ether or an amine. easily synthesized in the presence of

The reaction product [A] used in the present invention is a hydropolysiloxane represented by the above formula (), ()
It can be easily obtained by reacting a silicon compound represented by the formula or a condensate thereof with an organomagnesium compound represented by the general formula () by any method. For example, the reaction between a hydropolysiloxane and an organomagnesium compound reagent can be carried out by adding the hydropolysiloxane little by little to an organomagnesium compound synthesized in an appropriate solvent while stirring.
This can be done by heating for a predetermined period of time after adding the entire amount. This reaction proceeds at room temperature with a strong exotherm, but in order to complete the reaction it is preferred to heat the reaction mixture at 50-100°C for 1-5 hours. However, this operation is not always necessary. The charging ratio of hydropolysiloxane and organomagnesium compound is MgR ³ :Si molar ratio of 0.05.
It is preferable to set the ratio to 1:1. Further, the reaction between the silicon compound and the organomagnesium compound represented by the above formula () can be carried out by, for example, adding the organomagnesium compound synthesized in a suitable solvent little by little to the silicon compound while stirring in an inert gas atmosphere. After adding the entire amount, stirring is continued for a certain period of time to complete the reaction. In this case, the silicon compound may be used alone, but it is also preferable to use it diluted with a solvent such as a hydrocarbon solvent.
This reaction can generally be carried out at a temperature of -50℃ to 100℃, and the time required for the reaction is 30 minutes to 5 minutes.
Time is enough. The charging ratio is preferably such that the ratio of magnesium hydrocarbon bonds (Mg-R ³ ) to hydroxyl groups (OH) of the silicon compound OH:MgR ³ is in the range of 1:0.05 to 1 in terms of molar ratio. You can select any percentage within the range.

The reaction product [A] thus obtained can be used as a reaction mixture to produce the solid catalyst component [C] via the reaction product [B], but it contains a large amount of ethers derived from the organomagnesium compound. When the reaction product [B] is dissolved or suspended in an inert hydrocarbon solvent, generally some or all of the solvent is removed from the reaction mixture containing the reaction product [A], and the reaction product [B] is dissolved or suspended in an inert hydrocarbon solvent. Provided for manufacturing.

The titanium halogen-containing compound used in the production of the reaction product [B] in the present invention has the general formula TiXn(OR ⁴ ) _4-o (where X is a halogen atom,
R ⁴ is a hydrocarbon group having 1 to 8 carbon atoms, and
n represents an integer from 1 to 4. ), examples of which are TiCl ₄ , TiBr ₄ , Ti
(OC ₂ H ₅ ) Cl ₃ , Ti (OC ₄ H ₉ ) Cl ₃ , Ti
(OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti
(OC ₄ H ₉ ) ₂ Cl ₂ and the like. In addition, examples of vanadium halogen-containing compounds used in the production of the reaction product [B] in the present invention include:
Examples include VCl ₄ and VOCl ₃ .

The third component used in the production of reaction product [B] is aluminum alkoxide, which has the general formula
It is represented by Al(OR ⁵ ) ₃ (wherein R ⁵ represents a hydrocarbon group having 1 to 10 carbon atoms). Specific examples include triethoxyaluminum, tripropoxyaluminum, tributoxyaluminum, trioctoxyaluminum, and the like.

The fourth component used in the production of the reaction product [B] has the general formula SiXnY _4-o (where X: Cl or Br, Y: hydrogen, alkyl group or alkoxy group, n: 1 to 4 each represents an integer of ). Specifically, for example, silicon tetrachloride, silicon tetrabromide, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane,
These include dimethyldichlorosilane, ethoxytrichlorosilane, butoxytrichlorosilane, diethoxydichlorosilane, and the like.

In producing the reaction product [B], various methods can be used to react the four components consisting of the reaction product [A], a halogen-containing compound of titanium or vanadium, an aluminum alkoxide, and a halogen-containing silicon compound. However, it is preferable that the reaction product [A] is first reacted with a halogen-containing compound of titanium or vanadium, and then reacted with an aluminum alkoxide and a halogen-containing silicon compound. Either one of the aluminum alkoxide and the halogen-containing silicon compound may be added to the reaction system and the remaining components may be added after the reaction, or the two components may be added at the same time and reacted.
In the above reaction, an inert hydrocarbon solvent is used,
It is particularly preferred to carry out the reaction in an aromatic or halogenated aromatic solvent such as benzene, toluene, chlorobenzene and the like.

The reaction between the reaction product [A] and the halogen-containing compound of titanium or vanadium is usually carried out at -30 to 50°C for 30°C.
It lasts from minutes to 3 hours. The quantitative ratio of both components is 1 mol or less of the halogen-containing compound of titanium or vanadium per 1 gram atom of magnesium in the reaction product [A], preferably 0.05 to 0.5 mol. That is, even if the amount of titanium or vanadium is less than this range, there is a tendency for the bulk specific gravity to decrease.

The obtained reaction product is further reacted with an aluminum alkoxide and a halogen-containing silicon compound, but in both cases, the temperature is 30 to 150°C.
A reaction time of minutes to 5 hours is sufficient. In this case, the quantitative ratio of each component is 0.1 to 3 mol of aluminum alkoxide and 0.2 to 3 mol of halogen-containing silicon compound per 1 gram atom of magnesium in the reaction product [A].
In the range of 10 moles.

The reaction product [B] thus obtained is reacted again with a halogen-containing compound of titanium or vanadium to prepare a solid catalyst component [C]. In this case, the halogen-containing compound of titanium or vanadium is the compound specified above. chosen from the group. The reaction conditions are 0 to 150°C, 30 minutes to 5 hours, and the component amount ratio is halogenated titanium or vanadium per gram atom of magnesium in the reaction product [B].
The proportion is between 0.3 and 30 moles.

In this way, solid catalyst component [C] is produced,
The soluble components are removed from the reaction mixture by washing with an inert hydrocarbon solvent such as hexane, heptane, kerosene, etc., and the solid catalyst component [C] is recovered.

One component of the present catalyst system is an organoaluminum compound, specific examples of which are trimethylaluminum, triethylaluminum, tributylaluminum, diethylaluminum chloride, dibutylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum hydride, dibutylaluminum hydride diethyl Examples include aluminum ethoxide.

The ethylene polymerization catalyst used in the present invention can be produced by contacting the solid catalyst component [C] with the organoaluminum compound in the presence or absence of an inert solvent, for example, in a catalyst preparation container or in a polymerization reaction. It can be easily adjusted by charging both in the presence of a solvent in a vessel and stirring. The preferred ratio of the two for forming the ethylene polymerization catalyst is 1 to 1 aluminum per gram atom of titanium or vanadium in the solid catalyst component [C].
1000 grams atom. If the polymerization catalyst is prepared in a polymerization reactor, after the formation of the catalyst, ethylene is fed into the same vessel, or if the polymerization catalyst is prepared in a separate vessel, the catalyst suspension is Ethylene can be easily polymerized by charging it into a polymerization reactor and supplying ethylene into the same container.

The ethylene polymerization conditions in the ethylene polymerization method of the present invention may be almost the same as those when using a general Ziegler type catalyst. That is, this can be easily carried out by dispersing the catalyst of the present invention in a suitable inert hydrocarbon solvent such as hexane, heptane, kerosene, etc., and introducing ethylene into the solvent. The preferred polymerization temperature is 30 to 200°C, particularly 60 to 100°C, and the polymerization pressure is preferably normal pressure to 50 kg/cm ² . In this case, the amount of catalyst used is preferably 0.1 to 50 mmol, particularly 0.3 to 10 mmol, of the organoaluminum compound per solvent.

The molecular weight of the polymer obtained by the method of the present invention can be adjusted arbitrarily by changing the polymerization temperature, the amount of catalyst used, etc., but the most effective adjustment method is to add hydrogen to the polymerization system. be.

The polymerization catalysts used in the present invention are useful in the polymerization of ethylene and the copolymerization of ethylene with up to about 10% of alpha-olefins such as propylene, butene-1, hexene-1, and the like.

The present invention will be explained in more detail below with reference to Examples, but the technical scope of the present invention is not limited thereto.

The measurement method is as follows.

MI ₂ : Melt index (ASTM-D-1238
-65T, 190℃, load 2.16Kg) Bulk specific gravity: In accordance with JISK6721-1966.

Example 1 (1) Preparation of reaction product [A] 75 ml of a tetrahydrofuran solution of n-butylmagnesium chloride (0.167 mol as n-butylmagnesium chloride) was collected in a glass reactor whose interior had been thoroughly dried and purged with nitrogen. 10.5 ml (0.175 mol as Si) of methylhydropolysiloxane (viscosity at 25° C., approximately 30 centistokes) whose ends were capped with trimethylsilyl groups was gradually added dropwise with stirring. Since there was heat generation, the reactor was cooled with a refrigerant, and after the total addition, the reactor was kept at 70°C for 1 hour, and then cooled to room temperature to obtain a dark brown transparent solution. A portion of this solution was taken and published in the Journal of the American Chemical Society.
American Chemical Society) Volume 47 (1925)
The presence or absence of unreacted n-butylmagnesium chloride was examined by the method of Gilman et al. described on page 2002, and as a result, no unreacted n-butylmagnesium chloride was present.

Dilute this solution with 100 ml of toluene to remove excess tetrahydrofuran and add 160-170 m m
120 ml of a mixture of tetrahydrofuran and toluene was distilled off from this solution under reduced pressure of Hg. Next, add another 120 ml of toluene and prepare a mixture of tetrahydrofuran and toluene in the same manner as above.
120ml was distilled off. The obtained solution was diluted with toluene to give an Mg concentration of 1.48 mol/.

(2) Production of solid catalyst component [C] Into a glass reactor equipped with a stirrer whose interior was thoroughly dried and replaced with nitrogen, 70 ml of a toluene solution of the reactive product [A] obtained in (1) was added (103.6 as Mg). m
(equivalent to mol), take 89 ml of toluene, add 2.3 ml of titanium tetrachloride and 13 toluene separately collected in a dropping funnel.
ml was added dropwise over 10 minutes at 0°C. Next, 51.8 ml of a toluene solution (1 mol/) of aluminum triisopropoxide was added, followed by silicon tetrachloride.
A solution consisting of 23.7 ml and the same amount of toluene was heated to 50-60℃.
was added dropwise over 30 minutes. After dropping, the temperature is raised,
The reaction was carried out under reflux for 2 hours. Next, titanium tetrachloride
22.8 ml was added dropwise at 50°C, and the reaction was continued for 2 hours.

N-hexane was added to the slurry thus produced, and the soluble components were filtered through with a slant, and this operation was repeated several times to obtain an n-hexane slurry of solid catalyst component [C]. The titanium content in this solid catalyst component [C] was 27.9 mg/g.

(3) Polymerization of ethylene Pour 600 ml of n-hexane into a stainless steel autoclave with a capacity of 1.6 and equipped with a stirrer whose interior is dried and replaced with nitrogen, and a jacket for heating and cooling.
After heating to 60℃, triisobutylaluminum
0.5m mol, solid catalyst component [C]4 obtained in (2) above
mg were added sequentially.

Next, 2.5 kg/cm ² of hydrogen was introduced, the temperature was raised to 75° C., and then polymerization was carried out for 1 hour while continuously introducing ethylene so that the total pressure was 8 kg/cm ² (gauge pressure). After cooling, the polymer was directly separated from the solvent and dried.

91 g of white powdered polyethylene was obtained, which had a bulk specific gravity of 0.405 and an MI ₂ of 0.38. Catalytic activity is 815KgPE/gTi・hr and 22.7Kg
Corresponds to PE/gcat・hr. (Here, KgPE/gTi・
hr represents the polyethylene yield per 1 hour of polymerization time per 1 g of titanium, and KgPE/gcat·hr represents the polyethylene yield per 1 hour of polymerization time per 1 g of solid catalyst component [C]. ) Also, the average particle size of this polyethylene is 320μ,
The proportion of fine particles of 100μ or less was 1% or less, and the distribution was sharp.

Example 2 (2) Production of solid catalyst component [C] To the reaction product [A] obtained in the same manner as in Example 1, titanium tetrachloride was first added per gram atom of magnesium in the reaction product [A]. After adding at a rate of 0.5 mol, solid catalyst component [C] was produced in exactly the same manner as in Example 1 (2). The titanium content in the obtained solid catalyst component [C] was 35.5 mg/g.

(3) Polymerization of ethylene When ethylene was polymerized in exactly the same manner as in Example 1, 118 g of polyethylene was obtained. This polyethylene had a bulk specific gravity of 0.398 and an MI ₂ of 0.49. Catalytic activity is 831KgPE/gTi・hr and 29.5Kg
Corresponds to PE/gcat・hr.

Example 3 (2) Production of solid catalyst component [C] In the same manner as in Example 1, for the reaction product [A],
Titanium tetrachloride and aluminum triisopropoxide were added. Next, silicon tetrachloride was added in an amount twice the amount used in Example 1 (2), and the mixture was reacted under reflux for 2 hours. Subsequently, four times the amount of titanium tetrachloride used in Example 1 (2) was added, and the mixture was reacted under reflux for 2 hours.
The obtained solid catalyst component [C] contained 38.0 mg of titanium per gram.

(3) Polymerization of ethylene Ethylene was polymerized under exactly the same conditions as in Example 1, and 154 g of polyethylene was obtained. This polyethylene had a bulk specific gravity of 0.380 and an MI ₂ of 0.25. The catalyst activity in this case is 1013KgPE/gTi・hr and 8.5
Equivalent to KgPE/gcat・hr.

Comparative Example 1 (2) Production of solid catalyst component After diluting 70 ml of the toluene solution of the reaction product [A] produced in Example 1 (1) to 200 ml with toluene,
Cooled to ℃. 22 ml of titanium tetrachloride was gradually added dropwise to this while maintaining the internal temperature at 0°C, and after the dropwise addition, the reaction was allowed to continue for 2 hours. The obtained slurry was post-treated in the same manner as in Example 1(2) to obtain a solid catalyst component.
This solid catalyst component contained 90 mg titanium per gram.

(3) Polymerization of ethylene Ethylene polymerization was carried out in the same manner as in Example 1 except that the amount of solid catalyst component used was 2 mg.

138g of polyethylene was obtained, and the bulk specific gravity was
0.320, and MI ₂ was 0.67. The bulk specific gravity is clearly lower than in each example.

Comparative Example 2 (2) Production of solid catalyst component Example 3 except that aluminum triisopropoxide and silicon tetrachloride were added and reacted with the reaction product [A] without first reacting titanium tetrachloride. A solid catalyst component was produced in the same manner as above.
The titanium content in the obtained solid catalyst component was 37.7
mg/g.

(3) Polymerization of ethylene Ethylene polymerization was carried out in exactly the same manner as in Example 1 (3), and 63 g of polyethylene was obtained.
This polyethylene had a bulk specific gravity of 0.250 and an MI ₂ of 0.20.

The bulk specific gravity is extremely low compared to each example.

Example 4 (2) Production of solid catalyst component [C] Completely the same as Example 1 (2) except that aluminum tri-Sec-butoxide was used instead of aluminum triisopropoxide in Example 1 (2). A solid catalyst component [C] was produced. This solid catalyst component [C] contained 26.5 mg of titanium per gram.

(3) Polymerization of ethylene When ethylene was polymerized in exactly the same manner as in Example 1, 98 g of polyethylene was obtained, and the bulk specific gravity was
It was 0.375 and MI ₂ 0.32.

Example 5 (2) Production of solid catalyst component [C] A solid was prepared in the same manner as in Example 1 (2) except that aluminum 2-ethylhexanolate was used as the aluminum alkoxide in Example 1 (2). Catalyst component [C] was produced. This solid catalyst component [C] contained 24.1 mg of titanium per gram.

(3) Polymerization of ethylene Polymerization was carried out in the same manner as in Example 1, and polyethylene
Obtained 103g. The bulk specific gravity of this polyethylene is
0.386, and MI ₂ was 0.40.

Example 6 (2) Production of solid catalyst component [C] In Example 1 (2), methyltolylchlorosilane was used in twice the molar amount instead of silicon tetrachloride, and the second titanium tetrachloride was also used in twice the molar amount. A solid catalyst component [C] was produced in exactly the same manner as in Example 1 (2) except that the following was used. This solid catalyst component [C] is 22.9 per gram.
mg of titanium.

(3) Polymerization of ethylene Ethylene was polymerized in the same manner as in Example 1 to obtain 115 g of polyethylene. This polyethylene has a bulk specific gravity
It was 0.368 and MI ₂ 0.28.

Example 7 (1) Production of reaction product [A] In the same manner as in Example 1 (1) except that α,ω-dihydroxydimethylpolysiloxane with an average degree of polymerization of 9 was used instead of methylhydropolysiloxane, A reaction product [A] was produced. However, the α used,
n- of ω-dihydroxydimethylpolysiloxane
The amount ratio to butylmagnesium chloride is
SiOH/Mg=1.

(2) Production of solid catalyst component [C] Solid catalyst component [C] was produced in exactly the same manner as in Example 1 (2). The titanium content in this solid catalyst component [C] was 24.3 mg/g.

(3) Copolymerization of ethylene and butene-1 Before introducing ethylene, 3g of butene-1 was added, the amount of hydrogen added was 3.0Kg/ ^cm2 , and the polymerization temperature was 85℃.
Polymerization was carried out in the same manner as in Example 1 except that. density
93 g of polyethylene of 0.9511 g/cm ³ was obtained. This polyethylene had a bulk specific gravity of 0.410 and an MI ₂ of 4.0.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing a method for preparing a catalyst according to the present invention.

Claims (1)

[Scope of Claims] 1 (a) a reaction product [A] of a hydropolysiloxane or a silicon compound in which an organic group and a hydroxyl group are bonded to a silicon atom and an organomagnesium compound; (b) titanium or vanadium. The halogen-containing compound is added to magnesium 1 in the reaction product [A].
The reaction is carried out at a ratio of 0.05 to 0.5 mol per gram atom, and then (c) aluminum alkoxide, and (d) general formula SiXnY _4-o (where X: Cl or
Br, Y: hydrogen, alkyl group, or alkoxy group, n: an integer from 1 to 4, respectively. ) to the reaction product [B] obtained by reacting the halogen-containing silicon compound represented by (d)
Solid catalyst component [C] obtained by reacting a halogen-containing compound of titanium or vanadium,
and An improved method for polymerizing ethylene, which comprises polymerizing ethylene using a catalyst comprising an organoaluminum compound.