JPH05214033A - Production of ethylenic copolymer - Google Patents

Abstract

PURPOSE:To stably obtain an ethylenic copolymer excellent in flowability, handleability, etc., by copolymerizing ethylene and an alpha-olefin in the presence of a catalyst comprising a specific solid catalyst component and an organic Al compound component. CONSTITUTION:A product of the reaction of an aluminum halide with an organosilicon compound (c) represented by formula I (wherein R<1> is a 1-8C alkyl or phenyl, R<2> is a 1-8C alkyl, and m is 0, 1, 2, or 3) is infiltrated into a porous inorganic oxide (b). A Grignard compound (d) represented by formula II (wherein R<3> is a 1-8C alkyl and X<1> is a halogen) is added to the resulting oxide (b), and the reactants are allowed to react to produce a support (h). This support (h) is brought into contact with a titanium compound (e) represented by formula III (wherein R<4> is a 1-8C alkyl or phenyl, X<2> is a halogen, and n is 0 or 1-4) to produce a solid catalyst component (i). Ethylene is copolymerized with an alpha-olefin (e.g. propylene) in the presence of a catalyst obtained from this solid catalyst component (i) and an organoaluminum compound component (g), thereby giving an ethylene copolymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a copolymer of ethylene and α-olefin.

[0002]

2. Description of the Related Art Copolymerization of ethylene and .alpha.-olefin using a Ziegler-Natta type catalyst has hitherto been produced by a polymerization method such as solution polymerization, bulk polymerization, slurry polymerization and gas phase polymerization. In recent years, a process that does not require a step of separating a catalyst residue from a copolymer produced by increasing the catalyst activity has become widespread, and an inorganic solid is used for the purpose of preparing catalyst particles having high catalyst activation and good fluidity. Furthermore, many highly active catalysts in which a transition metal component such as titanium or vanadium is supported on an inorganic solid having a specific particle size have been proposed. Japanese Patent Publication No. 54-129983,
JP-A-58-17206, JP-A-59-49242 and JP-B-2-33045 disclose supported high-activity catalysts for copolymerization of ethylene and α-olefins to which the present invention relates. ..

When a copolymer of ethylene and α-olefin is produced by fluidized bed gas phase polymerization, the temperature in the fluidized bed is destabilized due to local accumulation of heat of polymerization, and a large lump polymer is formed. It is known that the fluid state is difficult to maintain. Therefore, for example, Japanese Examined Patent Publication No. 52-40350,
In JP-A-52-45749, JP-A-60-53044, and JP-A-59-30806, a prepolymer is prepared in advance, and the prepolymer is used in a fluidized bed polymerization reactor so that the weight per transition metal can be increased. Increase the amount of coalescence,
Also disclosed is a method for preventing rapid heat generation and particle agglomeration in the solid catalyst portion immediately after introduction into the fluidized bed polymerization reactor.

In this case, the particle shape of the polymer is likely to be a replica of the particle shape of the catalyst, and in order to efficiently and stably produce the polymer, the catalyst solid and the prepolymer used in the fluidized bed polymerization reaction are used. Control of particle shape, i.e.
It is important to form the catalyst solids and prepolymers that remain spherical.

Further, since a low molecular weight component having an adhesive property is produced and the fluidity of the polymer particles is deteriorated, a lump of the polymer may be produced or the reaction tube may be clogged. In addition, if the randomness of the α-olefin in the copolymer is poor, that is, if the distribution of the α-olefin units is biased, a tacky copolymer is produced and the same problems as described above occur. Therefore, a stable copolymerization reaction for a long period of time cannot be performed.

Generally, in the copolymerization of ethylene and α-olefin, a copolymer having a lower density can be produced by increasing the content of α-olefin. However, a low molecular weight component is generated in the polymerization reaction, or the composition distribution of α-olefin in the copolymer becomes wide, that is, if the composition between polymer chains is nonuniform, the surface of the molded film has tackiness. There is a problem.

In the copolymerization of ethylene and α-olefin, in order to solve the above problems, in particular, to narrow the composition distribution and suppress the formation of low molecular weight components, Zr
System catalysts (Japanese Patent Laid-Open Nos. 62-121707 and 62-121)
709, JP-A-3-234712, and JP-A-3-2233.
No. 06, No. 3-217404), or the use of an electron donor in a magnesium compound-supported catalyst (JP-A-61-61).
-271309, 61-217310, 63-
159411, 63-14008, 63-1
17019, Japanese Patent Publication No. 1-49296) and the like. However, the conventional techniques are not always satisfactory in terms of production and physical properties of the above-mentioned copolymer, and further improvement is desired.

[0008]

DISCLOSURE OF THE INVENTION The present invention improves the problems in the process for producing a copolymer of ethylene and an α-olefin, and particularly provides a stable long-term polymerization reaction when producing by fluidized bed gas phase polymerization. The present invention also provides a method for producing a copolymer which enables the copolymer to have excellent physical properties.

[0009]

DISCLOSURE OF THE INVENTION The present invention relates to an aluminum halide impregnated with a porous inorganic oxide and the formula R ¹ _m Si (OR ² ) _4-m (wherein R ¹ is a carbon number). 1
~ 8 alkyl group or phenyl group, R ² represents an alkyl group having 1 to 8 carbon atoms, m is 0, 1, 2 or 3
The reaction product of the organosilicon compound represented by
A carrier obtained by reacting with a Grignard compound represented by the formula R ³ MgX ¹ (in the formula, R ³ represents an alkyl group having 1 to 8 carbon atoms and X ¹ represents a halogen atom), the carrier represented by the formula T 3
_{^{i (OR 4) n X 2}} 4-n ( wherein, ^{R 4} is 1 to 8 carbon atoms
An alkyl group or a phenyl group, X ² represents a halogen atom, and n is 0, 1, 2, 3 or 4, and a solid catalyst component (A) obtained by contacting the titanium compound represented by The present invention relates to a method for producing an ethylene copolymer, which comprises copolymerizing ethylene and an α-olefin in the presence of a catalyst obtained from the organoaluminum compound component (B).

Hereinafter, each component used in the preparation of the catalyst of the present invention and its conditions will be described in detail. In the present invention, the preparation and polymerization of the catalyst component are all carried out under an atmosphere of an inert gas such as nitrogen or argon. Further, it is desirable that the raw material for preparing the catalyst component is substantially anhydrous.

Specific examples of the aluminum halide in the present invention include aluminum chloride, aluminum bromide and aluminum iodide, and among them, aluminum chloride is preferably used.

Specific examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane and tetra-n.
-Propoxysilane, tetra-n-butoxysilane, tetraisopentoxysilane, tetra-n-hexoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, methyltriisopentoxysilane, methyltri-n -Hexoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltriisopentoxysilane, n-
Butyltriethoxysilane, isobutyltriethoxysilane, isopentyltriethoxysilane, isopentyltri-n-butoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, dimethyldiisopentoxysilane, diethyldiethoxysilane, diethyl Diisopentoxysilane, diisobutyldiisopentoxysilane, di-n-butyldiethoxysilane, diisobutyldiisopentoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisobutoxysilane, triethylisopropoxysilane, tri-
n-propylethoxysilane, tri-n-butylethoxysilane, triisopentylethoxysilane, phenyltriethoxysilane, phenyltriisobutoxysilane, phenyltriisopentoxysilane, diphenyldiethoxysilane, diphenyldiisopentoxysilane,
Examples thereof include diphenyldioctoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylisopentoxysilane, benzyltriethoxysilane, benzyltributoxysilane and dibenzyldiethoxysilane. Of these, alkylalkoxysilanes such as methyltriethoxysilane are preferably used.

The proportion of aluminum halide used for the reaction of aluminum halide and organosilicon compound is
It is preferably 0.1 to 10 mol, and particularly preferably 0.1 to 2 mol, per mol of the organosilicon compound. The reaction is usually carried out by stirring both compounds in an inert organic solvent at a temperature in the range of -50 to 100 ° C for 0.1 to 2 hours. The reaction proceeds exothermically and the reaction product is obtained as a solution in an inert organic solvent.

Examples of the inert organic solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane and dodecane, and alicyclic compounds such as cyclopentane, cyclohexane and methylcyclohexane. Group hydrocarbons or aromatic hydrocarbons such as toluene, benzene, xylene and the like can be mentioned. These inert organic solvents can be similarly used in the following steps of preparing the solid catalyst component (A) or the polymerization step.

The reaction product is a solution in an inert organic solvent,
Subsequently, the porous inorganic oxide is impregnated.
Examples of the porous inorganic oxide in the present invention include silica, alumina, magnesium oxide and the like. Particularly, silica is preferable. The particle size of the porous inorganic oxide is 10 to 1
A spherical one having a diameter of 00 μm is preferable, and its BE
Those having a T surface area of 10 to 600 m ² / g are preferable.

The method of impregnating the porous inorganic oxide with the reaction product of the aluminum halide and the organosilicon compound is not particularly limited. For example, an organic solvent slurry of the porous inorganic oxide may be added to the aluminum halide. Slowly adding an inert organic solvent solution of the reaction product of the organosilicon compound or, conversely, adding a porous inorganic oxide to the inert organic solvent solution of the reaction product of the aluminum halide and the organosilicon compound. Can be added. The impregnation treatment of a porous inorganic oxide with a reaction product of an aluminum halide and an organic silicon compound is usually performed per 1 g of the porous inorganic oxide,
It can be carried out using the reaction product containing 0.1 to 50 milligram atoms, preferably 1 to 10 milligram atoms of Al. The impregnation treatment is usually 10 to 100.
C., preferably 20 to 80.degree. C. The above-mentioned porous inorganic oxide impregnated, the reaction product of the aluminum halide and the silicon compound continues,
A carrier is produced by reacting with a Grignard compound. The impregnated porous inorganic oxide is preferably separated in advance, washed with an inert organic solvent, and then reacted with a Grignard compound.

The Grignard compound represented by the formula R ³ MgX ¹ is preferably an alkylmagnesium chloride in which X ¹ is a chlorine atom, and specific examples thereof include methylmagnesium chloride, ethylmagnesium chloride and n-butylmagnesium. Examples thereof include chloride and n-hexyl magnesium chloride. The amount of the Grignard compound used is usually 0.1 to 50 per 1 g of the porous inorganic oxide used for the impregnation treatment with the reaction product of the aluminum halide and the organosilicon compound.
It is preferably in the range of millimole, particularly 1 to 20 millimole.

The reaction method with the Grignard compound is not particularly limited, but an ether solvent slurry of the Grignard compound or a mixed solvent solution of the ether and the aromatic hydrocarbon is impregnated with the organic solvent slurry of the porous inorganic oxide. It can be carried out by gradually adding to. Specific examples of ethers include diethyl ether, diisopropyl ether, di-n-butyl ether, diisoamyl ether, and cyclic ethers such as tetrahydrofuran.

The reaction temperature is usually -50 to 100.
C., preferably -20 to 25.degree. The reaction time is not particularly limited, but is usually 5 minutes or longer. The carrier thus obtained can be subjected to the next treatment as a reaction mixture, but the carrier is separated in advance, washed with an ether solvent and / or an inert organic solvent, and then subjected to the contact treatment with the next titanium compound. Preferably.

Specific examples of titanium compounds include methoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxychlorotitanium, ethoxytrichlorotitanium, diethoxydichlorotitanium, propoxytrichlorotitanium,
Dipropoxydichlorotitanium, butoxytrichlorotitanium, dibutoxydichlorotitanium, phenoxytrichlorotitanium, diphenoxydichlorotitanium, methoxytribromotitanium, phenoxytribromotitanium, methoxytriiodotitanium, phenoxytriiodotitanium, tetrachlorotitanium, Examples thereof include tetrabromotitanium, tetraiodotitanium, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium and tetrabutoxytitanium. Two or more kinds of these titanium compounds may be used in combination.

Among them, tetrachlorotitanium, methoxytrichlorotitanium, dimethoxydichlorotitanium, ethoxytrichlorotitanium, diethoxydichlorotitanium, propoxytrichlorotitanium, dipropoxydichlorotitanium,
Butoxytrichlorotitanium and dibutoxydichlorotitanium are preferably used.

The amount of the titanium compound used is preferably 1 mmol or more, particularly 10 to 100 mmol, per 1 gram of the porous inorganic oxide used when preparing the carrier. The contact treatment between the carrier and the titanium compound can be performed by the following method. The carrier is in the presence or absence of an inert organic solvent at 20 to 200 ° C., preferably 60 to 1
Contact with the titanium compound for 0.5 to 3 hours at a temperature of 40 ° C., after which the solid is separated from the reaction mixture and optionally washed with an inert organic solvent. The contact treatment with the titanium compound can be continuously performed a plurality of times.

From the mixture containing the treated solid thus obtained, the component (A) is separated by filtration, decantation, etc., and washed with an inert organic solvent if necessary. As the inert organic solvent, the same one used in the treatment with the titanium compound can be used. The solid catalyst component (A) obtained by the above method can be used in the polymerization reaction together with the organoaluminum compound (B).

Specific examples of the organoaluminum compound component (B) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum chloride,
Dibutyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dichloride, ethyl aluminum dibromide,
Propyl aluminum dibromide, butyl aluminum dibromide, diethyl aluminum hydride, dibutyl aluminum hydride, ethyl aluminum dihydride, propyl aluminum dihydride, butyl aluminum dihydride, ethyl aluminum ethoxy chloride, ethyl aluminum butoxycyclolide, ethyl aluminum ethoxy bromide, etc. Be done. Also, isopropenylaluminum obtained by the reaction of diisobutylaluminum hydride and isoprene can be used. Further, for example, an alkylalumoxane obtained by a reaction of trialkylaluminum with water dispersed in a solvent or a reaction of water of crystallization of an inorganic compound can be used.

Among them, trialkylaluminums such as triethylaluminum and triisobutylaluminum are preferably used. The amount of the organoaluminum compound component (B) used is usually 1 to 1000 mol per 1 gram atom of titanium in the solid catalyst component (A). In addition, two or more kinds of organoaluminum compounds can be used together.

In the present invention, ethylene and α-olefin are copolymerized by using a catalyst composed of component (A) and component (B). Specific examples of α-olefins include:
Propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1 and the like can be mentioned.

In the present invention, if necessary, the catalyst comprising the components (A) and (B) may be prepolymerized with ethylene or a mixture of ethylene and α-olefin. When carrying out the prepolymerization, it is preferred to carry out the polymerization until a particulate polymer containing 0.005 to 0.5 mmol of Ti atoms per gram of the prepolymer is obtained. An inert organic solvent may be used as a polymerization solvent, or a liquid α-olefin itself may be used.

As a preferable condition for producing the prepolymer, the polymerization pressure is usually atmospheric pressure to 10 kg / cm.
^{2. The} polymerization temperature is 100 ° C. or lower, usually 20 to 70 ° C. The polymerization time is usually 30 minutes to 5 hours, preferably 1
~ 60 minutes. The ratio of the component (A) and the component (B) in the prepolymerization is the molar ratio of Ti and Al, respectively,
Usually, Al / Ti = 0.1 to 1000, preferably 0.
5 to 200. When the component (B) is used in the preliminary polymerization, the copolymer can be produced without additionally using the component (B) in the main polymerization. The prepolymer can be subjected to the main polymerization after evaporating a polymerization solvent with, for example, an inert gas, drying and removing it to obtain a powder.

The main polymerization reaction can be carried out in the same manner as the polymerization reaction of α-olefin using a general Ziegler-Natta type catalyst. The main polymerization reaction can be carried out in the liquid phase or the gas phase using the solid catalyst component (A) or the prepolymer. Examples of the gas phase polymerization reaction include a fluidized bed polymerization method and a stirring polymerization method.

In particular, when the fluidized bed polymerization method is used, it is preferable to copolymerize gaseous ethylene and α-olefin in the fluidized bed polymerization reactor in the presence of the prepolymer produced as described above. .. The α-olefin used in the main polymerization may be the same as or different from that used in the preparation of the prepolymer. In the main polymerization, at the same time that the prepolymer is fluidized by the monomer gas,
The heat of polymerization is removed by the monomer gas, usually 50 to 1
Polymerization is carried out at 10 ° C. In the main polymerization, when a prepolymer is used as a catalyst, an organoaluminum compound (B) can be used together.

When the polymerization reaction is carried out in the liquid phase, an inert organic solvent may be used as the polymerization solvent, or a liquid α-olefin itself may be used. The concentration of the catalyst in the polymerization solvent is not particularly limited, but generally 1 L of the polymerization solvent is used.
Therefore, the solid catalyst component (A) is 0.001 to 1 milligram atom in terms of titanium metal, and the organoaluminum compound component (B) is 0.01 to 100 mmol. The polymerization reaction is carried out in a state where water and oxygen are substantially removed. The polymerization temperature is usually 30-100.
The polymerization pressure is usually 1 to 80 kg / cm ² . Further, hydrogen can be made to coexist as a molecular weight regulator of the produced polymer.

[0032]

In the present invention, in particular, in the fluidized bed gas phase polymerization method, the proportion of low-molecular-weight tacky product is small, and since the block copolymer of α-olefin is little produced by the copolymerization, In the present polymerization method, good fluidity of polymer particles can be maintained, and a polymerization reaction can be stably carried out for a long period of time without formation of lumps of particles or adhesion to a reactor. The final polymer produced also has a relatively large particle size and is easy to handle because it does not form fine particles. Moreover, since the polymerization activity is high, a deashing step of the produced copolymer is unnecessary.
In addition, since the copolymer produced has a narrow composition distribution, α-
Even if the olefin content is increased to reduce the density, the molded film has excellent physical properties such as low surface tackiness and high mechanical strength of the molded product.

[0033]

EXAMPLES Examples and comparative examples of the present invention will be described below. In the examples, the “polymerization activity” is a copolymer yield (kg) per 1 g of Ti component of the solid catalyst used in the polymerization reaction. "MI" means ASTM D-12
190 under a load of 2.16 kg / cm ² according to No. 38
It is the melting index of the polymer measured in. The titanium content of the solid catalyst component was measured by a colorimetric method. The content of α-olefin was measured by NMR. Density was measured by a density gradient tube. The composition distribution of the copolymer was evaluated by the relationship between the α-olefin content and the density. That is, in general, when the α-olefin content of the copolymer is the same, the density of the copolymer having a higher randomness is smaller, and thus the composition distribution is narrower.

Example 1 (1) Preparation of solid catalyst component Silica (TG-2040 manufactured by Fuji Devison Chemical Co., Ltd.)
2, average particle size 80μ, BET surface area 282m ² / g)
Was fired in a nitrogen stream at 200 ° C. for 2 hours and further at 600 ° C. for 7 hours. Obtained by adding 15 mmol of methyltriethoxysilane to 40 ml of a suspension of 15 mmol of anhydrous aluminum chloride in toluene, reacting the mixture at 25 ° C. for 0.5 hours, and then raising the temperature to 60 ° C. and further reacting for 1 hour. 4 g of the above silica was added to the reaction product mixture, and the mixture was added at 25 ° C. for 6 hours.
It was impregnated for an hour. The treated solid is filtered off, and toluene is 30 m.
It was washed 3 times with 1 and filtered, and 30 ml of toluene was added to obtain a silica slurry.

Next, the obtained silica slurry was added to -5
The mixture was cooled to 0 ° C, and 18 ml of a solution of 30 mmol of n-butylmagnesium S chloride in diisopropyl ether was added to 0.5
After adding over a period of time, the silica slurry is heated to 30 ° C. and
Reacted for hours. The reaction solid obtained was filtered off, washed with 30 ml of toluene three times and filtered. Obtained carrier 4.90
1 g of tetrachlorotitanium to 30 ml of a toluene suspension of g.
50 mmol was added and contact treatment was carried out at 90 ° C. for 1 hour. The catalytically treated solid was filtered off at 90 ° C. and then n-heptane 3o.
After washing 5 times with ml and filtering, it was made into a slurry of n-heptane 80 ml. Titanium content of the solid catalyst component is 3.0
It was 3% by weight.

(2) Prepolymerization 800 ml of heptane was added to a SUS 2L autoclave substituted with nitrogen gas, 10.0 mmol of tri-n-octylaluminum, and catalyst solid (Ti = 1 mmol).
Was introduced. After pressurizing with 1.5 kg / cm ² of hydrogen,
The temperature was raised to 60 ° C. and ethylene was introduced to initiate polymerization. Maintained at 68 ℃ during polymerization, ethylene flow rate is 0.93L
/ Min. Polymerize for 2 hours as 0.02 per gram
A prepolymer containing 3 mmol of Ti atoms was obtained.

(3) Gas phase copolymerization of ethylene and 1-butene 500 g of polyethylene powder produced in advance was placed in a heat-treated stirring gas phase polymerization reactor having a diameter of 20 cm and a length of 50 cm, and the powder was stirred at 1000 rpm. While 1
Pretreatment was carried out at 10 ° C. for 5 hours under a nitrogen atmosphere. afterwards,
From the bottom, ethylene / butene-1 / hydrogen (3/1 / 0.2
A mixed gas (molar ratio) of 45 ° C. was raised at a speed of 20 cm / sec and circulated. The copolymerization is carried out by introducing the prepolymer produced in (2) above at a rate of 10 g / hour and a polymerization temperature of about 75
˜85 ° C., polymerization pressure 2 kg / cm ² , Al / Ti atomic ratio 10 and continuous operation for 10 hours. During that time, the ethylene / butene-1 copolymer was continuously extracted and evaluated for activity and physical properties. The results are shown in Table 1.

Example 2 The molar ratio of the mixed gas in the main polymerization was changed to (ethylene / butene-1
/Hydrogen=2/1/0.2 molar ratio)
An ethylene / butene-1 copolymer was obtained in the same manner as in. The results are shown in Table 1.

Examples 3 and 4 The solid catalyst component was prepared under the same conditions and method as in Example 1 except that tetrahydrofuran was used instead of diisopropyl ether as the solvent for the Grignard compound. 3.32% by weight of solid catalyst component (A) was obtained. Then, prepolymerization was carried out in the same manner to obtain a prepolymer containing 0.025 mmol of Ti atom per gram. Further, copolymerization was carried out under the same conditions and methods as in Examples 1 and 2 to obtain an ethylene / butene-1 copolymer. The results are shown in Table 1.

Examples 5 and 6 Solid catalyst components were prepared under the same conditions and methods as in Example 1 except that phenyltriethoxysilane was used instead of methyltriethoxysilane, and the titanium content was 3%. ．
25% by weight of solid catalyst component (A) was obtained. Then, prepolymerization is carried out in the same manner, and 0.027 mmol of T per gram of T is added.
A prepolymer containing i atoms was obtained. Furthermore, Example 1
Copolymerization was carried out under the same conditions and methods as those in 1 and 2 to obtain an ethylene / butene-1 copolymer. The results are shown in Table 1.
Shown in.

Examples 7 and 8 100 mmol of tetrachlorotitanium and 50 parts of tetrabutoxytitanium were used instead of 150 mmol of tetrachlorotitanium.
A solid catalyst component was prepared under the same conditions and method as in Example 1 except that the amount of millimolar was used, and the titanium content was 3.6.
0% by weight of solid catalyst component (A) was obtained. Then, prepolymerization was carried out in the same manner to obtain 0.023 mmol of Ti per gram of Ti.
A prepolymer containing atoms was obtained. Further, copolymerization was carried out under the same conditions and methods as in Examples 1 and 2,
An ethylene / butene-1 copolymer was obtained. The results are shown in Table 1.

Examples 9 and 10 Example 1 except that n-hexyl magnesium chloride was used instead of n-butyl magnesium chloride.
A solid catalyst component was prepared under the same conditions and method as above to obtain a solid catalyst component (A) having a titanium content of 3.25% by weight. Then, prepolymerization is carried out in the same manner, and 0.0
A prepolymer containing 26 mmol of Ti atoms was obtained.
Further, copolymerization was carried out under the same conditions and methods as in Examples 1 and 2 to obtain an ethylene / butene-1 copolymer. The results are shown in Table 1.

In any of Examples 1 to 10, the copolymer particles after copolymerization were not tacky, and neither aggregates nor adhesion to the reactor wall or stirrer was observed.

[Brief description of drawings]

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

[Table 1]

Claims (1)

[Claims] 1. An aluminum halide and the formula R ¹ _m Si (OR ² ) impregnated into a porous inorganic oxide.
_4-m (In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, R ² represents an alkyl group having 1 to 8 carbon atoms, and m is 0, 1, 2 or 3) A Grignard compound represented by the formula R ³ MgX ¹ (in the formula, R ³ represents an alkyl group having 1 to 8 carbon atoms, and X ¹ represents a halogen atom). To the carrier obtained by reacting with the formula Ti (OR ⁴ ) _n X ²
_4-n (in the formula, R ⁴ represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, X ² represents a halogen atom, and n is 0, 1, 2, 3 or 4) Ethylene copolymerization characterized by copolymerizing ethylene and α-olefin in the presence of a catalyst obtained from a solid catalyst component (A) obtained by contacting a titanium compound and an organoaluminum compound component (B). Manufacturing method of coalescence.