JPH0776249B2 - Method for producing polyolefin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing polyolefin, and more specifically, efficiently produces a polyolefin having a narrow molecular weight distribution and good particle properties by using a specific solid catalyst component and an organometallic compound. Regarding the method.

Problems to be Solved by Conventional Techniques and Inventions Conventional polymerization catalysts for α-olefins are listed in the periodic table
It is well known that a catalyst (so-called Ziegler catalyst) composed of a combination of a group IV to VI transition metal compound with an organometallic compound is effective. In recent years, many attempts have been made to further improve the polymerization activity of olefins by adding a magnesium compound thereto and omit the step of catalyst removal. For example magnesium oxide (Belgian patent
759601), magnesium hydroxy chloride (Japanese Patent Publication No. 43)
-13050, Japanese Patent Publication No. 43-15826), magnesium hydroxide (Japanese Patent Publication No. 45-40295), magnesium chloride (Japanese Patent Publication No. 39)
No. 12105, Japanese Patent Publication No. 47-46269) and the like, catalyst systems containing a magnesium compound as one component have been proposed.

The present inventors have also proposed a catalyst system containing a reaction product of magnesium halide and a metal alkoxide as one component (Japanese Patent Publication No. 52-1151).
1, JP-B-54-13276, JP-A-56-95909, JP-A-5
No. 7-182303) has been proposed. However, in the present technical field, it is desired that the catalyst has as high activity as possible, the particle property of the produced polymer is as good as possible from the viewpoint of continuous operability, and the copolymerizability with other α-olefin is also good. From this point of view, further improvement of the above catalyst system is desired.

Means for Solving Problems The present inventors have found the present invention as a result of further studies from the viewpoint.

That is, the present invention provides a method for polymerizing or copolymerizing olefins using a solid catalyst component and an organoaluminum compound as a catalyst, wherein the solid catalyst component is (1) magnesium halogelated, (2) general formula Me (OR) _n X _zn (Where Me is Al or B
Indicates. R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. z represents the valence of Me, and n is 0 <n ≦.
z. (3) General formula Si (OR ') _{mX4 -m} (wherein R'represents a hydrocarbon residue having 1 to 20 carbon atoms and X represents a halogen atom.
Is 0 ≦ m ≦ 2. ), And (4) a titanium compound or a solid compound obtained by reacting a titanium compound and a vanadium compound with each other at 10 to 140 ° C. with titanium tetrahalide. The present invention relates to a method for producing a characteristic polyolefin.

In the above, the titanium compound means a trivalent or tetravalent titanium compound, and the vanadium compound means a pentavalent vanadium compound.

The first feature of the present invention is that the activity of the catalyst is extremely high, the amount of polymer produced per solid catalyst or transition metal is large,
That is, the catalyst residue in the polymer is small.

The second characteristic of the present invention is that the resulting polymer has good particle properties,
Even when producing a polymer having a density of 0.910 to 0.930 g / cm ^{3 in} a low density region, continuous operation is good.

The third feature of the present invention is that ethylene has a good copolymerizability with other α-olefins, and a smaller amount of α-olefin can reduce the density to a predetermined value.

As the magnesium halide used in the present invention, a substantially anhydrous one is used, and examples thereof include magnesium fluoride, magnesium chloride, magnesium bromide and magnesium iodide, and magnesium chloride is particularly preferable.

The general formula Me (OR) _n X _zn (where Me,
z, n and R are as defined above, and examples of the compound represented by: Al (OR) ₃ , Al (OR) ₂ X,
_{Al (OR) X 2, B} (OR) 3, B (OR) 2 X, B can be mentioned various compounds such as (OR) X _2, as a further preferred embodiment, aluminum trimethoxide, aluminum tri Ethoxide, diethoxymonochloroaluminum, monoethoxydichloroaluminum, monomethoxydiethoxyaluminum, aluminum tri-n-propoxide, aluminum triisopropoxide, diisopropoxymonochloroaluminum, monoisopropoxydichloroaluminum, monomethoxydiisopropoxyaluminum. , Aluminum tri-n-butoxide, aluminum tri-sec-butoxide, aluminum tri-t-
Examples thereof include butoxide, boron trimethoxide, dimethoxymonochloroboron, monomethoxydichloroboron, boron triethoxide, diethoxymonochloroboron and monoethoxydichloroboron, and aluminum trimethoxide, aluminum triethoxide and boron triethoxide are particularly preferable.

The general formula Si (OR ') _m X _4-m used in the present invention (wherein R'is a hydrocarbon residue such as an alkyl group, an aryl group or an aralkyl group having 1 to 24 carbon atoms, and X is a halogen atom). And m is 0 ≦ m ≦ 4. Examples of the compound represented by silicon tetrachloride, monomethoxytrichlorosilane,
Monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono-n-butoxytrichlorosilane,
Monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenoxytrichlorosilane, mono-p-methylphenoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, diisopropoxydichlorosilane, di-n- Butoxydichlorosilane, dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, trise
Mention may be made of c-butoxymonochlorosilane, tetraethoxysilane and tetraisopropoxysilane.

Examples of the titanium compound or titanium compound and vanadium compound used in the present invention include halides, alkoxy halides, alkoxides and halogenated oxides of these metals. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are preferable, and the tetravalent titanium compound is specifically represented by the general formula Ti
(OR) _n X _4-n (where R is an alkyl group having 1 to 20 carbon atoms,
It represents an aryl group or an aralkyl group, and X represents a halogen atom. n is 0 ≦ m ≦ 4. ) Are preferable, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, Triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxymonochlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxy. Examples thereof include citrichlorotitanium, diphethoxydichlorotitanium, triphenoxymonochlorotitanium and tetraphenoxytitanium. Examples of the trivalent titanium compound include trihalogenated compounds obtained by reducing titanium tetrahalide such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium or an organometallic compound of Group I to III metal of the periodic table. Examples include titanium. In addition, the general formula Ti (O
R) _m X _4-m (wherein R represents an alkyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and n is 0 <m <4). Examples thereof include trivalent titanium compounds obtained by reducing tetravalent alkoxytitanium halides with organometallic compounds of metals of groups I to III of the periodic table. Examples of the vanadium compound include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide and tetraethoxyvanadium, vanadium oxytrichloride, ethoxydichlorovanadyl, triethoxyvanadyl and tributoxyvanadyl. Examples thereof include trivalent vanadium compounds, trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide.

In the present invention, a tetravalent titanium compound is most preferable. When using a titanium compound and a vanadium compound together
The V / Ti molar ratio is preferably in the range of 2/1 to 0.01 / 1.

In the present invention, (1) magnesium halide, (2) compound represented by general formula Me (OR) _n X _zn , (3) compound represented by general formula Si (OR ') _m X _4-m , and (4) There is no particular limitation on the method for obtaining solid particles used for the present surface by reacting a titanium compound or a titanium compound and a vanadium compound, and the temperature is 20 to 400 ° C in the presence or absence of an inert solvent, preferably. Is 50 to 3
A method of reacting by contacting for 5 minutes to 20 hours under heating at 00 ° C, a method of reacting by co-grinding treatment,
Alternatively, the reaction may be carried out by appropriately combining these methods.

Further, the reaction order of the components (1) to (4) is not particularly limited, and four components may be simultaneously reacted, three components may be reacted, and then another one component may be reacted, and Two
After reacting the components, the other two components may be reacted,
After reacting the two components, the next one component may be reacted and then the remaining one component may be reacted.

The inert solvent used at this time is not particularly limited, and a hydrocarbon compound and / or a derivative thereof which does not inactivate the Ziegler type catalyst can be usually used. Specific examples thereof include various aliphatic saturated hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons and ethanol, diethyl ether. , Alcohols such as tetrahydrofuran, ethyl acetate and ethyl benzoate, ethers, esters and the like.

The mixing ratio of the magnesium halide of the general formula Me (OR) compound represented by _n X _zn is too also reversed the amount of the general formula Me (OR) _n X compound represented by _zn is too too small If it is too large, the polymerization activity tends to decrease,
Mg / Me molar ratio is in the range of 1 / 0.01 to 1/1, preferably 1 /
A range of 0.05 to 1 / 0.5 is desirable for the production of highly active catalysts.

In the present invention, if the amount of the compound represented by the general formula Si (OR ′) _m X _4-m is too large or too small, the effect of addition is not expected, and it is usually 0.1 to 100 g of magnesium halide. It is in the range of 50 g, preferably 0.5-10 g.

The amount of the titanium compound or the titanium compound and the vanadium compound is most preferably adjusted so that the titanium and vanadium contained in the solid catalyst component are in the range of 0.5 to 20% by weight, and the titanium and vanadium are well-balanced. 1 to obtain the activity of
A range of up to 10% by weight is particularly desirable.

The apparatus used for co-milling is not particularly limited, but usually a ball mill, a vibration mill, a rod mill, an impact mill, etc. are used, and the conditions such as the mixing order, the milling time and the milling temperature according to the milling method are particularly limited. Rather, it is easily determined by a person skilled in the art. Normally 0 ℃ ~ 200
It is desirable to co-mill for 0.5 to 30 hours at a temperature of 20 ° C to 100 ° C. Of course, the co-milling operation should be carried out in an inert gas atmosphere and moisture should be avoided as much as possible.

Examples of the titanium tetrahalide to be brought into contact with the solid particles thus obtained according to the present invention include titanium tetrachloride, titanium bromide and titanium tetraiodide, but titanium tetrachloride is particularly preferable.

When the titanium tetrahalide is brought into contact with the solid particles, it is preferable that an inert solvent coexists.

The inert solvent used at this time is not particularly limited, and a hydrocarbon compound and / or a derivative thereof that does not inactivate the Ziegler type catalyst can be used. Specific examples thereof include various saturated aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons and the like. it can.

When the titanium tetrahalide is brought into contact with the solid particles, the titanium tetrahalide can be added in an amount of 0.1 to 100 times the molar amount of titanium and / or vanadium in the solid particles.
Preferably, it can be added in an amount of 0.5 to 20 times.

The temperature when the titanium tetrahalide is brought into contact with the solid particles is in the range of 10 to 140 ° C, and the contact time is in the range of 0.1 to 10 hours. After the completion of the contact reaction, unreacted titanium tetrahalide is preferably washed and removed with an inert solvent.

It goes without saying that the above operation of bringing the titanium tetrahalide into contact with the solid particles may be performed twice or more.

The solid contact component thus obtained and the organoaluminum compound are combined to obtain the catalyst of the present invention.

The organoaluminum compound used in the present invention has a general formula
R ₃ Al, R ₂ AlX, RAlX ₂ , R ₂ AlOR, RAl (OR) X and R ₃ Al ₂
Organoaluminum compound of X ₃ (where R is 1 to 20 carbon atoms)
Is an alkyl group or an aryl group, X is a halogen atom, and R may be the same or different. Specific examples thereof include triethylaluminum, triisopropylaluminum, triisobutylaluminum and trise.
Examples thereof include c-butylaluminum, tritert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof. It is also possible to use a carboxylic acid ester such as ethyl benzoate together with these organoaluminum compounds.
The amount of the organoaluminum compound used is not particularly limited, but usually it can be used in an amount of 0.1 to 1000 mol times with respect to the titanium compound or the titanium compound and the vanadium compound.

Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization, and is particularly preferably used for gas phase polymerization. The polymerization reaction is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst. Ie all reactions are essentially oxygen,
It is carried out in the presence or absence of an inert hydrocarbon with water and the like removed. The olefin polymerization conditions are a temperature of 20 to 120 ° C., preferably 50 to 100 ° C., and a pressure of atmospheric pressure to 70 kg / cm ² , preferably 2 to 60 kg / cm ^2.
Is. The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it is effectively performed by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, it is possible to carry out a multi-step polymerization reaction of two steps or more with different polymerization conditions such as hydrogen concentration and polymerization temperature without any trouble.

INDUSTRIAL APPLICABILITY The method of the present invention is applicable to the polymerization of all olefins which can be polymerized with a Ziegler catalyst, and particularly, it has α to C 2-12 α
-Olefin is preferred, for example ethylene, propylene, 1-butene, hexene-1,4-methylpentene-
1, homopolymerization of α-olefins such as octene-1, ethylene and propylene, ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1, propylene and 1- It is preferably used for copolymerization of butene and ethylene with other two or more kinds of α-olefins.

Copolymerization with a diene for the purpose of modifying polyolefin is also preferably carried out. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene,
Examples thereof include ethylidene norbornene and dicyclopentadiene.

Examples will be given below, but these are for the purpose of carrying out the present invention and the present invention is not limited thereto.

Example 1. (a) Production of solid catalyst component A 300 ml three-necked flask equipped with a stirrer was charged with 30 g of aluminum triethoxide, 10 g of diethoxydichlorosilane and 150 ml of n-heptane, and reacted under reflux of n-heptane for 3 hours. After removing the supernatant, it was dried under reduced pressure at 50 ° C. to obtain an off-white solid (A).

In a nitrogen atmosphere, 10 g of anhydrous magnesium chloride, 5.2 g of the above solid (A), and 3.7 g of phenoxytrichlorotitanium were placed in a stainless steel pot with an internal volume of 400 ml containing 25 stainless steel balls with a diameter of 1/2 inch. Ball milling was performed for 16 hours at room temperature. 1 g of the obtained solid particles (B) contained 39 mg of titanium.

In a 300 ml three-necked flask equipped with a stirrer, 10 g of solid particles (B), 7.7 g of titanium tetrachloride and 150 ml of n-heptane were put, and n-
The reaction was carried out under a reflux of heptane for 3 hours. After completion of the reaction, it was thoroughly washed with hexane to obtain a solid catalyst component (C) containing 48 mg of titanium per 1 g.

(B) Polymerization The volume 2 stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and 1000 ml of hexane, 1 mmol of triethylaluminum and 5 m of the above solid catalyst component (C).
g was added and the temperature was raised to 70 ° C. The system is 1 kg with the vapor pressure of hexane.
Although it becomes / cm ² · G, hydrogen is charged until the total pressure becomes 1.5 kg / cm ² · G, then butene-1 35 g is added together with ethylene, and ethylene is added so that the total pressure becomes 7 kg / cm ² · G. It was supplied and polymerized for 1 hour. After completion of the polymerization, the copolymer slurry was transferred to a beaker and hexane was removed to obtain 212 g of the copolymer.

Catalytic activity is 160,600g copolymer / gTi · h · ethylene pressure, 7,
710g copolymer / g solid / h / ethylene pressure and extremely high,
The melt index (measured at 190 ° C. and 2.16 kg load; MI) and density (according to ASTM DI505) of the copolymer were 0.70 g / 10 min and 0.9220 g / cm ³ , respectively.

After the completion of the polymerization, the inside of the autoclave was inspected. As a result, no polymer was attached to the inner wall and the stirrer, the hexane solvent was transparent, and there was no stickiness.

FR value of the obtained copolymer (in accordance with ASTM D 1238,
Ratio of flow rate (MFR ¹⁰ ) and MI at 190 ℃, 10kg load: FR = MFR
¹⁰ / MI) was 6.9. The amount of hexane extracted from this copolymer film (extracted for 10 hours) was 1.5 wt%.

Comparative Example 1. Polymerization was carried out in the same manner as in Example 1 (b) except that 10 mg of the solid particles (B) of Example 1 (a) were used instead of the solid catalyst component (C) in Example 1 (b). Ivy. The results are shown in Table 1.

Example 2. (a) Production of solid catalyst component 20 g of anhydrous magnesium chloride and 8.6 g of aluminum triethoxide were placed in the same stainless steel pot as in Example 1 (a) and ball milled at room temperature for 16 hours under a nitrogen atmosphere. The white solid powder (A) was obtained.

The above solid powder (A) 20 in a 300 ml three-necked flask equipped with a stirrer.
g, 15 g of triethoxymonochlorosilane and 150 ml of n-heptane were added, and the mixture was reacted under reflux for 5 hours. After removing the supernatant, it was dried under reduced pressure at 200 ° C. to obtain a solid (B).

Then, 10 g of the solid (B) and 3.7 g of phenoxytrichlorotitanium were put in a pot as in the above, and ball milling was performed for 16 hours at room temperature under a nitrogen atmosphere to obtain solid particles (C) containing 40 mg of titanium per 1 g. .

Solid particles (C) (10 g) and titanium tetrachloride (7.7 g) were reacted under reflux of n-heptane for 3 hours and washed with hexane to obtain a solid catalyst component (D). 1 mg of the solid catalyst component (D) contained 50 mg of titanium.

(B) Polymerization Example 1 except that 5 mg of the above solid catalyst component (D) was used in place of the solid catalyst component (C) in Example 1 (b).
Polymerization was performed in the same manner as in (b). The results are shown in Table 1.

Example 3. 20 g of anhydrous magnesium chloride in a three-necked flask equipped with a stirrer,
12 g of aluminum tri-sec-butoxide, 10 g of tetraethoxysilane and 100 ml of n-heptane were added, and after reacting for 3 hours under reflux, 150 ml of hexane was added and allowed to stand, and after removing the supernatant liquid, 2
It was dried under reduced pressure at 00 ° C to obtain a solid (A).

12 g of the above solid (A) and 2.5 g of titanium tetrachloride were placed in the same stainless steel pot as in Example 1 (a), and ball milling was performed for 16 hours at room temperature under a nitrogen atmosphere.
Solid particles (B) containing 37 mg of titanium were obtained.

Then 10 g of solid particles (B), 3.1 g of titanium tetrachloride and n
-Heptane (150 ml) was reacted under reflux of n-heptane for 3 hours, washed with hexane to obtain a solid catalyst component (C) containing 48 mg of titanium per 1 g of titanium.

Example 1 except that 5 mg of the above solid catalyst component (C) was used in place of the solid catalyst component (C) in Example 1 (b).
Polymerization was carried out in the same manner as in (b). The results are shown in Table 1.

Example 4. 10 g of anhydrous magnesium chloride and tetraethoxysilane
Solid (A) that was previously ball milled at a rate of 3.5 g (1)
2.5 g and aluminum tri-n-hexoxide (7.0 g) were reacted with stirring under hexane reflux for 3 hours. After the reaction, the supernatant liquid was removed and vacuum drying was performed to obtain a solid powder (B). Then add 60 ml of diisopropoxydichlorotitanium and, with stirring,
After reacting for 1 hour, excess diisopropoxydichlorotitanium was removed by washing with hexane to obtain solid particles (C). 1 mg of solid particles (C) contained 18 mg of titanium.

While stirring 10 g of solid particles (C) and 12.7 g of titanium tetrachloride,
-After reacting for 3 hours under reflux of heptane, washing with hexane was performed to obtain a solid catalyst component (D). Titanium content is 46
It was mg / g.

Example 1 except that 5 mg of the above solid catalyst component (D) was used in place of the solid catalyst component (C) in Example 1 (b).
Polymerization was performed in the same manner as in (b). The results are shown in Table 1.

Comparative Example 2. Example 1 except that 10 mg of the solid particles (C) of Example 4 were used in place of the solid catalyst component (C) in Example 1 (b).
Polymerization was performed in the same manner as in (b). The results are shown in Table 1.

Example 5. 20 g of anhydrous magnesium chloride, 12 g of aluminum trisec-butoxide, 10 g of diethoxydichlorosilane and 100 ml of ethanol were reacted under reflux with stirring for 3 hours, 150 ml of hexane was added, the mixture was allowed to stand, the supernatant was removed, and the residue was dried under reduced pressure. The solid (A) was obtained.

In a stainless steel pot similar to that used in Example 1 (a), 10 g of solid (A) and 2.3 g of titanium tetrachloride were placed and ball-milled at room temperature for 16 hours in a nitrogen atmosphere to give 39 mg / g.
Solid particles (B) containing titanium were obtained. After reacting 10 g of the solid particles (B) and 3.1 g of titanium tetrachloride under reflux of n-heptane for 3 hours, washing with hexane was performed to obtain a solid catalyst component (C). The titanium content of component (C) is 49 mg / g
It was solid.

Example 1 except that 5 mg of the above solid catalyst component (C) was used in place of the solid catalyst component (C) in Example 1 (b).
Polymerization was performed in the same manner as in (b). The results are shown in Table 1.

Examples 6 to 10 and Comparative Examples 3 to 5 (Evaluation of Continuous Polymerization) For continuous polymerization, an apparatus composed of a stirring polymerization tank, a steam stripper, a fluid dryer and various flow rate controllers was used.

The amount of copolymer produced is 3kg / in a polymerization tank whose temperature is controlled at 70 ℃.
h, copolymer MI of 18-25g / 10min and density of 0.925g / c
Hexane, a catalyst, ethylene, butene-1 and hydrogen were supplied to carry out the copolymerization so as to be m ³ or less. Butene-1
The density was gradually reduced by adjusting the supply amount of the slurry, the slurry state, the shape of the polymer particles after drying, and the fouling condition with changes in the overall heat transfer coefficient of the heat transfer surface of the polymerization tank were evaluated as continuous operability. . The obtained results are shown in Table 2.

Example 11 (a) Production of solid catalyst component In Example 1 (a), except that 27 g of triethoxyboron was used instead of aluminum triethoxide,
A solid catalyst component was synthesized in the same manner as in Example 1 (a). The content of titanium in 1 g of the obtained solid catalyst component was 47 mg.

(B) Polymerization Ethylene and butene-1 were copolymerized in the same manner as in Example 1 (b).

After completion of the polymerization, the autoclave was opened and the inside was inspected, but no polymer was attached to the inner wall and the stirrer.

196 g of a copolymer was produced, and the copolymer had a MI of 0.67 g / 10 mi.
n, the density was 0.9225 g / cm ³ , and the FR value was 7.1.

Catalytic activity is 151600g copolymer / gTi · h · ethylene pressure, 713
It was 0 g copolymer / g solid · h · ethylene pressure. The amount of hexane extracted with boiling point of the obtained copolymer film (extracted for 10 hours) was 1.6 wt%.

Example 12 (a) Production of solid catalyst component In Example 3, when the solid (A) was reacted with titanium tetrachloride, titanium trichloride.1 / 3 was used instead of titanium tetrachloride.
A solid catalyst component was synthesized in the same manner as in Example 3 except that 2.6 g of aluminum trichloride was used. Obtained solid catalyst component
The content of titanium in 1 g was 48 mg.

(B) Gas phase polymerization Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 (b).

After completion of the polymerization, the autoclave was opened and the inside was inspected, but no polymer was attached to the inner wall and the stirrer.

210 g of a copolymer was produced, and the copolymer had a MI of 0.90 g / 10 mi.
n, the density was 0.9230 g / cm ³ , and the FR value was 7.7.

Catalytic activity is 159100g copolymer / gTi · h · ethylene pressure, 764
It was 0 g copolymer / g solid · h · ethylene pressure. The amount of hexane extracted with boiling point of the obtained copolymer film (extracted for 10 hours) was 2.5 wt%.

Example 13 (a) Production of solid catalyst component In Example 3, when the solid (A) was reacted with titanium tetrachloride, 2.5 g of titanium tetrachloride and 0.53 g of triethoxyvanadate were used instead of titanium tetrachloride. Except
A solid catalyst component was synthesized in the same manner as in Example 3. The obtained solid catalyst component was 48 mg of titanium and 8 mg of vanadium.

(B) Gas phase polymerization Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 (b).

After completion of the polymerization, the autoclave was opened and the inside was inspected, but no polymer was attached to the inner wall and the stirrer.

190 g of a copolymer is produced, and the copolymer has a MI of 0.83 g / 10 mi.
n, the density was 0.9210 g / cm ³ , and the FR value was 7.0.

The catalytic activity was 144000 g copolymer / g Ti + V · h · ethylene pressure and 6910 g copolymer / g solid · h · ethylene pressure.
The amount of hexane extracted with boiling point of the obtained copolymer film (extracted for 10 hours) was 1.3 wt%.

Example 14 (a) Production of solid catalyst component In Example 3, when the solid (A) was reacted with titanium tetrachloride, 2.5 g of titanium tetrachloride and 0.40 g of vanadium pentachloride were used instead of titanium tetrachloride. A solid catalyst component was synthesized in the same manner as in Example 3 except for the above. The obtained solid catalyst component was 48 mg of titanium and 8 mg of vanadium.

(B) Gas phase polymerization Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 (b).

After completion of the polymerization, the autoclave was opened and the inside was inspected, but no polymer was attached to the inner wall and the stirrer.

The copolymer produced 203 g, and the copolymer had a MI of 0.91 g / 10 mi.
n, the density was 0.9200 g / cm ³ , and the FR value was 7.3.

The catalytic activities were 154000 g copolymer / g Ti + V · h · ethylene pressure and 7390 g copolymer / g solid · h · ethylene pressure.
The amount of hexane extracted with boiling point of the obtained copolymer film (extracted for 10 hours) was 1.5 wt%.

EFFECT OF THE INVENTION By using the catalyst of the present invention, low density ethylene-α
-The olefin copolymer can be efficiently produced without any trouble in continuous operation. Also obtained ethylene-
The α-olefin copolymer is characterized by a narrow molecular weight distribution.

[Brief description of drawings]

 FIG. 1 is a flow chart of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuyuki Kuroda 185-2, Shirahatakami-cho, Kanagawa-ku, Yokohama, Kanagawa Prefecture (72) Inventor Kazuo Matsuura 22-18, 102, Higashiyukiya, Ota-ku, Tokyo

Claims (1)

[Claims] 1. A method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organoaluminum compound as a catalyst, wherein the solid catalyst component is (1) magnesium halide, (2) general formula Me (OR) _n X _zn (Where Me is A1 or B
Indicates. R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. z represents the valence of Me, and n is 0 <n.
≦ z. (3) General formula Si (OR ') _{mX4 -m} (wherein R'represents a hydrocarbon residue having 1 to 20 carbon atoms and X represents a halogen atom.
Is 0 ≦ m ≦ 2. ), And (4) a titanium compound selected from trivalent and tetravalent titanium compounds or a solid compound obtained by reacting the titanium compound and a pentavalent vanadium compound with tetrahalogen at 10 to 140 ° C. A process for producing a polyolefin, which comprises a substance obtained by contact treatment with titanium oxide.