JPS648642B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyolefin using a novel polymerization catalyst.

Conventionally, in this type of technical field, the
A catalyst in which a transition metal compound such as a titanium compound is supported on magnesium halide is known from Publication No. 12105, and further Belgian Patent No. 742112
A catalyst made by co-pulverizing magnesium halide and titanium tetrachloride is known.

However, in the production of polyolefins, it is desirable for the catalyst activity to be as high as possible, and from this point of view, the method described in Japanese Patent Publication No. 39-12105 has a still low polymerization activity, while the method described in Belgian Patent No. 742112 has a fairly high polymerization activity. Although the cost has increased, improvements are still desired.

Furthermore, in German Patent No. 2137872, the amount of magnesium halide used is substantially reduced by co-pulverizing magnesium halide, titanium tetrachloride, alumina, etc., but the activity per solid, which is a measure of productivity, No significant increase was observed, and a catalyst with even higher activity is desired.

Further, in the production of polyolefin, it is desirable that the bulk specific gravity of the polymer produced be as high as possible from the viewpoint of productivity and slurry handling. From this point of view, the method described in Japanese Patent Publication No. 39-12105 has a low bulk specific gravity and unsatisfactory polymerization activity, while the method described in Belgian Patent No. 742112 has a high polymerization activity but does not produce a polymer. There is a drawback that the bulk specific gravity of the polymer is low, and improvement is desired.

The present invention improves the above-mentioned drawbacks, provides a method for producing a novel polymerization catalyst that can obtain a polymer with high polymerization activity and high bulk specific gravity in high yield, and allows continuous polymerization to be carried out extremely easily, as well as a method for producing the polymerization catalyst. This method relates to catalytic polymerization or copolymerization of olefins, and because the polymerization activity is extremely high, the monomer partial pressure during polymerization is low, and the bulk specific gravity of the resulting polymer is high, making it possible to improve productivity. The amount of catalyst remaining in the resulting polymer after polymerization is extremely small, so the catalyst removal step can be omitted in the polyolefin manufacturing process, simplifying the polymer treatment process.
The present invention provides a method for producing polyolefins that is overall extremely economical.

In the method of the present invention, since the bulk specific gravity of the obtained polymer is large, the amount of polymer produced per unit polymerization reactor is large.

Furthermore, the advantages of the present invention are that although the bulk specific gravity of the produced polymer is high in terms of particle size, there are few coarse particles and fine particles of 50μ or less, so continuous polymerization reaction is facilitated, and polymer processing is possible. This facilitates the handling of polymer particles, such as centrifugation and powder transportation in the process.

Another advantage of the present invention is that the polyolefin obtained using the catalyst of the present invention has a large bulk specific gravity as described above, and the hydrogen concentration is required to obtain a polymer with a desired melt index compared to conventional methods. Therefore, the total pressure during polymerization can be made relatively small, and the effects on economy and productivity are also large.

In addition, when olefin is polymerized using the catalyst of the present invention, there is little decrease in the olefin absorption rate over time, so another advantage is that polymerization can be carried out for a long time with a small amount of catalyst.

Furthermore, the polymer obtained using the catalyst of the present invention has an extremely narrow molecular weight distribution and is characterized by extremely low by-products of low polymers, such as a small amount of hexane extraction. Therefore, it is possible to obtain a product of good quality, such as film grade, which has excellent blocking resistance.

The catalyst of the present invention has many of these characteristics,
Moreover, the present invention provides a novel catalyst system that improves the drawbacks of the prior art described above, and it must be said that it is surprising that these points can be easily achieved by using the catalyst of the present invention.

The present invention will be specifically explained below. That is,
The present invention has the following features: (1) []: (i) Magnesium dihalide (hereinafter referred to as magnesium halide) (ii) General formula Me (OR) _o X _zo (where Me is
Indicates an element selected from Zn, P, Mg, B, Al, Ca and Fe. R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. z represents the valence of Me, n is 0
<n≦z), and (iii) a substance obtained by reacting a titanium compound or a titanium compound and a vanadium compound []: General formula R′ _n Si(OR″) _o X _4-no ( Here R′,
R'' represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. m and n are 0≦m<4,
(2) []:( i) Magnesium halide, (ii) General formula Me (OR) _o X _zo (Here, Me is the same as above. R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom.z teeth,
and (iii) a solid substance obtained by reacting a titanium compound or a titanium compound and a vanadium compound [ ]: (iv) General formula R′ _n Si(OR″) _o X _4-no (where
R′, R″ are hydrocarbon residues having 1 to 24 carbon atoms,
X represents a halogen atom. m, n are 0≦m
<4,0<n≦4,0<m+n≦4); and (v) an organometallic compound. The present invention relates to a method for producing a polyolefin characterized by copolymerization.

The magnesium halide used in the present invention is substantially anhydrous and includes magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide, with magnesium chloride being particularly preferred.

Examples of the compound represented by the general formula Me(OR) _o X _zo (where Me, z, n and R are as defined above) used in the present invention include Mg
(OR) ₂ , Mg(OR)X, Ca(OR) ₂ , Zn(OR) ₂ , Zn
(OR)X, Al(OR) ₃ , Al(OR) ₂ X, B(OR) ₃ , B
Various _compounds such _{as ( OR ) 2 2} H ₅ ) ₂ ,
Mg(OC ₃ H ₅ ) ₂ , Ca(OC ₂ H ₅ )) ₂ , Zn(OC ₂ H ₅ ) ₂ ,
Zn(OC ₂ H ₅ ) Cl, Al(OCH ₃ ) ₃ , Al(OC ₂ H ₅ ) ₃ , Al
(OC ₂ H ₅ ) Cl, Al (OC ₃ H ₇ ) ₃ , Al (OC ₄ H ₉ ) ₃ , Al
(OC ₆ H ₅ ) ₃ , B(OC ₂ H ₅ ) ₃ , B(OC ₂ H ₅ ) ₂ Cl, P
Examples include compounds such as (OC ₂ H ₅ ) ₃ , P(OC ₆ H ₅ ) ₃ and Fe(OC ₄ H ₉ ).

In the present invention, in particular, the general formula Mg(OR) _o
Compounds represented by X _2-o , Al(OR) _o X _3-o and B(OR) _o X _3-o are preferred. Moreover, as R, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable.

Examples of the titanium compound or the titanium compound and vanadium compound used in the present invention include halides, alkoxy halides, alkoxides, and halogenated oxides of these metals. Preferred titanium compounds are tetravalent titanium compounds and trivalent titanium compounds, and specific examples of tetravalent titanium compounds include the general formula Ti(OR) _p
Those represented by X _4-p (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 24 carbon atoms, and X represents a halogen atom; p is 0≦p≦4) are preferable. , titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxy Titanium, Senoisopropoxytrichlorotitanium, Diisopropoxydichlorotitanium, Triisopropoxymonochlorotitanium, Tetraisopropoxytitanium, Monobutoxytrichlorotitanium, Dibutoxydichlorotitanium, Monopentoxytrichlorotitanium, Monophenoxytrichlorotitanium, Diphenoxy Examples include dichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium. Examples of trivalent titanium compounds include titanium trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of group metals of the periodic table. Can be mentioned. In addition, the general formula _Ti (OR) _q
<q<4. ) A trivalent titanium compound obtained by reducing a tetravalent alkoxy titanium halide represented by the following formula with an organometallic compound of a group metal of the periodic table is exemplified. Examples of vanadium compounds include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxyvanadium; Examples include trivalent vanadium compounds such as trivalent vanadium compounds, vanadium trichloride, and vanadium triethoxide.

In the present invention, tetravalent titanium compounds are most preferred.

In order to make the present invention even more effective, when a titanium compound and a vanadium compound are used together, V/
The Ti molar ratio is preferably in the range of 2/1 to 0.01/1.

General formula R′ _n Si(OR″ ₎ used in the present invention
X _4-no (here, R′, R″ are hydrocarbon residues such as alkyl groups, aryl groups, and aralkyl groups having 1 to 24 carbon atoms, and X is a halogen atom. m, n are 0≦m<
4,0<n≦4,0<n+m≦4), monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-butoxysilane, monomethyltrisec-butoxysilane,
Monomethyltriisoproboxysilane, monomethyltripentoxysilane, monomethyltrioctoxysilane, monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,
Dimethyldiisopropoxysilane, dimethyldiphenoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmonoisopropoxysilane, trimethylmonophenoxysilane, monomethyldimethoxymonochlorosilane, monomethyldiethoxymonochlorosilane, monomethylmonoethoxydichlorosilane , monomethyldiethoxymonochlorosilane, monomethyldiethoxymonobromosilane, monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltriisopropoxysilane, monoethyltriphenoxy Silane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonophenoxysilane, monoethyldimethoxymonochlorosilane, monoethyldiethoxymonochlorosilane,
Monoethyldiphenoxymonochlorosilane, monoisopropyltrimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, mono-sec-butyltriethoxysilane, monophenyltriethoxysilane, diphenyldiethoxysilane, diphenyltriethoxysilane enylmonoethoxymonochlorosilane, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono n-butoxytrichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenoxytrichlorosilane Chlorosilane, mono-p-methylphenoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, diisopropoxydichlorosilane, di-n-butoxydichlorosilane, dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triiso Examples include propoxymonochlorosilane, tri-n-butoxymonochlorosilane, trisec-butoxymonochlorosilane, tetraethoxysilane, and tetraisopropoxysilane.

(i) Magnesium halide in the present invention, (ii)
There is no particular restriction on the method of reacting the compound represented by the general formula Me( _OR ) _o Temperature 20-400℃, preferably 50℃ in the presence or absence of
The reaction may be carried out by contacting under heating at -300°C for usually 5 minutes to 20 hours, by co-pulverization, or by an appropriate combination of these methods. component
There is no particular restriction on the reaction order of (i) to (iii), and 3
The components may be reacted simultaneously, or two components may be reacted and then another component may be reacted.

The inert solvent used at this time is not particularly limited, and hydrocarbon compounds and/or derivatives thereof that do not normally inactivate the Ziegler type catalyst can be used. Specific examples of these include propane, butane, pentane, hexane,
Various aliphatic saturated hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons such as heptane, octane, benzene, toluene, xylene, and cyclohexane, and alcohols such as ethanol, diethyl ether, tetrahydrofuran, ethyl acetate, and ethyl benzoate; Examples include ethers and esters.

The equipment used for co-pulverization is not particularly limited, but ball mills, vibration mills, rod mills, impact mills, etc. are usually used, and those skilled in the art can easily determine conditions such as grinding temperature and grinding time depending on the grinding method. It is something that can be done. Generally, the grinding temperature is 0°C to 200°C, preferably 20°C to 100°C,
The grinding time is 0.5 to 50 hours, preferably 1 to 30 hours. Of course, these operations should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible.

In the present invention, a method using co-pulverization is particularly preferred.

Magnesium halide and general formula Me(OR) _o
The mixing ratio with the compound represented by the general formula Me(OR) _o X _zo is such that if the amount of the compound represented by the general formula Me ( _OR ) Yes, Mg/Me molar ratio is 1/0.001 to 1/20, preferably 1/0.01 to
The range is 1/1, most preferably 1/0.05~
A range of 1/0.5 is desirable for the production of highly active catalysts.

In addition, it is most preferable to adjust the amounts of the titanium compound or the titanium compound and the vanadium compound so that the titanium and vanadium contained in the catalyst component [] are within the range of 0.5 to 20% by weight. The range of 1 to 10% by weight is particularly desirable in order to obtain the activity per solid.

In the present invention, if the amount of the compound represented by the general formula R′ _n Si(OR _″ ) _o 0.1 to 100 mol per mol of titanium compound or titanium compound and vanadium compound,
Preferably it is within the range of 0.3 to 20 mol.

Examples of organometallic compounds used in the present invention include general formulas R ₃ Al, R ₂ AlX, RAlX ₂ , R ₂ AlOR, RAl
(OR) Organoaluminum compound of X and R ₃ Al ₂ X ₃ (where R is an alkyl group or aryl group having 1 to 20 carbon atoms, Examples include triethylaluminum, triisopropylaluminum, triisobutylaluminum, trisec
Specific examples include -butylaluminum, tritert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof. In addition, along with these organometallic compounds, ethyl benzoate, o-
Alternatively, organic carboxylic acid esters such as ethyl p-toluate and ethyl p-anisate may be used in combination. The amount of the organometallic compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the amount of the titanium compound or the titanium compound and the vanadium compound.

In addition, in the present invention, the general formula R′ _n Si(OR″) _o
A compound represented by X _4-no may be used by reacting it with the above-mentioned organometallic compound. The reaction ratio _at this time is the general formula R′ _n Si(OR″) _o :2 range.

The amount of the product obtained by reacting the general formula R′ _n Si(OR _″ ) _o
is preferably in the range of 0.1:1 to 100:1, and 0.3:1
A range of ˜20:1 is more preferred.

Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization, or gas phase polymerization, and it can be particularly preferably used for gas phase polymerization. The polymerization reaction is carried out in the same manner as an ordinary olefin polymerization reaction using a Ziegler type catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, and the like. The polymerization conditions for olefin are a temperature of 20 to 120°C, preferably 50 to 100°C, and a pressure of normal pressure to 70 kg/cm ² , preferably 2 to 60 kg/cm ² . Molecular weight can be adjusted by polymerization temperature,
Although it can be controlled to some extent by changing polymerization conditions such as the molar ratio of catalysts, it is effectively achieved by adding hydrogen to the polymerization system. of course,
Using the catalyst of the present invention, two-stage or more multi-stage polymerization reactions with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problems.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, and α-olefins having 2 to 12 carbon atoms are particularly preferred, such as ethylene, propylene, 1-butene, hexene-1,4-methyl Homopolymerization of α-olefins such as pentene-1 and octene-1, and ethylene and propylene, ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1, propylene and 1
- Suitable for use in copolymerization of butene, copolymerization of ethylene and two or more other α-olefins, etc.

Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of diene compounds used at this time include butadiene, 1,4-hexadiene, ethylidenenorbornene, dicyclopentadiene, and the like.

Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 (a) Preparation of solid catalyst component [] Commercially available anhydrous magnesium chloride 10 was placed in a stainless steel pot with an internal volume of 400 ml containing 25 stainless steel balls having a diameter of 1/2 inch.
g, aluminum triethoxide, 2.3 g, and titanium tetrachloride, 2.5 g, under a nitrogen atmosphere at room temperature.
Ball milling was carried out for 16 hours. After ball milling, 1g of solid catalyst component obtained contains 41mg
contained titanium.

(b) Polymerization A stainless steel autoclave was used as the gas phase polymerization apparatus, a loop was created with a blower, a flow controller, and a dry cyclone, and the temperature of the autoclave was adjusted by flowing hot water through the jacket.

The above solid catalyst component [] was fed at a rate of 50 mg/hr, monomethyltriethoxysilane 0.22 mmol/hr, and triethylaluminum at a rate of 5 mmol/hr to an autoclave adjusted to 80°C, and
Supply each gas while adjusting the butene-1/ethylene ratio (mole ratio) in the autoclave gas phase to 0.27 and hydrogen to 15% of the total pressure, and circulate the gas in the system using a blower. let the full pressure
Polymerization was carried out while maintaining the pressure at 10 kg/cm ² ·G.
The produced ethylene copolymer had a bulk specific gravity of 0.33, a melt index (MI) of 0.9, and a density of 0.9213.

The catalyst activity was 318,000 g copolymer/g Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

_This copolymer has _an FR value (FR
=MI ₁₀ /MI _2.16 ) was 7.0, and the molecular weight distribution was extremely narrow.

Furthermore, when a film of this copolymer was extracted in boiling hexane for 10 hours, the amount of hexane extracted was
The extractable content was 0.9wt%, which was extremely low.

Comparative Example 1 Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that 2.5 g of monomethyltriethoxysilane was not added. The produced ethylene copolymer had a bulk specific gravity of 0.33, a density of 0.9203, and a melt index of 1.3.

The catalyst activity was 346,000 g copolymer/g Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but some polymer was found adhering to the inner wall and the stirrer.

Further, the FR value of this copolymer was 8.3, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 4.3 wt%.

Example 2 In a 300c.c. three-necked flask with a magnetic induction stirrer,
10 ml of ethanol, 20 g of anhydrous magnesium chloride, and 4.6 g of triethoxyboron were added, and the mixture was reacted under reflux for 3 hours. After the reaction is complete, n-hexane
150 ml of the mixture was added to form a precipitate, and then allowed to stand, the supernatant liquid was removed, and vacuum drying was performed at 200°C to obtain a white dry powder.

11 g of the above white powder and 2.3 g of titanium tetrachloride 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, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours. Summer. 1 g of the solid catalyst component obtained after ball milling contained 43 mg of titanium.

Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that the above solid catalyst component [] was fed at a rate of 50 mg/hr. The produced ethylene copolymer has a bulk specific gravity of 0.35, a density of 0.9218,
The melt index was 1.3. The catalyst activity was extremely high at 374,000 g copolymer/g Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

Furthermore, the FR value of this copolymer was 7.1, and when the film was extracted in boiling hexane for 10 hours, the hexane extraction amount was 1.1 wt%, which was an extremely small amount.

Example 3 Into the ball mill pot described in Example 1, 10 g of anhydrous magnesium chloride and 3.1 g of diethoxymagnesium were added.
g and 2.1 g of titanium tetrachloride in a nitrogen atmosphere.
Ball milling was performed at room temperature for 16 hours. 1 g of solid catalyst component obtained after ball milling contains
Contains 35mg of titanium.

The same procedure as in Example 1 was repeated except that the above solid catalyst component [] was fed at a rate of 50 mg/hr and tetraethoxysilane was fed at a rate of 0.25 mmol/hr instead of monomethyltriethoxysilane. Phase polymerization was carried out. The produced ethylene copolymer has a bulk specific gravity of 0.34 and a density of
The melt index was 0.9208 and the melt index was 0.91.

Further, the catalyst activity was extremely high at 427,000 g copolymer/g Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

The FR value of this copolymer was 6.9, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane oil extracted was 1.0 wt%, which was an extremely small amount.

Example 4 In the ball mill pot described in Example 1, 10 g of anhydrous magnesium chloride and triethoxyphosphorus (P(OEt) ₃ ) were added.
2.1 g of titanium tetrachloride and 2.1 g of titanium tetrachloride were added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere.
Solid catalyst component obtained after ball milling []1
g contained 37 mg of titanium.

The above solid catalyst component [] was fed at a rate of 50 mg/hr, and monophenyltriethoxysilane was added at 0.25 mmol/hr instead of monomethyltriethoxysilane.
Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1, except that hr was fed. The produced ethylene copolymer has a bulk specific gravity
0.38, density 0.9218, and melt index 1.2.

Moreover, the catalyst activity was extremely high at 348,000 g copolymer/g Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

Furthermore, the FR value of this copolymer was 7.2, and when the film was extracted in boiling hexane for 10 hours, the hexane extraction amount was 1.2 wt%, which was an extremely small amount.

Example 5 10 g of anhydrous magnesium chloride, 3.5 g of diethoxyzinc, and 2 g of diisopropoxydichlorotitanium were placed in the ball mill pot described in Example 1, and ball milling was carried out at room temperature for 16 hours under a nitrogen atmosphere. 1 g of the solid catalyst component obtained after ball milling contained 32 mg of titanium.

A continuous gas phase of ethylene and butene-1 was carried out in the same manner as in Example 1, except that the above solid catalyst component [] was fed at a rate of 50 mg/hr and tetraethoxysilane was fed at a rate of 0.25 mmol/hr instead of monomethylethoxysilane. Polymerization was carried out. The produced ethylene copolymer had a bulk specific gravity of 0.39, a density of 0.9215, and a melt index of 1.1.

The catalyst activity was extremely high at 378,000 g copolymer/g Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

The FR value of this copolymer was 7.1, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 1.3 wt%, which was extremely small.

The stainless steel autoclave equipped with an induction stirrer from Example 6 2 was replaced with nitrogen, 1000 ml of hexane was added, 1 mmol of triethylaluminum, 0.05 mmol of tetraethoxysilane, and 10 mg of the solid catalyst component obtained in Example 1 were added and stirred. The temperature was raised to 90°C. At the vapor pressure of hexane, the system is 2
Kg/cm ²・G, but the total pressure of hydrogen is 4.8Kg/cm ²・G
, then add ethylene until the total pressure is 10
Polymerization was started by charging the autoclave to a pressure of 10 kg/cm ² ·G, and polymerization was carried out for 1 hour while maintaining the pressure of the autoclave at 10 kg/cm ² ·G. After the polymerization was completed, the polymer slurry was transferred to a beaker, and hexane was removed under reduced pressure to obtain 143 g of white polyethylene having a melt index of 1.2, a density of 0.9633, and a bulk specific gravity of 0.37. Catalytic activity is 67100g polyethylene/gTi・hr・C ₂ H ₄
The pressure was 2750 g polyethylene/g solids/hr/C ₂ H ₄ pressure.

The FR value of the obtained polyethylene was 8.0, the molecular weight distribution was extremely narrow compared to Comparative Example 2, and the hexane extraction amount was 0.18 wt%.

Comparative Example 2 Polymerization was carried out for 1 hour in the same manner as in Example 6 except that tetraethoxysilane was not added, and the melt index was 1.6 and the density was
149g of white polyethylene with a bulk specific gravity of 0.9637 and 0.32
I got it. Catalytic activity is 69900g polyethylene/
g Ti・hr・C ₂ H ₄ pressure, 2870 g polyethylene/g solid・hr・C ₂ H ₄ .

The FR value of the obtained polyethylene was 9.4, and the hexane extraction amount was 1.3 wt%.

Example 7 50% of the solid catalyst component obtained in Example 1
mg/hr, and the product obtained by reacting triethylaluminum and monomethyltriethoxysilane at a composition (molar ratio) of 5:0.22 at room temperature for 2 hours was fed at a rate of 5 mmol/hr in terms of aluminum. Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1. The produced ethylene copolymer has a bulk specific gravity of 0.32, a density of 0.9211,
The melt index was 0.97.

The catalyst activity was extremely high at 328,000 g copolymer/g Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

The FR value of this copolymer was 7.1, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane oil extracted was 1.2 wt%, which was an extremely small amount.

Example 8 In place of 2.5 g of titanium tetrachloride in Example 1,
2.5g titanium tetrachloride and triethoxyvanadyl
Synthesis was carried out in the same manner as in Example 1, except that 1.8 g was used, to obtain a solid powder containing 40 mg of titanium and 29 mg of vanadium per 1 g of solid powder.

Next, using the above solid catalyst component, polymerization was carried out in the same manner as in Example 1 to obtain an ethylene-butene-1 copolymer having a bulk specific gravity of 0.41, a melt index of 0.9, and a density of 0.9208. The catalyst activity was 287,000 g copolymer/g Ti, which was an extremely high activity.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

Furthermore, the FR value of this copolymer was 7.1, and when the film was extracted in boiling hexane for 10 hours, the hexane extraction amount was 1.0 wt%, which was an extremely small amount.

Example 9 The following gas phase polymerization was carried out using the apparatus described in Example 1. The solid powder (A) obtained in Example 1 was fed into an autoclave prepared at 60°C at a rate of 80 mg/hr and triethylaluminum at a rate of 5 mmol/hr. Propylene was also fed into the autoclave, and the gas in the system was removed using a blower. is circulated to a total pressure of 7 kg/
Polymerization was carried out in cm ² . The polypropylene produced had a bulk specific gravity of 0.43. In addition, the catalyst activity is 111000g
It was polypropylene/gTi.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

Example 10 Aluminum triethoxide in Example 1
A catalyst component was synthesized in the same manner as in Example 1, except that 2.5 g of Ca(OC ₂ H ₅ ) ₂ was used instead of 2.3 g, and a solid powder containing 39 mg of titanium was added to 1 g of solid powder. Obtained.

Using the above solid powder, gas phase polymerization was carried out in the same manner as in Example 1.

The produced ethylene copolymer has a bulk specific gravity of 0.35,
The density was 0.920 and the melt index was 0.9.

The catalyst activity was extremely high at 325,000 g copolymer/g Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

The FR value of this copolymer was 6.9, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 0.9 wt%, which was extremely small.

Example 11 Aluminum triethoxide in Example 1
A catalyst component was synthesized in the same manner as in Example 1 except that 3.5 g of Fe(OC ₄ H ₉ ) ₃ was used instead of 2.3 g, and a solid powder containing 41 mg of titanium per 1 g of solid powder was obtained. I got it. Using the above solid powder, gas phase polymerization was carried out in the same manner as in Example 1.

The produced ethylene copolymer has a bulk specific gravity of 0.37,
The density was 0.9223 and the melt index was 1.1.

Moreover, the catalyst activity was extremely high at 296,000 g copolymer/g Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

Furthermore, the FR value of this copolymer was 7.0, and when the film was extracted in boiling hexane for 10 hours, the hexane extraction amount was 1.1 wt%, which was an extremely small amount.

[Brief explanation of drawings]

FIG. 1 is a flow chart showing an example of catalyst preparation in olefin polymerization of the present invention.

Claims (1)

[Claims] 1 []: (i) Magnesium dihalide, (ii) General formula Me(OR) _o X _zo (where Me is
Indicates an element selected from Zn, P, Mg, B, Al and Fe. R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. z is
and (iii) a solid substance obtained by reacting a titanium compound or a titanium compound and a vanadium compound, []: General formula R' _n Si(OR″) _o X _4-no (where R′,
R″ represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. m and n are 0≦m<4,0<
A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin using a catalyst system comprising a combination of a compound represented by n≦4,0<m+n≦4 and [ ]: an organoaluminum compound. 2 []: (i) Magnesium dihalide, (ii) General formula Me (OR) _o X _zo (where Me is
Indicates an element selected from Zn, P, Mg, B, Al and Fe. R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. z is
and (iii) a solid substance obtained by reacting a titanium compound or a titanium compound and a vanadium compound [ ]: (iv) General formula R′ _n Si(OR″) _o X _4-no (where
R′, R″ are hydrocarbon residues having 1 to 24 carbon atoms,
X represents a halogen atom. m, n are 0≦m<
(4,0<n≦4,0<m+n≦4) and (v) an organoaluminum compound. A method for producing polyolefin, which is characterized by polymerization.