JPS6412288B2 - - 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.

Also, from the physical properties of the polyolefin produced,
For example, when molding a film, it is required to have as good transparency as possible and strong impact strength, and it is strongly desired that the molecular weight distribution of the resin be as narrow as possible.From this point of view, the above-mentioned Belgian patent 742112 The method of this issue did not provide a sufficiently narrow molecular weight distribution, and further improvements were desired.

Further, in the production of polyolefin, it is desirable that the bulk specific gravity of the produced polymer be as high as possible from the viewpoint of productivity. From this point of view, the above-mentioned special public service
In the method described in Publication No. 12105, the bulk specific gravity of the produced polymer is low and the polymerization activity is also unsatisfactory, while in the method of Belgian Patent No. 742112, although the polymerization activity is high, the bulk specific gravity of the produced polymer is low. Improvement is desired.

The present invention improves the above-mentioned drawbacks, and provides a novel polymerization method that can obtain polymers with high polymerization activity, narrow molecular weight distribution, and high bulk specific gravity in high yield, and can be carried out extremely easily in continuous polymerization. The present invention relates to a method for producing a catalyst and a method for polymerizing or copolymerizing an olefin using the polymerization catalyst,
Since the polymerization activity is extremely high, the monomer partial pressure during polymerization is low, and the bulk specific gravity of the produced polymer is high, so productivity can be improved, and the amount of catalyst residue in the produced polymer after polymerization is extremely small. Therefore, the catalyst removal step can be omitted in the polyolefin manufacturing process, thereby simplifying the polymer treatment process and providing an extremely economical polyolefin manufacturing method as a whole.

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 powder This makes it easier to handle the polymer particles, such as transporting them.

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,
[A] (1) Magnesium dihalide (hereinafter referred to as magnesium halide) (2) A compound represented by the general formula Al(OR) _o x _3-o , (3) A compound represented by the general formula Si(OR) _n A reaction product obtained by reacting a compound represented by X _4-n and (4) a titanium compound or a titanium compound vanadium compound is further reacted with ( ₅ ) a compound represented by the general formula AlR _p and [B] a catalyst consisting of a compound represented by the general formula _AlR3 (in the above formula, R is a hydrocarbon residue having 1 to 24 carbon atoms, X is a halogen atom, and 0<n≦
3, 0≦m≦4 and 0<p<3.

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.

General formula Al(OR) _o used in the present invention
X _3-o (here, R has 1 to 24 carbon atoms, preferably 1 to 24 carbon atoms)
Hydrocarbon residues such as 12 alkyl groups, aryl groups, and aralkyl groups are particularly preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred, and X represents a halogen atom. n is 0
≦n≦4),
Aluminum trimethoxide, aluminum triethoxide, diethoxymonochloroaluminum, monoethoxydichloroaluminum, monomethoxydiethoxyaluminum, aluminum tri-n-propoxide, aluminum triisopropoxide, diisopropoxymonochloroaluminum, monoisopropoxydichloroaluminum , monomethoxydiisopropoxyaluminum, aluminum tri-n-butoxide, aluminum trisec-butoxide, and aluminum t-butoxide, with aluminum trimethoxide and aluminum triethoxide being particularly preferred.

General formula Si(OR) _n used in the present invention
X _4-n (Here, R is a hydrocarbon residue such as an alkyl group, aryl group, or aralkyl group having 1 to 24 carbon atoms,
indicates a halogen atom. m is 0≦m≦4)
Examples of compounds represented by include silicon tetrachloride, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono n-butoxytrichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, Chlorosilane, monophenoxytrichlorosilane, monop
-Methylphenoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane,
Diisopropoxydichlorosilane, di-n-butoxydichlorosilane, dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, trisec-butoxymonochlorosilane, tetraethoxy Examples include silane and tetraisopropoxysilane.

Examples of the titanium compound or titanium compound 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 suitable, and the tetravalent titanium compound specifically has the general formula Ti(OR) _q X _4-q
(Here, R represents a hydrocarbon residue such as an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, and X represents a halogen atom. q is 0≦q≦4.) Preferred are titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, Tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium,
Examples include monobenoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, 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. It will be done. In addition, the general formula Ti(OR _{) r}
indicates a halogen atom. r is 0<r<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 I metal of the periodic table can be mentioned. 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.

In the present invention, (1) magnesium halide, (2) a compound represented by the general formula Al(OR) _o X _3-o , (3) a compound represented by the general formula Si(OR) _n X _4-n , and ( 4) There are no particular restrictions on the method for reacting titanium compounds or titanium compound-vanadium compounds, and the reaction may be carried out at a temperature of 20 to 400 ℃ in the presence or absence of an inert solvent.
℃, preferably 50 to 300℃ under heating, usually 5
The reaction may be carried out by contacting for minutes to 20 hours, by co-pulverization, or by an appropriate combination of these methods.

Furthermore, there is no particular restriction on the reaction order of components (1) to (4), and the four components may be reacted simultaneously, or the three components may be reacted simultaneously.
After reacting the components, one other component may be reacted, or after reacting two components, the other two components may be reacted, and after reacting the two components, the next one component may be reacted. may be reacted, and then the remaining one component may be reacted.

The inert solvent used at this time is not particularly limited, and any liquid organic compound that does not normally inactivate the Ziegler type catalyst can be used. Specific examples of these include propane, butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, various aliphatic saturated hydrocarbons such as cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons, and ethanol and diethyl. Examples include alcohols, ethers, and esters such as ether, tetrahydrofuran, ethyl acetate, and ethyl benzoate.

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

Magnesium halide and general formula Al(OR) _o
The mixing ratio with the compound represented by X _3-o is such that polymerization activity tends to decrease if the amount of the aluminum compound is too small or too large; The range is from 0.001 to 1/20, preferably from 1/0.01 to 1/1, and most preferably from 1/0.05 to 1/0.5 for the production of highly active catalysts.

In _the present invention, the amount of the compound represented by the general formula Si(OR) _n Preferably 0.5
~10g.

In addition, the amount of titanium compound or titanium compound vanadium compound is the amount of titanium and vanadium contained in the reaction product obtained by reacting components (1) to (4).
It is most preferable to adjust the content to within a range of 0.5 to 20% by weight, and a range of 1 to 10% by weight is particularly desirable in order to obtain a well-balanced activity per titanium and vanadium and activity per solid.

In the present invention, (1) magnesium halide, (2) a compound represented by the general formula Al(OR) _o X _3-o ,
(3) A reaction product obtained by reacting a compound represented by the general formula Si( _{OR ) n} React with the compound represented by _3-p . At this time, the amount of the compound represented by the general formula AlR _p X _{3 -p} to be used is such that the molar ratio of AlR _p 0.3~50
It is. Further, the reaction method at this time is not particularly limited, and for example, the reaction may be carried out in the presence of an inert hydrocarbon, or the reaction may be carried out by co-pulverization treatment. The reaction temperature is preferably in the range of 0 to 100°C, and the reaction time is preferably in the range of 5 minutes to 10 hours.

The general formula AlR _p X _3-p used in the present invention (where R
represents a hydrocarbon residue such as an alkyl group, aryl group, or aralkyl group having 1 to 24 carbon atoms, particularly preferably an alkyl group having 1 to 12 carbon atoms, and X represents a halogen atom. p is 0<p<3. ) Examples of the compound represented by: dimethylaluminum chloride, diethylaluminium chloride, diethylaluminum bromide, diethylaluminium iodide, diethylaluminum fluoride, diisopropylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof. I can do it.

The general formula AlR ₃ used in the present invention (where R is a hydrocarbon residue such as an alkyl group having 1 to 24 carbon atoms, an aryl group, an aralkyl group, particularly preferably a carbon number 1
-12 alkyl groups) are triethylaluminum, triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-
Mention may be made of butylaluminum, trihexylaluminum, trioctylaluminum and mixtures thereof. Also, the general formula AlR ₃
With the compound represented by ethyl benzoate, o
-Or organic carboxylic acid esters such as ethyl p-toluate and ethyl p-anisate can also be used in combination.

The amount of the compound represented by the general formula _AlR3 to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the mole of the titanium compound or the titanium compound 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 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 or more multi-stage polymerization reactions with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem.

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, ethylene and propylene, ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1, propylene and 1
- Suitably used for 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 are butadiene,
Examples include 1,4-hexadiene, ethylidene norbornene, and dicyclopentadiene.

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 10 g of commercially available anhydrous magnesium chloride, 4.3 g of aluminum triethoxide, and titanium tetrachloride were placed in a 400 ml stainless steel pot containing 25 stainless steel balls with a diameter of 1/2 inch.
2.8 g and 3.1 g of tetraethoxysilane were added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere. 1g of solid powder (A) obtained after ball milling
contained 35 mg of titanium.

Next, 100 ml of hexane, 10 g of the above solid powder (A), and 1.8 g of ethylaluminum sesquichloride (Al/Ti
(molar ratio) = 2) and reacted for 2 hours under refluxing hexane. After the reaction is complete, let it stand and remove the supernatant.
The solid component was then washed with hexane to obtain a solid catalyst component (B).

Polymerization A stainless steel autoclave was used as the gas phase polymerization apparatus, a loop was created with a blower, a flow rate 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 (B) was supplied to an autoclave adjusted to 80°C at a rate of 50 mg/hr and triethylaluminum 2 mmol/hr, and the butene-1/ethylene ratio (molar ratio) in the gas phase of the autoclave was set to 0.27. Furthermore, each gas was supplied while adjusting the hydrogen to 15% of the total pressure, and the gas in the system was circulated using a blower to reduce the total pressure to 10 kg/kg.
Polymerization was carried out while maintaining the temperature at cm ² ·G. The produced ethylene copolymer had a bulk specific gravity of 0.42, a melt index (MI) of 1.0, and a density of 0.9198.

Furthermore, the catalyst activity was extremely high at 923,000 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 (F.
R.=MI10/MI2.16) was 6.9, 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
It was 1.0wt%, and the extractable content was extremely small.

Comparative Example 1 Solid powder (A) obtained in Example 1 as a solid catalyst component
Polymerization was carried out in the same manner as in Example 1 except that ethylene-butene-1 was supplied at a rate of 50 mg/hr.
A copolymer was obtained. Catalytic activity is 412,000g copolymer/
gTi, and its activity was lower than that of Example 1.

The FR value of this copolymer was 7.1, and the amount of hexane extracted from the film was 1.3 wt%.

Comparative Example 2 The solid powder (A) obtained in Example 1 was placed in a 300 ml three-necked flask purged with nitrogen, together with 100 ml of hexane, and then 0.8 g of triethylaluminum (Al/
Ti (molar ratio)=1) was added thereto and the mixture was reacted for 2 hours under refluxing hexane. After the reaction was completed, the mixture was allowed to stand and the supernatant liquid was removed, and then the solid component was washed with hexane to obtain a solid catalyst component (C).

Polymerization was carried out in the same manner as in Example 1, except that the solid catalyst component (C) was supplied at a rate of 50 mg/hr, and ethylaluminum sesquichloride was supplied at a rate of 2 mmol/hr instead of triethylaluminum.
Bulk specific gravity 0.23, melt index 0.9, density
A copolymer of 0.9245 was obtained. The catalyst activity was 10,500 copolymer/gTi, which was significantly lower than in Example 1.

Comparative Example 3 Solid powder (A) obtained in Example 1 as solid catalyst component
was supplied at a rate of 50 mg/hr, triethylaluminum was supplied as organoaluminum compounds at 2 mmol/hr, and ethylaluminum sesquichloride was supplied as organoaluminum compounds.
Polymerization was carried out in the same manner as in Example 1 except that the copolymer was supplied at a rate of 2 mmol/hr to obtain a copolymer having a bulk specific gravity of 0.32, a melt index of 1.1, and a density of 0.9221.

The FR value of this copolymer was 8.0, and the amount of hexane extracted from the film was 3.5 wt%.

Example 2 A solid catalyst component was synthesized in the same manner as in Example 1, except that 1.1 g of diethylaluminum chloride was used instead of ethylaluminum sesquichloride.

Polymerization was carried out in the same manner as in Example 1 except that the above solid catalyst component was supplied at a rate of 50 mg/hr to obtain an ethylene-butene-1 copolymer having a bulk specific gravity of 0.38, a melt index of 1.2, and a density of 0.9223. Catalytic activity is
It was 974,000g copolymer/gTi, indicating 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.

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 1.0wt%, which was an extremely small amount.

Example 3 A solid catalyst component was synthesized in the same manner as in Example 1, except that 1.5 g of ethyl aluminum dichloride was used instead of ethyl aluminum sesquichloride.

Polymerization was carried out in the same manner as in Example 1, except that the solid catalyst component was fed at a rate of 50 mg/hr. The produced ethylene copolymer has a bulk specific gravity of 0.39 and a density of
The melt index was 0.9208 and the melt index was 1.0. The catalyst activity was extremely high at 883,000g/copolymer/gTi.

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 4 10 g of anhydrous magnesium chloride and tetraethoxysilane were placed in the ball mill pot described in Example 1.
3.5 g was added and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a grayish white solid powder (D).

Next, 100 ml of hexane, 12.5 g of the above solid powder (D), and 4.5 g of aluminum trisec-butoxide were added to a 300 c.c. three-necked flask equipped with a magnetic induction stirrer.
The reaction was carried out under reflux for 5 hours. After the reaction was completed, the mixture was allowed to stand at room temperature and the supernatant liquid was removed, followed by vacuum drying at 200°C to obtain a solid powder (E). Then, this solid powder
60 ml of diisopropoxydichlorotitanium was added to (E) and reacted at 130°C for 1 hour. After the reaction, remove excess diisopropoxydichlorotitanium and
-Repeat washing with hexane to produce grayish white solid powder (E)
I got it. 1 g of this solid powder (F) contained 18 mg of titanium.

Then, 100 ml of hexane, 10 g of the above solid powder (F), and 0.96 g of ethylaluminum sesquichloride (Al/Ti (molar ratio) = 2) were placed in a 300 ml three-neck flask purged with nitrogen, and reacted for 2 hours under reflux of hexane. After the reaction was completed, the mixture was allowed to stand, the supernatant liquid was removed, and the solid component was washed with hexane to obtain a solid catalyst component.

Polymerization was carried out in the same manner as in Example 1, except that the solid catalyst component was fed at a rate of 50 mg/hr. The produced ethylene copolymer has a bulk specific gravity of 0.39 and a density of
0.9215, and the melt index was 1.1. The catalyst activity was extremely high at 1058000g copolymer/gTi.

In addition, the F・R・value of this copolymer is 7.1,
When the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 1.1 wt%, which was an extremely small amount.

The autoclave made of stainless steel and equipped with an induction stirrer from Example 5 2 was purged with nitrogen, and 1000 ml of hexane was charged therein. 1 mmol of triethylaluminum and 10 mg of the solid catalyst component obtained in Example 1 were added thereto, and the temperature was raised to 90° C. with stirring. The vapor pressure of hexane is 2 Kg/cm ² G, but the total pressure of hydrogen is 4.8 Kg/cm ² G.
Pump it up until it reaches G, then add ethylene to the full pressure.
Polymerization was started by charging the autoclave to 10 kg/cm ² ·G, and polymerization was carried out for 1 hour while maintaining the autoclave pressure at 10 kg/cm ² ·G. After polymerization, the polymer slurry was transferred to a beaker, hexane was removed under reduced pressure, and the melt index was 1.3, the density was 0.9631,
265 g of white polyethylene with a bulk specific gravity of 0.37 was obtained. Catalyst activity is 145,600g polyethylene/gTi.hr.C ₂ H ₄ pressure,
5100g polyethylene/g solids. It was hr.C ₂ H ₄ pressure.

The F・R・value of the obtained polyethylene was 7.8.
The molecular weight distribution was extremely narrow compared to Comparative Example 4, and the hexane extraction amount was 0.15 wt%.

Comparative Example 4 Using 10 mg of the solid catalyst component used in Comparative Example 1, polymerization was carried out for 1 hour in the same manner as in Example 5 to obtain 198 g of white polyethylene having a melt index of 1.1, a density of 0.9633, and a bulk specific gravity of 0.32. Catalytic activity is
108800g polyethylene/gTi.hr.C ₂ H ₄ pressure, 3800g polyethylene/g solid. It was hr.C ₂ H ₄ pressure.

In addition, the F・R・value of the obtained polyethylene was 8.0.
The amount of hexane extracted was 0.21wt%.

Example 6 A catalyst component was synthesized in the same manner as in Example 1, except that 3.0 g of monobutoxytrichlorotitanium was used instead of 2.8 g of titanium tetrachloride, and solid powder (A) A solid powder (A) containing 34 mg of titanium per gram was obtained.

Then, 100 ml of hexane, 10 g of the above solid powder (A), and 1.8 g of ethylaluminum sesquichloride were placed in a 300 ml three-necked flask purged with nitrogen, and reacted for 2 hours under reflux of hexane. After the reaction was completed, the mixture was allowed to stand still and the supernatant liquid was removed, and then the solid component was washed with hexane to obtain a solid catalyst component (B).

Gas phase polymerization was performed in the same manner as in Example 1, and the bulk specific gravity was 0.40, the melt index was 0.90, and the density was 0.9218.
An ethylene-butene-1 copolymer was obtained. The catalyst activity was 854,000 g copolymer/g Ti, which was extremely high.

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.

In addition, this copolymer has an FR value of 7.0, and when the film was extracted in boiling hexane for 10 hours,
The amount of hexane extracted was 1.0wt%, which was an extremely small amount.

Example 7 Synthesis was performed in the same manner as in Example 1 except that 2.8 g of titanium tetrachloride and 1.8 g of triethoxyvanadyl were used in place of 2.8 g of titanium tetrachloride, and 1 g of solid powder was prepared. A solid powder containing 35 mg of titanium and 19 mg of vanadium was obtained.

Then, 100 ml of hexane, 10 g of the above solid powder (A), and 1.8 g of ethylaluminum sesquichloride were placed in a 300 ml three-necked flask purged with nitrogen, and reacted for 2 hours under reflux of hexane. After the reaction was completed, the supernatant liquid that was allowed to stand was removed, and then the solid component was washed with hexane to obtain a solid catalyst component (B).

Polymerization was carried out in the same manner as in Example 1, and the bulk specific gravity
An ethylene-butene-1 copolymer having a melt index of 0.41, a melt index of 1.1, and a density of 0.9199 was obtained. Catalytic activity is
It was 756,000g copolymer/gTi, and had 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.

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 1.2wt%, which was an extremely small amount.

Example 8 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 at a rate of 80 mg/hr and triethylaluminum 5 mmol/hr into an autoclave prepared at 60°C, and
Propylene was supplied into the autoclave, and the gas within the system was circulated using a blower to carry out polymerization at a total pressure of 7 kg/cm ² . The polypropylene produced had a bulk specific gravity of 0.39. Moreover, the catalyst activity was 330000g 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.

[Brief explanation of the drawing]

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

Claims (1)

[Claims] 1 [A] (1) Magnesium dihalide, (2) A compound represented by the general formula Al(OR) _o X _3-o , (3) General formula Si(OR) _n X _4-n and (4) a reaction product obtained by reacting a titanium compound or a titanium compound with a vanadium compound, and (5) a reaction product obtained by reacting a compound represented by the general formula AlR _p X _3-p. A solid substance and [B] A catalyst consisting of a compound represented by the general formula _AlR3 (in the above formula, R is a hydrocarbon residue having 1 to 24 carbon atoms, X is a halogen atom, and 0<n≦
3, 0≦m≦4 and 0<p<3.