JPH0132246B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing ethylene homopolymers or copolymers of ethylene and other α-olefins.

More specifically, using a novel solid catalyst consisting of a magnesium compound and a titanium compound, the polymer produced in a hydrocarbon solvent is dissolved in an ethylene homopolymer or ethylene and other α -Relating to a method for producing an olefin copolymer.

Generally speaking, in so-called solution polymerization, in which polymerization is carried out while the polymer is dissolved in a solvent, the polymerization temperature is preferably higher from the viewpoint of the process, such as reducing solution viscosity and improving heat recovery efficiency.

On the other hand, since the step of removing catalyst residue from the produced polymer is omitted, the higher the catalytic activity is, the more preferable it is. Many proposals have been made as highly active catalysts in the past, including magnesium compounds such as magnesium oxide, magnesium hydroxychloride, magnesium hydroxide, magnesium alkoxide, and magnesium dihalide as carriers; A catalyst system has been proposed that consists of a combination of a magnesium-containing compound pretreated with compounds such as water, alcohols, aldehydes, ketones, esters, ethers, and carboxylic acids, and a titanium compound.

However, although these catalyst systems have high activity in the temperature range of slurry polymerization, they only show extremely low polymerization activity at high temperatures of 150°C or higher even in the temperature range of solution polymerization. It has been difficult to simultaneously satisfy the two requirements of a highly active catalyst and a highly active catalyst.

Furthermore, with these catalyst systems, the molecular weight distribution of the resulting polymer or copolymer is not narrow enough, and especially when producing ethylene-α-olefin copolymers, the amount of low molecular weight components increases, resulting in poor yield. The disadvantage was that the mechanical properties and other physical properties of the resulting copolymer deteriorated.

Therefore, in view of the above-mentioned current situation, the present inventors have repeatedly studied methods for efficiently producing ethylene polymers or ethylene α-olefin copolymers with narrow molecular weight distributions at high polymerization temperatures, and have found that magnesium dihalogen A hydrocarbon-insoluble solid and an organic compound are obtained by treating a homogeneous hydrocarbon solution containing a magnesium alcoholate and a titanium compound with an organic aluminum halide compound in the presence of a compound, and adjusting the amounts of each component to a specific ratio. The present invention was achieved by discovering that a catalyst system comprising an aluminum compound in combination has sufficiently high activity at high polymerization temperatures and can yield a polymer or copolymer with a narrow molecular weight distribution.

That is, the gist of the present invention is that the general formula MgX ⁴ ₂ (wherein X ⁴
represents a halogen atom. ) in the presence of a magnesium dihalide represented by the general formula Mg
Magnesium alcoholate represented by (OR ² ) mX ² _2-n (wherein R ² represents an alkyl, aryl or cycloalkyl group, X ² represents a halogen atom, and m is 1 or 2), general formula Ti ( ^OR3 )
nX ³ _4-o (wherein R ³ represents an alkyl, aryl or cycloalkyl group, X ³ represents a halogen atom,
n is 1, 2, 3 or 4) and optionally hydroxy compounds of the general formula R ⁵ OH, in which R ⁵ represents an alkyl, aryl or cycloalkyl group. ^A homogeneous hydrocarbon solution containing the compound is prepared using the general formula AlR ¹ _l X ¹ _3-l (wherein R ¹ represents an alkyl, aryl or cycloalkyl group,
Indicates the number of ≦l≦2. ), the number of moles of magnesium alcoholate, titanium compound, hydroxyl compound, and organic aluminum halide compound is b,
When c, e and a are m in the general formula,
Between n and l 0.75≦
a×(3-l)+b×(2-m)+c×(4-n)/m
If the ratio is set so that ×b + n × c + e is satisfied, and the number of moles of magnesium dihalide is d between the number of moles of magnesium dihalide and magnesium alcoholate, then 2≦d/b≦100 is satisfied. A polymer produced in a hydrocarbon solvent using a catalyst system consisting of a combination of a hydrocarbon-insoluble solid and an organoaluminum compound obtained in a ratio such that the polymer is dissolved in the hydrocarbon solvent,
The present invention relates to a method for producing an ethylene polymer or an ethylene-α-olefin copolymer, which comprises polymerizing ethylene alone or a mixture of ethylene and another α-olefin.

To further explain the present invention in detail, the magnesium dihalide used in the present invention is represented by the general formula MgX ⁴ ₂ (wherein, X ⁴ represents a halogen atom). Examples of these include magnesium chloride, magnesium bromide, magnesium iodide, and the like. Among them, magnesium chloride is most preferred.

Although the magnesium dihalide used in the present invention does not necessarily have to be a pure magnesium dihalide in the strict sense, it is not preferable to use one containing a large amount of water of crystallization, for example.

Furthermore, regarding the particle size of the magnesium dihalide, it is preferable to use particles of 200 μm or less. For example, commercially available anhydrous magnesium dihalide may be pulverized using a ball mill or the like, or as a more preferable method, an organomagnesium compound with the general formula X ⁶ _o M _e R ⁶ _n (where Me is aluminum, boron, Element selected from silicon and tin, X ⁶ is a halogen atom, R ⁶ is an alkyl, aryl, or cycloalkyl group, n≧1, m≧
0 and n+m is a number that matches the valence of Me. )
A method for producing by reaction with a halogen compound represented by:

The organic magnesium compound used here has the general formula R ⁷ X ⁷ (wherein R ⁷ represents an alkyl, aryl or cycloalkyl group, and ^{X 7} represents a halogen atom. Alkyl, aryl, up to about 15 carbon atoms such as propyl, butyl, pentyl, hexyl, octyl, phenyl, tolyl, xylyl, cyclohexyl,
Examples include cycloalkyl groups. As ^X7 ,
Examples include chlorine and bromine. Examples include halogen-free organomagnesium and halogenated organomagnesium obtained by the reaction of a halogenated hydrocarbon represented by the following formula with magnesium metal.

These organomagnesium compounds are easily synthesized by conventional methods in an inert hydrocarbon medium such as hexane, heptane, octane, benzene, toluene, etc., or an ether compound medium such as di-n-butyl ether or isoamyl ether. Among these, the organomagnesium compound used in the present invention is preferably an organomagnesium compound that is synthesized in an inert hydrocarbon medium and is not complexed with an electron-donating compound. Further, as the halogen atom, chlorine is most preferable.

Examples of these organomagnesium compounds include n-butylmagnesium chloride, benzylmagnesium chloride, phenylmagnesium chloride, ethylmagnesium chloride, isopropylmagnesium chloride, and the like. Further, dihydrocarbyl magnesium such as di-n-butylmagnesium and diisopropylmagnesium is also used. These organomagnesium compounds are used in suspension or solution in an inert hydrocarbon medium.

Next, as a halogen compound, the general formula X ⁶ _o MeR ⁶ _n
(In the formula, Me is an element selected from aluminum, boron, silicon, and tin, X ⁶ is a halogen atom, R ⁶ is an alkyl, aryl, or cycloalkyl group,
n≧1, m≧0, and n+m is a number that matches the valence of Me. ) is used.

Among these, the above-mentioned halogen compound used in the present invention is preferably a liquid compound, and a gaseous or solid compound is not preferable from the viewpoint of reaction efficiency or ease of handling. Further, as the halogen atom, chlorine is most preferable.

These halogen compounds include chlorinated organoaluminum compounds such as ethylaluminum dichloride, ethylaluminum monochloride, and ethylaluminum sesquichloride, chlorinated organoboron compounds such as ethylboron dichloride, and silicon such as diethyldichlorosilane and silicon tetrachloride. compound, a tin compound such as tin tetrachloride.

The reaction between an organomagnesium compound and a halogen compound is usually carried out by mixing the two in the presence of an inert hydrocarbon solvent such as hexane, heptane, octane, benzene, or toluene. There is no particular restriction on the order in which they are added, but usually the halogen compound may be added to an inert hydrocarbon solvent suspension or solution of organomagnesium. After adding the halogen compound, the reaction should preferably be carried out at a temperature between room temperature and 60°C. By separating the generated hydrocarbon-insoluble solid and washing it with the above-mentioned inert hydrocarbon solvent, the solid containing magnesium dihalide can be removed. can get.

Regarding the usage ratio of the organomagnesium compound and the halogen compound, the atomic ratio of the magnesium atom in the organomagnesium compound to the Me in the halogen compound, and when the respective amounts are Mg and Me,
Me/Mg is 0.25<Me/Mg preferably 0.5<Me/
Selected from a range of Mg.

There are no particular restrictions on the upper limit of the above values, but
There is no practical point in making it too large.

In addition, magnesium alcoholate has the general formula Mg(OR ² ) _n X ² _2-n (wherein ^{R 2} represents an alkyl, aryl or cycloalkyl group, ) is used. Specifically, R ² is methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, phenyl, tolyl, xylyl,
Compounds that are alkyl, aryl, or cycloalkyl groups having up to about 15 carbon atoms such as cyclohexyl, and where X ² is chlorine, bromine, or iodine, such as dimethoxymagnesium, diethoxymagnesium, ethoxymagnesium chloride, diphenoxymagnesium, etc. can be mentioned. Among these, compounds in which m in the general formula is 2 are preferred.
Among them, diethoxymagnesium is most suitable.

On the other hand, titanium compounds have the general formula Ti(OR ³ ) _o
X ³ _4-o (wherein R ³ represents an alkyl, aryl or cycloalkyl group, X ³ represents a halogen atom,
n is 1, 2, 3 or 4. ) is used. R ³ and X ³ are the above R ² and X ²
Examples of n
Compounds where n is 2 include diethoxydichlorotitanium, di-n-propoxydichlorotitanium, di-n-butoxydichlorotitanium, etc. Compounds where n is 3 include triethoxymonochlortitanium, tri-n-propoxymonochlortitanium , tri-n-butoxymonochlorotitanium, etc.; compounds where n is 4 include tetraethoxytitanium, tetra-n-
Propoxytitanium, tetra-n-butoxytitanium, etc.; examples of compounds where n is 1 include ethoxytrichlortitanium, n-propoxytrichlortitanium, n-butoxytrichlortitanium. Of these, n is 3 or 2, especially n is 3
Preferably. Among them, tri-n-butoxymonochlorotitanium is most suitable.

As the hydroxy compound, a compound represented by the general formula R ⁵ OH (wherein R ⁵ represents an alkyl group, an aryl group, or a cycloalkyl group) is used. Examples of R ⁵ above include those exemplified for R ² above. Specific examples include ethyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, and n-octyl alcohol. Among them, n-butyl alcohol is most preferred.

In the method of the present invention, first, a homogeneous hydrocarbon solution containing a magnesium alcoholate, a titanium compound, and optionally a hydroxy compound as described above is prepared. To prepare a hydrocarbon solution,
It is preferable to mix the magnesium alcoholate, the titanium compound, and optionally the hydroxy compound in advance to prepare a uniform liquid. The order of mixing is not particularly limited and may be arbitrary. After mixing, the mixture is preferably heated to 100°C to 170°C to obtain a uniform liquid or a uniform solution of the hydroxy compound.

A hydrocarbon solvent is then added to form a hydrocarbon solution, and the resulting hydrocarbon solution can be subjected to the following reaction without substantially removing it, although if a hydroxy compound has been added, the compound may be removed. Subjected to processing.

That is, this hydrocarbon solution and the above-mentioned magnesium dihalide are mixed to form a suspension of magnesium dihalide in the hydrocarbon solution, and then an organic aluminum halide compound is added and treated to obtain a hydrocarbon-insoluble solid.

^The organic _aluminum halide ^compound has the general formula ^{AlR 1} _l ) is used. Examples of R ¹ and X ¹ in the general formula include those exemplified above for R ² and X ² . Specific examples include methylaluminum dichloride, methylaluminum sesquichloride, dimethylaluminum monochloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum monochloride, isobutylaluminum dichloride, isobutylaluminum sesquichloride,
Examples include diisobutylaluminum monochloride. Particularly preferred are ethylaluminum dichloride, ethylaluminum sesquichloride, and diethylaluminum monochloride, and among them, ethylaluminum sesquichloride and ethylaluminum dichloride give the most preferable results. The organic aluminum halide compound treatment can be carried out by adding the organic aluminum halide compound to the above-mentioned suspension and allowing the reaction to occur preferably at a temperature of 20 to 100°C. Since a hydrocarbon-insoluble solid is obtained, the solid can be separated. , and may be washed with a hydrocarbon solvent.

Therefore, regarding the amount of each component, when the number of moles of magnesium alcoholate, titanium compound, hydroxy compound, and organic halogenated compound are respectively b, c, e, and a, m, n, l in the general formula Between 0.75≦
a×(3-l)+b×(2-m)+c×(4-n)/m
×b+n×c+e......(1) When the ratio is set such that the following is satisfied, and the number of moles of magnesium dihalide used is d between the number of moles of magnesium dihalide and magnesium alcoholate, 2≦ d/b≦100...The ratio is selected such that (2) is satisfied.

Within this range, a catalyst that provides high polymerization activity can be obtained.

That is, when the value of the above formula (1) is less than 0.75, the polymerization activity is significantly reduced. There is no particular restriction on the upper limit of the value of formula (1), but increasing it too much will only unnecessarily increase the amount of the organic aluminum halide compound used and is essentially meaningless.

Regarding formula (2), when d/b<2, the polymerization activity per titanium in the obtained solid catalyst component is not as large as on the left, and when d/b>100, the polymerization activity per solid catalyst component decreases. do.

Further, within the above range, if 0.5≦b/c≦4, a catalyst with particularly high polymerization activity can be obtained.

Next, as an organoaluminum compound used as a cocatalyst, for example, the general formula AlR ⁶ _o X ⁸ _3-o (where R ⁸
represents an alkyl, aryl or cycloalkyl group, X ⁸ represents a halogen atom, and n represents a number from 1 to 3. ) can be mentioned.
Examples of R ⁸ and R ⁸ include those exemplified as R ² and X ² . Specifically, trialkylaluminum such as triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, diethylaluminum chloride, di-n
- Dialkyl aluminum chlorides such as propyl aluminum chloride and diisobutyl aluminum chloride; alkyl aluminum sesquichlorides such as ethyl aluminum sesquichloride, n-propylaluminum sesquichloride and isobutyl aluminum sesquichloride; and mixtures thereof.

Among these, those in which n is 3 or 2 in the above general formula are preferred because they provide a particularly highly active catalyst system. The proportion of the solid catalyst component and the organic aluminum compound used as a cocatalyst is within the range of 0.1 to 100, preferably 1 to 20, in terms of the atomic ratio of titanium to aluminum, that is, Al/Ti.

In the present invention, the above catalyst system is used to carry out homopolymerization of ethylene or copolymerization of ethylene and other α-olefins. As the ethylene-α-olefin copolymer, an ethylene-α-olefin copolymer containing up to 35% by weight, preferably 20% by weight of α-olefin other than ethylene is produced. In this case, the density of the copolymer will be approximately 0.88 g/cc, although it will vary depending on the type of α-olefin.

Other α-olefins used in the method of the present invention include α-olefins having about 3 to 15 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene.

The polymerization reaction uses a solution polymerization method in which the copolymer is dissolved in the presence of a hydrocarbon solvent while supplying a mixture of ethylene and other olefins. It is done by doing. Inert hydrocarbon solvents such as pentane, hexane,
Aliphatic hydrocarbons such as heptane, octane, and isooctane, aromatic hydrocarbons such as benzene and toluene, and alicyclic hydrocarbons such as cyclohexane are used.

The polymerization reaction is usually carried out at a pressure of 5 to 100 atm and at 120°C.
300°C is preferably chosen within the temperature range of 180-250°C, but the process of the invention has particular great advantages when carried out at elevated temperatures above 200°C.

Further, in the method of the present invention, when hydrogen is present in the polymerization reaction zone, the effect of controlling the molecular weight by hydrogen is large, and a polymer having a desired molecular weight can be easily obtained. The amount of hydrogen to be present varies depending on the polymerization conditions, the desired molecular weight of the ethylene copolymer, etc., and therefore it is necessary to adjust the amount of hydrogen introduced accordingly.

According to the method of the present invention as described above, the catalyst has extremely high activity, and the polymerization activity is not lost even at extremely high temperatures within the temperature range of solution polymerization. Therefore, the energy consumption of the process is significantly reduced due to the reduction in the viscosity of the polymer solution, the improvement of heat recovery efficiency, etc., and this, together with the omission of the step of removing catalyst residues in the polymer, has great advantages in terms of the process.

Furthermore, the obtained polymer or copolymer has a narrow molecular weight distribution and excellent mechanical properties.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

The melt index in the examples is ASTM・D・
Measured at 190℃ and 2.16Kg load based on 1238・57T.
Expressed in MI. Furthermore, the flow rate ratio (hereinafter abbreviated as FR), which is a measure of molecular weight distribution, is a value that indicates the dependence of melt viscosity on shear stress, and is based on ASTM D 1238.
According to 57T, shear stress 10 ⁶ dyne/cm ² and 10 ⁵ dyne/cm 2
It is expressed as a ratio of melt indexes measured in cm ² , and it is said that the larger the FR, the broader the molecular weight distribution, and the smaller the FR, the narrower the molecular weight distribution. The content of pendant ethyl groups was determined from the absorbance at 770 cm ^-1 by infrared absorption spectroscopy. The total methyl group content was determined from the absorbance at 1378 cm ^-1 by infrared absorption spectroscopy.

The polymerization activity per total amount of catalyst is K = (g polymer)/(g catalyst) (hr) (Kg/ ^cm2 olefin pressure), and the polymerization activity per titanium in the catalyst is:
K _Ti = (g polymer) / (g titanium in catalyst) (hr)
(Kg/cm ² olefin pressure). Also, the first
The figure is a flowchart diagram to help understand the technical content included in the present invention, and the present invention is not limited in any way by the flowchart diagram as long as it does not depart from the gist thereof.

Example 1 (1) Catalyst Preparation (a) Synthesis of n-butylmagnesium chloride 200 mmol of magnesium powder is placed in a 500 c.c. four-necked flask, a small amount of iodine is added thereto, and the mixture is heated to 70°C. At 70℃, 45 mmol of n-butyl chloride was added to 3 mmol/
Add in the form of ml normal heptane solution. Next, 200 ml of n-heptane is added, and then 155 mmol of n-butyl chloride is added while maintaining the temperature at 80°C. After the entire amount of n-butyl chloride was added, the mixture was heated under reflux for 30 minutes, and then n-heptane was distilled off under reduced pressure to obtain solid powder n-butylmagnesium chloride.

(b) Synthesis of magnesium chloride 70 mmol of the above-mentioned n-butylmagnesium chloride and 130 ml of benzene are mixed, and then 70 mmol of ethylaluminum dichloride is added thereto in the form of a 4 mol/benzene solution.

After the addition, the mixture is stirred at room temperature for 1 hour, and the solid portion is washed with benzene to obtain a benzene slurry of magnesium chloride.

(c) Preparation of homogeneous solution containing magnesium and titanium 4 mmol of diethoxymagnesium, 2 mmol of tributoxytitanium monochloride and 2 mmol of n-butyl alcohol were mixed and stirred at 130°C for 5 hours to obtain a homogeneous viscous body. Next, benzene was added to this to make a benzene solution, and the total volume was adjusted to 50 ml.

(d) Preparation of solid catalyst component Take 70.0 ml of the benzene slurry of magnesium chloride (1.38 g as magnesium chloride) synthesized in (b) above, and add 9.1 ml of the benzene solution prepared in (c) above. Stirred at 25°C for 1 hour. At 60°C, 3.62 mmol of ethylaluminum sesquichloride is added in the form of a benzene solution. After the addition, the mixture was stirred at 65° C. for 1 hour, and the resulting solid was washed with n-hexane to obtain a solid catalyst component. This solid is titanium
It contained 1.3% by weight.

(2) Polymerization 1000 c.c. of cyclohexane was placed in a 2 liter autoclave, and 12 mg of the above solid powder was charged therein. After raising the temperature to 200℃, hydrogen was introduced so that the molar ratio of hydrogen to ethylene in the gas phase was 0.01, then ethylene was introduced together with 0.02 mmol of diethylaluminum monochloride and 1130 g of butene, and the total pressure was reduced.
The weight was set at 40Kg/ ^cm2 . Ethylene absorption was observed as ethylene was introduced, but additional ethylene was introduced to maintain the total pressure at 40 Kg/cm ³ , and 30 minutes later, polymerization was stopped by injection of ethanol, resulting in MI = 1.5.
166 g of copolymer with FR=19 were obtained. This copolymer has 28 pendant ethyl groups per 1000 carbons and has a low butene unit content.
It was 11% by weight.

The polymerization activity was extremely high with K = 1330 and K _Ti = 102000.

Example 2 1000 c.c. of cyclohexane was placed in a 2-liter autoclave, and 6 mg of the solid powder used in Example 1 was charged therein.
After raising the temperature to 130°C, hydrogen was introduced so that the hydrogen/ethylene molar ratio in the gas phase was 0.15, and 0.01 mmol of diethylaluminum chloride, 1 butene,
Ethylene was introduced together with 85 g to give a total pressure of 23 Kg/cm ² .

The reaction was carried out for 30 minutes in the same manner as in Example 1, and copolymer 141 with MI = 2.0 g/10 min and FR = 19 was obtained.
g was obtained. This copolymer has 23 pendant ethyl groups per 1000 carbons and a butene content of 8.5
It was in weight%.

The polymerization activity was K=3150 and K _Ti =243000.

Example 3 (1) Catalyst preparation 4 mmol of diethoxymagnesium and 4 mmol of tributoxymagnesium were mixed and heated at 130°C.
A homogeneous viscous body was obtained by stirring for 5 hours. Benzene was added to this to make a benzene solution, and the total volume was made up to 50 ml. Using the above solution instead of the solution prepared in (c) in Example 1,
A solid catalyst component was prepared in exactly the same manner as in Example 1 except that the amount of ethylaluminum sesquichloride used was 4.37 mmol. This solid is titanium
It contained 2.0% by weight.

(2) Polymerization 1000 c.c. of cyclohexane was placed in a 2 liter autoclave, and 6 mg of the above solid powder was charged therein. After raising the temperature to 190°C, hydrogen was introduced so that the molar ratio of hydrogen to ethylene in the gas phase was 0.01, and then 0.02 mmol of diethylaluminum monochloride and butene were added.
1. Introduce ethylene with 110g and increase the total pressure.
The weight was set at 40Kg/ ^cm2 . Following the same operation as in Example 1,
Perform the reaction for 30 minutes, MI = 0.90g/10min, FR
165 g of a copolymer of =20 was obtained. This copolymer had 25 pendant ethyl groups per 1000 carbons and a butene content of 10% by weight.

The polymerization activity was K=2360 and K _Ti =118000.

Example 4 1000 c.c. of cyclohexane was placed in a 2-liter autoclave, and 6 mg of the solid powder prepared in Example 3 (1) was charged therein. After raising the temperature to 150°C, hydrogen was introduced so that the molar ratio of hydrogen/ethylene in the gas phase was 0.2, and ethylene was introduced together with 0.02 mmol of diethylaluminum monochloride to make the total pressure 25 Kg/cm ² .
The reaction was carried out for 30 minutes in the same manner as in Example 1.
150 g of polymer with MI=0.52 g/10 min and FR=19 was obtained. The polymerization activity was K=2990 and K _Ti =150000.

Example 5 1000 c.c. of cyclohexane was placed in a 2-liter autoclave, and 12 mg of the solid powder prepared in Example 3 (1) was charged therein. After raising the temperature to 200°C, hydrogen was introduced so that the molar ratio of hydrogen to ethylene in the gas phase was 0.03, and then 0.03 mmol of diethylaluminium chloride,
Ethylene was introduced together with 110 g of butene-1 to give a total pressure of 30 Kg/cm ² . Hereinafter, the reaction was carried out for 30 minutes in the same manner as in Example 1, MI = 18 g / 10 min, FR =
160 g of copolymer No. 18 was obtained. This copolymer is
It had 38 pendant ethyl groups per 1000 carbons and a butene content of 15.5% by weight.

The polymerization activity was K=2080 and K _Ti =104000.

Example 6 Polymerization was carried out in the same manner as in Example 3 except that 110 g of butene-1 was replaced with 150 g of octene-1. As a result, MI=1.5g/10min,
198 g of a copolymer with FR=21 was obtained. The total methyl group content of this copolymer was 15 per 1000 carbons, and the octene-1 unit content was 12.0% by weight.

Example 7 (1) Catalyst Preparation In Example 3, the amount of homogeneous solution containing magnesium and titanium used was 2.3 ml, and ethyl aluminum dichloride was used instead of 4.37 mmol of ethyl aluminum sesquichloride.
A solid catalyst component was prepared in exactly the same manner as in Example 3 except that 1 mmol was used. This solid is titanium
It contained 0.65% by weight.

(2) Polymerization 900 ml of cyclohexane was placed in a 2 liter autoclave, and 24 mg of the above solid powder was charged therein. After raising the temperature to 230℃, the molar ratio of hydrogen and ethylene in the gas phase is
Hydrogen was introduced so that the concentration was 0.005, then 0.01 mmol of diethylaluminum monochloride,
Ethylene was introduced together with 130 g of butene-1 to give a total pressure of 50 Kg/cm ² .

The reaction was carried out for 30 minutes in the same manner as in Example 1, and the copolymer 162 with MI = 11 g/10 min and FR = 19 was produced.
g was obtained.

This copolymer had 26 pendant ethyl groups per 1000 carbons and a butene content of 10% by weight.

The polymerization activity was K=590 and K _Ti =91000.

Example 8 Polymerization was carried out in exactly the same manner as in Example 7 except that 0.01 mmol of triethyl aluminum was used instead of 0.01 mmol of diethylaluminium monochloride, and 150 g of a copolymer with MI = 18 g/10 min and FR = 20 was obtained. It was done. This copolymer had 24 pendant ethyl groups per 1000 carbons and a butene content of 9.5% by weight.

The polymerization activity was K=546 and K _Ti =92000.

Example 9 20 mmol of magnesium diethylate and 20 mmol of tri-n-butoxymonochlorotitanium were mixed and stirred at 140°C for 4 hours to obtain a homogeneous liquid. Then, after cooling to 80°C, 200 ml of benzene was added to make a homogeneous solution.

Add 380 mmol of commercially available flake magnesium chloride ball-milled at room temperature for 72 hours,
Then, at 40°C, 120.6 mmol of ethylaluminum sesquichloride was added in the form of a 4.0 mol/benzene solution. Thereafter, the temperature was raised to 60°C, and the mixture was stirred for 1 hour to ripen. The generated precipitate was washed with n-hexane and subjected to polymerization in the form of n-hexane slurry. The titanium content in this catalyst was 1.9% by weight.

Next, add cyclohexane to a 2L autoclave.
1000 c.c. was taken and 9 mg of the above solid powder was charged.

After raising the temperature to 200℃, hydrogen was introduced so that the molar ratio of hydrogen to ethylene in the gas phase was 0.01, and 0.025 mmol of diethylaluminium chloride and 85 g of butene-1 were added.
was introduced together with ethylene to give a total pressure of 40 Kg/cm ² .
As ethylene was introduced, absorption of ethylene was observed, but ethylene was additionally introduced to maintain the total pressure at 40 kg/cm ² , and 30 minutes later, the polymerization was stopped by injection of ethanol. As a result, the polymer with MI=1.2 and FR=20
160g was obtained. K = 1550, K _Ti = 81700.

This copolymer had 23 pendant ethyl groups per 1000 carbons and a butene-1 content of 8.5% by weight.

Example 10 (1) Catalyst preparation 20 mmol of magnesium diethylate, 10 mmol of tri-n-butoxymonochlorotitanium and 10 mmol of n-butanol were mixed and heated at 140°C.
The mixture was stirred for 4 hours to form a homogeneous solution. Then 60
The temperature was lowered to ℃ and 150 c.c. of benzene was added to make a homogeneous solution.

Next, 100 mmol of ethylaluminum sesquichloride was added dropwise over 20 minutes at 60℃, and then
The mixture was stirred at 60°C for 1 hour.

The generated precipitate was washed with normal hexane and dried to obtain a solid powder. This solid contained 11% by weight of titanium.

(2) Polymerization 1000 c.c. of cyclohexane was placed in a 2 liter autoclave, and 15 mg of the above solid powder was charged therein. After raising the temperature to 200°C, hydrogen was introduced so that the hydrogen/ethylene molar ratio in the gas phase was 0.01, and then ethylene was introduced together with 0.12 mmol of diethylaluminium monochloride and 38 g of butene-1, and the total pressure was reduced.
The weight was set at 23Kg/ ^cm2 .

As ethylene was introduced, absorption of ethylene was observed, but ethylene was additionally introduced to maintain the total pressure at 25 kg/ ^cm2 , and 30 minutes later, the polymerization was stopped by injection of ethanol, resulting in 56 g of copolymer with MI = 6.0 and FR = 22. was gotten. This copolymer has 1000
It had 25 pendant ethyl groups per carbon and a butene-1 unit content of 10% by weight.

The polymerization activity K was high at 885, but the K _Ti was low at 8050.

Comparative Example 1 (1) Catalyst Preparation 20 mmol of anhydrous magnesium chloride was suspended in 100 ml of normal heptane, and then ethanol was added.
Add 20 mmol and stir at room temperature for 1 hour. Next, add 200 mmol of titanium tetrachloride and heat at 90°C.
Stir for 2 hours. The obtained solid is washed with cyclohexane to obtain a solid catalyst component. This solid contained 3.5% titanium by weight.

(2) Polymerization Polymerization was carried out in exactly the same manner as in Example 6 except that the above solid was used. The amount of polymer obtained was only 16 g, and the polymerization activity was K = 54, K _Ti = 1540.
It was low.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing one embodiment of the present invention.

Claims (1)

[Claims] 1. In the presence of a magnesium dihalide represented by the general formula MgX ⁴ ₂ (in the formula, X ⁴ represents a halogen atom), the general formula Mg(OR ² ) mX ² _2-n (in the formula, R ² represents an alkyl, aryl or cycloalkyl group, X ² represents a halogen atom, m is 1 or 2);
General formula Ti(OR ³ )nX ³ _4-o (wherein R ³ represents an alkyl, aryl or cycloalkyl group, X ³ represents a halogen atom, and m is 1, 2, 3 or 4)
A homogeneous hydrocarbon solution containing a titanium compound represented ^by the ^general formula
_An organic compound ^{represented by} _AlR ^{1 l} When treating with an aluminum halide compound, when the number of moles of magnesium alcoholate, titanium compound, hydroxy compound, and organic aluminum halide compound are respectively b, c, e, and a regarding the quantitative ratio of each compound, the general formula Between m, n, and l in the middle, 0.75≦
a×(3-l)+b×(2-m)+c×(4-n)/m
If the ratio is set so that ×b + n × c + e is satisfied, and the number of moles of magnesium dihalide is d between the number of moles of magnesium dihalide and magnesium alcoholate, then 2≦d/b≦100 is satisfied. A polymer produced in a hydrocarbon solvent using a catalyst system consisting of a combination of a hydrocarbon-insoluble solid and an organoaluminum compound obtained in a ratio such that the polymer is dissolved in the hydrocarbon solvent,
A method for producing a polyolefin, which comprises polymerizing ethylene alone or a mixture of ethylene and other α-olefins.