JPS63168408A - Preparation of polyolefin - Google Patents

Abstract

PURPOSE:To prepare a polyolefin in a high yield, by using a catalyst system consisting of a solid catalyst ingredient obtained by reacting a specified transition metal compound with magnesium halide and an organoaluminum compound in an excellent catalytic activity. CONSTITUTION:A transition metal compound (a) of the formula as shown [where (C5R<2>n) is a (substd.) cyclopentadiene group; R is H or 1-20C hydrocarbyl group; R<1> is 1-4C alkylene bonding two (C5R<2>n) groups; R<3-4> is 1-20C hydrocarbyl group, a halogen or H; M is Ti, Zr, V or Hf; m is 0 or 1; n is 5 when m=0 or 4 when m=1] is reacted with a magnesium halide or with an addition product thereof with an electron donating compound (e.g. alcohol) (b) and, if necessary the resulting product is treated with an aluminum halide compound (c) to give a solid catalyst ingredient A. The ingredient A is then blended with an organoaluminum compound B (e.g. aluminoxane) in such a ratio that 1g atom of the element M in the ingredient A corresponds to 1-10<5>g atom of aluminum in the ingredient B, to give a catalyst system, and an olefin is polymerized in the presence of said catalyst system.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing polyolefins using a novel catalyst system. More specifically, the present invention relates to a method for efficiently producing polyolefin using a catalyst system having a specific component composition.

[Conventional technology]

The olefin polymerization ability of metallocenes consisting of a cyclopentadienyl metal compound moiety is already known.
It is widely used in research on the reaction mechanism of Ziegler catalysts.

However, since its polymerization activity is extremely low, it is hardly used in the industrial production of polyolefins. However, recently, it has been reported that very high polymerization activity can be obtained by using aluminoxane as an organoaluminum component, for example, in JP-A-58-19309, JP-A-60-35006, and JP-A-60. -3
This method is known from Japanese Patent Application Laid-open No. 5007, Japanese Patent Application Laid-Open No. 60-35008, and Japanese Patent Application Laid-open No. 60-130604. The activity of this catalyst system is extremely high, but such high activity is specifically expressed only when aluminoxane is used, and the ratio of aluminoxane used must be significantly higher than that of metallocenes. . The aluminoxane used here has poor manufacturing stability and is considered to be difficult to use in large quantities for industrial production.

[Problem that the invention seeks to solve]

It is an object of the present invention to solve the above-mentioned problems of the prior art, and to solve the problem sufficiently even if the ratio of aluminoxane used as a catalyst component is reduced or a commonly used organoaluminum compound other than aluminoxane is used. The object of the present invention is to provide a catalyst system capable of producing polyolefins with high activity.

[Means for solving problems]

As a result of intensive studies to achieve the above object, the inventors found that (A) (1) General formula R'-(CsR"-) JR"
R4 (in the formula, (CsR'') is a cyclopentadienyl group or a substituted cyclopentadienyl group, R2 is a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, and R2 are the same as each other) It may be different even if
Two adjacent carbon atoms forming a cyclopentagenyl group or a substituted cyclopentagenyl group may form a ring having 4 to 6 carbon atoms together with R2 bonded to each, and R1 has two (C5R2n) is an alkylene group having 1 to 4 carbon atoms, and R3 and R4
are each a hydrocarbyl group having 1 to 20 carbon atoms, a halogen atom or a hydrogen atom, M is titanium, zirconium, vanadium or hafnium, m is O
or l, and n is 5 when m is O and 4 when m is 1. ) and (2) magnesium halide or an adduct of magnesium halide and an electron-donating compound, and in some cases, it can be obtained by further treatment with an aluminum halide compound. The inventors have discovered that the above object can be achieved by using a catalyst system consisting of a solid catalyst component and (B) an organoaluminum compound, and have arrived at the present invention.

The transition metal compound used in the present invention has the general formula:
R'-(CsR'',,) !MR3R'.R
2 is a hydrogen atom or a carbon number of 1 to 2 such as alkyl, alkenyl, aryl, alkylaryl, aralkyl
20 hydrocarbyl groups, R2 may be the same or different, and two adjacent carbon atoms forming the cyclopentagenyl group or substituted cyclopentagenyl group each Together with the bonding R2, a ring having 4 to 6 carbon atoms may be formed. R1 has two (C5R
2n), which is an alkylene group having 1 to 4 carbon atoms. R3 and R4 each have 1 to 20 carbon atoms.
a hydrocarbyl group such as an alkyl, aryl, alkenyl, alkylaryl, aralkyl group, or a halogen atom or a hydrogen atom. M is titanium, zirconium, vanadium or hafnium. m is O or 1; n is 5 when m is O; and 4 when m is 1.

Specific examples of the hydrocarbyl group in RZ, R2 and R4 above include methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl, etc. can be mentioned. R1 above
Specific examples of the alkylene group in are methylene, ethylene, propylene, and the like.

Specific examples of compounds represented by the general formula R'-(CsR2ゎ) JR'R' include bis(cyclopentadienyl)dimethyltitanium, bis(methylcyclopentadienyl)dimethyltitanium, and bis(pentamethylcyclopentagenyl). ethylene bis(tetrahydroindenyl)dimethyltitanium, ethylenebis(tetrahydroindenyl)dimethyltitanium, bis(cyclopentajenyl)dimethyltitanium, bis(cyclopentajenyl)dichlorotitanium, bis(indenyl)dimethyltitanium, ethylenebis(tetrahydroindenyl)dimethyltitanium, ethylenebis(tetrahydroindenyl)dimethyltitanium ) dichlorotitanium, bis(cyclopentagenyl) dimethylzirconium, bis(methylcyclopentagenyl) dinotylzirconium, bis(pentamethylcyclopentagenyl) dimethylzirconium, bis(cyclopentagenyl)methylchlorozirconium, bis (cyclopentagenyl)dichlorozirconium, bis(indenyl)dimethylzirconium, ethylenebis(tetrahydroindenyl)dimethylzirconium, ethylenebis(tetrahydroindenyl)
Dichlorozirconium, bis(cyclopentagenyl)
Examples include dichlorovanadium, bis(cyclopentagenyl)dimethylhafnium, and bis(cyclopentagenyl)dichlorohafnium.

Specific examples of the magnesium halide used to obtain the solid catalyst component in the present invention include magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride, with magnesium chloride being particularly preferred. Commercially available magnesium halides can be used as they are, but other magnesium compounds or halogenated magnesium compounds can also be used.

Examples of the electron-donating compound to be added to the magnesium halide include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters, ethers, oxygen-containing electron donors such as acid amides, ammonia, amines, nitriles,
Nitrogen-containing electron donors such as isocyanates can be used.

Specific examples of electron-donating compounds include methanol, ethanol, propatool, pentanol, hexanol,
octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, n
- Alcohols with 1 to 18 carbon atoms such as butyl cellosolve, l-butoxy-2-propatol, etc., carbon atoms that can contain lower alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, naphthol, etc. Phenols having 6 to 15 carbon atoms, ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone, and 2 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde. to 15 aldehydes, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, Ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, toluyl amyl acid, ethyl ethyl benzoate,
Methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc. with 2 to 1 carbon atoms
8 organic acid esters, acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride, toluyl chloride, anisyl chloride, methyl ether,
Ethers having 2 to 20 carbon atoms such as ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, acid amides such as acetamide, benzoic acid amide, toluic acid amide, methylamine, ethylamine, diethylamine, Examples include amines such as tributylamine, aniline, tribenzylamine, pyridine, picoline, and tetramethylethylenediamine, and nitriles such as acetonitrile, benzonitrile, and tolnitrile. Two or more types of these electron donors can be used.

To add an electron donor to magnesium halide, generally the magnesium halide and electron donor are brought into contact at a temperature of about 0 to 200°C for about 10 minutes to 48 hours in the presence or absence of an inert solvent. Just let it happen. The amount of electron donor used is usually 0.1 to 30 mol, preferably 0.1 to 30 mol, preferably 0.1 to 30 mol, per 1 mol of magnesium halide.
5 to 20 mol, particularly preferably 0.5 to 10
It is a mole.

When the reaction is carried out in the presence of an inert solvent, an electron donor is allowed to act while magnesium halide is jQJ in the inert solvent. Although it varies depending on the type and amount of electron donor, reaction temperature and time, type of inert solvent, etc., adducts of magnesium halide and electron donating compounds can be obtained in a suspended state in an inert solvent. In some cases, it can be obtained in a state dissolved in an inert solvent, and both can be used in the present invention. A method for synthesizing in the absence of an inert solvent includes a method in which magnesium halide is suspended or dissolved in an electron-donating compound and the reaction is carried out in the same manner as in the presence of an inert solvent. Another method is to contact the magnesium halide and the electron donating compound under mechanical grinding conditions. An example of a method for mechanically bringing magnesium halide and an electron-donating compound into contact is to charge both components into a pulverizer such as a rotary ball mill, a vibrating ball mill, or an impact mill, and usually at room temperature for 1 to 7
A method of co-pulverizing for 0 hours, preferably 10 to 40 hours is mentioned.

When the transition metal compound is reacted with magnesium halide or an adduct of magnesium halide and an electron-donating compound, the amount of magnesium halide used is 1 to 1000 (molar ratio) to the transition metal compound. Good range, more preferably 3 to 500 (molar ratio)
is within the range of

The reaction is carried out in the presence or absence of an inert solvent. When carried out in an inert solvent, the temperature is usually -20°C or higher, preferably 0 to 100°C for 15 minutes to 6 hours, preferably 3
This is carried out by reacting for about 0 minutes to 3 hours. As for the method carried out in the absence of an inert solvent, both components are charged into a grinder such as a rotary ball mill, a vibrating ball mill, or an impact mill, and the mixture is usually heated at room temperature for 1 to 70 hours, preferably 10 to 4 hours.
A method of co-pulverizing for 0 hours is mentioned.

In the production of a solid catalyst component, a solid catalyst component may not be produced due to the reaction between a transition metal compound, an adduct of a magnesium halide, and an electron-donating compound;
In that case, a solid catalyst component can be obtained by further treatment with an aluminum halide compound. The aluminum halide compound used here has the general formula R5, ^eX3-. (wherein R5 is an alkyl group having at most 12 carbon atoms, X is a halogen atom, and p is a number from 0 to 2) can be used.

Specific examples of aluminum halide compounds include dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride,
Examples include diisobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, isobutylaluminum dichloride, aluminum chloride, and aluminum bromide. The amount of the aluminum halide compound to be used is preferably in the range of 1 to 100 (molar ratio) to the electron donating compound, and the reaction is usually carried out at -20°C or higher, preferably 30°C at 0-100°C.
The process is carried out for 9 minutes to 20 hours, preferably 1 to 12 hours.
The solid catalyst component that is insoluble in the hydrocarbon solvent obtained as described above is thoroughly washed with a hydrocarbon (e.g., n-hexane, n-hebutane, cyclohexane, etc.), and then fed directly to the polymerization system as a slurry. Alternatively, after drying under reduced pressure, it may be used in powder form.

Among the organoaluminum compounds used in the present invention, a typical one is aluminoxane obtained by the reaction of trialkylaluminum or dialkylaluminum monohalide with water, and has the general formula (where R6 has a large number of carbon atoms). Both are 6 alkyl groups or halogen atoms, R7 is an alkyl group having at most 6 carbon atoms, and when R6 is an alkyl group, R? is R
6, and q is an integer of 1 or more.

) or a mixture thereof. Specific examples of R& include methyl group, ethyl group, propyl group, butyl group, and chlorine atom, and specific examples of R7 include:
Examples include methyl group, ethyl group, propyl group, and butyl group.

The above reaction can be easily carried out by gradually adding a predetermined amount of water to trialkylaluminum or dialkylaluminum monohalide dissolved in an inert hydrocarbon solvent such as toluene, and heating it slightly if necessary. It can also be carried out using crystal water such as copper sulfate hydrate or aluminum sulfate hydrate. The amount of water used is usually a molar ratio of O01 to 5.0 to A1 atom,
Preferably the molar ratio is 0.5 to 3.0. Outside this range, the catalytic activity decreases rapidly.

In addition to the above aluminoxane, general formula A J R”
An organoaluminum compound represented by rXl-r (wherein R6 is an alkyl group having at most 12 carbon atoms, X is a halogen atom or hydrogen, and r is a number from 1 to 3) is also used. can do. Specific examples include trimethylaluminum, triethylaluminum, 1-IJ-n-propylaluminium, tri-isopropylaluminum, tri-n-butylaluminum,
Trialkylaluminums such as triisobutylaluminum and trihexylaluminum; dialkyls such as dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, di-isobutylaluminum hydride, and diethylaluminum hydride; Aluminum hydrides, dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-isobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, n-propylaluminium sesquichloride,
Examples include aluminum sesquichlorides such as isobutylaluminum sesquichloride, and alkylaluminum cybarides such as methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, and isobutylaluminum dichloride. Particularly favorable results are obtained when trialkylaluminum or dialkylaluminum halides are used.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler catalysts, and specific examples of suitable olefins include ethylene, propylene, l-butene,
Examples include 1-hexene, 4-methyl-1-pentene, 1-octene, -decene, vinylcyclohexane, and styrene, and a mixture of two or more of these components can also be used for copolymerization. Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Specific examples of dienes include butadiene, l.

Examples include 4-hexadiene, ethylidene norbornene, and dicyclopentadiene. In the method of the present invention, the olefin polymerization method is not particularly limited,
Liquid phase polymerization methods such as slurry polymerization and solution polymerization, gas phase polymerization, etc. are possible.

The liquid phase polymerization method is usually carried out in a hydrocarbon solvent, and hydrocarbon solvents include butane, isobutane, hexane, octane, decane, cyclohexane, benzene, toluene,
Inert hydrocarbons such as xylene may be used alone or in mixtures. Moreover, the raw material olefin can also be used as it is as a solvent. The polymerization temperature is generally -50°C to 200°C, and practically -20°C to 150°C.
It is.

Gas phase polymerization is carried out in a gas phase state substantially free of solvent, and a known reactor such as a fluidized bed stirring tank can be used as the reactor.

The polymerization temperature is usually 0 to 150°C, preferably 20 to 150°C.
The temperature is 100°C.

In the method of the present invention, a mixture of the catalyst component (A) and the catalyst component (B) may be supplied to the reaction system,
Alternatively, the above components may be separately supplied to the reaction system. component(
The usage ratio of A) and component (B) is such that the amount of aluminum in component (B) is 1 to 105 g per 1 g atom of titanium, zirconium, vanadium, or hafnium in component (A).
atomic range, preferably in the range of 10 to 104 g atoms. Furthermore, in the present invention, the molecular weight of the polymer is controlled by the use of hydrogen and/or the polymerization temperature.

〔Effect of the invention〕

According to the method of the present invention, compared to the conventional catalyst system consisting of a transition metal compound and aluminoxane, the catalyst can be used even if the ratio of aluminoxane used is greatly reduced or an organoaluminum compound other than aluminoxane is used. It has high activity and can efficiently produce polyolefins.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 5 g (52.5 mmoj!) of magnesium chloride, 100 mZ of n-heptane, and 21 g of 2-ethylhexanol were placed in a 500-mm trifluorescent flask that was purged with nitrogen.
A colorless and transparent solution was obtained by adding ol and reacting at 90° C. for 3 hours. After cooling this solution to room temperature, 1.
101 ml of 2-dichloroethane solution was added, and stirring was continued for 30 minutes. Next, diethylaluminum chloride 630 steel mo1 was added dropwise over 2 hours, and after the addition was completed, the reaction was continued for another 6 hours. After thoroughly washing the solid component thus obtained with n-hexane,
After drying for 1 hour under reduced pressure at ℃, 7.8 g of solid catalyst component was obtained.
I got it. Note that the Ti content in this solid catalyst component is 0.4
% by weight.

Isobutane 21 in the stainless steel autoclave of Goto yetatsurikin 31
, 240 mg of the above solid catalyst component (0.02 m in terms of Tt)
mol) and triisobutylaluminum 2m5oj!
was charged and the internal temperature was raised to 50°C. Ethylene was then pressurized to a partial pressure of 5 kg/cti to start polymerization. Polymerization was carried out for 1 hour while introducing ethylene so as to maintain the ethylene partial pressure at 5 kg/ci. Then, the polymerization was terminated by discharging the contained gas to the outside of the system. As a result, 213 g of white powdery polymer was obtained. Catalytic activity is 10650kg/l1ol-Ti-h
It was r.

Example 2 A stainless steel vibrating ball mill container with an internal volume of 11 that was purged with nitrogen was filled with porcelain balls with a diameter of 10 mm to 50% of the apparent volume, and 20 g of magnesium chloride and 2 g of diisobutyl phthalate were charged. Grinding contact was carried out for 20 hours. Then, bis(cyclopentagenyl)dichlorotitanium Igt- was added, and co-pulverization was further carried out for 20 hours to obtain a uniform co-pulverized product (Ti content: 0.84% by weight).

As a solid catalyst component, the co-pulverized product obtained above 114.3
Ethylene polymerization was carried out in the same manner as in Example 1 except that mg was used. As a result, 265 g of white powdery polymer was obtained. Catalytic activity is 13250 kg/mol-T
It was i-hr.

Examples 3-5 In Example 2, instead of diisobutyl phthalate,
Example 2 except for using the electron donating compound shown in Table 1
A solid catalyst component was prepared in the same manner as above, and ethylene was polymerized. The results are shown in Table 1.

Table 1 Comparative Example 1 In the example process, 0.02 m of bis(cyclopentagenyl) dichlorotitanium was added instead of the solid catalyst component.
Ethylene polymerization was carried out in the same manner as in Example 1 except that mo1 was used, but almost no polymer was obtained.

Example 6 A porcelain ball mill with a diameter of 10 mm was placed in a stainless steel vibrating ball mill container with an internal volume of 11 that had been replaced with 9°'1 nitrogen and the apparent volume was 50%.
20g of magnesium chloride, 1g of bis(cyclopentadienyl)dichlorozirconium Ig, and 20g of magnesium chloride.
Co-pulverization was carried out for 0 hours, and a homogeneous co-pulverized product (Zr content 1
．． 49% by weight).

100 mmol of copper sulfate pentahydrate (500 mmoJ as water) was added to a 300-mm Mitsuro flask in which the aluminoxane was replaced with nitrogen.
and suspended in 100% of toluene. Then, 300 mmof of trimethylaluminum was added at 30° C., and the reaction was continued at that temperature for 48 hours. Then, this reaction product was filtered through a glass filter to obtain a solution of methylaluminoxane. When toluene was distilled off, 8.2 g of white crystals were obtained.

Isobutane 21 in a stainless steel autoclave with a metal tip 31
147+wg (0.024 mmo/2 in terms of Zr) of the solid catalyst component obtained above and 2.4 mmof of methylaluminoxane obtained above were charged, and ethylene polymerization was carried out in the same manner as in Example 1. As a result, 472 g of white powdery polymer was obtained, and the catalyst activity was 19,670 kg.
/mol-Zr-hr.

Examples 7 to 9 In Example 6, a solid catalyst component was prepared in the same manner as in Example 6, except that the transition metal compounds shown in Table 2 were used instead of bis(cyclopentadienyl) dichlorozirconium. Polymerization was carried out. The results are shown in Table 2.

The following is a blank table - Comparative Example 2 Ethylene polymerization was carried out in the same manner as in Example 6 except that bis(cyclopentagenyl)dichlorozirconium was used at 0.024o+moA instead of the solid catalyst component in the ethylene polymerization of Example 6. I did it. As a result, 100 g of a white powdery polymer was obtained. Its catalytic activity is 4170k
g/lll01・zr-hr.

Example 10 f A of ethylene and butene-1 In a 31 stainless steel autoclave purged with nitrogen, isobutane 2N and 360 m of the solid catalyst component prepared in Example 1
g and 3 mmo e of triisobutylaluminum were charged, and the temperature of the indoor bath was raised to 50°C. Then, butene-130
Polymerization was initiated by injecting ethylene. After polymerization was carried out for 1 hour while maintaining the ethylene partial pressure at 5 kg/crA, the polymerization was terminated by discharging the content gas to the outside of the system. As a result, 271 g of ethylene-butene-1 copolymer was obtained. Catalyst activity is 9030kg
/moJ-Ti-hr.

Example 11 In a stainless steel autoclave 1 and 21 which had been purged with metal nitrogen, 400 mZ of dehydrated toluene, 400-1 propylene, 0.02 mmol of the solid catalyst component obtained in Example 6, and the solid catalyst component obtained in Example 6 were added. methylaluminoxane 2fflLIIol
was charged, and propylene polymerization was carried out at 20°C for 10 hours. After terminating the polymerization by adding a small amount of methanol, unreacted propylene was purged, toluene was removed from the obtained toluene solution of the polymer, and 66 g of atactic polypropylene with a molecular fi of 9800 was obtained by drying. Catalytic activity is 330 kg/mol-
It was Zr-hr.

Claims (1)

[Claims] (A) (1) General formula R^1_m (C_5R^2_n)
_2MR^3R^4 (in the formula, (C_5R^2_n) is a cyclopentadienyl group or a substituted cyclopentadienyl group, and R^2 is a hydrogen atom or a carbon number of 1 to 20
is a hydrocarbyl group, in which R^2 may be the same or different, and two adjacent carbon atoms forming the cyclopentadienyl group or substituted cyclopentadienyl group are each A ring having 4 to 6 carbon atoms may be formed together with R^2, which is bonded to R^1.
5R^2_n), which is an alkylene group having 1 to 4 carbon atoms, and R^3 and R^4 are each a hydrocarbyl group having 1 to 20 carbon atoms, a halogen atom, or a hydrogen atom. , M is titanium, zirconium, vanadium or hafnium, m is 0 or 1, n is 5 when m is 0, and 4 when m is 1.
It is. ) and (2) magnesium halide or an adduct of magnesium halide and an electron-donating compound, and in some cases, it can be obtained by further treatment with an aluminum halide compound. A method for producing a polyolefin, which comprises polymerizing an olefin using a catalyst system comprising a solid catalyst component and (B) an organoaluminum compound.