JPH03185004A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain the title polymer having narrow distribution of molecular weight and good strength, transparency and heat seal property by using a catalyst obtained by blending a solid consisting of oxides of Si and Al, Mgnesium halide, Ti compound and OH compound, etc., with an organomagnesium compound. CONSTITUTION:An olefin is polymerized or olefins are copolymerized using a catalyst obtained by reacting (A) a reaction product prepared by reacting a reaction product obtained by reacting Si oxide and/or Al oxide with magnesium halide, compound expressed by formula I (Me is element of the groups I to IV of periodic table; z is valence of element Me; X is halogen; R is 1-20C hydrocarbon; 0<n<=z) and titanium compound expressed by formula II (R' is 1-20C hydrocarbon; 0<=n<4) in the presence of a compound expressed by the formula ROH (R is 6-20C organic residue) with (B) organoaluminum compound expressed by formula III (R is 1-24C hydrocarbon residue; 0<n<=3) to provide the aimed polymer.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a novel method for producing polyolefins.

More specifically, the present invention significantly increases the polymer yield per solid and the polymer yield per transition metal, thereby eliminating the need for the step of removing catalyst residues in the polymer, and at the same time reducing the The present invention relates to a method for producing a polyolefin which not only can increase the density and reduce the fine powder portion of the produced polymer but also has a large average particle size and good particle properties.

(FFJ to be solved by the prior art and the invention) Conventionally, in this type of technical field, an inorganic magnesium solid such as magnesium halide, magnesium oxide, or magnesium hydroxide is used as a carrier, and a compound of a transition metal such as titanium or vanadium is used as a carrier. Many catalysts are known that support T. However, in these known techniques, the bulk specific gravity of the polyolefin obtained is generally small, the average particle size is also relatively small, and the particle size distribution is generally wide. There is a strong need for improvement from the viewpoint of productivity and polymer handling.Furthermore, when molding these polymers, problems such as generation of dust and reduction in efficiency during molding occur. In addition, there was a strong desire to increase the bulk density and reduce the particulate powder portion as described above.Furthermore, improvements are still needed to omit the pelletizing process, which has been increasing in demand in recent years, and to feed the powdered polymer directly into the processing machine. is needed.

The present inventors have previously discovered a new catalyst component that improves the above-mentioned drawbacks, and have already filed various patent applications (Japanese Patent Publication No. 1-11
651, JP 1-12289, JP 60-1496
05, JP-A-62-32105, JP-A-62-2073
06 etc.). When using this catalyst hole, the bulk density is high,
Although it was possible to obtain a polymer with a large average particle size, further improvements were required in order to omit the pelletizing step and directly apply the powdered polymer to a processing machine.

The present invention has been made with the aim of improving these drawbacks and obtaining a highly active polymer with a high bulk density, a narrow particle size distribution, a significantly small amount of fine particles, and good fluidity. As a result of research, the present invention was arrived at.

That is, the present invention provides a method for polymerizing or copolymerizing onfin using a solid catalyst component and an organometallic compound as a catalyst, in which the solid catalyst component is [I]D) silicon oxide and/or aluminum oxide, (2) ) magnesium halide and -a formula MclOR).

X knee. (Here, Me is an element of groups I to II of the periodic table, 2 is the valence of the element Me, n is O< n≦z, X is a halogen atom, and R is a hydrocarbon residue having 1 to 20 carbon atoms. ) and the reaction product obtained by reacting the compound represented by (
31-8 Formula Ti (OR')nX4-, A titanium compound represented by (41-a formula ROH (where R represents a hydrocarbon group having 6 to 20 carbon atoms or an organic residue containing elements such as oxygen, nitrogen, sulfur, and chlorine) The reaction product obtained by reacting with each other in the presence of the other compounds has the general formula AIR,X3-n (where R is a hydrocarbon residue having 1 to 24 carbon atoms and X is a halogen atom) represents,
1. A method for producing a polyolefin, comprising a substance obtained by reacting an organoaluminum compound represented by n (O<n≦3).

By using the method of the present invention, a polyolefin having a relatively large average particle size, a narrow particle size distribution, and a small particulate portion can be obtained with extremely high activity, and the resulting polyolefin has a high bulk specific gravity and has good free-flowing properties. It is very advantageous in terms of polymerization operation, and it can be used not only as pellets but also in powder form. However, it can be subjected to molding, there are few troubles during molding, and polyolefin can be produced very advantageously.

The polymer obtained using the catalyst of the present invention is characterized by having an extremely narrow molecular weight distribution, a small amount of hexane extraction, and very little by-product of low polymers. Therefore, when the polyolefin with a narrow molecular weight distribution obtained by the method of the present invention is used for film, it has many advantages such as high strength, excellent transparency, and excellent anti-blocking and heat sealing properties. have

The present invention will be specifically explained below.

The catalyst used in the method for producing polyolefin of the present invention is [IHl] silicon oxide and/or L and aluminum oxide.

(2) Magnesium halide and general formula Me(OR)n
A reaction product obtained by reacting a compound represented by X, and (31-general formula T i (OR')nX4-,
A titanium compound represented by X, , (4)-general formula R
In the presence of a compound represented by OH, a substance obtained by reacting with each other (the [I] acid component, and [I] an organoaluminum compound represented by the general formula AIR, X3-n (the [I] acid component) It consists of a solid catalyst component made of a substance obtained by reaction and an organometallic compound.

1> Solid catalyst component 1, [I] acid component 1) The silicon oxide used in the present invention is silica or a double oxidation of silicon and at least -m other metals of groups 1 to 2 of the periodic table. It is a thing.

The aluminum oxide used in the present invention is a double oxide of alumina or aluminum and at least one other member of Groups I to II of the Periodic Table.

Silicon or aluminum and at least one other member of Groups I to ■ of the Periodic Table! A typical example of a double oxide with the rl group is Al2O3・M g Op A +203 ・C
a Op A I Q O3・S + 02 P A
120 QMgO・Cab, At203・MgO・5i
02. At203・Cub.

Al20J-Fe203. A.I. 0.・Nio,
Examples include various natural or synthetic complex oxides such as Sio2.MgO. Here, the above formula is not a molecular formula, but only represents the composition, and is not particularly limited to the structure and component ratio (f) of the double oxide used in the present invention. The silicon oxide and/or aluminum oxide used in the invention may adsorb a small amount of water without any problem, or may contain a small amount of impurities.

Further, the properties of these silicon oxides and/or aluminum oxides are not particularly limited as long as they do not impair the purpose of the present invention, but preferably have a particle size of 1 to 200 μm and a pore volume of 0.3 ml/ml. g or more, surface area is 50rr
Silica having an i” of 78 or more is desirable.

Further, before use, it is desirable to perform a firing treatment in advance at 200 to 800°C by a conventional method.

(2) 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.

In the present invention, these magnesium halides may be treated with an electron donor such as alcohol, ester, ketone, carboxylic acid, ether, amine, or phosphine.

The general formula Me(OR)X (
Here, Me is an element of groups I to II of the periodic table, 2 is the valence of the element Me, n is 0<n≦z, and X is a halogen atom. In addition, R represents a hydrocarbon residue such as an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and each may be the same or different. Na ORp M g
(OR) 22M g (OR)
R) 2p Z n (OR) 2-Cd (OR)2.
B (Out)3. AI(OR), AI(OR)
2X, AI(OR)X2. Si(OR)4.5i(
OR)3X, 5i(OR)2X2.5i(OR)X3
．． Can you name various compounds represented by 5n(OR), etc.? Preferred specific examples of these include Mg
(OC2115)2. Mg(OC2H5)CI, A
I(OCH31,,AI(OC2H5)3.AI(O
n-C3H,)3. AI(Oi-C, I7),, A
I(On-C4H3)3. AI (Osee-C4H,)
,, AI(Ot-C, I9)2. AI (OCR,)
, CI, AI(OC2H5)2C1, At(OC2H
5) C1,,AI(Oi-C:)I7)2Cl,AI
(Oi-C,I7)C12,Al(QC6H,)3,A
, I(QC,I5), CI, AI(OC6H5)CI2
．． AI (QC6H.

CH3),,AI(0 to 6H4CH3)2C1,AI(
QC6H4CH3)C12, AI(OCH3C6H,)
3,5i(OC2H5),,5i(OC2H5).

CI, 5i (QC, I5) 2C12, 3i (QC2Hj
C13,5i(QC6H,>4,5i(OC6H5)3
CI, 5i (QC, I5) 2C1□, 5i (QC2H,
) C1, 5i(OCH2C6H5)4, etc. Can you name a compound?

Magnesium halide and general formula Me(OR),,X
The reaction rate with the compound represented by , is M e /
M g (molar ratio) is 001 to 10, preferably 0.1
A range of 5 to 5 is desirable.

Magnesium halide and general formula Me(OR),,X
There are no particular limitations on the method of reaction with the compounds represented by , , and . , a shaking mill, a rod mill, a dark mill, etc. may be used. or a mixture thereof in an organic solvent consisting of
5 minutes to 1 at a temperature of 400°C, preferably 50 to 300°C
A method may be used in which the mixture is mixed and heated for 0 hours, and then the solvent is removed by evaporation.

In the present invention, a method in which both are co-pulverized is preferably used.

(3) General formula Ti(OR')nX used in the present invention
4-. x4-, (where R' is a hydrocarbon residue such as an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, X is a halogen atom, and n is O≦n ( 4), specifically, titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium. , monoethoxytrichlorotitanium, monoethoxytrifluorotitanium, monoethoxytriprorotitanium, jetoxydifluorotitanium, jetoxydichlorotitanium, jetoxydichlorotitanium, jetoxydifluorotitanium, triethoxyfluorotitanium,
Triethoxychlorotitanium, monopropoxytrichlorotitanium, monoisopropoxytrichlorotitanium, diproboquine dichlorotitanium, diisopropoxydichlorotitanium, diisopropoxydichlorotitanium, 1-liisopropoxyfluorotitanium, tripropoxychlorotitanium,
Monobutoxytrichlorotitanium, monoisobutoxytrichlorotitanium, jetoxydichlorotitanium, diisopropoxydichlorotane, tributoxyfluorotitanium, tributoxychlorotitanium, triisobutoxytrichlorotitanium, monopentoxy I-lichlorotitanium, dipentoxydichlorotitanium, trichlorotitanium Pentoxymonochlorotitanium, monooctyloxytrichlorotitanium, dioctyloctyldichlorotitanium, trioctyloxymonochlorotitanium, mono-2-ethyl\xyloxytrichlorotitanium, di-2-ethylhexyloxydichlorotitanium, tri-2-ethyl Xyloxymonoc T1″-1
Examples include titanium, monophenoquine dichlorotitanium, diphenoquine dichlorotitanium, triphenoxychlorotitanium, tri-xyleneoxychlorotitanium, or any mixture thereof, preferably titanium tetrachloride,
Monoethoxy! - Lichlorotitanium, jetoxydichlorotitanium, monobutoxytrichlorotitanium, and dibutoxydichlorotitanium are preferable.

(4) The [1l component] of the present invention is the silicon oxide and/or aluminum oxide (component [I]
-(1)), (2) magnesium halide and general formula Me(OR). The reaction product (component [1l-(2)) obtained by reacting the compound represented by
,,Titanium compound represented by Te (component [I]-(3))
are obtained by reacting them with each other in the presence of a compound represented by the general formula ROH. - In the compound represented by the general formula ROH, R in the formula is an organic residue having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and contains a hydrocarbon group or an element such as oxygen, nitrogen, sulfur, or chlorine. There are organic residues.

The hydrocarbon group is preferably an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc., and a hydrocarbon group having a branched structure is particularly preferred. Specifically, the compounds represented by the above general formula include 1-hexanol, 2-methyl-1-pentanol, 4-methyl-1-
Pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptatool, 2-heptatool, 3-heptatool, 4-heptatool, 2,4
-dimethyl-3-pentanol, 1-octatool, 2
-octatool, 2-ethyl-1-hexanol, 3゜5-dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, 1-nonanol, 5-nonanol, 3,5-dimethyl-4- Heptatool, 2,6-dimethyl-4-heptatool, 3,5.5-trimethyl-
1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, 2,6.8-trimethyl-4-
Nonanol, 1-tridecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1
- Octadecanol, 1-nonadecanol, 1-eicosanol, phenol, chlorophenol, benzyl alcohol, methyl cellosolve, or any mixture thereof, preferably 2-methyl-1-pentanol, 4-methyl-1 -Pentanol, 4-methyl-
2-pentanol, 2-ethyl-1-butanol, 2,
4-dimethyl-3-pentanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 2
Preferred are 2,4-trimethyl-1-pentanol, 3,5-dimethyl-4-heptatool, 2,6-dimethyl-4-heptatool, 3,55-trimethyl-1-hexanol, and the like.

Components [I]-(1) to [I]- when obtaining the [I] acid component
The reaction method of (3) is not particularly limited as long as it is carried out in the presence of the compound represented by the general formula ROH, and the reaction sequence is (A) component [I] - (1) to
Method of contacting component [I]-(3) simultaneously, (B) Contacting component [I]-(1) and component [I]-+2) and then further contacting component [I]-(3) Method, (C) Component [I]-(1) and component [I]-(
Method (D) of contacting component [I]-(2) with component [I]-(2) after contacting component [I]-(2).
]-(3) and then further contacting component [I]-(1). However, the method (D) above is preferred, and more preferably, the method (D) is more preferable. It is preferable to use the represented compound as a solvent and bring component [I]-(2) and component [I]-(3) into contact with each other by dissolving them in advance, and then bring them into contact with component [I]-+11. The order of dissolving [I]-(2)a and component [I]-(3) into the compound represented by the general formula ROH is not particularly limited, and both may be dissolved at the same time, or either - may be dissolved first. In addition, component [I]-(2) and/or component [I]-(2)
]-(3) in advance, which has fewer carbon atoms than the compound represented by the general formula ROM (i.e., has 1 to 5 carbon atoms)
After dissolving the compound having a hydrocarbon group, a so-called lower alcohol, in the presence of a compound represented by the general formula ROH, component [I]-(21 and/or component [I]
A method of bringing a lower alcohol solution containing -(3) into contact with other components is also preferably used. The lower alcohol used at this time is preferably an alcohol having an alkyl group having 1 to 5 carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-propanol, etc. Methyl-1-propatol, 2-methyl-2-propatol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-
1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol,
Examples include 2,2-dimethyl-1-propanol,
Of course, various denatured alcohols such as methanol-denatured ethanol and hexane-denatured ethanol, which are commercially available as industrial alcohols, can also be used without any problem.

The method of contacting these components [I]-+1) to II]-(3) is in the presence of a compound represented by the general formula ROM,
Component [I]-(11, component [I]-(21 and component [
I]-(31 according to the above contact order, 20-300°C,
Preferably, the mixture reaction is carried out at a temperature of 50 to 150°C for 1 minute to 48 hours, preferably 1 to 5 hours, and then the general formula R
It is desirable to perform an operation to remove the compound represented by OH by methods such as reduced pressure and/or heating.

In addition, regarding the reaction ratio of each component, first, component [I]
-(1) and component [I]-(21 are component [I]-(
1) Per Ig, the number of moles of Mg in component [■]-(2) is O, O1 to 20 ms+ol, preferably O1 to 10
It is desirable that the reaction be carried out in such a manner that the amount is 1 mmol, more preferably 02 to 4.0 a+m5 ol.

Additionally, component [I]-(11, component [I]-(3), and 1) 0.01 to 10.0+u* of component [I]-(3) per Ig
It is desirable to react using 0.1 to 5.0 mmol, more preferably 0.2 to 2.0 mmol.

In addition, the amount of the compound represented by the general formula ROH to be used is 1 g of the general component [I 1-(2)],
5 to 50 g of the compound represented by 5, preferably 10 to 3
It is desirable to use 0g.

2 Component [II] In the organoaluminum compound represented by the general formula AIRoX used in the present invention, R is an alkyl group, aryl group, aralkyl group, etc. having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. a hydrocarbon group, X represents a hydrogen atom or a halogen atom, and n is 0 < n ≦
3.

These organoaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum,
Triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminium, diethylaluminum hydride, diisobutylaluminum hydride, dimethylaluminum chloride, diethylaluminum fluoride, diethylaluminium chloride, diethylaluminum bromide, diethylaluminium iodide, diisobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquipromide, methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, phenylaluminum dichloride, diphenylaluminum chloride, benzylaluminum dichloride, dibenzylaluminum chloride, or any mixture thereof. Especially preferred are ethylaluminum sesquichloride, diethylaluminum chloride, and ethylaluminum dichloride.

3. Production of solid catalyst component The solid catalyst component used in the present invention is obtained by reacting the above-mentioned [I] acid component and the above-mentioned [I] component. However, in the presence of so-called inert hydrocarbon solvents that are inert to the common Ziegler catalysts, such as pentane, hexane, cyclohexane, heptane, octane, nonane, decane, benzene, toluene, xylene, etc., or mixtures thereof. Alternatively, a method is preferably used in which the reaction is mixed and heated at a temperature of 0 to 300°C, preferably 20 to 150°C, for 5 minutes to 10 hours in the absence of the solvent, and then the solvent is removed by evaporation.

In addition, the reaction ratio of the [I] acid component and the [R1] component is as follows:
II] component/(component [I] in the [I] component - (31
) (molar ratio) is 001 to 100, preferably 02 to
10, more preferably 0.5 to 5.

Of course, each reaction operation concerning the preparation of the [I] acid component and the solid catalyst component should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible.

2) Organometallic Compound The catalyst used in the present invention consists of the solid catalyst component described above and an organometallic compound, and the organometallic compound is an organometallic member of Groups 1 to 2 of the periodic table, which is known as a component of Ziegler's catalyst. Although compounds can be used, organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include the general formula R3Al, R.

AIX, RAIX, RAlOR, RAI(OR)x, 1:l/RA12x3 organoaluminum compound (R is an alkyl group or aryl group having 1 to 20 carbon atoms, X is a halogen atom, and R may be the same or or the general formula R, Z, (wherein R has 1 to 1 carbon atoms)
20 alkyl groups, which may be the same or different), including trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, triffee-butylaluminum, trimethylaluminum, Examples include tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof. There is no particular limit to the amount of the organometallic compound used, but it is usually 0.1 to 10010% of the titanium compound.
It can be used 00 times.

In the present invention, the organometallic compound component may preferably be used as a mixture or addition compound of the organometallic compound and an organic acid ester.

If the organometallic compound and organic acid ester are used as a mixture, the organic acid ester is usually 0.1 to 1 mol, preferably 0.2 to 1 mol, per 1 mol of the organometallic compound.
Use 0.5 mol.

When used as an addition compound of an organometallic compound and an organic acid ester, the molar ratio of organometallic compound:organic acid ester is preferably 2:1 to 1:2.

The organic acid ester used in case (B) has 1 to 1 carbon atoms.
It is an ester of 24 saturated or unsaturated monobasic or dibasic organic carboxylic oxygens and an alcohol having 1 to 30 carbon atoms. Specifically, methyl formate, ethyl acetate,
Amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, ethyl benzoate, n-propyl benzoate, di-propyl benzoate, butyl benzoate, hexyl benzoate, cyclopentyl benzoate, benzoate cyclohexyl acid, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate, benzyl salicylate, ethyl α-resorcinate, methyl anisate, ethyl anisate, Phenyl anisate, benzyl anisate, ethyl 0-methoxybenzoate, methyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate% p-) phenyl toluate, ethyl toluate, m-) Ethyl ruylate, p-
Examples include methyl aminobenzoate, ethyl p-aminobenzoate, vinyl benzoate, allyl benzoate, benzyl benzoate, methyl naphthoate, and ethyl naphthoate. Among these, particularly preferred is benzoic acid, 0
- or P-) alkyl esters of ruyl acid or p-anisic acid, and methyl esters and ethyl esters thereof are particularly preferred.

3> Olefin polymerization Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization, or gas phase polymerization.

In particular, the catalyst of the present invention can be suitably used for gas phase polymerization, and the polymerization reaction can be carried out in the same manner as an olefin polymerization reaction using a typical Ziegler type catalyst. That is, all reactions should be carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, etc. The olefin polymerization conditions include a temperature of 20 to 120°C, preferably 50 to 100°C, and a pressure of normal pressure to 70 kg/c.
lIr, preferably 2 to 60 kg/cd. Although the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, other polymerization reactions of two or more stages with different polymerization conditions such as hydrogen concentration and polymerization temperature can also be carried out without any hindrance.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, and alpha-olefins having 2 to 12 carbon atoms are particularly preferred, such as ethylene, propylene, 1-butene, hexene-1,4- Homopolymerization of a-olefins such as methylpentene-1, and ethylene and α-olefins having 3 to 12 carbon atoms, such as ethylene and propylene, ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1, etc. It is suitably used for copolymerization of olefins, copolymerization of propylene and 1-butene, copolymerization of ethylene and two or more other α-olefins, and the like.

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.

The comonomer content during copolymerization can be selected arbitrarily, but for example, ethylene and carbon atoms of 3 to 12
In the case of copolymerization with a-olefin, the a-olefin content in the ethylene/α-olefin copolymer is 0 to 40
It is desirable that the amount is mol %, preferably 0 to 30 mol %.

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

Example 1 (al) Production of solid catalyst component 10 g of commercially available anhydrous magnesium chloride 1 4.2 g of aluminum triethoxide were placed in a stainless steel pot with an internal volume of 400 mj containing 25 stainless steel balls each having a diameter of 1/2 inch. Ball milling was carried out at room temperature for 16 hours in a nitrogen atmosphere to obtain a reaction product. A Mitsuro flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and the dehydrated 2-methyl-1- 100 g of pentanol, 10.0 g of jetoxydichlorotitanium
After stirring at room temperature for 1 hour, add 5.0 g of the above reaction product of anhydrous magnesium chloride and aluminum triethoxide.
was added and reacted at 80°C for 1 hour. After cooling to room temperature, 4
Silica calcined at 00℃ for 3 hours (Fuji Davison, #95
5) After adding 46g and reacting again at 80°C for 2 hours,
Drying was performed under reduced pressure at 120° C. for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane and 106 g of diethylaluminium chloride were added and reacted at room temperature for 1 hour, followed by nitrogen blowing at 60° C. for 3 hours to remove hexane and obtain a solid catalyst component.

(bl Gas-phase polymerization A stainless steel autoclave with an agitator was used as the gas-phase polymerization apparatus. A loop was created with a blower-1 flow controller and a dry cyclone, and the temperature of the autoclave was regulated by flowing hot water through the jacket. .8
Two of the above solid catalyst components were placed in an autoclave adjusted to 0°C.
50■/hr, and triethylaluminum 50m
Each gas was supplied at a rate of mol/hr, and the butene-1/ethylene molar ratio in the gas phase of the autoclave was adjusted to 0.25, and hydrogen was adjusted to 15% of the total pressure. While maintaining the total pressure at 8 kg/cIIrG, the gas in the system was circulated using a blower, and continuous polymerization was carried out for 10 hours while the produced polymer was intermittently taken out.

The produced ethylene copolymer has a melt flow rate (M
FR) 1.04g/10win, density 0.92
06 g/cd, and the gas density is 044 g/as? ,
It was a round granule with an average particle size of 860μ.

The catalyst efficiency was 230,000 g copolymer/g Ti, indicating extremely high activity. In addition, after 10 hours of continuous polymerization,
When the inside of the autoclave was inspected, no polymer was found to be attached to the inner wall or the stirrer.

Copolymer QASTM-D1238-65T (7) Method 1), melt flow rate (MFR2□6) measured at 190°C, load fi 2.16 kg and melt flow rate (MFR, ) measured at load 10 kg. The FR value expressed as the ratio (FR=MFR, 0/MFR2□6) was 7.4, and the molecular weight distribution was extremely narrow. Further, the melting point of this copolymer was 121.7° C., and the hexane extraction amount was 2.7 wt%.

Example 2 A solid catalyst component was prepared in the same manner as in Example 1, except that 15.0 g of dibutoxydichlorotitanium was used instead of jetoxydichlorotitanium. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was as high as 210.000 g copolymer/g Ti, and M F R0.97 g/g.
10 win, density 0.9215g/ear, bulk specific gravity 0.43g yad.

Round granules with an average particle size of 880 μm were obtained. In addition, the FR is 75, which is a narrow molecular weight distribution, and the melting point is 1219°C.
The hexane extraction amount was 2.8 wt%.

Example 3 A solid catalyst component was prepared in the same manner as in Example 1, except that 100 g of titanium tetrachloride was used instead of jetoxydichlorotitanium. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 270,000 g copolymer/g Ti
and high activity, MFRo, 88g/10 pairs n, density 0.9
209 g/d, bulk specific gravity 0.42 g/c; r
Round granules with an average particle size of 930 μm were obtained. In addition, the FR is 7.6, which is a narrow molecular weight distribution, and the melting point is 12.
At 2.2°C, the hexane extraction amount was 3.1 wt%.

Example 4 (1) Preparation of solid catalyst components 10 g of commercially available anhydrous magnesium chloride and 4 aluminum triethoxide were placed in a stainless steel pot with an internal volume of 400@I containing 25 stainless steel balls having a diameter of 1/2 inch. A reaction product was obtained by ball E'Jing for 16 hours at room temperature under a nitrogen atmosphere.A Mitsuro flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 5wt of methanol was added into it. % of denatured ethanol, 20.0 g of 2-methyl-1-pentanol, and 8.0 g of jetoxydichlorotitanium. After stirring at room temperature for 1 hour, the above reaction product of anhydrous magnesium chloride and aluminum triethoxide was added. 5.0g was added and reacted at 80°C for 1 hour.After cooling to room temperature, 400g
Silica calcined at ℃ for 3 hours (Fuji Davison, #9551
After adding 46g and reacting again at 80℃ for 2 hours, 12
Drying under reduced pressure was performed at 0° C. for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane and 100 g of diethyl aluminum chloride were added and reacted at room temperature for 1 hour, followed by nitrogen blowing at 60° C. for 3 hours to remove hexane and obtain a solid catalyst component.

(bl Gas phase polymerization When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was as high as 220.000 g copolymer/g Ti, and M F R0, 94 g 710
win, density 0.9222 g/ci, bulk ratio M
Round granules having a shape of O, 43 g/ctj and an average particle size of 820 μm were obtained. In addition, the FR is 74, which is a narrow molecular weight distribution, the melting point is 121.5℃, and the hexane extraction amount is 2.6w.
It was t%.

Example 5 A solid catalyst component was prepared in the same manner as in Example 4, except that 20.0 g of 3.5-methyl-1-hexonol was used instead of 2-methyl-1-pentanol. Prepared.

When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was as high as 230.000 g copolymer/g Ti, and the V F R was 1,07 g/1.
Round granules having a shape of 0 win, a density of 0.9211 g/cal, a specific gravity of 042 g/cal, and an average particle size of 840 μm were obtained.

In addition, FR is 74, which is a narrow molecular weight distribution, and melting point is 122.
At 0°C, the hexane extraction amount was 3.0 wt%.

Example 6 (1) Preparation of solid catalyst component 10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide were placed in a 400mj stainless steel pot containing 25 stainless steel balls each having a diameter of 1/2 inch. Put it under nitrogen atmosphere,
Ball E IJ song was performed at room temperature for 16 hours to obtain a reaction product. A Mitsuro flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and ethanol 140w + Z, 2
- Add 17.0 g of methyl-1-hexanol and 12.0 g of jetoxydichlorotitanium and stir at room temperature for 1 hour.
4.2 g of the above reaction product of anhydrous magnesium chloride and aluminum triethoxide was added and reacted at 80° C. for 1 hour. After cooling to room temperature, silica (
46 g of Fuji Davison, #955) was added and reacted again at 80°C for 2 hours, followed by drying under reduced pressure at 120°C for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane and 10.0 g of diethylaluminium chloride were added and reacted at room temperature for 1 hour, followed by nitrogen blowing at 60° C. for 3 hours to remove hexane to obtain a solid catalyst component.

(bl Gas phase polymerization Polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, and the catalyst efficiency was as high as 270.000 g copolymer/g Ti, and M F Ro, 89 g/g Ti.
Round granules in the shape of 10 win, density 0.9211 g/ci, bulk ratio i[0,44 g/cm and average particle size 910 μm were obtained. Also, what about FR? , 4, the molecular weight distribution is narrow, the melting point is 1218°C, and the hexane extraction amount is 2.
．． It was 9wt%.

Example 7 In Example 6, dibutoxydichlorotiqune was substituted for jetoxydichlorotitanium15. A solid catalyst component was prepared in the same manner as in Example 6 except that f was used. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was as high as 260.000 g copolymer/g Ti, and M F R1,12 g/g.
10 win, density 0.9211 g/lyd, bulk specific gravity 0.40 g/ci.

Round granules with an average particle size of 880 μm were obtained. In addition, FR has a narrow molecular weight distribution of 75, and a melting point of 1f122.
At 1°C, the amount of hexane extracted was 3.0+vt%.

Example 8 (,) Preparation of solid catalyst component 10 g of commercially available anhydrous magnesium chloride 1 4.2 g of aluminum triethoxide were added to a stainless steel pot with an internal volume of 400 ml containing 25 stainless steel balls having a diameter of 1/2 inch. Ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere to obtain a reaction product.

A Mitsuro flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 140 mJ of denatured ethanol containing 5 wt% methanol and 17 mL of 2-methyl-1-hexanol were added to the flask.
．． 0 g, dibutoxydichlorotitanium 15.0 g was heated at room temperature for 1 hour, and then 5.0 g of the above reaction product of anhydrous magnesium chloride and aluminum triethoxide was added.
The reaction was carried out at 0°C for 1 hour. After cooling to room temperature, 3 at 400℃
Time-calcined silica (Fuji Davison, $955) 46
g and reacted again at 80°C for 2 hours, then at 120°C.
The mixture was dried under reduced pressure for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane and 100 g of diethylaluminum chloride were added and reacted at room temperature for 1 hour.
Nitrogen blowing was performed at 0° C. for 3 hours to remove hexane and obtain a solid catalyst component.

(b) Gas phase polymerization Polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, and the catalyst efficiency was as high as 240.000 g copolymer/g Ti, with M F R1,14 g/g. 1
Round granules in the shape of 0 +uin, density 0.9230 g/cod, bulk specific gravity 0.42 g/d, average particle size 830 μm were obtained. In addition, the molecular weight distribution is narrow, with an FR of 7.3, and a melting point of 121. The amount of hexane extracted at e°C was 2.7 wt%.

Example 9 A solid catalyst component was prepared in the same manner as in Example 8, except that 10.0 g of jetoxydichlorotitanium was used instead of dibutoxydichlorotitanium. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was as high as 250.000 g copolymer/g Ti, and M F R0.97 g/g.
10 win, density 0.9205 g lcd, bulk specific gravity 0.44 g/cnr.

Round granules with an average particle size of 780 μm were obtained. In addition, the FR is 75, which is a narrow molecular weight distribution, and the melting point is 1224℃.
The amount of hexane extracted was 31%.

Example 10 In Example 6, di-2-ethylhexyloxydichlorotitanium 15.0 was used instead of jetoxydichlorotitanium.
A solid catalyst component was prepared in the same manner as in Example 6, except that g was used. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 2.
High activity of 00.000 g copolymer/gTi, M F
R0,88g/10 min, density 0.9200
Round granules with a bulk specific gravity of 0.43 g/ct/ and an average particle size of 800 μm were obtained. Also, F
The molecular weight distribution was narrow with R of 7.6, the melting point was 1221°C, and the amount extracted with hexane was 3.3 wt%.

Example 11 <nl Production of solid catalyst component 10 g of commercially available anhydrous magnesium chloride and 5.0 g of ethoxyboron were added to a stainless steel pot with an internal volume of 400 l containing 25 stainless steel balls each having a diameter of 172 inches. 16 at room temperature under nitrogen atmosphere.
A reaction product was obtained by carrying out a ring for a time ball i. A Mitsuro flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and dehydrated 2-methy-5-1-pentanol 1 was placed in it.
After adding 100 g of jetoxydichlorotitanium and stirring at room temperature for 1 hour, 50 g of the above reaction product of anhydrous magnesium chloride and triethoxy boron was added and reacted at 80° C. for 1 hour. After cooling to room temperature, 46 g of silica (Fuji Davison, $955) calcined at 400°C for 3 hours was added, reacted again at 80°C for 2 hours, and then dried under reduced pressure at 120°C for 2 hours to obtain a solid powder. Next, dehydrated hexane 100
cc and 10.0 g of diethylaluminium chloride were added and reacted at room temperature for 1 hour, followed by nitrogen blowing at 60° C. for 3 hours to remove .\xane to obtain a solid catalyst component.

(bl Gas phase polymerization When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 210.000 g copolymer/gTi, high activity, MFRo, 97 g/10 m1
n, density 0.9207 g/c/, bulk specific gravity 0.4
Round granules with a shape of 4 g/1 ffl and an average particle size of 800 μm were obtained. In addition, the FR is 7.6, which is a narrow molecular weight distribution, the melting point is 122.0℃, and the hexane extraction amount is 3.2wt%.
Met.

Example 12 A solid catalyst component was prepared in the same manner as in Example 11, except that 75 g of jetoxymagnesium was used instead of triethoxyboron. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 220.000 g copolymer/
High activity with gTi, MFRl, 08g/10 win
S density 0.9232 g LCD, bulk specific gravity 0.42
g lcd, round granules in the form of an average particle size of 800 μm were obtained. Further, the molecular weight distribution was narrow with FR of 75, the melting point was 122.2°C, and the hexane extraction amount was 2.8 wt%.

Example 13 A solid catalyst component was prepared in the same manner as in Example 6 except that silica alumina was used instead of silica. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 190.
000 g copolymer/gTi and high activity, MFRo, 7
7g/10mln, density 0.9235g lcd, specific gravity 0.40g/eat', average particle size 770
Round granules with a μ-biased shape were obtained. Also, FR is 75
The molecular weight distribution was narrow, the melting point was 122.3°C, and the hexane extraction amount was 2.9 wt%.

Example 14 A solid catalyst component was prepared in the same manner as in Example 6, except that alumina was used instead of silica. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 200.000.
g copolymer/gTi and high activity, MFRo, 86g7
Round granules having a shape of 10 m1n, a density of 0.9199 g lcd, a bulk specific gravity of 0.40 g/c++r and an average particle size of 780 μm were obtained. In addition, the FR is 76, which is a narrow molecular weight distribution, the melting point is 122.5℃, and the hexane extraction amount is 3.2.
It was wt%.

Example 15 A solid catalyst component was prepared in the same manner as in Example 1, except that 14.5 g of ethyl aluminum chloride was used instead of diethylaluminum chloride. When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 250.000.
g copolymer/gTi and high activity, MF R1,11g
/10 win1 density 0.9201 g lcd, bulk specific gravity 0.42 g/ci, average particle size 890 μm round granules were obtained.

In addition, the molecular weight distribution is narrow with FRI of 74, and the melting point is i! 1
At 22.0°C, the hexane extraction amount was 3.0 wt%.

Comparative Example 1 +a+ Manufacture of solid catalyst component 1/2a) 10g of commercially available anhydrous magnesium chloride and 4.2g of aluminum trietkind were placed in a stainless steel pot with an internal volume of 400a+1 containing 25 stainless steel balls with a diameter of under nitrogen atmosphere.
Ball E'Jing was performed at room temperature for 16 hours to obtain a reaction product. A three-way flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and the above reaction product 5 was added to the three-way flask.
5iO (Raishi Davison, #
952), then add 100 g of tetrahydrofuran.
After adding mZ and reacting at 60°C for 2 hours, 120°C
Drying was performed under reduced pressure at °C to remove tetrahydrofuran.

Next, 50 cc of hexane was added and stirred, and then 1.1 mA' of titanium tetrachloride was added and reacted for 2 hours under reflux of hexane to obtain a solid catalyst component. The content of titanium in 1 g of the obtained solid catalyst component was 40 .

(bl Gas phase polymerization When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was as low as 112.000 g copolymer/g Ti, and the M F R1.2 g/10
win, density 0.9218/m, bulk density 0.41
Amorphous granules with an average particle diameter of 700 μg/at/F R7,6 were obtained. Further, the melting point was 123.2°C, and the hexane extraction amount was 4.2 wt%.

Comparative Example 2 (Production of solid catalyst component) 10 g of commercially available anhydrous magnesium chloride and 4.3 g of ethoxyaluminum were placed in a stainless steel pot with an internal volume of 400 mj containing 25 stainless steel balls each having a diameter of 172 inches, and heated with nitrogen. Ball milling was performed in an atmosphere at room temperature for 16 hours to obtain a reaction product. A three-way flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 140 cc of dehydrated ethanol1 100 g of dehydrated 2-methyl-1-pentanol1 tetran
- Add 20 g of ethoxy titanium and 50 g of the above reaction product of anhydrous magnesium chloride and triethoxyaluminum, and
After reacting at 0°C for 1 hour, drying under reduced pressure was performed at 120°C for 2 hours to obtain a solid powder. Next, 100c of dehydrated hexane
c and 2.0 g of diethylaluminium chloride were added and reacted at room temperature for 1 hour, followed by nitrogen blowing at 60° C. for 3 hours to remove hexane to obtain a solid catalyst component.

When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the stirrer became unable to rotate 30 minutes after the start of polymerization, and the polymerization had to be stopped. When the inside of the autoclave was inspected, melted polymer was found adhering to the stirring blades.

Comparative Example 3 (al) Production of solid catalyst component 10 g of commercially available anhydrous magnesium chloride was placed in a stainless steel pot with an internal volume of 4040 and containing 25 stainless steel balls each having a diameter of 172 inches, and the mixture was heated at room temperature under a nitrogen atmosphere for 16 hours. Ball milling was carried out for an hour. A three-way flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and the inside contained 140 cc of dehydrated ethanol, 17.0 g of dehydrated 2-ethyl-1-hexanol, and 12 g of tetraethoxytitanium. After adding .0g and stirring at room temperature for 1 hour,
Add 7.5 g of the above anhydrous magnesium chloride pulverized product, and
The reaction was carried out at 0°C for 1 hour. After cooling to room temperature, 3 at 400℃
Time-calcined silica (Fuji Davison, #955) 46g
After reacting again at 80°C for 2 hours, drying under reduced pressure was performed at 120°C for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane and 10.0 g of diethylaluminum chloride were added and reacted at room temperature for 1 hour, and then 60 cc of
Nitrogen blowing was performed at ℃ for 3 hours to remove hexane and obtain a solid catalyst component.

fbl Gas phase polymerization When polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 140.000 g copolymer/g Ti, MFR 0.98 g / 10 win,
Density 0.9220 g/cffr, bulk specific gravity 0.3
Amorphous granules with a weight of 8 g/cd and an average particle size of 710 μm were obtained. In addition, the FR is 82, the molecular weight distribution is relatively wide, the melting point is 1230°C, and the hexane extraction amount is 4.0wt.
%Met.

[Brief explanation of drawings]

FIG. 1 is a flow chart showing the manufacturing process of the catalyst of the present invention.

Claims (1)

[Claims] 1. A method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as a catalyst, wherein the solid catalyst component is [I] (1) silicon oxide and/or aluminum oxide, ( 2) Magnesium halide and the general formula Me(OR)_nX_z_-_n (where Me is an element of groups I to IV of the periodic table, z is the valence of the element Me, n
is 0<n≦z, X is a halogen atom, and R has 1 to 20 carbon atoms.
and (3) a reaction product obtained by reacting a compound represented by the general formula Ti(OR')_nX_4_-_n (where R' is a hydrocarbon residue having 1 to 20 carbon atoms). group, X represents a halogen atom, and n is 0≦n<4), with the general formula ROH (where R represents an organic residue having 6 to 20 carbon atoms). [II] General formula AlR_X_3_-_n (where R represents a hydrocarbon residue having 1 to 24 carbon atoms, X represents a halogen atom, A method for producing a polyolefin, comprising a substance obtained by reacting an organoaluminum compound represented by n=0<n≦3.