JP2002167405A - Trialkylaluminium compound for olefin polymerization, catalyst for olefin polymerization, and method for olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a trialkylaluminium compound for olefin polymerization which enables the polymerization with high cavity and high stereospecificity, a catalyst for the polymerization, and to provide a method for the polymerization using the catalyst. SOLUTION: The trialkylaluminium compound is characterized in that the content of hydride contained in the compound (a value of dialkylaluminium monohydride, alkylaluminium dihydride and/or aluminium trihydride converted to aluminium trihydride) is 0.1 wt.% or less with respect to the compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a trialkylaluminum compound for olefin polymerization, an olefin polymerization catalyst containing the same, and an olefin polymerization method using the catalyst. More specifically, the present invention relates to a trialkylaluminum compound for olefin polymerization containing a low content of aluminum hydride, an olefin polymerization catalyst containing the same, and an olefin polymerization method using the same.

[0002]

BACKGROUND OF THE INVENTION There have been many proposals for solid catalysts comprising a solid titanium catalyst containing magnesium, titanium and halogen, an electron donor, and an organoaluminum compound such as trialkylaluminum as a co-catalyst. And such a solid catalyst has 3 carbon atoms.
The use of the above-mentioned α-olefin in the polymerization has made it possible to produce a polymer having high stereoregularity at a high yield.

[0003] In recent years, attempts have been made to develop catalysts that enable highly active and highly stereospecific polymerization by using a novel electron donor as an external donor or an internal donor for various solid titanium catalysts. ing. But,
Even at present, depending on the conditions of use of the solid catalyst, a few percent of the atactic polymer may be contained as a whole, and under various conditions of use, a catalyst that enables more active and highly stereospecific polymerization. The development of was desired.

[0004] Among the above solid catalysts, trialkylaluminum used as a co-catalyst is 19%.
A method for directly synthesizing trialkylaluminum from aluminum, hydrogen and olefin was discovered by K. Ziegler in 1980, and various improved methods and the like have been developed. As a method for synthesizing trialkylaluminum, for example,
Former West German Patent Nos. 96153 and 1031792,
Nos. 1086699, 1118782, 2058
487 and the like. Specifically, as a conventionally known method, for example, the following method is known. (1) One-step synthesis method Al + 3 / 2H ₂ +2 R-CH = CH ₂ → Al (R-CH _2-
CH ₂ ) ₃ (2) Two-step synthesis method Al + 3 / 2H ₂ + 2Al (R-CH-CH ₂ ) ₃ → 3Al (R-
_{CH 2 -CH 2) 2 H 3Al} (R-CH 2 -CH 2) 2 H + 2R-CH = CH 2 → 3A
l (R—CH ₂ —CH ₂ ) ₃ (wherein, R is hydrogen or an alkyl group having 1 to 18 carbon atoms.) In such a process for producing trialkylaluminum, Aluminum hydride is usually contained in the alkyl aluminum in an amount of about 0.3 to 1% (in terms of aluminum hydride in terms of AlH ₃ ).

Under these circumstances, the present inventors have conducted intensive studies and have found that trialkylaluminum in which the amount of aluminum hydride produced in the preparation of the trialkylaluminum compound used as such a cocatalyst is reduced to a certain amount or less is reduced. When used as a cocatalyst, the catalyst activity of the solid catalyst is remarkably improved, and a polyolefin obtained using the solid catalyst is found to be a polymer having an excellent isotactic index (II). I came to.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is directed to a trialkylaluminum compound for olefin polymerization, a catalyst for olefin polymerization, which enables high activity and high stereospecific polymerization. An object of the present invention is to provide an olefin polymerization method using the same.

[0007]

SUMMARY OF THE INVENTION The trialkylaluminum compound for olefin polymerization according to the present invention is characterized in that the content of aluminum hydride contained in the trialkylaluminum compound (dialkylaluminum monohydride, alkylaluminum dihydride and / or aluminum trihydride is replaced by aluminum trihydride) ) Is 0.1% by weight or less based on the trialkylaluminum compound.

The olefin polymerization catalyst according to the present invention comprises:
(A) The content of aluminum hydride contained in the trialkylaluminum compound (the value obtained by converting dialkylaluminum monohydride, alkylaluminum dihydride and / or aluminum trihydride into aluminum trihydride) is based on the trialkylaluminum compound. 0.1% by weight or less of a trialkylaluminum compound for olefin polymerization, (B) a solid titanium catalyst component containing magnesium, titanium and halogen as essential components, and (C) an electron donor. I have.

The solid titanium catalyst component comprises an electron donor (D) in addition to magnesium, titanium and halogen.
May be included. In the olefin polymerization method according to the present invention, (A) the content of hydride contained in the trialkylaluminum compound (a value obtained by converting dialkylaluminum monohydride, alkylaluminum dihydride and / or aluminum trihydride into aluminum trihydride) is: 0.1% by weight or less based on the trialkylaluminum compound, a trialkylaluminum compound for olefin polymerization,
An olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising (B) a solid titanium catalyst component containing magnesium, titanium and halogen as essential components and (C) an electron donor. .

The solid titanium catalyst component comprises an electron donor (D) in addition to magnesium, titanium and halogen.
May be included.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises a trialkylaluminum compound (A) for olefin polymerization and a solid titanium catalyst component (B) containing magnesium, titanium and halogen as essential components.
And an electron donor (C). Further, the solid titanium catalyst (B) may further contain an electron donor (D).

First, the trialkylaluminum compound (A) for olefin polymerization will be described. [Trialkylaluminum for olefin polymerization (A)]
Olefin polymerization trialkylaluminum compound according to the present invention (A) is a trialkyl aluminum compound represented by AlR _3. In the formula, the hydrocarbon groups R are each independently preferably an alkyl group having preferably 1 to 20, more preferably 1 to 6, and particularly preferably 1 to 4 carbon atoms. Specific examples of such a trialkylaluminum compound (A) include trimethylaluminum, thiethylethylaluminum, tripropylaluminum, triisobutylaluminum and the like. Among them, triethylaluminum can be preferably used.

[0013] The trialkylaluminum compound for olefin polymerization usually contains aluminum hydride in the production process. The content of the aluminum hydride contained in the trialkylaluminum compound (dialkylaluminum monohydride, alkylaluminum dihydride and / or Or a value obtained by converting aluminum trihydride to aluminum trihydride) is 0.1% by weight or less, preferably 0.01% by weight or less, more preferably 0 to 0.01% by weight, Preferably, it is 0 to 0.005% by weight.

When the content of aluminum hydride contained in the trialkylaluminum compound is within the above range, the trialkylaluminum compound (A), the solid titanium catalyst component (B), and the electron donor (C) The catalyst activity of the resulting olefin polymerization catalyst is improved, and the stereoregularity of the polyolefin polymerized using the present olefin polymerization catalyst is improved.

As described above, when the content of aluminum hydride contained in the trialkylaluminum compound is reduced, a catalyst which gives a highly active and highly stereospecific polyolefin can be obtained because an electron donor (C ) Is suppressed, and the electron donor can be maintained at a high activity. In addition, by reducing the content of aluminum hydride in this way, not only can the activity of the olefin polymerization catalyst be improved, but also the amount of the electron donor (C) added can be reduced. An active catalyst having excellent properties can be provided.

Such a trialkylaluminum compound (A) for olefin polymerization according to the present invention can be produced, for example, by the following method. In the synthesis reaction, an aluminum metal, an olefin, and hydrogen are reacted directly or in the presence of a trialkylaluminum with an aluminum metal, hydrogen, and an olefin at a constant temperature and a constant pressure to react. By controlling the time, a trialkylaluminum containing aluminum hydride at a desired content can be obtained.

Such a reaction can be carried out in a one-step method or a two-step method as described below, but is not particularly limited. (1) One-step synthesis method Al + 3 / 2H ₂ + 2R-CH = CH ₂ → Al (R-CH-CH ₂ ) ₃ (2) Two-step synthesis method As described below, activated aluminum is replaced with trialkylaluminum. And hydrogen to produce a dialkylaluminum monohydride, which is then reacted with an olefin to grow the trialkylaluminum. (Stage _{1) Al + 3 / 2H 2 +} 2Al (R'-CH-CH 2) 3 → 3Al (R'-
CH ₂ —CH ₂ ) ₂ H (second stage) 3Al (R′-CH—CH ₂ ) ₂ H + 2R′-CH = CH ₂ → 3
_{Al (R'-CH 2 -CH 2} ) 3 ( In the formula, R 'is an alkyl group having 1 to 18 carbon atoms.) Of these, in the present invention, preferably used a two-step synthesis Can be.

In this case, for example, when the above-mentioned two-step synthesis method is used, after the dialkylaluminum hydride is produced in the first step, the reaction temperature is preferably 50 to 200 ° C., more preferably in the second step. 60
It is desirable that the temperature is 150 ° C. In the second step, the olefin for deriving the alkyl group R is preferably 0.2 to 4 MPa at a gauge pressure, more preferably 0.1 to 4 MPa.
It is desirable to charge at a pressure of 5 to 3.5 MPa and perform the reaction within the pressure range. Further, the reaction time of the second stage is preferably 30 minutes to 10 hours, more preferably 1 minute.
Desirably, the time is from 6 to 6 hours.

The aluminum metal is titanium,
It is preferable to use aluminum activated by zirconium or the like. Although the shape of such metallic aluminum is not particularly limited, it is preferably in the form of powder.
When a trialkylaluminum compound is synthesized under such conditions, a trialkylaluminum compound with a reduced content of alkyl hydride can be obtained. [Solid titanium catalyst component (B)] The solid titanium catalyst component (B) used in the present invention is a catalyst component containing magnesium, titanium and halogen as essential components. As such a catalyst component, a known catalyst component can be used and is not particularly limited.

Such a solid titanium catalyst component (B) comprises:
It can be prepared by contacting the following magnesium compound and titanium compound. In the present invention, the titanium compound used for preparing the solid titanium catalyst component (B), for example _{Ti (OR '') g X} 4-g
(R ″ is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦
The tetravalent titanium compound represented by 4) can be exemplified.

[0021] More specifically, TiCl _4, TiBr _4, Ti
Titanium tetrahalides, such as _{I 4; Ti (OCH 3)} C
_{l 3, Ti (OC 2 H} 5) Cl 3, Ti (On-C 4 H 9) Cl 3,
_{Ti (OC 2 H 5) Br} 3, Ti (OisoC 4 H 9) trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 C
l ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ C
_{l 2, Ti (OC 2 H} 5) dihalogenated dialkoxy titanium, such as _{2 Br 2; Ti (OCH 3} ) 3 Cl, Ti (OC 2 H 5) 3 C
_{l, Ti (On-C 4} H 9) 3 Cl, Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as Br; Ti (OC
_{H 3) 4, Ti (OC} 2 H 5) 4, Ti (On-C 4 H 9) and the like tetraalkoxytitanium such as _4.

Among these, a halogen-containing titanium compound, particularly a titanium tetrahalide, is preferable, and titanium tetrachloride is more preferably used. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component (B) include a magnesium compound having a reducing property and a magnesium compound having no reducing property. Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of the magnesium compound having such a reducing property include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesiumchloride, propylmagnesiumchloride, and butylmagnesium. Examples include magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, and butyl magnesium halide. These magnesium compounds can be used alone or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid.

Specific examples of the non-reducing magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, and isopropoxy magnesium chloride. Alkoxy magnesium halides such as magnesium chloride, butoxy magnesium and octoxy magnesium chloride; Alkoxy magnesium halides such as magnesium phenoxy chloride and methyl phenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium Alkoxymagnesium such as;
Allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylate such as magnesium laurate and magnesium stearate;

The non-reducing magnesium compound may be a compound derived from the above-described reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is converted to a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. What is necessary is just to contact with a compound.

In the present invention, in addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property, a magnesium compound is a complex compound, a double compound or another compound of the above-mentioned magnesium compound and another metal. It may be a mixture with a metal compound. Further, a mixture of two or more of the above compounds may be used.

In the present invention, among these, magnesium compounds having no reducing property are preferred, and halogen-containing magnesium compounds are particularly preferred. Of these, magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are preferably used. Can be (Electron Donor (D)) In the present invention, when preparing the solid titanium catalyst component (B), it is preferable to use an electron donor (D) as a so-called internal donor. As such an electron donor, a known electron donor can be used and is not particularly limited. Examples of the electron donor (D) include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, ammonia, and amines. , Nitriles, and nitrogen-containing electron donors such as isocyanates.

As the electron donor (D), an organosilicon compound represented by the following general formula [I] can also be used. R _n Si (OR ') _4-n [I] wherein R and R' are hydrocarbon groups, and 0 ≦ n <4
These electron donors (D) can be used in combination of two or more.

The electron donor which is desirably contained in the titanium catalyst component is an ester.

[0030]

Embedded image

(Where R¹ Is a substituted or unsubstituted carbonized
Hydrogen group, R^Two , R^Five , R⁶ Is hydrogen or substituted or
An unsubstituted hydrocarbon group, R^Three , R^Four Is hydrogen or substituted
Or an unsubstituted hydrocarbon group, preferably
At least one is a substituted or unsubstituted hydrocarbon group. Ma
R^Three And R^Four May be connected to each other. R above¹
~ R^Five Examples of the substituted hydrocarbon group include N, O, S and the like.
Containing hetero atoms, for example, C—O—C, COOR, C
OOH, OH, SO_Three H, -C-N-C-, NH _Two Such
Having a group of Having a skeleton represented by)
Things.

Of these, particularly preferred are R ¹ and R ²
Is a diester of a dicarboxylic acid in which at least one is an alkyl group having 2 or more carbon atoms. Among these polyfunctional esters, compounds having a skeleton of the general formula described above are preferable, and phthalic acid, maleic acid, and more preferably
An ester of a substituted malonic acid or the like and an alcohol having 2 or more carbon atoms is preferable, and a diester of phthalic acid and an alcohol having 2 or more carbon atoms is particularly preferable.

Other electron donors (D) which can be supported on the solid titanium catalyst component (B) include R ⁷ COO
R ⁸ (R ⁷ and R ⁸ are an optionally substituted hydrocarbyl group, at least one of which is a branched (including alicyclic) or ring-containing group) Monocarboxylic acid esters are exemplified. Specifically, R ⁷
And as R ⁸

[0034]

Embedded image

And the like. If one of R ^{7 and} R ⁸ is the above group, the other may be the above group, or may be another group such as a linear or cyclic group. Specifically, various monoesters such as dimethylacetic acid, trimethylacetic acid, α-methylbutyric acid, β-methylbutyric acid, methacrylic acid, and benzoylacetic acid, and various monocarboxylic acid esters of alcohols such as isopropanol, isobutyl alcohol and tert-butyl alcohol Can be exemplified.

As the electron donor, a carbonate ester can also be selected. Specifically, diethyl carbonate, ethylene carbonate, diisopropyl carbonate, phenylethyl carbonate, diphenyl carbonate and the like can be exemplified. When supporting these electron donors, it is not always necessary to use them as starting materials, and it is also possible to use compounds that can be changed to these during the preparation of the titanium catalyst component.

These electron donors (D) are used alone or in combination of two or more. Other electron donors (D) may coexist in the titanium catalyst component,
Since coexistence in an excessively large amount has an adverse effect, it is desirable to suppress the coexistence in a small amount. A titanium compound as described above,
When the magnesium compound and the electron donor are brought into contact, a carrier-supported titanium catalyst component (B) can be prepared using a particulate carrier. (Production of solid titanium catalyst component (B)) In the present invention,
The solid titanium catalyst component (B) can be produced by bringing a magnesium compound (or metallic magnesium) as described above into contact with a titanium compound and preferably an electron donor (D). In order to produce the solid titanium catalyst component (B), a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and an electron donor (D) can be employed. The above components may be brought into contact with each other in the presence of another reaction reagent such as silicon, phosphorus, and aluminum.

The method for producing the solid titanium catalyst component (B) will be described below with reference to several examples. (1) A method of reacting a magnesium compound or a complex compound comprising a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be performed in the presence of a grinding aid or the like. Further, when reacting as described above, the solid compound may be pulverized. (2) a liquid magnesium compound having no reducing property;
A method in which a liquid titanium compound is reacted in the presence of an electron donor to precipitate a solid titanium complex. (3) A method of further reacting the reaction product obtained in (2) with a titanium compound. (4) A method in which an electron donor and a titanium compound are further reacted with the reaction product obtained in (1) or (2). (5) A solid compound obtained by pulverizing a magnesium compound or a complex compound comprising a magnesium compound and an electron donor (D) in the presence of a titanium compound is converted into a halogen,
A method of treating with either a halogen compound or an aromatic hydrocarbon. In this method, a magnesium compound or a complex compound comprising a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound composed of a magnesium compound and an electron donor may be pulverized in the presence of a titanium compound, pretreated with a trialkylaluminum (A), and then treated with a halogen or the like. (6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon. (7) A method of contacting a reaction product of a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron donor and a titanium compound. (8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an electron donor (D), a titanium compound and / or a halogen-containing hydrocarbon.

Among the methods for preparing the solid titanium catalyst component (B) described in the above (1) to (8), a method using a liquid titanium halide at the time of preparing the catalyst, a method using a titanium compound, or a method using When using a compound, a method using a halogenated hydrocarbon is preferred. The amount of each component used in preparing the solid titanium catalyst component (B) as described above differs depending on the preparation method and cannot be specified unconditionally. For example, the amount of the electron donor (D) is about 1 mol per magnesium compound. In an amount of 0.01 to 5 moles, preferably 0.05 to 2 moles, the titanium compound is
It is used in an amount of ５００500 mol, preferably 0.05-300 mol.

The solid titanium catalyst component (B) thus obtained contains magnesium, titanium and halogen as essential components, and optionally contains an electron donor (D). In the solid titanium catalyst component (B), the halogen / titanium (atomic ratio) is preferably about 2 to 200,
More preferably, it is about 5 to 100, and the electron donor (D) / titanium (molar ratio) is preferably about 0.1 to 1
0, more preferably about 0.2 to about 6, and magnesium / titanium (atomic ratio) is preferably about 1 to 100,
More preferably, it is desirable to be about 2 to 50.

Such a solid titanium catalyst component (B) contains a magnesium halide having a small crystal size as compared with a commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g or more, preferably about 60 to 50 m ² / g. 10
00 m ² / g, more preferably about 100-800 m ² / g
It is. And since this solid titanium catalyst component (B) forms the catalyst component by integrating the above components,
The composition is not substantially changed by washing with hexane.

Such a solid titanium catalyst component (B) comprises:
Although it can be used alone, it can also be used after being diluted with an inorganic compound or an organic compound such as a silicon compound, an aluminum compound, or a polyolefin. In addition, when a diluent is used, even if it is smaller than the above-mentioned specific surface area, it shows high catalytic activity. For the method of preparing such a highly active titanium catalyst component, for example,
JP-A-50-108385, JP-A-50-126590, JP-A-51-202
No. 97, No. 51-28189, No. 51-64586, No. 51
-92885, 51-136625, 52-87489, 52-100596, 52-147688, and 52-104
No. 593, No. 53-2580, No. 53-40093, No. 53
No. -40094, No. 53-43094, No. 55-135102, No. 55-135103, No. 55-152710, No. 56-811
JP-A-56-11908, JP-A-56-18606, JP-A-58-8
No. 3006, No. 58-138705, No. 58-138706,
No. 58-138707, No. 58-138708, No. 58-138709
JP-A-58-138710, JP-A-58-138715, JP-A-60
No. -23404, No. 61-21109, No. 61-37802,
No. 61-37803, and the like. [Electron donor (C)] The electron donor (C) used in the present invention.
Is not particularly limited, and a known electron donor can be used. As such an electron donor (C),
For example, the same electron donor (D) as the electron donor (D) that can be contained as necessary in the solid titanium catalyst component (B) can be used.

These electron donors (C) are used alone or in combination of two or more. [Olefin polymerization catalyst] In the case of olefin polymerization,
An olefin polymerization composition comprising the trialkylaluminum compound (A) for olefin polymerization according to the present invention, the solid titanium catalyst component (B) containing magnesium, titanium and halogen as essential components, and the electron donor (C). A catalyst can be used.

The trialkylaluminum compound (A) is used as the titanium atom 1 in the solid titanium catalyst component (B).
Mole of trialkylaluminum compound (A)
Usually, about 10 to about 10 aluminum atoms are preferable.
It is desirable to use 500 mol, preferably 20 to 200 mol. In addition, the solid titanium catalyst component (B) is usually preferably about 0.001 to about 1.0 in terms of titanium atom per liter of polymerization volume.
Desirably, it is used in an amount of about 0.005 mmol, more preferably about 0.005 to 0.5 mmol.

The electron donor (C) is usually preferably about 0.001 to 10 mol, more preferably 0.01 to 2 mol, particularly preferably 0.01 to 2 mol per mol of aluminum atom in the trialkylaluminum compound (A). Is 0.05
It is desirable to use it in such an amount that it becomes 1 mol. [Olefin polymerization method] In the olefin polymerization method of the present invention, the solid titanium catalyst component (B) containing the trialkylaluminum compound (A) for olefin polymerization and magnesium, titanium and halogen as essential components as described above. And the above-mentioned electron donor (C), and the olefin polymerization catalyst can be polymerized by using the above amount.

As the polymerization method, a known method can be used and is not limited. Further, pre-polymerization can be performed before polymerization (main polymerization). The olefin that can be polymerized with the olefin polymerization catalyst according to the present invention is not particularly limited, and is used for polymerization of ethylene, propylene, butene, α-olefin, conjugated polyene, non-conjugated polyene, and the like, and copolymerization thereof. be able to.

The olefin can be polymerized in any of a liquid phase polymerization method such as suspension polymerization and solution polymerization or a gas phase polymerization method. When such polymerization is performed by a liquid phase polymerization method, as a polymerization medium, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclohexane Inert hydrocarbon solvents such as alicyclic hydrocarbons such as pentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and mixtures thereof can be used. Alternatively, propylene can be used as a solvent.

When such a polymerization is carried out by a suspension polymerization method, it is usually -50 to 100 ° C, preferably 0 to 90 ° C.
C. It is desirable to carry out the solution polymerization at a temperature of 0 to 250.degree. C., preferably 20 to 200.degree. When carrying out the gas phase polymerization method, the polymerization is usually carried out at 0 to 120 ° C., preferably 20 to 100 ° C.
Is desirable. The polymerization be carried out at a temperature of ℃ is usually normal pressure to 100 kg / cm ^2, preferably at a pressure of normal pressure to 50 kg / cm ^2.

The polymerization can be carried out by any of batch, semi-continuous and continuous methods. Further, the polymerization can be performed in two or more stages under different reaction conditions. The olefin molecular weight thus obtained can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and the polymerization pressure. The olefin polymer thus obtained is a homopolymer,
Any of a random copolymer and a block copolymer may be used.

In the present invention, the activity of the olefin polymerization catalyst is high, and the stereoregularity per unit amount of the solid titanium catalyst component;
Specifically, the yield of a polymer having a high isotactic index is high. Further, in the olefin polymer obtained by using the catalyst according to the present invention, the amorphous polymer component is extremely small, and thus the hydrocarbon-soluble component is small,
Films formed from this polymer have low surface tack.

In the present invention, the following physical properties were measured by the following methods. (1) Isotactic index (II) A boiling heptane-insoluble component of the obtained polymer was prepared as follows. That is, 3 g of the polymer sample, 2,6-di-tert-butyl-4- were placed in a 1-liter flask equipped with a stirrer.
Add 20 mg of methylphenol and 500 ml of n-decane, and add 1
Heat and dissolve on a 45 ° C. oil bath. After the polymer sample is dissolved, it is cooled to room temperature over about 8 hours, and then kept on a 23 ° C. water bath for 8 hours. The n-decane suspension containing the precipitated polymer (23 ° C. decane-insoluble component) was prepared using G-4 (or G
After filtration and separation through a glass filter of -2) and drying under reduced pressure, 1.5 g of the polymer was subjected to Soxhlet extraction using heptane for 6 hours or more to obtain a boiling heptane-insoluble component. (2) Molecular weight distribution (Mw / Mn) The molecular weight distribution was measured at 140 ° C. in an orthodichlorobenzene solvent using gel permeation chromatography (GPC).

[0052]

According to the present invention, the aluminum hydride produced in the preparation of the trialkylaluminum compound used as such a cocatalyst is reduced to a certain amount or less, so that the catalytic activity of the olefin polymerization catalyst is remarkably improved. In addition, the polyolefin obtained using this catalyst has an excellent isotactic index.

[0053]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0054]

Example 1 [Preparation of trialkylaluminum for olefin polymerization] 162 g of titanium-containing activated aluminum powder
(6 mol) (AL-TI-150 (trade name), Minarco Co., Ltd.
), 200 liters (8.9 moles) of hydrogen and 1142 g (10 moles) of triethylaluminum (TEAL (trade name), manufactured by Nippon Alkyli Aluminum Co., Ltd.) were placed in a high-pressure reaction vessel at 130 ° C. under a pressure of 15 MPa. The mixture was stirred for 5 hours to react.

A 1 L mixture of the obtained diethyl aluminum hydride (80 mol%), triethyl aluminum (13 mol%) and titanium-containing activated aluminum powder (6.7 mol%) was placed in a high-pressure vessel, and ethylene pressure was reduced to 4 MPa (gauge pressure) at 80 ° C. And reacted for 2 hours. From the reaction product, unreacted aluminum powder was removed by filtration, and the obtained triethylaluminum was hydrolyzed to examine the composition. The aluminum hydride content (AlH ₃
(Converted value) was 0.01%. [Preparation of Solid Titanium Catalyst Component] 4.28 kg of anhydrous magnesium chloride, 22.5 liters of decane and 21.1 liters of 2-ethylhexyl alcohol were heated and reacted at 140 ° C. for 5 hours to obtain a homogeneous solution. After that, 1 kg of phthalic anhydride was added to this solution,
The mixture was stirred and mixed for a period of time to dissolve phthalic anhydride in the homogeneous solution.

After cooling the thus obtained homogeneous solution to room temperature, titanium tetrachloride 12 kept at -15 ° C.
41.9 liters were dropped into 0 liters over 6.5 hours. After the dropwise addition, the temperature of the resulting solution was raised to 20 ° C. over 2 hours, and when the temperature reached 20 ° C., 2.4 kg of diheptyl phthalate was added. Subsequently, the temperature was raised to 92 ° C. over 1.2 hours, and the mixture was stirred at that temperature for 1 hour. Thereafter, the solid portion was recovered by hot filtration, and the solid portion was resuspended in 132 liters of titanium tetrachloride, and then heated to 110 ° C. When the temperature reached 110 ° C., 0.44 kg of diisobutyl phthalate was added, and the mixture was stirred at that temperature for 45 minutes. Thereafter, the solid portion was recovered again by hot filtration. This operation (suspension in titanium tetrachloride, raising the temperature, and addition of diisobutyl phthalate) was further repeated twice, and the substrate was washed with hexane until no titanium was detected in the cleaning solution.

The composition of the solid titanium catalyst component thus obtained was 3.4% by weight of titanium, 16% by weight of magnesium, 5% by weight of diheptyl phthalate, and 15% by weight of diisobutyl phthalate. The triethylaluminum, the solid titanium catalyst component and propylene obtained above were charged into an autoclave, and propylene was polymerized. As a result, polypropylene having high stereoregularity was obtained in high yield.

[0058]

Example 2 [Preparation of trialkylaluminum for olefin polymerization] 810 g of activated titanium powder containing titanium
(30 mol) (AL-TI-150), ethylene 2100 g (7
5 mol), 840 liters (37.5 mol) of hydrogen and 1500 g (13 mol) of triethylaluminum (TEA
L) into a high-pressure reaction vessel, and under a pressure of 9 MPa, 130
The mixture was stirred and reacted at a temperature of 8 ° C. for 8 hours.

A mixture 1 of 5 mol% of the obtained diethyl aluminum hydride, 90 mol% of triethyl aluminum and 5 mol% of titanium-containing activated aluminum powder
L was placed in a high-pressure vessel, stirred at 140 ° C. under an ethylene pressure of 1 MPa (gauge pressure), and reacted for 1 hour. From the reaction product was removed by filtration aluminum powder unreacted where triethylaluminum obtained was examined for its composition by hydrolysis, the content of aluminum hydride (AlH ₃ conversion value) is 0.005% there were.

The triethylaluminum obtained above,
The solid titanium catalyst component and propylene were charged into an autoclave, and propylene was polymerized, whereby a polypropylene having high stereoregularity was obtained in high yield.

[0061]

Example 3 [Preparation of trialkylaluminum for olefin polymerization] A mixture of 5 mol% of titanium-containing activated aluminum powder, 5 mol% of diethylaluminum hydride, and 90 mol% of triethylaluminum prepared in Example 2 was distilled. , Purified triethylaluminum was prepared. This purified triethylaluminum contained 3 mol% of diethylaluminum hydride. Two liters of this purified triethylaluminum was put into a high-pressure reactor, and stirred at 80 ° C. under an ethylene pressure of 0.5 MPa (gauge pressure), and reacted for 3 hours. When the obtained triethylaluminum was hydrolyzed and the composition was examined, the content of aluminum hydride (in terms of AlH ₃ ) was 0.005.
%Met.

The triethylaluminum obtained above,
The solid titanium catalyst component and propylene were charged into an autoclave, and propylene was polymerized, whereby a polypropylene having high stereoregularity was obtained in high yield.

[0063]

[Example 4] [Preparation of trialkylaluminum for olefin polymerization] 97.2 activated aluminum powder containing titanium
g (3.6 mol) (AL-TI-150), 454 g of propylene
(10.8 mol), 121 liters of hydrogen (5.4 mol)
And 203 g (1.3 mol) of tripropylaluminum (TNPA (trade name), manufactured by Nippon Alkyl Aluminum Co., Ltd.)
Was put into a high-pressure reaction vessel, and the mixture was stirred and reacted at a temperature of 120 ° C. for 15 hours under a pressure of 3 MPa.

A mixture of 80 mol% of the obtained dipropylaluminum hydride, 15 mol% of tripropylaluminum and 5 mol% of titanium-containing activated aluminum powder was placed in a high pressure vessel at a pressure of 4 MPa (gauge pressure) at 80 ° C. The mixture was stirred for 2 hours. From the reaction product, unreacted aluminum powder is removed by filtration,
When the composition was examined by hydrolyzing the obtained tripropylaluminum, the content of aluminum hydride (in terms of AlH ₃ ) was 0.01%.

The above-obtained tripropylaluminum, solid titanium catalyst component and propylene were charged into an autoclave, and propylene was polymerized to obtain a highly stereoregular polypropylene in high yield.

[0066]

Comparative Example 1 [Preparation of trialkylaluminum for olefin polymerization] 162 g of titanium-containing activated aluminum powder
(6 mol) (AL-TI-150), 200 liters of hydrogen (8.
9 mol) and 1142 g of triethylaluminum (1
0 mol) in a high-pressure reaction vessel, and under a pressure of 15 MPa,
The mixture was stirred and reacted at a temperature of 130 ° C. for 5 hours.

A 1 L mixture of 80 mol% of the obtained diethylaluminum hydride, 13 mol% of triethylaluminum and 6.7 mol% of titanium-containing activated aluminum powder was placed in a high-pressure vessel, and was heated at 80 ° C. under an ethylene pressure of 1 MPa (gauge pressure). The mixture was stirred for 2 hours. From the reaction product, unreacted aluminum powder was removed by filtration, and the obtained triethylaluminum was hydrolyzed to examine the composition. The aluminum hydride content (AlH ₃
(Converted value) was 0.3%.

Propylene was polymerized in the same manner as in Example 1 except that the above-obtained triethylaluminum was used. In each case, stereoregularity and catalytic activity were inferior to those in Example 1.

[0069]

Comparative Example 2 [Preparation of trialkylaluminum for olefin polymerization] 810 g of activated titanium powder containing titanium
(30 mol) (AL-TI-150), ethylene 2100 g (7
5 mol), 80 liters (37.5 mol) of hydrogen and 1500 g (13 mol) of triethylaluminum (TEAL)
Was put into a high-pressure reaction vessel, and the mixture was stirred and reacted at a temperature of 130 ° C. for 8 hours under a pressure of 9 MPa.

A mixture 1 of 5 mol% of the obtained diethyl aluminum hydride, 90 mol% of triethyl aluminum and 5 mol% of activated aluminum powder containing titanium.
L was placed in a high-pressure vessel, stirred at 130 ° C. under an ethylene pressure of 1 MPa (gauge pressure), and reacted for 0.5 hour. From the reaction product, unreacted aluminum powder was removed by filtration, and the obtained triethylaluminum was hydrolyzed to examine the composition. The aluminum hydride content (AlH ₃
(Converted value) was 0.5%.

Polymerization of propylene was carried out in the same manner as in Example 1 except that the above-obtained triethylaluminum was used. In each case, stereoregularity and catalytic activity were inferior to those in Example 1.

[0072]

Comparative Example 3 [Preparation of trialkylaluminum for olefin polymerization] 5 mol% of titanium-containing activated aluminum powder, 5 mol% of diethylaluminum hydride and 90 mol% of triethylaluminum prepared in Example 2
Was distilled to prepare purified triethylaluminum. This purified triethylaluminum contained 3 mol% of diethylaluminum hydride. 2 liters of this purified triethylaluminum is placed in a high-pressure reactor, and ethylene pressure is 0.2 MPa (gauge pressure).
The mixture was stirred at ℃ for 5 hours. When the obtained triethylaluminum was hydrolyzed and the composition was examined, the content of aluminum hydride (in terms of AlH ₃ ) was 1.0.
%Met.

The polymerization of propylene was carried out in the same manner as in Example 1 except that the triethylaluminum obtained above was used. In each case, stereoregularity and catalytic activity were inferior to those in Example 1.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Horita 1-5-5 Takasago, Takaishi-shi, Osaka Inside Alkyll Aluminum Co., Ltd. (72) Inventor Tadao Nishida 1-5-5 Takasago, Takaishi-shi, Osaka Japan Alkali Aluminum Co., Ltd. F-term (reference) 4J028 AA01A AB01A AC04A AC05A AC06A AC07A BA01A BA01B BB00A BB01B BC05A BC06A BC07A BC15B CA15A CA16A CB91C CB92C EB01 EB02 EB04 EB05 AC01 AC01 FA01 AC04 BA01B BB00A BB01B BC05A BC06A BC07A BC15B CA15A CA16A CB91C CB92C EB01 EB02 EB04 EB05 EB12 EB15 EC01 EC02 FA02 FA03 FA04 GA14 GB01

Claims (5)

[Claims] 1. The content of aluminum hydride contained in a trialkylaluminum compound (a value obtained by converting dialkylaluminum monohydride, alkylaluminum dihydride and / or aluminum trihydride into aluminum trihydride).
Is 0.1 to the trialkylaluminum compound.
A trialkylaluminum compound for olefin polymerization, which is at most 1% by weight. 2. The content of aluminum hydride contained in the (A) trialkylaluminum compound (a value obtained by converting dialkylaluminum monohydride, alkylaluminum dihydride and / or aluminum trihydride into aluminum trihydride) is the trialkylaluminum compound. A trialkylaluminum compound for olefin polymerization in an amount of 0.1% by weight or less based on the aluminum compound; (B) a solid titanium catalyst component containing magnesium, titanium and halogen as essential components; and (C) an electron donor. An olefin polymerization catalyst, comprising: 3. The solid titanium catalyst component comprises an electron donor (D) in addition to magnesium, titanium and halogen.
The olefin polymerization catalyst according to claim 2, comprising: 4. The content of the hydride contained in the (A) trialkylaluminum compound (the value obtained by converting dialkylaluminum monohydride, alkylaluminum dihydride and / or aluminum trihydride into aluminum trihydride) is the trialkylaluminum. 0.1% by weight or less of a trialkylaluminum compound for olefin polymerization with respect to the compound, (B) a solid titanium catalyst component containing magnesium, titanium and halogen as essential components, and (C)
An olefin polymerization method comprising polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst comprising an electron donor. 5. The method according to claim 1, wherein the solid titanium catalyst component comprises an electron donor (D) in addition to magnesium, titanium and halogen.
The olefin polymerization method according to claim 4, comprising: