JPH09124723A - Alpha-olefin polymerization catalyst and method for polymerizing alpha-olefin therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst capable of producing a highly stereoregular polymer excellent in moldability in a high yield and to provide a method for polymerizing an α-olefin therewith. SOLUTION: This catalyst comprises a solid catalyst component obtd. by bringing a solid component essentially comprising titanium, magnesium, and a halogen, a compd. selected from among an org. acid ester, an org. acid halide, and an ether compd., and a sulfonic ester represented by the formula: R<1> SO3 R<2> (wherein R<1> and R<2> are each a hydrocarbon group) into contact with each other, an organoaluminum compd., and a silicon compd. represented by the formula: R<3> R<4> 3-n Si(OR<5> )n (wherein R<3> and R<4> are each a hydrocarbon or an alkoxy group; R<5> is a hydrocarbon group; and (n) is 1-3). This polymerizing method uses the catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an α-olefin polymerization catalyst and an α-olefin polymerization method using the same. More specifically, the present invention is excellent in moldability and has extremely high stereoregularity by polymerizing an α-olefin using a catalyst obtained by combining a specific solid catalyst component and an organoaluminum compound component. The present invention relates to an olefin polymerization catalyst for obtaining a polymer in high yield and an α-olefin polymerization method using the same.

[0002]

2. Description of the Related Art In recent years, many proposals have been made for producing a highly stereoregular polymer of an α-olefin in a high yield by using a solid component containing titanium, magnesium and halogen as essential components (for example, JP-A-57-63
No. 310, No. 57-63311, No. 57-63312
Issue 58-138705, Issue 58-138706.
No. 58-138711). Among these, the polymerization catalyst obtained by using the solid component in combination with the organoaluminum compound and the silicon compound is highly practical. Further, a method of contacting an organic acid ester compound or an organic acid halide compound at the time of preparing the solid component, and a method of contacting a sulfonic acid ester compound at the time of preparing the solid component have been proposed.

However, the inventors of the present invention have found that even in this catalyst system, the stereoregularity of the polymer is not sufficient, and in general, the molding processability is poor due to the narrow molecular weight distribution. Improvement was desired.

[0004]

Therefore, there has been a demand for a catalyst for producing an α-olefin polymer having a higher stereoregularity and a broader molecular weight distribution, and a method for producing the catalyst.

[0005]

[Means for Solving the Problems]

<Summary> In order to solve the above-mentioned problems, the present invention has revealed that a specific organic sulfonic acid ester compound, an organic acid ester compound,
By combining a solid catalyst component prepared by subjecting both an organic acid halide compound or an ether compound to a contact treatment with an organoaluminum compound component and a silicon compound component, the molecular weight distribution is wide and α of extremely high stereoregularity is obtained. -Based on the discovery of the fact that olefin polymers can be provided in high yield.

That is, the catalyst for α-olefin polymerization according to the present invention is characterized by comprising the following components (A), (B) and (C) in combination. Component (A): Solid catalyst component obtained by contacting the following component (A1), component (A2) and component (A3) Component (A1): Solid component containing titanium, magnesium and halogen as essential components Component (A2) ): At least one compound selected from organic acid ester compounds, organic acid halide compounds and ether compounds Component (A3): Sulfonic acid ester compound represented by the following general formula [I] R ¹ SO ₃ R ² [I] (wherein, R ¹ and R ² is a hydrocarbon group.) component (B): an organoaluminum compound component component (C): a silicon compound represented by the following general formula [II] R ³ R ⁴ _{3- n} Si (OR ⁵ ) _n [II] (Here, R ³ and R ⁴ are the same or different hydrocarbon groups or alkoxy groups, R ⁵ is a hydrocarbon group, and n is 1 to ^3. ) The present invention Also relates to polymerization of α- olefins using the above catalyst. That is, the method for polymerizing an α-olefin according to the present invention is characterized in that an α-olefin is brought into contact with a catalyst formed by combining the components (A), (B) and (C) to polymerize the catalyst. It is a thing. <Effect> According to the present invention, it is possible to obtain an α-olefin polymer having a wide molecular weight distribution and extremely high stereoregularity in a high yield. Therefore, according to the present invention, it is possible to obtain an olefin polymer preferably used for applications such as automobile parts, home electric appliance parts, and packaging materials for which high rigidity is required.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an α-olefin polymer according to the present invention comprises contacting an α-olefin with a catalyst comprising a combination of specific components (A), (B) and (C). It is characterized by being polymerized. <Olefin Polymerization Catalyst> The catalyst used in the present invention is
It is a combination of specific components (A), (B) and (C). Here "combined"
This does not mean that the components are only those listed (ie, component (A), component (B), and component (C)), and other components within a range that does not impair the effects of the present invention. Does not exclude the coexistence of the following components. (1) Solid catalyst component The component (A) of the catalyst of the present invention includes a specific solid component (component (A1)), a specific organic acid ester compound, an organic acid halide compound, an ether compound (component (A2)) and a specific organic acid halide compound. It is a contact product of the sulfonic acid ester compound (component (A3)). The component (A) of the present invention does not exclude the coexistence of other purposeful components other than the above three essential components. Component (A1) The solid component used in the present invention is a solid component containing titanium, magnesium and halogen as essential components. Here, "containing as an essential component" means that besides the three components listed, it may contain other purposeful elements, and each of these elements is present as a purposeful arbitrary compound. And that these elements may be present as bonded to each other.

The solid component itself containing titanium, magnesium and halogen is known. For example, JP-A Nos. 53-45688, 54-3894, and 54-
31092, 54-39483, 54-945.
No. 91, No. 54-118484, No. 54-13158.
No. 9, No. 55-75411, No. 55-90510,
55-90511, 55-127405, 5
5-147507, 55-155003, 56
-18609, 56-70005, 56-72
001, 56-86905, 56-90807.
56-155206, 57-3803, 57-34103, 57-92007, 57-.
121003, 58-5309, 58-531
0, 58-5311, 58-8706, 5
8-27732, 58-32604, 58-3
2605, 58-67703, 58-1172.
06, 58-127708, 58-18370.
No. 8, No. 58-183709, No. 59-149905.
No. 59-149906, No. 63-108008, etc. are used.

As the magnesium compound used as the magnesium source in the present invention, magnesium dihalide, dialkoxy magnesium, alkoxy magnesium halide, magnesium oxyhalide, dialkyl magnesium, magnesium oxide, magnesium hydroxide, carboxylate of magnesium, etc. Is mentioned. Among these, Mg (OR ⁶ ) _2-m X _m such as magnesium dihalide and dialkoxymagnesium (here, R ⁶
Is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X represents halogen, and m is 0 ≦ m ≦ 2. )
A magnesium compound represented by

The titanium compound serving as the titanium source is represented by the general formula Ti (OR ⁷ ) _4-p X _p (wherein R ⁷ is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X represents halogen, and p is 0 ≦ p ≦ 4). For example, TiCl ₄ , T
iBr ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H
₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O-
_{iC 3 H 7) Cl 3,} Ti (O-nC 4 H 9) Cl 3,
_{Ti (O-nC 4 H 9} ) 2 Cl 2, Ti (OC 2 H 5)
_{Br 3, Ti (OC 2 H} 5) (O-nC 4 H 9) 2 C
_{l, Ti (O-nC 4} H 9) 3 Cl, Ti (OC
_{6 H 5) Cl 3, Ti} (O-iC 4 H 9) 2 Cl 2, T
_{i (O-nC 5 H 11} ) Cl 3, Ti (O-nC 6 H 13)
_{Cl 3, Ti (OC 2 H} 5) 4, Ti (O-nC
_{3 H 7) 4, Ti (} O-nC 4 H 9) 4, Ti (O-i
_{C 4 H 9) 4, Ti} (O-nC 6 H 13) 4, Ti (O-
nC ₈ H ₁₇ ) ₄ , Ti (OCH ₂ CH (C ₂ H ₅ ) C ₄
H ₉ ) _{4 and the} like.

Further, a molecular compound obtained by reacting TiX ' ₄ (where X'is a halogen) with an electron donor described later can also be used as a titanium source. Specific examples of such molecular compounds include TiCl ₄ .CH ₃ CO
C ₂ H ₅ , TiCl ₄ · CH ₃ CO ₂ C ₂ H ₅ , TiC
l ₄ C ₆ H ₅ NO ₂ , TiCl ₄ CH ₃ COCl,
TiCl ₄ · C ₆ H ₅ COCl, TiCl ₄ · C ₆ H ₅
CO ₂ C ₂ H ₅ , TiCl ₄ · ClCOC ₂ H ₅ , Ti
Cl ₄ · C ₄ H ₄ O and the like.

Further, TiCl ₃ (including those obtained by reducing TiCl ₄ with hydrogen, those obtained with aluminum metal, or those obtained with organometallic compounds), TiBr
_{3, Ti (OC 2 H 5} ) Cl 2, TiCl 2, the use of dicyclopentadienyl titanium dichloride, cyclopentadienyl titanium trichloride titanium compounds such as chloride are also possible. Among these titanium compounds, Ti
Cl ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₂ H ₅ ) C
l _{3 and the} like are preferable.

Halogen is usually supplied from the above-mentioned magnesium and / or titanium halogen compounds, but other halogen sources, for example aluminum halides such as AlCl ₃ or silicon halogens such as SiCl _4. Halides, phosphorus halides such as PCl ₃ , PCl ₅ , tungsten halides such as WCl ₆ , Mo
It can also be supplied from a known halogenating agent such as a halide of molybdenum such as Cl ₅ . The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

Furthermore, when producing this solid component,
It can also be prepared using an electron donor as an internal donor. Electron donors that can be used to produce this solid component include alcohols, phenols, aldehydes,
Oxygen-containing electron donors such as ketones and nitrogen-containing electron donors such as amines and nitriles can be used. Two or more of these electron donors can be used. Component (A2) In the present invention, at least one compound selected from organic acid ester compounds, organic acid halide compounds and ether compounds is used.

The organic acid ester compound and the organic acid halide compound that can be used in the present invention are preferably carboxylic acid ester compounds or carboxylic acid halide compounds, and specific examples are as follows. (A) Organic acid monoesters such as methyl formate, methyl acetate, ethyl acetate,
Vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl cellosolve, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Acid benzyl, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate,
Organic acid esters having 2 to 20 carbon atoms of (b) organic acid polyvalent ester such as methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, α-valerolactone, coumarin, and phthalide, for example, phthalic acid Diethyl, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, ethylene carbonate, norbornanedienyl-1,2-dimethylcarboxylate, cyclopropane-1,2-dicarboxylic acid Acid-n-hexyl,
1,1-cyclobutanedicarboxylate diethyl, etc.,
(C) Alkoxy ester compounds such as ethyl 2- (ethoxymethyl) -benzoate, ethyl 2- (t-butoxymethyl) -benzoate, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxypropionate. , Ethyl 3-ethoxy-2-s-butylpropionate, ethyl 3-ethoxy-2-t-butylpropionate, etc., and (di) keto ester compounds such as ethyl 2-benzoylbenzoate and 2- (4′-methyl). Benzoyl)
(V) Acid halides having 2 to 15 carbon atoms such as ethyl benzoate and ethyl 2-benzoyl-4,5-dimethylbenzoate, for example, acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, iso. Examples thereof include phthaloyl chloride. Preferred are benzoic acid ester compounds, phthalic acid diester compounds, acetic acid cellosolve ester compounds, and phthalic acid dihalide compounds.

The ether compound which can be used in the present invention is preferably a diether compound, specifically 2,2.
-Dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-
Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-t-butyl-2-methyl -1,3
-Dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2, 2-
Examples thereof include diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane and 2,2-diisobutyl-1,3-diethoxypropane. Component (A3) The sulfonic acid ester compound used in the present invention is represented by the general formula R ¹ SO ₃ R ² (wherein R ¹ and R ² are hydrocarbon groups). Specifically, R ¹
Is preferably an aromatic hydrocarbon group, a cyclic aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, and further has 6 to 6 carbon atoms.
An aromatic hydrocarbon group having 20 carbon atoms, a cyclic aliphatic hydrocarbon group having 5 to 15 carbon atoms or a branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. And a cyclic aliphatic hydrocarbon group having 5 to 10 carbon atoms or a branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, particularly preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. R ²
May be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, in which the carbon atom directly bonded to the oxygen atom (that is, the carbon atom at the α-position) is a secondary carbon or a tertiary carbon. A branched aliphatic hydrocarbon group (including an alicyclic hydrocarbon group) is preferable, and specifically, a branched aliphatic hydrocarbon group or carbon branched at the α-position carbon atom having 3 to 10 carbon atoms. A cycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, preferably a branched aliphatic hydrocarbon group having 3 to 8 carbon atoms and branched at the α-position carbon atom, or a cycloaliphatic hydrocarbon group having 5 to 10 carbon atoms Is.

Specific examples of the sulfonate compound that can be used in the present invention are as follows. Examples of the aromatic sulfonic acid ester include methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, hexyl benzene sulfonate, and benzene sulfonic acid -t-.
Butyl, phenyl benzene sulfonate, methyl p-toluene sulfonate, ethyl p-toluene sulfonate, p-
Butyl toluenesulfonate, hexyl p-toluenesulfonate, cyclohexyl p-toluenesulfonate, p-
Toluene sulfonate-t-butyl, p-toluene sulfonate phenyl, p-ethylbenzene sulfonate methyl,
Ethyl p-ethylbenzenesulfonate, butyl p-ethylbenzenesulfonate, hexyl p-ethylbenzenesulfonate, -t-butyl p-ethylbenzenesulfonate, phenyl p-ethylbenzenesulfonate, pt-
Methyl butylbenzenesulfonate, ethyl pt-butylbenzenesulfonate, butyl pt-butylbenzenesulfonate, hexyl pt-butylbenzenesulfonate, tert-butyl pt-butylbenzenesulfonate,
Phenyl p-t-butylbenzenesulfonate, methyl m-toluenesulfonate, ethyl m-toluenesulfonate, butyl m-toluenesulfonate, hexyl m-toluenesulfonate, t-butyl m-toluenesulfonate, m- Phenyl toluenesulfonate, methyl m-ethylbenzenesulfonate, ethyl m-ethylbenzenesulfonate, butyl m-ethylbenzenesulfonate, hexyl m-ethylbenzenesulfonate, t-butyl m-ethylbenzenesulfonate, phenyl m-ethylbenzenesulfonate, Methyl tert-butylbenzenesulfonate, ethyl mt-butylbenzenesulfonate, mt
-Butyl butyl benzene sulfonate, hexyl mt-butyl benzene sulfonate, tert-butyl m-t-butyl benzene sulfonate, phenyl m-t-butyl benzene sulfonate, methyl 1-naphthalene sulfonate, 1-
Examples thereof include ethyl naphthalenesulfonate, butyl 1-naphthalenesulfonate, hexyl 1-naphthalenesulfonate, -t-butyl 1-naphthalenesulfonate, and phenyl 1-naphthalenesulfonate. Examples of the aliphatic sulfonic acid ester include methyl cyclohexyl sulfonate, ethyl cyclohexyl sulfonate, butyl cyclohexyl sulfonate, hexyl cyclohexyl sulfonate, -t-butyl cyclohexyl sulfonate, phenyl cyclohexyl sulfonate, methyl cyclopentyl sulfonate,
Ethyl cyclopentyl sulfonate, butyl cyclopentyl sulfonate, hexyl cyclopentyl sulfonate, -t-butyl cyclopentyl sulfonate, phenyl cyclopentyl sulfonate, methyl isobutyl sulfonate, ethyl isobutyl sulfonate, butyl isobutyl sulfonate, hexyl isobutyl sulfonate, isobutyl sulfonate, isobutyl sulfone Cyclohexyl acid, t-butyl isobutyl sulfonate, phenyl isobutyl sulfonate, methyl t-butyl sulfonate, ethyl t-butyl sulfonate, butyl t-butyl sulfonate, hexyl t-butyl sulfonate, t
-Butyl sulfonate-t-butyl, phenyl t-butyl sulfonate, methyl t-amyl sulfonate, ethyl t-amyl sulfonate, butyl t-amyl sulfonate, t-
Hexyl amyl sulfonate, t-amyl sulfonic acid-t
-Butyl, phenyl t-amyl sulfonate and the like can be mentioned.

Among these, R ¹ is an aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ² is a branched aliphatic hydrocarbon group having 3 to 8 carbon atoms or carbon atoms branched at the α-position carbon atom. Those having a cycloaliphatic hydrocarbon group of several 5 to 10 are preferable.

Specific examples of preferred sulfonic acid ester compounds that can be used in the present invention are as follows.

As the ester of aromatic sulfonic acid,
(A) Alkyl aromatic sulfonates such as isopropyl benzene sulfonate, benzene sulfonic acid -sec-
Butyl, benzenesulfonic acid-tert-butyl, benzenesulfonic acid-tert-amyl, isopropyl p-toluenesulfonate, p-toluenesulfonic acid-sec
-Butyl, p-toluenesulfonic acid-tert-butyl, p-toluenesulfonic acid-tert-amyl, p-
Isopropyl ethylbenzenesulfonate, sec-butyl p-ethylbenzenesulfonate, tert-butyl p-ethylbenzenesulfonate, tert-amyl p-ethylbenzenesulfonate, isopropyl p-tert-butylbenzenesulfonate, p-tert-butyl Benzenesulfonic acid-sec-butyl, p-tert
-Butylbenzenesulfonic acid-tert-butyl, p-
tert-Butylbenzenesulfonic acid-tert-amyl, m-toluenesulfonic acid isopropyl, m-toluenesulfonic acid-sec-butyl, m-toluenesulfonic acid-tert-butyl, m-toluenesulfonic acid-te
rt-amyl, isopropyl m-ethylbenzenesulfonate, sec-butyl m-ethylbenzenesulfonate, tert-butyl m-ethylbenzenesulfonate, tert-amyl m-ethylbenzenesulfonate, isopropyl m-tert-butylbenzenesulfonate , M-tert-butylbenzenesulfonic acid-se
c-Butyl, m-tert-butylbenzenesulfonic acid-tert-butyl, m-tert-butylbenzenesulfonic acid-tert-amyl, 1-naphthalenesulfonic acid isopropyl, 1-naphthalenesulfonic acid-sec-
Butyl, 1-naphthalene sulfonate-tert-butyl, 1-naphthalene sulfonate-tert-amyl, etc., (b) aromatic cycloalkyl sulfonates, for example, cyclopentyl benzene sulfonate, cyclohexyl benzene sulfonate, norbornyl benzene sulfonate,
cyclopentyl p-toluenesulfonate, cyclohexyl p-toluenesulfonate, norbornyl p-toluenesulfonate, cyclopentyl p-ethylbenzenesulfonate, cyclohexyl p-ethylbenzenesulfonate,
Norbornyl p-ethylbenzene sulfonate, p-te
Cyclopentyl rt-butylbenzenesulfonate, p-
cyclohexyl tert-butylbenzenesulfonate,
Norbornyl p-tert-butylbenzenesulfonate, cyclopentyl m-toluenesulfonate, cyclohexyl m-toluenesulfonate, norbornyl m-toluenesulfonate, cyclopentyl m-ethylbenzenesulfonate, cyclohexyl m-ethylbenzenesulfonate, m-ethylbenzenesulfonate Norbornyl, m-
cyclopentyl tert-butylbenzenesulfonate,
Cyclohexyl m-tert-butylbenzenesulfonate, norbornyl m-tert-butylbenzenesulfonate, cyclopentyl 1-naphthalenesulfonate, 1-
Examples thereof include cyclohexyl naphthalene sulfonate and norbornyl 1-naphthalene sulfonate.

As the ester of aliphatic sulfonic acid,
(C) Aliphatic alkyl sulfonates such as isopropyl cyclohexyl sulfonate, cyclohexyl sulfonate-sec-butyl, cyclohexyl sulfonate-te
rt-butyl, cyclohexyl sulfonic acid-tert-
Amyl, isopropyl cyclopentyl sulfonate, sec-butyl cyclopentyl sulfonate, tert-butyl cyclopentyl sulfonate, tert-amyl cyclopentyl sulfonate, isopropyl isobutyl sulfonate, isobutyl sulfonate-sec-butyl, isobutyl sulfonate-tert- Butyl, isobutyl sulfonate-tert-amyl, tert-butyl sulfonate isopropyl, tert-butyl sulfonate-se
c-butyl, tert-butyl sulfonic acid-tert-
Butyl, tert-butyl sulfonate-tert-amyl, tert-amyl sulfonate isopropyl, ter
(d) Aliphatic sulfonate cycloalkyls such as t-amyl sulfonate-sec-butyl, tert-amyl sulfonate-tert-butyl, tert-amyl sulfonate-tert-amyl, for example, cyclopentyl cyclohexyl sulfonate, cyclohexyl sulfone Cyclohexyl acid, norbornyl cyclohexyl sulfonate, cyclopentyl cyclopentyl sulfonate, cyclohexyl cyclopentyl sulfonate, norbornyl cyclopentyl sulfonate, cyclopentyl isobutyl sulfonate, cyclohexyl isobutyl sulfonate, norbornyl isobutyl sulfonate, cyclopentyl tert-butyl sulfonate, tert-butyl sulfonate Cyclohexyl, tert-butyl sulfonate norbornyl, t
ert-cyclopentyl amyl sulfonate, tert-
Examples thereof include cyclohexyl amyl sulfonate and norbornyl tert-amyl sulfonate. Manufacture of Component (A) Although the contact conditions of each component constituting the above-mentioned component (A) need to be carried out in the absence of oxygen, they may be arbitrary as long as the effect of the present invention is recognized. Generally, the following conditions are preferable. The contact temperature is -50 to 200
The temperature is about 0 ° C, preferably 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring and pulverizing machine, and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, and polysiloxanes.

The amount ratio of the respective components used constituting the component (A) may be arbitrary as long as the effect of the present invention is recognized, but generally, the following range is preferable. The titanium compound may be used in a molar ratio of 0.0001 to 1000, preferably 0.01 to 10 with respect to the amount of the magnesium compound used. When a compound for that purpose is used as a halogen source, the amount of the compound used is 0.01 molar ratio with respect to the amount of the magnesium used, regardless of whether the titanium compound and / or the magnesium compound contains halogen. -10
The range of 00 is preferable, and the range of 0.1 to 100 is preferable. The amount of the organic acid ester compound, organic acid halide compound or ether compound of the component (A2) used is 0. 1 in terms of the molar ratio to the titanium component constituting the component (A1).
It is within the range of 001 to 1000, preferably 0.01 to 100 (when a plurality of compounds are used in combination, the total amount thereof). The amount of the sulfonic acid ester compound as the component (A3) used is 0.001 to 1000, preferably 0.01 to 100, in terms of molar ratio to the titanium component constituting the component (A1).
It is within the range of 0.

The component (A) includes the component (A1) and the component (A2).
) And component (A3), if necessary, using other components such as an electron donor, for example, by the following production method. (A) A method in which a magnesium halide is optionally contacted with an electron donor, a titanium-containing compound, and at least one compound selected from an organic acid ester compound, an organic acid halide compound or an ether compound and a sulfonic acid ester compound. (B) Alumina or magnesia is treated with a phosphorus halide compound, and magnesium halide, an electron donor, and at least one compound selected from an organic acid ester compound, an organic acid halide compound or an ether compound, a titanium halogen-containing compound and A method of contacting a sulfonate compound. (C) A reaction product obtained by contacting a titanium halogen compound and / or a halogen compound of silicon with a solid component obtained by contacting magnesium halide with titanium tetraalkoxide and a specific polymer silicon compound with an inert organic solvent. After washing, a method of contacting at least one compound selected from an organic acid ester compound, an organic acid halide compound or an ether compound with a sulfonic acid ester compound, or separately contacting each other.

As the polymer silicon compound, those represented by the following formula are suitable.

[0025]

Embedded image (Here, R ⁸ is a hydrocarbon group having about 1 to 10 carbon atoms, and q is the viscosity of the polymer silicon compound of 1 to 100.
The degree of polymerization is about centistokes. ) Specifically, methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane, phenylhydrogenpolysiloxane, cyclohexylhydrogenpolysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,5. 7,9-Pentamethylcyclopentasiloxane and the like are preferable. (D) A solid component prepared by dissolving a magnesium compound with titanium tetraalkoxide and / or an electron donor and precipitating with a halogenating agent or a titanium halogen compound is selected from an organic acid ester compound, an organic acid halide compound or an ether compound. The at least one compound titanium compound and the sulfonic acid ester compound are brought into contact with each other, or separately brought into contact with each other. (E) After reacting an organomagnesium compound such as a Grignard reagent with a halogenating agent, a reducing agent, etc., an electron donor is brought into contact therewith, and then an organic acid ester compound, an organic acid halide compound or an ether compound At least one compound selected from the group consisting of titanium compound and sulfonic acid ester compound is contacted with each other, or they are separately contacted with each other. (F) a halogenating agent and / or a titanium compound, and at least one compound selected from an organic acid ester compound, an organic acid halide compound or an ether compound and a sulfonic acid ester compound in an alkoxy magnesium compound in the presence of an electron donor or A method of contacting in the absence of each other or separately contacting each other.

Among these production methods, (a)
(C), (d) and (f) are preferred. Component (A)
Is an inert organic solvent such as an aliphatic or aromatic hydrocarbon solvent (eg, hexane, heptane, toluene, cyclohexane, etc.) or a halogenated hydrocarbon solvent (eg, n chloride chloride) during and / or at the end of its production. -Butyl, 1,2-dichloroethylene, carbon tetrachloride chlorobenzene, etc.).

Component (A) used in the present invention is a compound containing a carbon-carbon unsaturated bond, such as olefins,
It can also be used as it has undergone a prepolymerization step of contacting and polymerizing a diene compound, styrene and the like. Specific examples of the olefins used in performing the prepolymerization include, for example, those having about 2 to 20 carbon atoms,
Specifically, ethylene, propylene, 1-butene, 3-methylbutene-1, 1-pentene, 1-hexene, 4-methylpentene-1, 1-octene, 1-decene, 1-undecene, 1-eicosene, etc. Yes, specific examples of diene compounds include 1,3-butadiene, isoprene,
4-hexadiene, 1,5-hexadiene, 1,3-pentadiene, 1,4-pentadiene, 2,4-pentadiene, 2,6-octadiene, cis-2, trans
-4-hexadiene, trans-2, trans-4
-Hexadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,4-heptadiene, dicyclopentadiene,
1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclopentadiene, 1,3-cycloheptadiene, 4-methyl-1,4-hexadiene, 5-methyl-
1,4-hexadiene, 1,9-decadiene, 1,13
-Tetradecadiene, p-divinylbenzene, m-divinylbenzene, o-divinylbenzene, dicyclopentadiene and the like. In addition, as specific examples of styrenes,
Examples include styrene, α-methylstyrene, allylbenzene, and chlorostyrene.

A treatment for prepolymerizing these compounds by using the component (A) and the organoaluminum compound described later can be carried out.

The reaction conditions for the titanium component and the above compounds are:
As long as the effects of the present invention can be recognized, any one can be used, but generally the following range is preferable. The amount of the prepolymerized carbon-carbon unsaturated bond-containing compound is 0.001 to 100 grams, preferably 0.1% per gram of titanium solid component.
It is in the range of 1 to 50 grams, more preferably 0.5 to 10 grams. The reaction temperature during prepolymerization is -150 to 1
It is 50 ° C, preferably 0 to 100 ° C. Then, a "main polymerization", that is, a polymerization temperature lower than the polymerization temperature at the time of the polymerization of the α-olefin is preferable. The reaction is generally preferably carried out under stirring, at which time n-hexane, n
It is also possible for an inert solvent such as heptane to be present.

The solid catalyst component (A) thus obtained is in the state of being wet with a solvent or in the state of a slurry dispersed in the solvent.
-Although it can be used for olefin polymerization, it can also be dried and used as a powder. (2) Organoaluminum Compound Component Component (B) is an organoaluminum compound. Specific preferred examples of the organoaluminum compound used in the present invention include R ⁹ _3-r AlX _r or R ¹⁰ _3-s Al (O
R ¹¹ ) _s (wherein R ⁹ and R ¹⁰ are a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, R ¹¹ is a hydrocarbon group,
Preferably, it is a hydrocarbon group having 1 to 20 carbon atoms, X is halogen, and r and s are 0 ≦ r <3 and 0 <s, respectively.
<3. ). In particular,
(A) Trialkylaluminum, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. (b)
Alkyl aluminum halides such as diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, etc., (C) alkyl aluminum hydrides such as diethyl aluminum hydride, diisobutyl aluminum hydride, etc., (D) alkyl aluminum alkoxides, such as Diethyl aluminum ethoxide, diethyl aluminum phenoxide and the like can be mentioned.

In addition to these organoaluminum compounds (a) to (d), other organometallic compounds such as R ¹² _3-t Al (O
R ¹³ ) _t (wherein R ¹² and R ¹³ are hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different, and t is 0 <
t ≦ 3. )) Can also be used in combination. For example, combined use of triethylaluminum and diethylaluminum ethoxide, combined use of diethylaluminum monochloride and diethylaluminum ethoxide, combined use of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum, diethylaluminum ethoxide and diethylaluminum monochloride. And the like. The ratio of the organoaluminum compound and the titanium component in the solid catalyst is Al / Ti = 1 to 1000.
Mol / mol is common, preferably A1 / Ti =
It is used in a proportion of 10 to 500 mol / mol. (3) Silicon Compound The silicon compound used in the present invention has the general formula R ³ R ⁴
_3-n Si (OR ⁵ ) _n (wherein R ³ and R ⁴ are the same or different hydrocarbon groups or alkoxy groups,
R ⁵ is a hydrocarbon group, and n is 1 ≦ n ≦ 3. ). The silicon compound may be a mixture of plural kinds of silicon compounds of the formula. Where R
³ is preferably a branched hydrocarbon group or a cycloaliphatic hydrocarbon group. When R ³ is a branched hydrocarbon group, it is preferably branched from a carbon atom adjacent to a silicon atom.
In this case, the branching group is preferably an alkyl group, a cycloalkyl group, or an aryl group (for example, a phenyl group or a methyl-substituted phenyl group). More preferred R
³ is a carbon atom adjacent to a silicon atom, that is, an α-position carbon atom is a secondary or tertiary carbon atom. In particular, there are 3 carbon atoms bonded to the silicon atom.
Grades are preferred. When R ³ is a branched hydrocarbon group, the number of carbon atoms is usually 3 to 20, preferably 4 to 10.
When R ³ is a cycloaliphatic hydrocarbon group, the carbon number is usually 4 to 20, preferably 5 to 10. R ⁴ is R
^A hydrocarbon group or an alkoxy group which is the same as or different from ³ is preferable, and a hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. R ⁵ has 1 carbon atom
-20, preferably 1-10, hydrocarbon groups. Further, it is preferable that n is 2 ≦ n ≦ 3.

Specific examples of the silicon compound that can be used in the present invention are as follows. (CH ₃ ) ₃ CSi (CH ₃ )
(OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ )
_{2) (OCH 3) 2,} (CH 3) 3 CSi (CH 3)
(OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (C ₂ H ₅ )
_{(OCH 3) 2, (CH} 3) 3 CSi (n-C 3 H 7)
_{(OCH 3) 2, (CH} 3) 3 CSi (n-C 6 H 13)
(OCH ₃ ) ₂ , (C ₂ H ₅ ) ₃ CSi (CH ₃ ) (O
_{CH 3) 2, (CH 3} ) (C 2 H 5) CHSi (C
_{H 3) (OCH 3) 2} , ((CH 3) 2 CHCH 2) 2
_{Si (OCH 3) 2, (} C 2 H 5) (CH 3) 2 CSi
_{(CH 3) (OCH 3)} 2, (C 2 H 5) (CH 3) 2
_{CSi (CH 3) (OC 2} H 5) 2, (CH 3) 3 CS
_{i (OCH 3) 3, (} CH 3) 3 CSi (OC 2 H 5)
_{3, (CH 3) (C} 2 H 5) CHSi (OCH 3) 3,
_{(CH 3) 2 CH (CH} 3) 2 CSi (CH 3) (OC
H ₃ ) ₂ , ((CH ₃ ) ₃ C) ₂ Si (OCH ₃ ) ₂ ,
_{(C 2 H 5) (CH} 3) 2 CSi (OCH 3) 3, (C
₂ H ₅ ) (CH ₃ ) ₂ CSi (OC ₂ H ₅ ) ₃ , (CH
₃ ) ₃ CSi (OC (CH ₃ ) ₃ ) (OCH ₃ ) ₂ ,
_{((CH 3) 2 CH)} 2 Si (OCH 3) 2, ((CH
₃ ) ₂ CH) ₂ Si (OC ₂ H ₅ ) ₂ , (C ₅ H ₉ ) ₂
Si (OCH ₃ ) ₂ , (C ₅ H ₉ ) ₂ Si (OC
_{2 H 5) 2, (C} 5 H 9) (CH 3) Si (OCH 3)
_{2, (C 5 H 9)} ((CH 3) 2 CHCH 2) Si (O
_{CH 3) 2, (C 6} H 11) Si (CH 3) (OCH 3)
_{2, (C 6 H 11)} 2 Si (OCH 3) 2, (C 6 H 11)
_{((CH 3) 2 CHCH 2} ) Si (OCH 3) 2,
_{((CH 3) 2 CHCH 2} ) ((C 2 H 5) (CH 3)
CH) Si (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CHC
_{H 2) ((CH 3)} 2 CH) Si (OC 5 H 11) 2, H
C (CH ₃ ) ₂ C (CH ₃ ) ₂ Si (CH ₃ ) (OCH
₃ ) ₂ , HC (CH ₃ ) ₂ C (CH ₃ ) ₂ Si (C
_{H 3) (OC 2 H 5} ) 2, HC (CH 3) 2 C (C
H ₃ ) ₂ Si (OCH ₃ ) ₃ , HC (CH ₃ ) ₂ C (C
_{H 3) 2 Si (OC 2} H 5) 3,

[0033]

Embedded image (CH ₃ ) ₃ CSi (OCH (CH ₃ ) ₂ ) (OC
_{H 3) 2, (CH 3} ) 3 CSi (OC (CH 3) 3)
(OCH ₃ ) _{2 and the} like can be mentioned.

The amount of the silicon compound used may be in any range as long as the effects of the present invention are observed, but generally, the molar ratio is 0.01 to 10 relative to the organoaluminum compound (component B) used. , Preferably 0.05 to 1.

Other electron donors may be added in addition to the silicon compound, and as the electron donors, alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids are used. Examples thereof include oxygen-containing electron donors such as compounds, ethers, acid amides and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines and nitriles. <Polymerization of α-Olefin> The polymerization of α-olefin of the present invention is applied to slurry polymerization using a hydrocarbon solvent, liquid phase solventless polymerization or gas phase polymerization using substantially no solvent. As a polymerization solvent in the case of slurry polymerization, a hydrocarbon solvent such as pentane, hexane, heptane or cyclohexane is used. The polymerization method employed may be any method such as continuous polymerization, batch polymerization or multi-stage polymerization. The polymerization temperature is usually about 30 to 200 ° C., preferably 50 to 150 ° C., and hydrogen can be used as a molecular weight regulator at that time.

The α-olefin polymerized by the catalyst system of the present invention has the general formula R ¹⁴ --CHCH ₂ (wherein R ¹⁴ is a hydrocarbon group having 1 to 20 carbon atoms and has a branched group). May be used)). Specifically, there are α-olefins such as propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1. In addition to homopolymerization of these α-olefins, copolymerization with a monomer copolymerizable with the α-olefin (for example, ethylene, α-olefin, dienes, styrenes, etc.) can be performed. These copolymerizable monomers can be used up to 15% by weight in random copolymerization and up to 50% by weight in block copolymerization.

[0037]

【Example】

Example 1 [Production of component (A)] In a flask sufficiently purged with nitrogen,
200 ml of dehydrated and deoxygenated n-heptane were introduced, followed by 0.4 mol of MgCl ₂ , Ti (O-n
0.8 mol of C ₄ H ₉ ) ₄ was introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.

Then, in a flask that had been sufficiently replaced with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced, and the solid component synthesized as above was added in an amount of 0.1 mg in terms of Mg atoms.
24 moles were introduced. Next, 0.4 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane. Next, 0.024 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, and the mixture was introduced into the flask at 70 ° C. for 30 minutes.
The reaction was performed at 0 ° C. for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane. Then p-to 25 ml of n-heptane
Mix 0.18 mol of ethyl toluenesulfonate to give 7
The mixture was introduced into the flask at 0 ° C for 30 minutes, and reacted at 90 ° C for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane. Then, 10 ml of SiCl ₄ was introduced and the mixture was added at 80 ° C.
Allowed to react for hours. After completion of the reaction, it was thoroughly washed with n-heptane to obtain a solid catalyst component of component (A) mainly containing magnesium chloride. The titanium content of this product is 1.2% by weight.
Met. [Polymerization of Propylene] 500 g of sufficiently dehydrated and deoxygenated n-heptane was placed in a stainless steel autoclave having an internal volume of 1.5 liter equipped with a stirring and temperature control device.
100 ml of triethylaluminum as component (B), (C ₆ H ₁₁ ) S as component (C)
i (CH ₃ ) (OCH ₃ ) ₂ 33.0 mg and component (A) produced above (15 mg), hydrogen (60 ml) were introduced, the temperature was raised, and the polymerization pressure was 5 kg / cm ² G. Temperature = 75 ° C., polymerization time = 2
Propylene was polymerized under the condition of time. After completion of the polymerization, the obtained polymer slurry was separated by filtration, and the polymer was dried. As a result, 90.5 grams of polymer was obtained. From the filtrate, 0.6 gram of polymer was obtained. Further, the obtained polymer had MFR = 20 (g /
10 minutes), the polymer density was 0.9083 (g / cc), and the polymer bulk density was 0.47 (g / cc). Moreover, when the Q value (Mw / Mn) was examined by GPC, it was Q = 4.8. Example-2 In the production of the component (A) of Example-1, the component (A3)
Except that ethyl benzenesulfonate was used in place of ethyl p-toluenesulfonate, the polymerization was carried out in the same manner as in the component (C) (C ₆ H ₁₁ ) Si (CH ₃ ).
Instead of (OCH ₃ ) ₂ , (C ₅ H ₉ ) ₂ Si (OCH
₃ ) Exactly the same except that 40.0 mg of ₂ was used. As a result, 95.3 grams of polymer was obtained. From the filtrate, 0.5 gram of polymer was obtained. The obtained polymer had MFR = 19 (g / 10
Min), polymer density = 0.090 (g / cc), and polymer bulk density = 0.49 (g / cc).
Moreover, when the Q value (Mw / Mn) was examined by GPC, it was Q = 4.9. Example-3 [Production of Component (A)] In a flask thoroughly replaced with nitrogen,
100 ml of dehydrated and deoxygenated toluene was introduced, and then 10 g of Mg (OEt) ₂ was introduced to form a suspension. Then, 20 ml of TiCl ₄ was introduced and the temperature was raised to 90 ° C. to di-n-butyl phthalate 2.
Introduce 5 ml and further raise the temperature to 110 ° C. for 3
Allowed to react for hours. After completion of the reaction, it was washed with toluene. Then, 20 ml of TiCl ₄ , 2.4 g of ethyl p-toluenesulfonate and 100 ml of toluene were introduced and reacted at 110 ° C. for 2 hours. After completion of the reaction, it was thoroughly washed with n-heptane to obtain a solid catalyst component of component (A). The titanium content of this product is 2.6% by weight.
Met. [Polymerization of propylene] Polymerization was carried out under the same polymerization conditions as in Example-1. As a result, 90.0 grams of polymer was obtained. From the filtrate, 0.5 gram of polymer was obtained. The obtained polymer had MFR = 22 (g / 10
Min), the polymer density was 0.9088 (g / cc), and the polymer bulk density was 0.49 (g / cc).
Moreover, when the Q value (Mw / Mn) was examined by GPC, it was Q = 4.8. Comparative Example-1 In the production of the component (A) of Example-1, the component (A3)
Polymerization was carried out in exactly the same manner, except that the p-toluenesulfonate of p. As a result, 114.5 grams of polymer was obtained. From the filtrate, 1.0 gram of polymer was obtained. The obtained polymer had MFR = 21 (g / 10 min), polymer density = 0.060 (g / cc), and polymer bulk density = 0.45 (g / cc). Moreover, when the Q value (Mw / Mn) was examined by GPC, it was Q = 4.4. Comparative Example-2 [Production of Component (A)]
200 ml of dehydrated and deoxygenated n-heptane were introduced, followed by 0.4 mol of MgCl ₂ , Ti (O-n
0.8 mol of C ₄ H ₉ ) ₄ was introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.

Then, in a flask in which nitrogen was sufficiently replaced,
50 ml of n-heptane purified in the same manner as above was introduced, and the solid component synthesized as above was added in an amount of 0.1 mg in terms of Mg atoms.
24 moles were introduced. Then, 25 ml of n-heptane was mixed with 0.4 mol of SiCl ₄ and 0.18 mol of ethyl p-toluenesulfonate, and the mixture was introduced into the flask at 30 ° C for 30 minutes and reacted at 70 ° C for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane. Then TiCl ₄ 30
After introducing milliliter, the mixture was reacted at 90 ° C. for 3 hours. After the reaction was completed, the supernatant was removed and TiC was again treated under the same conditions.
Contact treatment with l ₄ was performed. After completion of the reaction, it was thoroughly washed with n-heptane to obtain a solid catalyst component of component (A). The titanium content of this product was 4.5% by weight. [Polymerization of propylene] Polymerization was carried out under the same polymerization conditions as in Example-1. As a result, 91.0 grams of polymer was obtained. The filtrate yielded 1.2 grams of polymer. The obtained polymer had MFR = 24 (g / 10
Min), the polymer density was 0.9062 (g / cc), and the polymer bulk density was 0.44 (g / cc).
Moreover, when the Q value (Mw / Mn) was examined by GPC, it was Q = 4.5.

[0040]

[Table 1] Example 4 After thoroughly replacing a stirring autoclave with an internal volume of 200 liters with propylene, 45 liters of purified n-heptane were introduced, and 10.5 g of triethylaluminum, (C ₆ H ₁₁ ) Si (CH ₃ ) ( OCH ₃ ) ₂ 3.
5 grams and solid catalyst component prepared in Example-1 6.
5 grams were introduced under a propylene atmosphere while maintaining 70 ° C. The first-stage polymerization was started by raising the temperature of the autoclave to 75 ° C. and then introducing propylene at a feed rate of 9.0 kg / hour while maintaining the hydrogen concentration at 7.0% by volume. After 220 minutes, the introduction of propylene was stopped. The pressure in the autoclave at this time is 6.0.
kg / cm ² G. Further, the polymerization was continued at 75 ° C. for 90 minutes. After that, 0.2 kg of vapor phase propylene
/ Cm ² G. Next, after lowering the temperature of the autoclave to 65 ° C., the second-stage polymerization was conducted with propylene 1.1.
A feed rate of 3 kilograms / hour and 2.63 kilograms / hour of ethylene was introduced for 79 minutes, and then the polymerization was continued for 30 minutes. The obtained slurry was filtered and dried to obtain 32.7 kg of a powdery block copolymer.
The block copolymer obtained had MFR = 24 (g / 10
Min), flexural modulus = 14000 (kg / cm ² ), Izod impact strength (23 ° C.) = 7.2 (kg · cm / cm)
² ). Comparative Example-3 The same operation as in Example-4 was performed except that 6.5 g of the solid catalyst component prepared in Comparative Example-1 was used in preparing the block copolymer. As a result, 32.8 kg of a powdery block copolymer was obtained. The obtained block copolymer had MFR = 21 (g / 10 min), flexural modulus = 13100 (kg / cm ² ), Izod impact strength (23 ° C.) = 7.1 (kg · cm / cm ² ). Met. Example-5 [Production of component (A)] In the production of the component (A) of Example-1, except that isopropyl p-toluenesulfonate was used in place of ethyl p-toluenesulfonate.
The component (A) was produced in the same manner as in Example-1. The titanium content of the obtained component (A) was 1.2% by weight. [Polymerization of propylene] Polymerization of propylene was carried out in the same manner as the polymerization of propylene of Example-1 except that the component (A) obtained above was used as the component (A). as a result,
91.0 grams of polymer were obtained. From the filtrate,
0.7 gram of polymer was obtained. The obtained polymer had MFR = 21 (g / 10 minutes) and polymer density =
0.9086 (g / cc), polymer bulk density =
It was 0.48 (g / cc). In addition, Q by GPC
When the value (Mw / Mn) was examined, Q = 4.9. Example-6 In the production of the component (A) of Example-5, the component (A3)
Except that sec-butylbenzenesulfonate was used in place of isopropyl p-toluenesulfonate, the polymerization was carried out in the same manner as in (C ₆ H ₁₁ ) of the component (C).
Instead of Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₅ H ₉ )
_The procedure was exactly the same except that 40.0 mg of ₂ Si (OCH ₃ ) ₂ was used. As a result, 98.6 g of polymer was obtained. 0.4 g of polymer was obtained from the filtrate. Further, the obtained polymer has an MFR =
20 (g / 10 minutes), polymer density = 0.9092 (g
/ Cc) and polymer bulk density = 0.49 (g / c)
c). In addition, Q value by GPC (Mw / Mn)
Was examined and it was Q = 4.9. Example-7 [Production of component (A)] In the production of the component (A) of Example-3, p-toluenesulfonate-sec-butyl was used in place of ethyl p-toluenesulfonate. The component (A) was produced in the same manner as in Example-3. The titanium content of the obtained component (A) was 2.6% by weight. [Polymerization of Propylene] Polymerization was carried out under the same polymerization conditions as in Example-3. As a result, 91.3 grams of polymer was obtained. From the filtrate, 0.6 gram of polymer was obtained. The obtained polymer had MFR = 21 (g / 10
Min), the polymer density was 0.9091 (g / cc), and the polymer bulk density was 0.49 (g / cc).
Moreover, when the Q value (Mw / Mn) was examined by GPC, it was Q = 4.8. Example-8 A pre-stage polymerization and a post-stage polymerization were carried out in the same manner as in Example-4 except that the same component (A) as used in Example-5 was used as a solid catalyst component. Filtering the resulting slurry,
It was dried to obtain 32.9 kg of a powdery block copolymer. The block copolymer obtained has MFR = 25.
(G / 10 minutes), flexural modulus = 14300 (kg / cm
² ), Izod impact strength (23 ° C) = 7.3 (kg ・
cm / cm ² ). Example-9 In the production of the component (A) of Example-1, the component (A2)
Polymerization was performed in exactly the same manner except that ethyl cellosolve acetate was used instead of phthaloyl chloride. As a result, 89.8 g of polymer was obtained. From the filtrate, 0.8 gram of polymer was obtained. The obtained polymer had MFR = 22 (g / 10
Min), polymer density = 0.079 (g / cc), and polymer bulk density = 0.46 (g / cc).
Moreover, when the Q value (Mw / Mn) was examined by GPC, it was Q = 4.7. Also, the bending elastic modulus = 1430
It was 0 (kg / cm ² ). Example-10 In the production of the component (A) of Example-1, the component (A2)
Except that 2,2-diisopropyl-1,3-dimethoxypropane was used in place of the phthalic acid chloride in Example 1, and the polymerization was also performed in exactly the same manner. As a result, 9
2.0 grams of polymer were obtained. From the filtrate,
0.4 gram of polymer was obtained. The obtained polymer had MFR = 20 (g / 10 minutes) and polymer density =
0.9080 (g / cc), polymer bulk density =
It was 0.48 (g / cc). In addition, Q by GPC
When the value (Mw / Mn) was examined, it was Q = 4.6. Further, the flexural modulus was 14400 (kg / cm ² ). Example-11 In the production of the component (A) of Example-3, the component (A2)
2-t-butyl-2 instead of di-n-butyl phthalate
Polymerization was performed in exactly the same manner except that -methyl-1,3-dimethoxypropane was used. As a result, 92.2 g of polymer was obtained. 0.4 g of polymer was obtained from the filtrate. The obtained polymer had MFR = 18 (g / 10 minutes), polymer density = 0.9085 (g / cc), and polymer bulk density = 0.48 (g / cc). Moreover, when the Q value (Mw / Mn) was examined by GPC, it was Q = 4.7. The flexural modulus was 14900 (kg / cm ² ). [Practical Physical Property Measuring Method] The practical physical property measurements carried out in Example-4, Example-8 and Comparative Example-3 were carried out as follows. The following additives were added to the powdery block copolymers obtained in Example-4, Example-8 and Comparative Example-3, and the mixture was pelletized by an extruder under the same conditions. A millimeter sheet was prepared and the physical properties were evaluated.

Additives 2,6-tert-butylphenol 0.10% by weight RA1010 (manufactured by Ciba Geigy) 0.05% by weight Calcium stearate 0.10% by weight Physical property evaluation Various physical properties were measured by the following methods.

(A) Flexural modulus: ASTM-D790 (b) Izod impact strength (23 ° C.): ASTM-D2
56 (with notch)

[0043]

According to the present invention, an α-olefin polymer having a wide molecular weight distribution and an extremely high stereoregularity can be obtained in a high yield, and therefore an automobile having high rigidity is required. It can be preferably used for parts, home electric appliances, packaging materials and the like, as described above in the section "Outline of the Invention".

[Brief description of the drawings]

FIG. 1 is an explanatory diagram for helping understanding of the technical content of the present invention regarding a Ziegler catalyst.

Claims (11)

[Claims] 1. A catalyst for α-olefin polymerization, which comprises a combination of the following components (A), (B) and (C). Component (A): Solid catalyst component obtained by contacting the following component (A1), component (A2) and component (A3) Component (A1): Solid component containing titanium, magnesium and halogen as essential components Component (A2) ): At least one compound selected from organic acid ester compounds, organic acid halide compounds and ether compounds Component (A3): Sulfonic acid ester compound represented by the following general formula [I] R ¹ SO ₃ R ² [I] (wherein, R ¹ and R ² is a hydrocarbon group.) component (B): an organoaluminum compound component component (C): a silicon compound represented by the following general formula [II] R ³ R ⁴ _{3- n} Si (OR ⁵ ) _n [II] (Here, R ³ and R ⁴ are the same or different hydrocarbon groups or alkoxy groups, R ⁵ is a hydrocarbon group, and n is 1 to ^3. ) 2. The organic acid ester compound of component (A2) is
It is a carboxylic acid ester, It is characterized by the above-mentioned.
The catalyst for α-olefin polymerization described in 1. 3. The organic acid ester compound of component (A2) is
The catalyst for α-olefin polymerization according to claim 1, which is at least one compound selected from the group consisting of a benzoic acid ester, a phthalic acid diester compound and an acetic acid cellosolve ester. 4. An organic acid halide compound of component (A2),
A carboxylic acid halide, characterized in that
The catalyst for α-olefin polymerization described in 1. 5. The organic acid halide compound of component (A2) is
A phthalic acid dihalide, characterized in that
The catalyst for α-olefin polymerization described in 1. 6. The catalyst for α-olefin polymerization according to claim 1, wherein the ether compound as the component (A2) is a diether. 7. A sulfonic acid ester compound as component (A3), wherein R ¹ is an aromatic hydrocarbon group, a cycloaliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, and R ² is an aromatic hydrocarbon group. Or it is an aliphatic hydrocarbon group, The catalyst for alpha-olefin polymerization of Claim 1 characterized by the above-mentioned. 8. The α- according to claim 1, wherein R ² of the sulfonic acid ester compound as the component (A3) is a branched aliphatic hydrocarbon group or a cycloaliphatic hydrocarbon group. Olefin polymerization catalyst. 9. A sulfonic acid ester compound as component (A3), wherein R ² is a branched aliphatic hydrocarbon group or a cycloaliphatic hydrocarbon group, and R ¹ is an aromatic hydrocarbon group. The catalyst for α-olefin polymerization according to claim 1, 7 or 8. 10. R ² of the sulfonic acid ester compound of component (A3) has a carbon atom directly bonded to an oxygen atom of 2
It is a branched aliphatic hydrocarbon group or a cycloaliphatic hydrocarbon group which is a primary or tertiary carbon, characterized by the above-mentioned.
9. The catalyst for α-olefin polymerization according to any one of 9. 11. An α-olefin polymerization method, which comprises contacting an α-olefin with the α-olefin polymerization catalyst according to any one of claims 1 to 10 for polymerization.