JP2004124090A - POLYMERIZATION CATALYST FOR alpha-OLEFIN AND PROCESS FOR PRODUCTION OF alpha-OLEFIN POLYMER THEREWITH - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst with high catalytic activity which enables production of an α-olefin polymer improved in stereoregularity by decreasing amorphous component and to provide a method for production of the α-olefin polymer. <P>SOLUTION: The catalyst for α-olefin polymerization is obtained by combining (A) a solid catalyst component comprising magnesium, titanium, and halogen as the essential components and containing at need a silicon compound, an organoaluminum compound and/or an electron donor, (B) an organoaluminum compound, (C) a compound having a C(=O)N linkage such as amide or urea, etc., and if necessary, (D) a silicon compound or a diether compound, and a process of polymerizing α-olefins by using the catalyst. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to an α-olefin polymerization catalyst and a method for producing an α-olefin polymer using the same. More specifically, the present invention relates to an α-olefin polymerization catalyst comprising a combination of a solid catalyst component, an organoaluminum compound, and an organic compound containing a specific oxygen atom and a nitrogen atom. The present invention relates to a method for producing an α-olefin polymer, wherein a highly crystalline α-olefin polymer having an extremely small amount of an amorphous component can be obtained in a high yield by carrying out the polymerization.

Polyolefins represented by polyethylene, polypropylene and the like are one of the most important and highly practical plastics, and are currently widely used in automobile parts, home electric appliances and the like.
To produce polyolefins by polymerization, the polymerization activity of general olefins is extremely low, but the polymerization activity of olefins is increased by a Ziegler-based catalyst using a transition metal compound and organoaluminum, and industrial production is realized. Development and improvement of catalyst technology such as improvement of physical properties of polymers by molecular weight distribution and improvement of stereoregularity of α-olefin have been continued.

Specifically, for example, a number of techniques have been disclosed for producing a highly stereoregular polymer of an α-olefin polymer in high yield using a solid catalyst component containing titanium, magnesium and halogen as essential components. (For example, see Patent Documents 1 to 3). Among them, as seen in Patent Document 3, a polymerization catalyst comprising a combination of the above-mentioned solid catalyst component, an organoaluminum compound and an electron donor component has good catalytic activity and stereoregularity and is practically useful. It is expensive. Recently, it has been proposed to add a new organosilicon compound to the catalyst component to further improve polymerization activity and stereoregularity, or to broaden the molecular weight distribution (for example, see Patent Documents 4 and 5). There have been many proposals for improvements.

However, the present inventors know that the stereoregularity of the α-olefin polymer produced even in such a catalyst system is still not sufficient, and particularly, a recent high crystalline α-olefin polymer is required. In such fields, further improvements to the reduction of amorphous components are desired.

JP-A-57-63310 (claims, upper right column on page 3) JP-A-57-63311 (Claims, upper left column on page 3) JP-A-58-138706 (Claims, upper left column on page 1) JP-A-7-145204 (abstract) JP-A-9-241318 (abstract)

The present invention provides a catalyst capable of producing an α-olefin polymer having improved stereoregularity by further reducing an amorphous component in the state of the prior art, and a method for producing such an α-olefin polymer. It is an object of the invention to realize a method.

The present inventors have conducted intensive studies on various catalyst components in order to solve the above-mentioned problems, and as a result, if an oxygen atom-containing organic compound component is newly used in combination, the amorphous component has a very small amount of highly crystalline α. -It has been found that an olefin polymer can be obtained in a high yield, and a patent application has been filed (Japanese Patent Application No. 2001-68169; Japanese Patent Application Laid-Open No. 2002-265517; Japanese Patent Application No. 2001-68093; Japanese Patent Application Laid-Open No. 2002-2002). 265518). The present inventors have further been concerned with solving the above-mentioned problems, and in order to obtain a highly crystalline α-olefin polymer having an extremely small amount of an amorphous component in a high yield, coordination with a catalytic active site and selective From the viewpoint of low poisoning, we conducted comprehensive thoughts to search for new catalyst components, and repeated experimental studies. As a result, organoaluminum compounds and specific C (= O) N bond-containing compounds were used as solid catalyst components. It has been found that a high-crystalline α-olefin polymer having an extremely small amount of an amorphous component can be obtained in a high yield by combining them, and the present invention has been achieved.

A newly created invention characterized by employing a new specific compound as a catalyst component of a Ziegler-based catalyst basically comprises the following invention units [1] to [11].
[1] α- formed by combining component (A) a solid catalyst component containing magnesium, titanium, and halogen as essential components, component (B) an organoaluminum compound, and component (C) a C (＝ O) N bond-containing compound. Olefin polymerization catalyst.

[2] The component (C) wherein the compound containing a C (＝ O) N bond is selected from the compounds represented by the following general formula [1] or [2], Olefin polymerization catalyst. (Where R ^{1 to} R ⁷ are an aliphatic hydrocarbon group having one or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a hetero atom-containing hydrocarbon group,
Any of R ^{1 to} R ³ and any of R ^{4 to} R ⁷ may form a cyclic structure. )

　　　

　　　

[3] The α-olefin polymerization catalyst according to the above [1] or [2], further comprising a combination of a component (D) a silicon compound or a compound having at least two ether bonds.

[4] The α-olefin polymerization catalyst according to any of [1] to [3] above, wherein the component (A) is brought into contact with the following component (A1) and component (A2).
Component (A1): a solid component containing titanium, magnesium, and halogen as essential components;
Component (A2): a silicon compound represented by the following formula,
R ⁸ R ⁹ _3-m Si (OR ¹⁰ ) _m
(Here, R ⁸ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a hetero atom-containing hydrocarbon group, and R ⁹ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a hetero atom-containing group. A hydrocarbon group, halogen or hydrogen, R ¹⁰ is a hydrocarbon group, and m represents 1 ≦ m ≦ 3.)

[5] The α-olefin polymerization catalyst according to the above [4], wherein the component (A) is further contacted with the following component (A3).
Component (A3): Organoaluminum compound

[6] The α-olefin polymerization catalyst according to any one of the above [1] to [3], wherein the component (A) further contains a component (E) an electron donor.

[7] The α-olefin polymerization catalyst according to the above [4] or [5], wherein the component (A1) further contains a component (E) an electron donor.

[8] The α-olefin polymerization catalyst according to any one of the above [3] to [7], wherein the component (D) silicon compound is a silicon compound represented by the following formula:
R ⁸ R ⁹ _3-m Si (OR ¹⁰ ) _m
(Here, R ⁸ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a hetero atom-containing hydrocarbon group, and R ⁹ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a hetero atom-containing group. A hydrocarbon group, halogen or hydrogen, and R ¹⁰ are a hydrocarbon group, and m represents 1 ≦ m ≦ 3.)

[9] The α-olefin polymerization catalyst according to any one of the above [3] to [7], wherein the compound having at least two ether bonds is an aliphatic diether or an aromatic diether.

[10] The above-mentioned [6] to [[, wherein the component (E) electron donor is a phthalic acid diester compound, a cellosolve acetate compound, a phthalic acid dihalide compound, a succinic acid diester compound, and an aliphatic or aromatic diether compound. 9].

[11] A method for producing an α-olefin polymer, comprising homopolymerizing or copolymerizing an α-olefin using the α-olefin polymerization catalyst according to any one of the above [1] to [10].

The α-olefin polymerization catalyst of the present invention has a high catalytic activity and is excellent in yield during polymerization, and the α-olefin polymer polymerized by the α-olefin polymerization catalyst of the present invention has an amorphous component. It has excellent features with very little stereoregularity, high density, high rigidity and heat resistance, and excellent mechanical properties.
In addition, the α-olefin polymer can be suitably used for applications such as automobile parts, home electric parts, and packaging materials that require high rigidity and high heat resistance.

The invention described generally in paragraphs 0008 to 0019 is described in more detail below.
1. Catalyst for α-Olefin Polymerization The catalyst used in the present invention is a combination of the component (A), the component (B) and the specific component (C). Here, “combined” does not mean that the components are only those listed (ie, component (A), component (B), and component (C)), and that the present invention Other components are allowed to coexist within a range not to impair the effect.

(1) Solid catalyst component (component (A))
The catalyst of the present invention comprises an α-combination of (A) a solid catalyst component containing magnesium, titanium, and halogen as essential components, (B) an organoaluminum compound, and (C) a C (＝ O) N-containing compound. It is an olefin polymerization catalyst. Also preferably, the component (A) may contain the component (E) an electron donor.
Preferably, a contact product of a specific solid component (component (A1)) and a specific silicon compound (component (A2)) is used as component (A). More preferably, as the component (A), a contact product of a specific solid component (component (A1)), a specific silicon compound (component (A2)) and a specific organoaluminum compound (component (A3)) is used. Is done. Preferably, the component (A1) may contain the component (E) an electron donor. (The component (E) electron donor optionally used for component (A) and the component (E) electron donor optionally used for component (A1) may be selected from the same group.) The component (A) of the present invention allows the coexistence of other components for the purpose of the present invention other than the above three components.

1) Component (A1)
The solid component used in the present invention is a solid component for stereoregular polymerization of α-olefin, which contains titanium, magnesium and halogen as essential components. Here, "contained as an essential component" means that other than the three components listed, other elements in accordance with the object of the present invention may be included, and each of these elements is in accordance with the object of the present invention. It indicates that it may be present as an arbitrary compound, and that these elements may be present as being bonded to each other.
The solid components themselves containing titanium, magnesium and halogen are known.

As the magnesium compound serving as a magnesium source used in the present invention, magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, alkylmagnesium halide, allyloxymagnesium, allyloxymagnesium halide, metallic magnesium, Examples include magnesium oxide, magnesium hydroxide, and magnesium carboxylate.
Among these, Mg (OR ¹¹ ) _2-n X _n such as magnesium dihalide, dialkoxymagnesium, and alkoxymagnesium halide (where R ¹¹ is a hydrocarbon group, preferably about 1 to 10 carbon atoms, X represents a halogen, and n is 0 ≦ n ≦ 2), and a magnesium compound represented by the following formula is preferable, and magnesium dihalide is more preferable.

The titanium compound serving as a titanium source includes a general formula Ti (OR ¹² ) _4-p X _p (where R ¹² is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, and X represents a halogen. And p is 0 ≦ p ≦ 4). Among them, a tetravalent titanium compound is preferable, and a tetravalent titanium compound containing halogen is more preferable.
Specific _{examples, TiCl 4, TiBr 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 Cl, Ti} (O-nC 4 H 9) 3 Cl, Ti (OC 6 H 5) Cl 3, Ti (O-iC 4 H 9) 2 Cl 2, Ti (OC 5 H 11) Cl _{3, Ti (OC 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-iC 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 an electron donor described later with TiX ′ ₄ (where X ′ represents a halogen) can also be used as a titanium source. Specific examples of such molecular _{compounds, TiCl 4 · CH 3 COC 2} H 5, TiCl 4 · CH 3 CO 2 C 2 H 5, TiCl 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, TiCl 4 · C 4 H 4 O and the like.
Also, TiCl ₃ (including TiCl ₄ reduced with hydrogen, reduced with aluminum metal, or reduced with an organometallic compound), TiBr ₃ , Ti (OC ₂ H ₅ ) Cl ₂ , TiCl ₂ , It is also possible to use titanium compounds such as dicyclopentadienyltitanium dichloride and cyclopentadienyltitanium trichloride.
Among these titanium compounds, TiCl ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₂ H ₅ ) Cl _{3 and the} like are preferable, and TiCl ₄ and Ti (OC ₄ H ₉ ) ₄ are more preferable.

The halogen is usually supplied from the above-mentioned halides of magnesium and / or titanium, but other halogen sources, for example aluminum such as AlCl ₃ , AlBr ₃ , AlI ₃ , EtAlCl ₂ , Et ₂ AlCl. Halides, boron halides such as BCl ₃ , BBr ₃ , and BI ₃ ; silicon halides such as SiCl ₄ and MeSiCl ₃ ; phosphorus halides such as PCl ₃ and PCl ₅ ; and tungsten halides such as WCl ₆ , MoCl _{5 and the} like, and a known halogenating agent such as a halide of molybdenum. The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

Furthermore, when producing the component (A) solid component, the component (E) electron donor can be used as an optional component as an internal donor. When the component (A) is brought into contact with the component (A2) or the component (A2) and the component (A3), the component (E) electron donor is preferably contained in the component (A1).
Components (E) electron donors (internal donors) that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, and acids. Examples include oxygen-containing electron donors such as amides and acid anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, and sulfur-containing electron donors such as sulfonic acid esters. .

More specifically, (a) methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropylbenzyl alcohol, ethylene glycol, propylene glycol, 1,3- C1-C18 alcohols such as propanediol.

(B) Phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol, naphthol and 1,1'-bi-2-naphthol.

(C) Ketones having 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and acetylacetone.

(D) Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde.

(E) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, butyl cellosolve acetate, 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, phenyl benzoate, butyl cellosolve , Methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, etc. Acid monoester, or diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, diethyl succinate, 2,3-diethyl-dibutyl succinate, 2,3-diisopropyl-dibutyl succinate, dibutyl tartrate, maleic acid Dibutyl acid, diethyl 1,2-cyclohexanecarboxylate, ethylene carbonate, norbornanedienyl-1,2-dimethylcarboxylate, cyclopropane-1,2-dicarboxylic acid-n-hexyl, diethyl 1,1-cyclobutanedicarboxylate and the like Organic acid esters having 2 to 20 carbon atoms of the organic acid polyhydric esters described above.

(F) Inorganic acid esters such as silicate esters such as ethyl silicate and butyl silicate.

(2) Acid halides having 2 to 15 carbon atoms such as (g) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride and phthaloyl isochloride.

(H) Methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, 2,2′-dimethoxy-1,1′-binaphthalene, 1,3-dimethoxypropane, 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-Dicyclopentyl-1,3-dimethoxypropane, 2 2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 1,3-diethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 1,3- Carbon such as dipropoxypropane, 1,3-dibutoxypropane, 2,2-diisopropyl-1,3-diethoxypropane, 1,2,3-trimethoxypropane, 1,1,1-trimethoxymethyl-ethane Ethers of numbers 2 to 20;

リ (ii) Acid amides such as acetic amide, benzoic amide and toluic acid amide.

ア ミ ン (nu) Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylethylenediamine.

(ル) Nitriles such as acetonitrile, benzonitrile and tolunitrile.

(ヲ) Ethyl 2- (ethoxymethyl) -benzoate, ethyl 2- (t-butoxymethyl) -benzoate, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxypropionate, 3-ethoxy-2 Alkoxy ester compounds such as ethyl-s-butylpropionate and ethyl 3-ethoxy-2-t-butylpropionate;

(E) Ketoester compounds such as ethyl 2-benzoylbenzoate, ethyl 2- (4'-methylbenzoyl) benzoate and ethyl 2-benzoyl-4,5-dimethylbenzoate.

(F) Sulfonic acids such as methyl benzenesulfonate, ethyl benzenesulfonate, ethyl p-toluenesulfonate, isopropyl p-toluenesulfonate, n-butyl p-toluenesulfonate, and s-butyl p-toluenesulfonate Esters and the like can be mentioned.

二 Two or more of these electron donors can be used. Among these, preferred are organic acid ester compounds, acid halide compounds and ether compounds, and particularly preferred are phthalic acid diester compounds, acetic acid cellosolve ester compounds, phthalic acid dihalide compounds, succinic acid diester compounds and aliphatic or aromatic compounds. Is a diether compound.

2) Component (A2)
The silicon compound component used as a preferred embodiment in the present invention is represented by the following formula.
R ⁸ R ⁹ _3-m Si (OR ¹⁰ ) _m
(Here, R ⁸ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a hetero atom-containing hydrocarbon group, and R ⁹ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a hetero atom-containing group. A hydrocarbon group, halogen or hydrogen, and R ¹⁰ is a hydrocarbon group, and m represents 1 ≦ m ≦ 3.)

When R ⁸ is an aliphatic hydrocarbon group, it is preferably a branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, i-propyl group, i-butyl group, t-butyl group, i-hexyl group. And a texyl group, among which a t-butyl group is more preferred. Further, when R ⁸ is a cyclic aliphatic hydrocarbon group, the number of carbon atoms is usually 4 to 20, preferably 5 to 10, and preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like. Of these, a cyclopentyl group and a cyclohexyl group are more preferred. The hetero atoms that R ⁸ can contain are nitrogen, oxygen, silicon, phosphorus, and sulfur, with nitrogen and oxygen being more preferred.

R ⁹ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, a heteroatom-containing hydrocarbon group, halogen or hydrogen. More specifically, it is a halogen group such as hydrogen, chlorine, bromine, iodine and the like, and usually a hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group. Group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, i-hexyl group, cyclopentyl group, cyclohexyl group, etc., and among them, methyl group, ethyl group, n group -Propyl, i-propyl, t-butyl, n-hexyl, cyclopentyl, and cyclohexyl groups are more preferred for increasing stereoregularity.

R ¹⁰ is a hydrocarbon group, and usually has 1 to 20, preferably 1 to 10, more preferably 1 to 5, carbon atoms, and includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n- Preferable examples include a butyl group, an i-butyl group and a t-butyl group. Among them, a methyl group and an ethyl group are more preferable.

Specific examples of the silicon compound component 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) (OCH 3) 2, (CH 3) (C 2 H 5) CHSi (CH 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 CSi (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 ) (OCH 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 (OCH 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 CHCH 2) ((CH 3) 2 CH) Si (OC 5 H 11) 2, HC ( _{CH 3) 2 C (CH 3} ) 2 Si (CH 3) (OCH 3) 2, HC (CH 3) 2 C (CH 3) 2 Si (CH 3) (OC 2 H 5) 2, HC (CH 3 ) ₂ C (CH ₃ ) ₂ Si (OCH ₃ ) ₃ , HC (CH ₃ ) ₂ C (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₃ , (CH ₃ ) ₃ CSiH (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSiCl (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSiF (OCH ₃ ) ₂ ,

(CH ₃ ) ₃ CSi (OCH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (OC (CH ₃ ) ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (N (C _{2 H 5) 2) (OCH} 3) 2, (CH 3) 3 CSi (NC 4 H 8) (OCH 3) 2, (CH 3) 3 CSi (NC 5 H 10) (OCH 3) 2, (CH ₃ ) ₃ CSi (NC ₉ H ₁₆ ) (OCH ₃ ) ₂ , ((CH ₃ ) ₂ HCO) ₂ Si (OCH ₃ ) ₂ , ((CH ₃ ) ₃ CO) ₂ Si (OCH ₃ ) ₂ , (C _{6 H 11 O) 2 Si (} OCH 3) 2, (4-CH 3 -C 6 H 11 O) 2 Si (OCH 3) 2, (4-C 2 H 5 -C 6 H 11 O) 2 Si ( _{OCH 3) 2, (4-} C 4 H 9 -C 6 H 11 O) 2 Si (OCH 3) 2, (C 10 H 17 O) 2 Si (OCH 3) 2, ((C 2 H 5) 2 N) ₂ Si (OCH ₃ ) ₂ , (C _{4 H 8) 2 Si (OCH 3} ) 2, can be mentioned _{(C 5 H 10 N) 2} Si (OCH 3) 2, (C 9 H 16 N) 2 Si (OCH 3) 2 and the like.

Of these, (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 5 H 9) 2 Si (OCH 3) 2, (C 5 H 9) 2 Si (OC 2 H 5) 2, (C ₆ H ₁₁ ) Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) ₂ Si (OCH ₃ ) _{2 and the} like.
Two or more of these silicon compounds can be used.

3) Component (A3)
The organoaluminum compound (component (A3)) preferably used in the present invention is used in contact with a solid component. Here, “contacting” does not mean that the number of times of contact is limited to one time, but that the organic aluminum compound (component (A3)) is repeatedly contacted within a range that does not impair the effects of the present invention. Tolerate.
Specific examples of the organic aluminum compound used in the present invention (component (A3)) is, R ¹³ AlR ¹⁴ R ¹⁵ and / or _{^{R 16 2-n R 17 AlX}} n ( ^{wherein, R 13, R 14, R} 15 , R ¹⁶ and R ¹⁷ are each independently a hydrocarbon group having 1 to 20 carbon atoms, preferably about 1 to 10 carbon atoms, X is hydrogen or halogen, and n is 0 <n <2. ).

Specifically, (a) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, diisopropylmethylaluminum, diisopropylethylaluminum, isopropyldimethylaluminum, isopropyldiethylaluminum, tri-n-butylaluminum, triisobutyl Aluminum, diisobutylmethylaluminum, diisobutylethylaluminum, diisobutylpropylaluminum, isobutyldimethylaluminum, isobutyldiethylaluminum, isobutyldipropylaluminum, tri-s-butylaluminum, di-s-butylmethylaluminum, di-s-butylethylaluminum, Di-s-butylpropylaluminum, s-butyldi Butyl aluminum, s-butyl diethyl aluminum, s-butyl dipropyl aluminum, tri-t-butyl aluminum, di-t-butyl methyl aluminum, di-t-butyl ethyl aluminum, di-t-butyl propyl aluminum, t-butyl Trialkylaluminum such as dimethylaluminum, t-butyldiethylaluminum, t-butyldipropylaluminum,

(B) Dimethyl aluminum monochloride, diethyl aluminum monochloride, dipropyl aluminum monochloride, diisopropyl aluminum monochloride, dibutyl aluminum monochloride, diisobutyl aluminum monochloride, di-s-butyl aluminum monochloride, di-t-butyl aluminum monochloride Alkyl aluminum halides such as amide, dimethylaluminum monobromide, diethylaluminum monobromide, dipropylaluminum monobromide, diisopropylaluminum monobromide, dibutylaluminum monobromide, di-s-butylaluminum monobromide and di-t-butylaluminum monobromide , Diethyl aluminum hydride, diisobutyl Hydride, alkyl aluminum hydride such as di -n- octyl aluminum hydride.
Two or more of these organoaluminum compounds can be used.

Of these, preferred are trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-s-butylaluminum, tri-t-butylaluminum, or diethylaluminum monochloride, diisopropylaluminum monochloride, dibutylaluminum monochloride. Ride, diisobutylaluminum monochloride, di-s-butylaluminum monochloride, di-t-butylaluminum monochloride, diethylaluminum hydride, and diisobutylaluminum hydride.

4) Other Optional Components Furthermore, in the production of the component (A) of the present invention, as described above, optional components may be contained in addition to the above-mentioned components. Examples include the following compounds.
The (a) vinylsilane compound vinylsilane compound is replaced with a monosilane (SiH ₄₎ at least one hydrogen atom is vinyl group in (CH ₂ = CH-), and the remaining number of hydrogen atoms, halogen ( (Preferably Cl), an alkyl group (preferably a hydrocarbon group having 1 to 12 carbon atoms), an aryl group (preferably a phenyl group), an alkoxy group (preferably an alkoxy group having 1 to 12 carbon atoms), and the like. 3 shows the structure.

More _{specifically, CH 2 = CH-SiH 3} , CH 2 = CH-SiH 2 (CH 3), CH 2 = CH-SiH (CH 3) 2, CH 2 = CH-Si (CH 3) 3, _{CH 2 = CH-SiCl 3,} CH 2 = CH-SiCl 2 (CH 3), CH 2 = CH-SiCl (CH 3) 2, CH 2 = CH-SiH (Cl) (CH 3), CH 2 = CH _{-Si (C 2 H 5) 3} , CH 2 = CH-SiCl (C 2 H 5) 2, CH 2 = CH-SiCl 2 (C 2 H 5), CH 2 = CH-Si (CH 3) 2 ( _{C 2 H 5), CH 2} = CH-Si (CH 3) (C 2 H 5) 2, CH 2 = CH-Si (n-C 4 H 9) 3, CH 2 = CH-Si (C 6 H _{5) 3, CH 2 = CH} -Si (CH 3) (C 6 H 5) 2, CH 2 = CH-Si (CH 3) 2 (C 6 H 5), CH 2 = CH-Si (CH 3) _{2 C 6 H 4 CH 3),} (CH 2 = CH) (CH 3) 2 Si-O-Si (CH 3) 2 (CH = CH 2), (CH 2 = CH) 2 SiH 2, (CH 2 = CH) ₂ SiCl ₂ , (CH ₂ ＣＨCH) ₂ Si (CH ₃ ) ₂ , (CH ₂ ＣＨCH) ₂ Si (C ₆ H ₅ ) _{2 and the} like can be exemplified.

(B) Organometallic compounds of metals of Groups I to III of the periodic table It is also possible to use organometallic compounds of metals of Groups I to III of the periodic table (short-period type). The organometallic compounds of Group I to Group III metals used in the present invention have at least one organic group-metal bond. In this case, the organic group is typically a hydrocarbyl group having about 1 to 20 carbon atoms, preferably about 1 to 6 carbon atoms. The remaining valences (if any) of the metal of the organometallic compound in which at least one of the valences is filled with an organic group are a hydrogen atom, a halogen atom, a hydrocarbyloxy group (a hydrocarbyl group has 1 to 1 carbon atoms). about 20, preferably (specifically, -O-Al (CH ₃ in the case of methyl alumoxane) the metal through the 1-6 degree), or oxygen atom -) is satisfied otherwise.

Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium, and t-butyllithium; (b) butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium, and butylmagnesium. There are organomagnesium compounds such as chloride and t-butylmagnesium bromide, and (c) organozinc compounds such as diethylzinc and dibutylzinc.

The above optional components (a) and (b) can be used alone or in combination of two or more. At this time, a known halogenating agent such as a halogen compound of titanium such as TiCl ₄ , a halide of tungsten such as WCl _6, or a halide of molybdenum such as MoCl ₅ may be used. When these optional components are used, the effect of the present invention is further increased.

5) Production of Component (A) The component (A) is obtained by bringing the components constituting the component (A) into contact with each other or, if necessary, the above-mentioned optional components in a stepwise or temporary manner, and intermediate and / or intermediate the components. Finally, it can be produced by washing with an organic solvent such as a hydrocarbon solvent or a halogenated hydrocarbon solvent.
In this case, a solid product (A1) containing titanium, magnesium and halogen as essential components is first produced, and the solid product (A2) of the above general formula and the (A3) organoaluminum are simultaneously or sequentially contacted. The component (A) can be produced at once by the presence of the (A2) silicon compound component in the process of producing a solid product containing titanium, magnesium and halogen as essential components. It is also possible to use a method (a one-step method). The preferred scheme is the former.

The contact condition of each component constituting the component (A) needs to be carried out in the absence of oxygen, but may be any condition as long as the effects of the present invention can be recognized. The following conditions are preferred. The contact temperature is about −50 to 200 ° 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 / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Inert diluents used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes and the like.

量 The amount ratio of each component constituting the component (A) can be arbitrary as long as the effect of the present invention is recognized, but generally, the following range is preferable. The amount of the titanium compound to be used is preferably in the range of 0.0001 to 1000, and more preferably in the range of 0.01 to 10 in molar ratio with respect to the amount of the magnesium compound to be used. When a compound for such a purpose is used as a halogen source, the amount of the compound used is 0.01 mol in terms of the amount of magnesium used, regardless of whether the titanium compound and / or the magnesium compound contains halogen or not. It is good to be in the range of -1000, preferably in the range of 0.1-100. The amount of the silicon compound component (A2) used is 0.01 to 1000, preferably 0.1 to 100 in terms of the atomic ratio of silicon to the titanium component (silicon / titanium) constituting component (A1). is there. The amount of the organoaluminum used as the component (A3) is generally from 0.1 to 100 mol / mol in terms of the atomic ratio of aluminum to the titanium component (aluminum / titanium) constituting the component (A1). ５０50 mol / mol.

When the vinylsilane compound is used as an optional component, the amount thereof is preferably in the range of 0.001 to 1000, and more preferably 0.01 to 100, in terms of molar ratio to the titanium component constituting component (A1). Is within. When an organometallic compound is used as an optional component, its amount is preferably in the range of 0.001 to 100, more preferably 0.01 to 10 in terms of molar ratio with respect to the amount of the magnesium compound. Is within. When the electron donor as an optional component is used, the amount of the electron donor is preferably in the range of 0.001 to 10 in terms of molar ratio with respect to the amount of the magnesium compound, and more preferably in the range of 0.01 to 5. Is within.

The component (A) is produced using other components such as an electron donor as necessary, for example, by the following production method.
(A) A method of contacting a magnesium halide with an electron donor, a titanium-containing compound and / or a silicon compound component as required.
(B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and a magnesium halide, an electron donor, a titanium halide-containing compound and / or a silicon compound component are brought into contact therewith.
(C) a reaction product obtained by contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound component with an inert organic solvent; After washing, a method of contacting a silicon compound component or separately contacting each other.

ポ リ マ ー As the polymer silicon compound, a compound represented by the following formula is suitable.

　　　

　　　

(Here, R ¹⁸ is a hydrocarbon group having about 1 to 10 carbon atoms, and q indicates a degree of polymerization such that the viscosity of the polymer silicon compound becomes about 1 to 100 centistokes.) Methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl Cyclopentasiloxane and the like are preferred.

(D) dissolving a magnesium compound with a titanium tetraalkoxide and / or an electron donor, and bringing a titanium compound and / or a silicon compound component into contact with a solid component precipitated with a halogenating agent or a titanium halide compound, or How to contact separately.

(E) After reacting an organomagnesium compound such as a Grignard reagent with a halogenating agent, a reducing agent or the like, contacting it with an electron donor, if necessary, and then contacting a titanium compound and / or a silicon compound component. Or, a method of contacting each separately.

(F) A method in which a halogenating agent and / or a titanium compound is brought into contact with an alkoxymagnesium compound in the presence or absence of an electron donor, and then a titanium compound and / or a silicon compound component is brought into contact with the alkoxy magnesium compound, or separately. .

の Among these manufacturing methods, (a), (c), (d) and (f) are preferable. Component (A) may be used during and / or at the end of its preparation, in an inert organic solvent, for example an aliphatic or aromatic hydrocarbon solvent (for example hexane, heptane, toluene, cyclohexane, etc.), or a halogenated hydrocarbon solvent (for example, , N-butyl chloride, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, etc.).

成分 As the component (A) used in the present invention, a compound having undergone a pre-polymerization step of contacting and polymerizing a vinyl group-containing compound such as an olefin, a diene compound, or styrene can also be used. Specific examples of the olefins used when 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, and the like. Specific examples of the diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, 2,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 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, 2,6-octadiene, Clopentadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 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 and the like. Specific examples of styrenes include styrene, α-methylstyrene, allylbenzene, chlorostyrene, and the like.

反 応 The reaction conditions of the titanium component in the component (A1) and the above-mentioned vinyl group-containing compound may be any conditions as long as the effects of the present invention are recognized, but generally, the following ranges are preferable. The pre-polymerization amount of the vinyl group-containing compound is in the range of 0.001 to 100 g, preferably 0.1 to 50 g, more preferably 0.5 to 10 g per gram of the titanium solid component. The reaction temperature at the time of the prepolymerization is -150 to 150C, preferably 0 to 100C. Then, a polymerization temperature lower than the polymerization temperature at the time of “main polymerization”, that is, the polymerization of α-olefin, is preferable. In general, the reaction is preferably performed with stirring, and at that time, an inert solvent such as hexane and heptane may be present. Further, pre-polymerization can also be carried out at the time of contacting the components (A1), (A2) and (A3).

(2) Organoaluminum compound (component (B))
As the organoaluminum compound used in the present invention (component _{^{(B)), R 19 3}} -r AlX r, R 20 3-s Al (OR 21) s ( wherein, R ¹⁹ and R ²⁰ 1 carbon atoms 20 is a hydrocarbon group or a hydrogen atom, R ²¹ is a hydrocarbon group, X is a halogen, and r and s are each represented by 0 ≦ r <3 and 0 <s <3.) There is something.

Specifically, (a) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and (b) diethylaluminum monochrome Alkyl aluminum halides such as chloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride, (c) alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, (d) diethylaluminum ethoxide and diethylaluminum phenoxide Alkyl aluminum alkoxide and the like. As a compound similar to the above, an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can also be used. Specifically _{(e) (C 2 H 5) 2} AlOAl (C 2 H 5) 2, (C 2 H 5) 2 AlN (C 2 H 5) 2 Al (C 2 H 5) 2, methylalumoxane , Isobutylalumoxane, methylisobutylalumoxane, and the like.

A plurality of these organoaluminum compounds (a) to (e) may be used in combination, or other organometallic compounds, for example, R ²² _2-t Zn (OR ²³ ) _t (where R ²² and R ²³ are the same or different. Or a hydrocarbon group having 1 to 20 carbon atoms, and t is 0 ≦ t ≦ 2). For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum and diethylaluminum ethoxide and diethylaluminum monochloride And triethylaluminum and diethylzinc.

The ratio of the organoaluminum compound of the component (B) to the titanium component in the solid catalyst component of the component (A) is generally Al / Ti = 1 to 1000 mol / mol, and preferably Al / Ti = 10 mol / mol. It is used at a rate of ５００500 mol / mol.

(3) C (＝ O) N bond-containing compound (component (C))
The C (ＣO) N bond-containing compound used in the present invention is preferably selected from the following compounds. (Where R ^{1 to} R ⁷ are an aliphatic hydrocarbon group having one or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a hetero atom-containing hydrocarbon group, and any of R ^{1 to} R ³ And any of R ^{4 to} R ⁷ may have a cyclic structure.)

When R ^{1 to} R ⁷ are each composed of an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, substitution with a structurally small bulk such as an alkyl group or a cycloalkyl group having 1 to 20, more preferably 1 to 10 carbon atoms. It is preferably a group. Specifically, methyl, ethyl, vinyl, allyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-hexyl, i-hexyl Groups, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. Among them, a methyl group, an ethyl group, and an n-propyl group are particularly preferable. When R ^{1 to} R ⁷ are each composed of an aromatic hydrocarbon group, it is preferably a substituent such as an unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. These substituents are considered to have the property that the carbonyl group is more easily coordinated due to distortion of the ring structure, and are preferable. Specific examples include a phenyl group, a biphenyl group, an indenyl group, and a fluorenyl group, and a phenyl group, a biphenyl group, and an indenyl group are particularly preferable. The hetero atoms that can be contained in R ^{1 to} R ⁷ are nitrogen, oxygen, silicon, phosphorus, and sulfur, and nitrogen and oxygen are more preferable. Further, a cyclic structure may be formed in which arbitrary R ^{1 to} R ³ and arbitrary R ^{4 to} R ⁷ are connected, preferably, R ¹ and R ² , R ¹ and R ³ , R ⁴ and R ⁵ , R ⁴ and R ⁶ or R ⁶ and R ⁷ are connected to form a cyclic structure, more preferably R ¹ and R ³ , and R ⁴ and R ⁶ are connected to form a cyclic structure. is there. Particularly preferably, the component (C) is a cyclic amide compound in which R ¹ and R ³ form a 5- to 7-membered cyclic structure, or R ⁴ and R ⁶ , and R ⁵ and R ⁷ are the same saturated hydrocarbon group. Or a urea compound in which R ⁴ and R ⁶ form a 5- to 7-membered cyclic structure.

Specifically, the following amide compounds and urea compounds can be exemplified.
(A) N, N-dimethylacetamide, N, N-dimethylpropionamide, N, N-diethylacetamide, N, N-dimethylbenzamide, N-methyl-N-phenylacetamide, 1-methyl-2-pyrrolidinone, -Methyl-2-piperidinone, 1-ethyl-2-pyrrolidinone, 1-dodecyl-2-pyrrolidinone, 1-cyclohexyl-2-pyrrolidinone, 1-phenyl-2-pyrrolidinone, 1-methyl-2-pyridone, N-methyl Amide compounds such as -ε-caprolactam, (ii) tetramethylurea, tetraethylurea, tetrabutylurea, N, N'-dimethyl-N, N'-diphenylurea, bis (tetramethylene) urea, 1,3-dimethyl -2-imidazolidinone, 1,3-diacetyl-2-imidazolidinone, 1,3-dimethyl Le 3,4,5,6-tetrahydro -2 (IH) - pyrimidinone, 1,3-dimethyl - can be exemplified urea compounds such as barbituric acid.

Among these C (＝ O) N bond-containing compounds, N, N-dimethylpropionamide, 1-methyl-2-pyrrolidinone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl -3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1-methyl-2-pyrrolidinone, 1-ethyl-2-pyrrolidinone, 1-dodecyl-2-pyrrolidinone, 1-cyclohexyl-2-pyrrolidinone Preference is given, inter alia, to tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1-methyl-2-pyrrolidinone, 1-ethyl-2-pyrrolidinone is preferred.

Since these C (ＯO) N bond-containing compounds contain N atoms, the overall bulk is reduced, and the carbonyl group coordinates to an active site where an amorphous component is generated, and selectively poisons. Can be. Therefore, it is presumed that R ^{1 to} R ^{7 in the} vicinity of the carbonyl group have a structurally small bulk, or a structure in which the carbonyl group is more easily coordinated due to distortion of the ring structure, exhibits an excellent effect.

Also, two or more of these C (＝ O) N bond-containing compounds can be used.
The ratio of the C (＝ O) N bond-containing compound of the component (C) and the organoaluminum compound of the component (B) is preferably in the range of 0.001 to 1 in a molar ratio to the amount of the organoaluminum compound used. , Preferably in the range of 0.005 to 0.5.

(4) Silicon compound component or compound having at least two ether bonds (component (D))
The component (D) preferably used in the present invention is a silicon compound component or a compound having at least two ether bonds, and the silicon compound component is represented by the following formula.
R ⁸ R ⁹ _3-m Si (OR ¹⁰ ) _m
(Here, R ⁸ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a hetero atom-containing hydrocarbon group, and R ⁹ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a hetero atom-containing group. A hydrocarbon group, halogen or hydrogen, R ¹⁰ is a hydrocarbon group, and m represents 1 ≦ m ≦ 3.)

When R ⁸ is an aliphatic hydrocarbon group, it is a branched aliphatic hydrocarbon group having usually 3 to 20, preferably 3 to 10 carbon atoms, i-propyl group, i-butyl group, t-butyl group. , I-hexyl group and the like are preferable, and among them, a t-butyl group is more preferable. Further, when R ⁸ is a cyclic aliphatic hydrocarbon group, the number of carbon atoms is usually 4 to 20, preferably 5 to 10, and preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like. Of these, a cyclopentyl group and a cyclohexyl group are more preferred. The hetero atoms that R ⁸ can contain are nitrogen, oxygen, silicon, phosphorus, and sulfur, with nitrogen and oxygen being more preferred.

R ⁹ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, a heteroatom-containing hydrocarbon group, halogen or hydrogen. More specifically, a halogen group such as hydrogen, chlorine, bromine and iodine, the number of carbon atoms is usually 1 to 20, preferably 1 to 10, and methyl, ethyl, n-propyl, i-propyl, n- A butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, an i-hexyl group, a cyclopentyl group, a cyclohexyl group and the like are preferable. Among them, a methyl group, an ethyl group, an n-propyl group, i-propyl, t-butyl, n-hexyl, cyclopentyl and cyclohexyl are more preferred.

R ¹⁰ is a hydrocarbon group, and usually has 1 to 20, preferably 1 to 10, and more preferably 1 to 5 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, i-butyl group, t-butyl group and the like are preferable, and among them, a methyl group and an ethyl group are more preferable.
The silicon compound component of the component (D) and the silicon compound component of the component (A2) are selected from the same group, and may be the same or different.

The compound having at least two ether bonds of the component (D) is selected from the same group as the diether compound suitably used as an electron donor for the component (A) solid catalyst component and the component (A1) solid component. Yes, they may be the same or different.

Specifically, 1,3-dimethoxypropane, 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-tert-butyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl- 1,3-dimethoxypropane, 1,3-diethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 1, -Dipropoxypropane, 1,3-dibutoxypropane, 2,2-diisopropyl-1,3-diethoxypropane, 2,2′-dimethoxy-1,1′-binaphthalene, 1,2,3-trimethoxypropane , 1,1,1-trimethoxymethyl-ethane and the like.

The ratio of the silicon compound component of the component (D) or the compound having at least two ether bonds to the organoaluminum compound component of the component (B) is 0.01 to 10 in a molar ratio to the amount of the organoaluminum compound component used. And preferably in the range of 0.05 to 1.

2. α-Olefin Polymerization The α-olefin polymerization using the novel catalyst of the present invention is applied to slurry polymerization using a hydrocarbon solvent, liquid-phase solventless polymerization substantially using no solvent, or gas-phase polymerization. As a polymerization solvent in the case of slurry polymerization, a hydrocarbon solvent such as pentane, hexane, heptane, and 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. At that time, hydrogen can be used as a molecular weight regulator.

The α-olefin polymerized by the catalyst system of the present invention has a general formula R ²⁴ —CH ＝ CH ₂ (where R ²⁴ is a hydrocarbon group having 1 to 20 carbon atoms and may have a branched group. )). Specifically, it is an α-olefin such as propylene, butene-1, pentene-1, hexene-1,4-methylpentene-1. In addition to homopolymerization of these α-olefins, copolymerization with monomers copolymerizable with α-olefins (eg, ethylene, α-olefins, dienes, styrenes, etc.) can also 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.

3. α-Olefin polymer The α-olefin polymer to be polymerized according to the present invention is characterized by having very few amorphous components, high stereoregularity, and good odor and hue.
In particular, in the α-olefin polymer produced by bulk polymerization, the content of cold xylene solubles (CXS) as an amorphous component is preferably 1% by weight or less, more preferably 0.1 to 1% by weight, even more preferably. 0.2-0.7% by weight. Here, CXS is obtained by completely dissolving a sample (about 5 g) in xylene (300 ml) at 140 ° C., cooling to 23 ° C., allowing to stand for 12 hours, filtering, and evaporating the filtrate using an evaporator. After solidifying and drying under reduced pressure at 110 ° C. for 2 hours, the mixture is allowed to cool to room temperature and its weight is measured.

Further, the α-olefin polymer produced by slurry polymerization preferably has an attack amount of 1.2% by weight or less as an amorphous component, more preferably 0.1 to 0.9% by weight, and still more preferably 0.1 to 0.9% by weight. 1 to 0.5% by weight. Here, the amount of attack is, in the α-olefin polymer produced by slurry polymerization, after the polymerization is completed, the obtained polymer slurry is separated by filtration, and the amount of the polymer obtained by drying the filtrate is measured. The ratio of the amount of polymer dissolved therein to the total amount of polymer is calculated, and this is defined as the amount of attack (% by weight).

Boiling heptane-insoluble matter (II) is preferably 97% by weight or more, more preferably 97 to 99.5% by weight, still more preferably 98 to 99.5% by weight, particularly preferably 98.5 to 99%, as stereoregularity. 0.5% by weight.

In the α-olefin polymer produced by bulk polymerization, the boiling heptane-insoluble component (II) is preferably 97% by weight or more, more preferably 97 to 99.5% by weight, and still more preferably 98 to 99%, as stereoregularity. 0.5% by weight, particularly preferably 98.5 to 99.5% by weight. Here, II is obtained by performing Soxhlet extraction with boiling heptane for 3 hours and measuring the ratio of the extraction residue.

Further, in the α-olefin polymer produced by slurry polymerization, product II (T-II) is preferably 95% by weight or more, more preferably 96 to 99.5% by weight, further preferably 97. 5 to 99.5% by weight. Here, T-II is an α-olefin polymer produced by slurry polymerization, after the polymerization is completed, the obtained polymer slurry is separated by filtration, the polymer is dried, and the amount of boiling peptane-insoluble matter in this portion is measured. I do. The total amount of polymer in the polymer slurry was calculated in consideration of the amount of attack PP dissolved in the filtrate as the total amount of polymer, and the ratio of the amount of boiling heptane-insoluble matter to the total amount of polymer was determined. -II).

The α-olefin polymer to be polymerized according to the present invention has a high density, a high rigidity and a high heat resistance, and has excellent characteristics, since it has very little amorphous component and high stereoregularity.
Further, the α-olefin polymer is produced with a high yield and can be suitably used for applications such as automobile parts, home electric parts, and packaging materials that require high rigidity and high heat resistance.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The method and apparatus for measuring each physical property value in the present invention are described below.

1) MFR
Apparatus: Melt indexer manufactured by Takara Co., Ltd. Measurement method: Evaluated at 230 ° C. and 21.18 N based on JIS-K6921.
2) Polymer bulk density The bulk density of the powder sample was measured using an apparatus according to ASTM D1895-69.
3) Cold xylene solubles [CXS]
Measurement method: A sample (about 5 g) was completely dissolved once in xylene (300 ml) at 140 ° C., then cooled to 23 ° C., allowed to stand for 12 hours, filtered, and the filtrate was evaporated to dryness using an evaporator. After drying under reduced pressure at 110 ° C. for 2 hours, the mixture was allowed to cool to room temperature and its weight was measured to obtain CXS.
4) Attack amount In the α-olefin polymer produced by the slurry polymerization, after the polymerization is completed, the obtained polymer slurry is separated by filtration, and the amount of the polymer obtained by drying the filtrate is measured. The ratio of the amount of the polymer dissolved to the total amount of the polymer was calculated, and this was defined as the attack amount (% by weight).
5) Boiling heptane insolubles [II]
For boiling heptane insolubles, Soxhlet extraction with boiling heptane was performed for 3 hours, and the ratio of the extraction residue was defined as II.
6) All products II [T-II]
In the α-olefin polymer produced by the slurry polymerization, after the polymerization is completed, the obtained polymer slurry is separated by filtration, the polymer is dried, and the amount of the insoluble portion of boiling peptane in this portion is measured. The total polymer amount in the polymer slurry was calculated in consideration of the amount of attack PP dissolved in the filtrate as the total polymer amount, and the ratio of the boiling heptane-insoluble content to the total polymer amount was determined. T-II).

Example-1
[Production of component (A)]
200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then 0.4 mol of MgCl ₂ and 0.8 mol of Ti (OnC ₄ H ₉ ) ₄ were introduced. At 95 ° C. for 2 hours. After the completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced, followed by a reaction for 3 hours. The resulting solid component was washed with n-heptane.
Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 0.06 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 0.1 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, 0.006 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the flask at 70 ° 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. Next, 2.5 mol of TiCl ₄ was introduced and reacted at 90 ° C. for 3 hours. After completion of the reaction, the resultant was sufficiently washed with n-heptane, and 2.5 mol of TiCl _{4 was} further introduced and reacted at 90 ° C. for 3 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a solid component (A1) for producing the component (A). Its titanium content was 2.6% by weight.
Further, a sufficiently nitrogen-purged flask, a n- heptane purified in the same manner as above was introduced 50 ml, was introduced 5 g of synthesized solid component in the _{above, (t-C 4 H 9} ) Si (CH 3) 1.2 ml of (OCH ₃ ) _{2 and} 1.7 g of Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. This had a titanium content of 2.3% by weight.

[Polymerization of propylene]
A 3.0-liter stainless steel autoclave having a stirring and temperature control device was heated and dried under vacuum, cooled to room temperature and replaced with propylene, and then Al (C ₂ H ₅ ) ₃ was added as component (B). 550 milligrams, 56 milligrams of tetramethylurea and 5,000 milliliters of hydrogen as the component (C) were introduced, and then 1,000 grams of liquid propylene were introduced. After adjusting the internal temperature to 75 ° C., the mixture was produced as described above. 7 mg of the component (A) was injected to polymerize propylene. One hour later, 10 ml of ethanol was injected under pressure to terminate the polymerization, and the obtained polymer was recovered and dried. As a result, 238.5 (g) of a polymer was obtained. The obtained polymer had MFR = 23 (g / 10 min), polymer bulk density = 0.48 (g / cc), and CXS = 0.7 (wt%).

Example-2
Example 1 was carried out in exactly the same manner as in Example 1 except that 55 mg of 1,3-dimethyl-2-imidazolidinone was used in place of tetramethylurea as the component (C). As a result, 205.8 (g) of a polymer was obtained. The obtained polymer had MFR = 23 (g / 10 min), polymer bulk density = 0.48 (g / cc), and CXS = 0.6 (wt%).

Example-3
Example 1 except that 61 mg of 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone was used in place of the tetramethylurea of the component (C) of Example-1. Performed exactly as in 1. As a result, 225.6 (g) of a polymer was obtained. The obtained polymer had MFR = 23 (g / 10 min), polymer bulk density = 0.48 (g / cc), and CXS = 0.8 (wt%).

Example-4
Example 1 was carried out in the same manner as in Example 1 except that 49 mg of N, N-dimethylpropionamide was used instead of tetramethylurea as the component (C). As a result, 280.3 (g) of a polymer was obtained. The obtained polymer had MFR = 32 (g / 10 min), polymer bulk density = 0.46 (g / cc), and CXS = 0.9 (wt%).

Example-5
Example 1 was carried out in the same manner as in Example 1 except that 116 mg of N, N'-dimethyl-N, N'-diphenylurea was used instead of tetramethylurea as the component (C). As a result, 256.0 (g) of a polymer was obtained. The obtained polymer had MFR = 30 (g / 10 min), polymer bulk density = 0.48 (g / cc), and CXS = 0.9 (wt%).

Example-6
Example 1 was carried out in exactly the same manner as in Example 1 except that 82 mg of 1,3-diacetyl-2-imidazolidinone was used in place of tetramethylurea as the component (C). As a result, 219.7 (g) of a polymer was obtained. The obtained polymer had MFR = 31 (g / 10 minutes), polymer bulk density = 0.48 (g / cc), and CXS = 0.9 (wt%).

Comparative Example-1
Example 1 was carried out in exactly the same manner as in Example 1 except that the component (C) tetramethylurea was not used. As a result, 308.2 (g) of a polymer was obtained. The obtained polymer had MFR = 34 (g / 10 minutes), polymer bulk density = 0.48 (g / cc), and CXS = 1.4 (wt%).

Comparative Example-2
Without using tetramethylurea the ingredients of Example -1 (C), the embodiment except that as the component (D) to _{(t-C 4 H 9)} Si (CH 3) (OCH 3) 2 was used 80 mg Performed exactly in the same manner as -1. As a result, 291.3 (g) of a polymer was obtained. The obtained polymer had MFR = 31 (g / 10 min), polymer bulk density = 0.47 (g / cc), and CXS = 1.1 (wt%).

Comparative Example-3
Example 1 was carried out in exactly the same manner as in Example 1 except that 43 mg of methyl carbonate was used instead of the tetramethylurea of the component (C). As a result, 102.3 (g) of a polymer was obtained. The obtained polymer had MFR = 32 (g / 10 min), polymer bulk density = 0.48 (g / cc), and CXS = 0.9 (wt%).

Comparative Example-4
Example 1 was carried out in exactly the same manner as in Example 1 except that 91 mg of 2,2-diisopropyl-1,3-dimethoxypropane was used instead of the tetramethylurea of the component (C). As a result, 203.7 (g) of a polymer was obtained. The obtained polymer had MFR = 39 (g / 10 min), polymer bulk density = 0.46 (g / cc), and CXS = 0.8 (wt%).
Table 1 shows the above results.

　　　

　　　

Example-7
[Production of component (A)]
200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then 0.4 mol of MgCl ₂ and 0.8 mol of Ti (OnC ₄ H ₉ ) ₄ were introduced. At 95 ° C. for 2 hours. After the completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced, followed by a reaction for 3 hours. The resulting solid component was washed with n-heptane.
Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 0.06 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 0.1 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. Subsequently, 0.006 mol of butyl acetate was mixed with 25 ml of n-heptane, introduced into the flask at 70 ° 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. Next, 2.5 mol of TiCl ₄ was introduced and reacted at 90 ° C. for 3 hours. After completion of the reaction, the resultant was sufficiently washed with n-heptane, and 2.5 mol of TiCl _{4 was} further introduced and reacted at 90 ° C. for 3 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a solid component (A1) for producing the component (A). Its titanium content was 2.6% by weight.
Then, into a flask sufficiently purged with nitrogen, 50 ml of n-heptane purified in the same manner as above was introduced, and 5 g of the solid component synthesized above was introduced, and (t-C ₄ H ₉ ) Si (n-C 1.5 ml of ₃ H ₇ ) (OCH ₃ ) _{2 and} 1.7 g of Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. This had a titanium content of 2.2% by weight.

[Polymerization of propylene]
Example 1 was carried out in the same manner as in Example 1, except that the above-mentioned component was used as the component (A), and 83 mg of tetraethylurea was used instead of the tetramethylurea of the component (C). As a result, 272.3 (g) of a polymer was obtained. The obtained polymer had MFR = 31 (g / 10 minutes), polymer bulk density = 0.48 (g / cc), and CXS = 0.9 (wt%).

Example-8
[Production of component (A)]
100 ml of dehydrated and deoxygenated toluene was introduced into a flask sufficiently purged with nitrogen, and then 10 g of Mg (OEt) ₂ was introduced to form a suspended state. Next, 20 ml of TiCl ₄ was introduced, the temperature was raised to 90 ° C., 2.5 ml of di-n-butyl phthalate was introduced, and the temperature was further raised to 110 ° C. to carry out a reaction for 3 hours. After the completion of the reaction, the resultant was washed with toluene. Next, 20 ml of TiCl ₄ and 100 ml of toluene were introduced and reacted at 110 ° C. for 2 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane, and further, 20 ml of TiCl ₄ and 100 ml of toluene were introduced, and the mixture was reacted at 110 ° C. for 2 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a solid component (A1) for producing the component (A). This had a titanium content of 2.7% by weight.
Then, into a flask sufficiently purged with nitrogen, 50 ml of n-heptane purified in the same manner as above was introduced, and 5 g of the solid component synthesized above was introduced, and (C ₅ H ₉ ) ₂ Si (OCH ₃ ) _{2 was} introduced. 1.5 milliliters and 1.7 grams of Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. This had a titanium content of 2.3% by weight.

[Polymerization of propylene]
The same procedure as in Example 1 was carried out except that the above-mentioned component was used as the component (A) and 48 mg of 1-methyl-2-pyrrolidinone was used instead of the tetramethylurea of the component (C). As a result, 238.5 (g) of a polymer was obtained. The obtained polymer had MFR = 10 (g / 10 min), polymer bulk density = 0.48 (g / cc), and CXS = 1.0 (wt%).

Example-9
[Production of component (A)]
100 ml of dehydrated and deoxygenated toluene was introduced into a flask sufficiently purged with nitrogen, and then 10 g of Mg (OEt) ₂ was introduced to form a suspended state. Next, 20 ml of TiCl ₄ was introduced, the temperature was raised to 90 ° C., 2.5 ml of 2,2-diisopropyl-1,3-dimethoxypropane was introduced, and the temperature was further raised to 110 ° C. to react for 3 hours. . After the completion of the reaction, the resultant was washed with toluene. Next, 20 ml of TiCl ₄ and 100 ml of toluene were introduced and reacted at 110 ° C. for 2 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane, and further, 20 ml of TiCl ₄ and 100 ml of toluene were introduced, and the mixture was reacted at 110 ° C. for 2 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a solid component (A1) for producing the component (A). This had a titanium content of 2.7% by weight.
Then, into a flask sufficiently purged with nitrogen, 50 ml of n-heptane purified in the same manner as above was introduced, and 5 g of the solid component synthesized above was introduced, and (C ₆ H ₁₁ ) CH ₃ Si (OCH ₃ ) was introduced. ₂ 2.7 milliliters and 1.7 grams of Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. This had a titanium content of 2.3% by weight.

[Polymerization of propylene]
The same procedure as in Example 1 was carried out except that the above-mentioned component was used as the component (A) and 81 mg of bis (tetramethylene) urea was used instead of the tetramethylurea of the component (C). As a result, 205.8 (g) of a polymer was obtained. The obtained polymer had MFR = 15 (g / 10 min), polymer bulk density = 0.47 (g / cc), and CXS = 0.7 (wt%).
Table 2 shows the above results.

　　　

　　　

Example -10
[Propylene block copolymerization]
A 3.0-liter stainless steel autoclave having a stirring and temperature control device was heated and dried under vacuum, cooled to room temperature and replaced with propylene, and then Al (C ₂ H ₅ ) ₃ was added as component (B). After introducing 550 milligrams, 56 milligrams of tetramethylurea and 10,000 milliliters of hydrogen as the component (C), and then introducing 1,000 grams of liquid propylene, and adjusting the internal temperature to 75 ° C, Example-1 7 mg of the component (A) was injected to polymerize propylene. After one hour, propylene and hydrogen were sufficiently purged to terminate the first stage polymerization. The polymer yield in the first stage was 219.3 (g). 20 g was extracted under a flow of purified nitrogen.
Next, the temperature was raised to 80 ° C. with stirring, and after the temperature was raised, propylene gas and ethylene gas were charged so that the total polymerization pressure became 2.0 MPa, and the second stage polymerization was started. Polymerization was carried out at 80 ° C. for 20 minutes while supplying a mixed gas of propylene and ethylene so that the total polymerization pressure became constant at 2.0 MPa. Here, the propylene / (propylene + ethylene) ratio was 45.3 mol% on average.
Thereafter, the mixed gas was purged to terminate the polymerization. The polymer yield of the obtained propylene block copolymer was 236.2 (g), the content of the second-stage polymer was 16 wt%, the MFR was 32 (g / 10 min), and the polymer bulk density was 0.48 (g). g / cc). Further, the MFR of the polymer obtained in the first stage was 95 (g / 10 min), the bulk density of the polymer was 0.47 (g / cc), CXS was 0.8 (wt%), and II was 97.27 ( wt%) density = 0.9101 (g / cc).

Example-11
[Polymerization of propylene]
A 3.0-liter stainless steel autoclave having a stirring and temperature control device was heated and dried under vacuum, cooled to room temperature and replaced with propylene, and then Al (C ₂ H ₅ ) ₃ was added as component (B). 550 milligrams, tetramethyl urea 56 mg, and component _{(D) (t-C 4} H 9) Si (CH 3) (OCH 3) 2 to 80 milligrams, and hydrogen was introduced 5,000 ml as component (C) Then, 1,000 g of liquid propylene was introduced, the internal temperature was adjusted to 75 ° C., and then 7 mg of the solid component (A1) produced in Example 1 was injected to polymerize propylene. One hour later, 10 ml of ethanol was injected under pressure to terminate the polymerization, and the obtained polymer was recovered and dried. As a result, 215.2 (g) of a polymer was obtained. The obtained polymer had MFR = 15 (g / 10 min), polymer bulk density = 0.49 (g / cc), and CXS = 0.9 (wt%).

Example-12
Example 11 was carried out in exactly the same way as in Example 11 except that 55 mg of 1,3-dimethyl-2-imidazolidinone was used in place of tetramethylurea as the component (C). As a result, 219.8 (g) of a polymer was obtained. The obtained polymer had MFR = 11 (g / 10 min), polymer bulk density = 0.48 (g / cc), and CXS = 0.7 (wt%).

Example-13
Example 11 Example 61 was repeated except that 61 mg of 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone was used instead of the tetramethylurea of the component (C) of Example-11. And went exactly the same. As a result, 206.5 (g) of a polymer was obtained. The obtained polymer had MFR = 11 (g / 10 min), polymer bulk density = 0.48 (g / cc), and CXS = 0.8 (wt%).

Example-14
Example 11 was carried out in the same manner as in Example 11 except that 49 mg of N, N-dimethylpropionamide was used in place of tetramethylurea as the component (C). As a result, 215.2 (g) of a polymer was obtained. The obtained polymer had MFR = 13 (g / 10 minutes), polymer bulk density = 0.48 (g / cc), and CXS = 0.8 (wt%).

Example-15
Instead of tetramethylurea ingredients of Example -11 (C), 1,3-dimethyl-2-imidazolidinone 55 milligrams used as component _{(D) (t-C 4} H 9) Si (CH 3 ) (OCH _{3) 2} in place, except for using 104 mg of 2,2-diisopropyl 1,3-dimethoxypropane was carried out in the same manner as in example -11. As a result, 154.3 (g) of a polymer was obtained. The obtained polymer had MFR = 32.5 (g / 10 minutes), polymer bulk density = 0.48 (g / cc), and CXS = 0.7 (wt%).

Comparative Example-5
Example 11 was carried out in the same manner as in Example 11 except that the component (C) tetramethylurea was not used. As a result, 204.2 (g) of a polymer was obtained. The obtained polymer had MFR = 25 (g / 10 min), polymer bulk density = 0.47 (g / cc), and CXS = 1.5 (wt%).

Comparative Example-6
Example 11 was carried out in exactly the same manner as in Example 11 except that 36 mg of methyl acetate was used instead of the tetramethylurea as the component (C). As a result, 208.8 (g) of a polymer was obtained. The obtained polymer had MFR = 40 (g / 10 minutes), polymer bulk density = 0.46 (g / cc), and CXS = 1.5 (wt%).
Table 3 shows the above results.

　　　

　　　

Example-16
[Polymerization of propylene]
Using the components (A) the solid component (A1) prepared in Example -7 as, instead of tetramethylurea component (C), tetraethyl urea 83 mg, components _{(D) (t-C 4} H 9 _{) Si (CH 3) (OCH} 3) 2 in _{place, (t-C 4 H 9} ) Si (n-C 3 H 7) (OCH 3) ₂ a except for using 90 milligrams example -11 exactly Performed similarly. As a result, 203.6 (g) of a polymer was obtained. The obtained polymer had MFR = 16 (g / 10 min), polymer bulk density = 0.47 (g / cc), and CXS = 0.9 (wt%).

Example-17
[Polymerization of propylene]
Using the solid component (A1) produced in Example-8 as the component (A), 48 mg of 1-methyl-2-pyrrolidinone was used instead of the tetramethylurea of the component (C), and (t) of the component (D) _{-C 4 H 9) Si (CH} 3) (OCH 3) 2 in place, was carried out in the same manner as _{(C 5 H 9) 2 Si} (OCH 3) 2 110 milligrams except for using example -11. As a result, 198.5 (g) of a polymer was obtained. The obtained polymer had MFR = 20 (g / 10 minutes), polymer bulk density = 0.46 (g / cc), and CXS = 1.0 (wt%).

Example-18
[Polymerization of propylene]
As the component (A), the solid component (A1) produced in Example-9 was used, and instead of the tetramethylurea of the component (C), 81 mg of bis (tetramethylene) urea and the (t- _{C 4 H 9) Si (CH} 3) (OCH 3) 2 in place, was carried out in the same manner as _{(C 9 H 17 N) 2} Si (OCH 3) ₂ a except for using 180 mg example -11 . As a result, 225.7 (g) of a polymer was obtained. The obtained polymer had MFR = 16 (g / 10 min), polymer bulk density = 0.47 (g / cc), and CXS = 0.7 (wt%).

Comparative Example-7
[Polymerization of propylene]
Using the component (A1) produced in Example-9 as the component (A), the same polymerization as in Example-18 was carried out except that the component (C) was not used.
Table 4 shows the above results.

　　　

　　　

Example-19
[Polymerization of propylene]
After sufficiently replacing a 1.5 liter stainless steel autoclave having a stirring and temperature control device with propylene gas, 500 ml of sufficiently dehydrated and deoxygenated n-heptane was used as a component (B) of Al (C ₂ H _{5) 3} 125 mg, component (C) as 1,3-dimethyl-2-imidazolidinone 12 mg, as component _{(D) (t-C 4} H 9) Si (CH 3) (OCH 3 ₂ ) 17 milligrams, 15 milligrams of the component (A1) produced in Example 1, then 390 milliliters of hydrogen were introduced, and the temperature was increased and the polymerization temperature was increased, the polymerization pressure was 5 g / cm ² G, the polymerization temperature was 75 ° C., and the polymerization was performed. Propylene was polymerized under the condition of time = 2 hours. After completion of the polymerization, the obtained polymer slurry was separated by filtration, and the polymer was dried. As a result, 144.5 g of a polymer was obtained.
The amount of the low stereoregular attack polymer dissolved in the filtrate was 0.2% by weight. From the boiling heptane extraction test, the total product II (T-II) was 98.5% by weight. The obtained polymer had MFR = 8.4 (g / 10 minutes) and polymer bulk density = 0.42 (g / cc).
Table 5 shows the above results.

Example-20
[Production of component (A)]
200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then 0.4 mol of MgCl ₂ and 0.8 mol of Ti (OnC ₄ H ₉ ) ₄ were introduced. At 95 ° C. for 2 hours. After the completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced, followed by a reaction for 3 hours. The resulting solid component was washed with n-heptane.
Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 0.06 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 0.2 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 90 ° C. for 4 hours. After the completion of the reaction, the resultant was washed with n-heptane to obtain a solid component for producing the component (A). This had a titanium content of 3.5% by weight.
Then, into a flask sufficiently purged with nitrogen, 50 ml of n-heptane purified in the same manner as above was introduced, 5 g of the solid component synthesized above was introduced, and 0.2 mol of SiCl ₄ , (t-C ₄ H) was added. ₉ ) 2.8 ml of Si (CH ₃ ) (OCH ₃ ) _{2 and} 9.0 g of Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. This had a titanium content of 3.0% by weight.

[Polymerization of propylene]
After a stainless steel autoclave having an internal volume of 1.5 liters and having a stirring and temperature control device was sufficiently replaced with propylene gas, 500 ml of sufficiently dehydrated and deoxygenated n-heptane was used as a component (B), and Al (C ₂ H _{5) 3} 125 mg, component (C) as 1,3-dimethyl-2-imidazolidinone 12 milligrams, and manufacturing the components (a) to 15 mg in the above, then hydrogen was introduced 130 ml, Noboru The temperature was increased, and propylene was polymerized under the conditions of polymerization pressure = 5 g / cm ² G, polymerization temperature = 75 ° C., and polymerization time = 2 hours. After completion of the polymerization, the obtained polymer slurry was separated by filtration, and the polymer was dried. As a result, 46.5 g of a polymer was obtained.
The amount of the low stereoregular attack polymer dissolved in the filtrate was 0.9% by weight. From the boiling heptane extraction test, T-II was 96.4% by weight. The obtained polymer had MFR = 6.6 (g / 10 minutes) and polymer bulk density = 0.36 (g / cc).

Example-21
Example 20 was carried out in exactly the same manner as in Example 20 except that N, N-dimethylpropionamide was used instead of 1,3-dimethyl-2-imidazolidinone of component (C). As a result, 48.3 (g) of a polymer was obtained. The obtained polymer had an attack amount = 1.2% by weight, T-II = 95.9% by weight, MFR = 7.0 (g / 10 min), and polymer bulk density = 0.38 (g / cc). Was.

Comparative Example-8
Example 20 was carried out in exactly the same manner as in Example 20 except that the component (C) 1,3-dimethyl-2-imidazolidinone was not used. As a result, 64.0 (g) of a polymer was obtained. The obtained polymer had an attack amount = 1.5% by weight, T-II = 92.9% by weight, MFR = 8.6 (g / 10 min), and polymer bulk density = 0.34 (g / cc). Was.

Comparative Example-9
Embodiment except that in place of 1,3-dimethyl-2-imidazolidinone component (C) of Example -20 a _{(t-C 4 H 9)} Si (CH 3) (OCH 3) 2 was used 17 mg Performed exactly as in Example-20. As a result, 47.4 (g) of a polymer was obtained. The obtained polymer had an attack amount = 1.0% by weight, T-II = 95.3% by weight, MFR = 7.3 (g / 10 minutes), and polymer bulk density = 0.35 (g / cc). Was.
Table 6 shows the above results.

　　　

　　　

Example-22
[Production of component (A)]
100 ml of dehydrated and deoxygenated toluene was introduced into a flask sufficiently purged with nitrogen, and then 10 g of Mg (OEt) ₂ was introduced to form a suspended state. Next, 20 ml of TiCl ₄ was introduced, the temperature was raised to 90 ° C., 2.5 ml of 2,2-diisopropyl-1,3-dimethoxypropane was introduced, and the temperature was further raised to 110 ° C. to react for 3 hours. After the completion of the reaction, the resultant was washed with toluene. Next, 20 ml of TiCl ₄ and 100 ml of toluene were introduced and reacted at 110 ° C. for 2 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a solid component (A1). Its titanium content was 2.6% by weight.
Then, into a flask sufficiently purged with nitrogen, 50 ml of n-heptane purified in the same manner as above was introduced, and 5 g of the solid component synthesized above was introduced, and (C ₅ H ₉ ) ₂ Si (OCH ₃ ) _{2 was} introduced. 1.5 milliliters and 1.7 grams of Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. This had a titanium content of 2.3% by weight.

[Polymerization of propylene]
After a stainless steel autoclave having an internal volume of 1.5 liters and having a stirring and temperature control device was sufficiently replaced with propylene gas, 500 ml of sufficiently dehydrated and deoxygenated n-heptane was used as a component (B), and Al (C ₂ H _{5) 3} 125 mg, component (C) as 1,3-dimethyl-2-imidazolidinone 12 milligrams, and manufacturing the components (a) to 15 mg in the above, then hydrogen was introduced 130 ml, Noboru The temperature was increased, and propylene was polymerized under the conditions of polymerization pressure = 5 g / cm ² G, polymerization temperature = 75 ° C., and polymerization time = 2 hours. After completion of the polymerization, the obtained polymer slurry was separated by filtration, and the polymer was dried. As a result, 92.4 g of a polymer was obtained.
The amount of the low stereoregular attack polymer dissolved in the filtrate was 0.2% by weight. From the boiling heptane extraction test, the total product II (T-II) was 98.9% by weight. The obtained polymer had an MFR of 18.5 (g / 10 minutes) and a polymer bulk density of 0.40 (g / cc).

Example-23
[Polymerization of propylene]
As the component (A), the solid component (A1) produced in Example 22 was used, and instead of the component (C) 1,3-dimethyl-2-imidazolidinone, 13 mg of tetramethylurea was used as the component (D). _{(t-C 4 H 9)} Si (CH 3) (OCH 3) except for using ₂ 17 mg was performed in the same manner as in example -22. As a result, 135.3 (g) of a polymer was obtained. The obtained polymer had an attack amount = 0.5% by weight, T-II = 98.0% by weight, and MFR =
14.6 (g / 10 minutes) and polymer bulk density = 0.38 (g / cc).
Table 7 shows the above results.

　　　

　　　

Examples 24 to 29
[Polymerization of propylene]
The same polymerization as in Example 1 was carried out except that 7 mg of the component (A) produced in Example 1 was used as the component (A) and a predetermined amount of the compound shown in Table 8 was used as the component (C). did.
Table 8 shows the above results.

　

　

[Consideration of results of Examples and Comparative Examples]
In the present invention, the yield, the bulk density, the cold xylene solubles (CXS), the boiling heptane insolubles (II), etc., are compared by comparing each of Examples 1 to 29 and Comparative Examples 1 to 9 described above. It is clear that excellent results were obtained in comparison with the comparative example in all cases.
Specifically, in Comparative Example-1 in which the component (C) is not used and in Comparative Example-2 in which the component (C) is not the one of the present invention, although the yield alone is superior to those of Examples 1 to 6, it is soluble in cold xylene. (CXS) is very poor, and in Comparative Example 1, the boiling heptane-insoluble matter (II) is also poor. In Comparative Example-3 in which the component (C) is not of the present invention, the yield is extremely poor, and in Comparative Example-4 in which the component (C) is not of the present invention, the yield and the boiling heptane-insoluble matter (II) are poor. . Similarly, the physical properties of the cold xylene solubles (CXS) and the boiling heptane insolubles (II) are particularly low even when the component (C) is not used or the comparative examples -5 to 7 are not the present invention. It's getting worse. In Comparative Example-8 not using the component (C), the attack amount and the total product II (T-II) were poor, and in Comparative Example-9 in which the component (C) was not of the present invention, the total product II (T-II) was not used. II) has a bad result.

FIG. 2 is a flowchart for clarifying the understanding of the catalyst of the present invention.

Claims (11)

For α-olefin polymerization obtained by combining component (A) a solid catalyst component containing magnesium, titanium, and halogen as essential components, component (B) an organoaluminum compound, and component (C) a C (＝ O) N bond-containing compound. catalyst. The component (C) C (＝ O) N bond-containing compound is selected from compounds represented by the following general formula [1] or [2], for α-olefin polymerization according to claim 1. catalyst. (Where R ^{1 to} R ⁷ are an aliphatic hydrocarbon group having one or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a hetero atom-containing hydrocarbon group, and any R ^{1 to} R ³ And any of R ^{4 to} R ⁷ may be linked to form a cyclic structure.)

The α-olefin polymerization catalyst according to claim 1 or 2, further comprising a combination of a component (D) a silicon compound or a compound having at least two ether bonds. The α-olefin polymerization catalyst according to any one of claims 1 to 3, wherein the component (A) is obtained by contacting the following component (A1) and component (A2).
Component (A1): a solid component containing titanium, magnesium, and halogen as essential components;
Component (A2): a silicon compound represented by the following formula,
R ⁸ R ⁹ _3-m Si (OR ¹⁰ ) _m
(Here, R ⁸ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a hetero atom-containing hydrocarbon group, and R ⁹ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a hetero atom-containing hydrocarbon group. A hydrocarbon group, halogen or hydrogen, R ¹⁰ is a hydrocarbon group, and m represents 1 ≦ m ≦ 3.) The α-olefin polymerization catalyst according to claim 4, wherein the component (A) is further contacted with the following component (A3).
Component (A3): Organoaluminum compound The α-olefin polymerization catalyst according to any one of claims 1 to 3, wherein the component (A) further contains a component (E) an electron donor. The α-olefin polymerization catalyst according to claim 4 or 5, wherein the component (A1) further contains a component (E) an electron donor. The α-olefin polymerization catalyst according to any one of claims 3 to 7, wherein the silicon compound (D) is a silicon compound represented by the following formula:
R ⁸ R ⁹ _3-m Si (OR ¹⁰ ) _m
(Here, R ⁸ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a hetero atom-containing hydrocarbon group, and R ⁹ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a hetero atom-containing hydrocarbon group. A hydrocarbon group, halogen or hydrogen, R ¹⁰ is a hydrocarbon group, and m represents 1 ≦ m ≦ 3, respectively.) The α-olefin polymerization catalyst according to any one of claims 3 to 8, wherein the component (D) the compound having at least two ether bonds is an aliphatic diether or an aromatic diether. The component (E), wherein the electron donor is a phthalic acid diester compound, a cellosolve acetate compound, a phthalic acid dihalide compound, a succinic acid diester compound, or an aliphatic or aromatic diether compound. Α-olefin polymerization catalyst. A method for producing an α-olefin polymer, comprising homopolymerizing or copolymerizing an α-olefin using the α-olefin polymerization catalyst according to any one of claims 1 to 10.

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