JP6996345B2 - A method for producing a solid catalyst component for α-olefin polymerization, a method for producing a solid catalyst component for α-olefin polymerization, a catalyst for α-olefin polymerization, and a method for producing an α-olefin polymer using the catalyst. - Google Patents

Description

The present invention relates to a solid catalyst component for α-olefin polymerization, a method for producing a solid catalyst component for α-olefin polymerization, a catalyst for α-olefin polymerization, and a method for producing an α-olefin polymer using the same.

Polyolefins such as polyethylene and polypropylene are the most important plastic materials as industrial materials, such as packaging materials and electrical materials as films and sheets, industrial materials such as automobile parts and home appliances as molded products, and textile materials. It is widely used for various purposes such as building materials.
Due to the wide variety of applications, polyolefins continue to be required to be improved and improved in various properties from the aspect of their applications, and in order to meet those demands, the polymerization catalyst is mainly improved. Technology development has been developed by.

A Ziegler-based catalyst using a transition metal compound and an organometallic compound greatly enhanced the polymerization activity of the olefin and realized industrial production. After that, the physical properties of the polymer were improved by the molecular weight distribution and α-. Various performance improvements have been made, including improvements in the stereoregularity of olefins.
Specifically, a catalyst using a solid catalyst component containing a magnesium compound as a catalyst carrier and titanium and halogen as essential components has been developed, and a catalyst having an electron donor to enhance catalytic activity and stereoregularity has been developed. (For example, refer to Patent Documents 1 to 3), and thereafter, it has been proposed to newly add a specific organic silicon compound to the catalyst component to further improve the catalytic activity and steric regularity (Patent Documents). 4). Further, by using a silicon compound having a special structure having an alkenyl group such as a vinyl group or an allyl group in combination with a specific organosilicon compound, the catalytic activity and stereoregularity are further improved, and as a molecular weight adjusting agent. Proposals have also been made to improve performance, such as improving the response of the hydrogen used (see, for example, Patent Documents 5 to 8). Further, it has been proposed to reduce the amorphous component by using a specific amide compound or sulfite ester in combination with an organosilicon compound as an external donor (see Patent Documents 9 and 10). Further, many improved techniques are disclosed, such as improving the stericity by treating the solid catalyst component with two specific kinds of organoaluminum compounds twice or more (see, for example, Patent Document 11).

However, as far as the researchers know, it is still sufficient to improve various properties such as the stereoregularity of the α-olefin polymer produced and the reduction of amorphous components in any of these catalyst systems. However, it is necessary to improve various properties in each application field. For example, in the field of automobile parts materials, high rigidity is required as a molded product, and particularly for high crystallinity, that is, improvement of stereoregularity and cold xylene. Further improvement in reducing the amount of amorphous components to be dissolved is desired, and further improvement in stickiness is strongly requested in the field of packaging materials.

Japanese Unexamined Patent Publication No. 58-138706 Japanese Unexamined Patent Publication No. 57-59909 Japanese Unexamined Patent Publication No. 58-147409 Japanese Unexamined Patent Publication No. 62-187707 Japanese Unexamined Patent Publication No. 03-234707 Japanese Unexamined Patent Publication No. 07-2923 Japanese Unexamined Patent Publication No. 2006-169283 Japanese Unexamined Patent Publication No. 2008-163151 Japanese Unexamined Patent Publication No. 2004-124090 Japanese Unexamined Patent Publication No. 2006-225449 Japanese Unexamined Patent Publication No. 2001-40028

The object of the present application is to further increase the rigidity in order to meet the demand for further performance improvement from a wide range of applications in the situation of the above-mentioned prior art in the field of polyolefin materials and catalysts for olefin polymerization. It is an object of the present invention to provide a catalyst capable of producing an α-olefin polymer having improved stereoregularity and a method for producing an α-olefin polymer using the catalyst.

As a result of diligent research to achieve the above objectives, the present researchers can obtain an olefin polymer having a low soluble content and high stereoregularity in a high yield, the amount of electron donor is extremely small, and the amount of the electron donor is extremely small. , A catalyst for α-olefin polymerization containing a solid catalyst component for α-olefin polymerization containing an alkoxysilane compound has been found.

The solid catalyst component for α-olefin polymerization of the present invention is the solid catalyst component (A) for α-olefin polymerization containing magnesium, titanium, halogen, an electron donor and an alkoxysilane compound.
The electron donor is one or a mixture of two or more selected from the group consisting of organic acids and inorganic acids and their derivative compounds, ether compounds, and ketone compounds.
The content of the electron donor is 5 to 40 μmol / g.

In the solid catalyst component for α-olefin polymerization of the present invention, the electron donor may be at least one selected from the group consisting of an organic acid ester compound and an acid halide compound.

The method for producing a solid catalyst component for α-olefin polymerization of the present invention is a method for producing a solid catalyst component (A) for α-olefin polymerization containing magnesium, titanium, halogen, an electron donor and an alkoxysilane compound.
It is characterized in that a series of steps of contacting (A2), (A3) and (A4) with the following component (A1) and then washing with a solvent is repeated two or more times.
Component (A1): Solid component containing titanium, magnesium, halogen, and electron donor as essential components Component (A2): Silane compound having an alkenyl group Component (A3): Alkoxysilane compound [However, a silane compound having an alkenyl group Is different. ]
Component (A4): Organoaluminium compound

In the method for producing a solid catalyst component for α-olefin polymerization of the present invention, the component (A2) may be a vinylsilane compound.

In the method for producing a solid catalyst component for α-olefin polymerization of the present invention, the component (A3) may be a silicon compound represented by the following general formula (1).
R ¹ R ² _m Si (OR ³ ) _n ... (1)
(Here, R ¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group; R ² represents any free group selected from hydrogen, halogens, hydrocarbon groups and heteroatom-containing hydrocarbon groups. R ³ represents. It is a hydrocarbon group and indicates 0 ≦ m ≦ 2, 1 ≦ n ≦ 3, m + n = 3).

The catalyst for α-olefin polymerization of the present invention is characterized by containing the solid catalyst component (A) for α-olefin polymerization and the following component (B).
Component (B): Organoaluminium compound

The α-olefin polymerization catalyst of the present invention is characterized by containing the α-olefin polymerization solid catalyst component (A) obtained by the above-mentioned production method and the following component (B).
Component (B): Organoaluminium compound

The method for producing an α-olefin polymer of the present invention is characterized by homopolymerizing or copolymerizing an α-olefin using the α-olefin polymerization catalyst.

According to the present invention, an olefin polymer having a low soluble content and high stereoregularity can be obtained in a high yield, the amount of electron donors is extremely small, and a solid for α-olefin polymerization containing an alkoxysilane compound. A catalyst for α-olefin polymerization containing a catalyst component can be provided.

1. 1. Solid catalyst component for α-olefin polymerization (A)
The solid catalyst component for α-olefin polymerization of the present invention is the solid catalyst component (A) for α-olefin polymerization containing magnesium, titanium, halogen, an electron donor and an alkoxysilane compound.
The electron donor is one or a mixture of two or more selected from the group consisting of organic acids and inorganic acids and their derivative compounds, ether compounds, and ketone compounds.
The content of the electron donor is 5 to 40 μmol / g.

Hereinafter, the solid catalyst component for α-olefin polymerization and the like of the present invention will be described in detail for each item. In addition, in this specification, "-" indicating a numerical range is used in the sense that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

The solid catalyst component (A) for α-olefin polymerization of the present invention includes magnesium (A1a-1), titanium (A1a-2), halogen (A1a-3), electron donor (A1a-4) and an alkoxysilane compound (A1a-4). A3) is included.
In the present invention, a solid component containing magnesium, titanium, halogen, and an electron donor as essential components is referred to as a component (A1).

1-1. Magnesium (A1a-1)
Any magnesium compound as a magnesium source used in the solid component (A1) according to the present invention can be used. As a typical example thereof, the compound disclosed in JP-A-3-234707 can be mentioned.
Generally, magnesium halide compounds typified by magnesium chloride, alkoxymagnesium compounds typified by diethoxymagnesium, metallic magnesium, oxymagnesium compounds typified by magnesium oxide, and magnesium hydroxide are typified. Hydroxymagnesium compounds, glignal compounds typified by butylmagnesium chloride, organic magnesium compounds typified by butyloctylmagnesium, inorganic and organic acid magnesium salt compounds typified by magnesium carbonate and magnesium stearate, and A mixture thereof or a compound whose average composition formula is a mixed formula thereof (for example, a compound such as Mg (OEt) _m Cl _2-m ; 0 <m <2) can be used.
Of these, magnesium chloride, diethoxymagnesium, metallic magnesium and butylmagnesium chloride are particularly preferable.

In particular, when producing large particles, it is preferable to use dialkoxymagnesium whose catalyst particle size can be easily controlled. As the dialkoxymagnesium, not only those prepared in advance but also those obtained by reacting metallic magnesium with a halogen or a halogen-containing metal compound in the presence of an alcohol in the catalyst manufacturing step can be used. ..

Further, in the present invention, the dialkoxymagnesium suitable as the component (A1a-1) is in the form of granules or powder, and the shape thereof may be amorphous or spherical.
For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution can be obtained, the handling operability of the produced polymer powder during the polymerization operation is improved, and the produced polymer powder is improved. Problems such as blockage caused by the fine powder contained in the polymer are solved.

The above-mentioned spherical dialkoxymagnesium does not necessarily have to be a true spherical shape, and an elliptical shape or a potato-shaped one can also be used. Specifically, the shape of the particles is such that the ratio (l / w) of the major axis diameter l to the minor axis diameter w is 3 or less, preferably 1 to 2, and more preferably 1 to 1.5. be.
Further, the average particle size of the dialkoxymagnesium may be 1 to 200 μm. It is preferably 5 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle size is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm.
As for the particle size, it is desirable to use one having a narrow particle size distribution with few fine powders and coarse powders. Specifically, the amount of particles having a size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the amount of particles having a size of 100 μm or more is 10% or less, preferably 5% or less.
Further, the particle size distribution is expressed as ln (D90 / D10) (where D90 is the particle size at 90% of the integrated particle size and D10 is the particle size at 10% of the integrated particle size), which is 3 or less. It is preferably 2 or less.

Examples of the method for producing spherical dialkoxymagnesium as described above include JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, and Japanese Patent Publication No. 4-368391. It is exemplified in Kaihei 8-7338A.

1-2. Titanium (A1a-2)
Any titanium compound as a titanium source used in the solid component (A1) according to the present invention can be used. As a typical example, the compound disclosed in JP-A-3-234707 can be mentioned.
Regarding the valence of titanium, titanium compounds having arbitrary valences of tetravalent, trivalent, divalent, and 0 valence can be used, but tetravalent and trivalent titanium compounds are preferable, and tetravalent is more preferable. It is desirable to use the titanium compound of.

Specific examples of the tetravalent titanium compound include titanium halide compounds represented by titanium tetrachloride, alkoxy titanium compounds represented by tetrabutoxy titanium, and tetrabutoxy titanium dimer (BuO) ₃ Ti-O-Ti (. OBu) Condensed compounds of alkoxytitanium having a Ti—O—Ti bond typified by ₃ , organic metal titanium compounds typified by dicyclopentadienyltitanium dichloride, and the like can be mentioned. Of these, titanium tetrachloride and tetrabutoxytitanium are particularly preferable.
Moreover, as a specific example of a trivalent titanium compound, a halogenated titanium compound represented by titanium trichloride can be mentioned. As the titanium trichloride, a compound produced by any known method such as a hydrogen-reduced type, a metal-aluminum-reduced type, a metal-titanium-reduced type, and an organoaluminum-reduced type can be used.
The above titanium compounds can be used not only alone but also in combination with a plurality of compounds. Further, a mixture of the above titanium compounds, a compound whose average composition formula is a mixture thereof (for example, a compound such as Ti (OBu) _m Cl _4-m ; 0 <m <4), or a phthalate ester. Complexes with other compounds such as Ph (CO ₂ Bu) ₂ , TiCl ₄ and the like can be used.

1-3. Halogen (A1a-3)
As the halogen used in the solid component (A1) according to the present invention, fluorine, chlorine, bromine, iodine, and a mixture thereof can be used. Of these, chlorine is particularly preferable.
The halogen is generally supplied from the above-mentioned titanium compounds and / or magnesium compounds, but can also be supplied from other compounds. Typical examples are silicon halide compounds typified by silicon tetrachloride, aluminum halogenated compounds typified by aluminum chloride, halogenated organic compounds typified by 1,2-dichloroethane and benzyl chloride, and the like. Halogenated borane compounds typified by trichloroboran, halogenated phosphorus compounds typified by phosphorus pentoxide, halogenated tungsten compounds typified by tungsten hexachloride, halogenated molybdenum compounds typified by molybdenum pentoxide , Etc. can be mentioned. These compounds can be used not only alone but also in combination. Of these, silicon tetrachloride is particularly preferable.

1-4. Electron donor (A1a-4)
As a typical example of the electron donor (A1a-4) used in the solid component (A1) according to the present invention, the compound disclosed in Japanese Patent Application Laid-Open No. 2004-124090 can be mentioned. In general, organic and inorganic acids and their derivatives (esters, acid anhydrides, acid halides, amides) compounds, ether compounds, ketone compounds, aldehyde compounds, alcohol compounds, amine compounds, etc. can be used. It may be one kind or a mixture of two or more kinds selected from the group consisting of an organic acid and an inorganic acid, a derivative compound thereof, an ether compound, and a ketone compound.

Examples of the organic acid compound that can be used as an electron donor (A1a-4) include aromatic polyvalent carboxylic acid compounds represented by phthalic acid, aromatic carboxylic acid compounds represented by benzoic acid, and 2-n. One or two substituents or 2- and 3-positions at 2-positions such as malonic acid having one or two substituents at 2-positions such as butyl-malonic acid and 2-n-butyl-succinic acid. Aromatic polyvalent carboxylic acid compounds typified by succinic acid having one or more substituents, aliphatic carboxylic acid compounds typified by propionic acid, and fragrances typified by benzenesulfonic acid and methanesulfonic acid. Group and aliphatic sulfonic acid compounds, etc. can be exemplified.
These carboxylic acid compounds and sulfonic acid compounds may have any number of unsaturated bonds at any place in the molecule, such as maleic acid, regardless of whether they are aromatic or aliphatic.

Examples of the organic acid derivative compound that can be used as the electron donor (A1a-4) include the above-mentioned organic acid ester (carboxylic acid ester compound), acid anhydride, acid halide, amide, and the like.
Aliphatic and aromatic alcohols can be used as the alcohol which is a component of the ester. Among these alcohols, an alcohol composed of an aliphatic free group having 1 to 20 carbon atoms such as an ethyl group, a butyl group, an isobutyl group, a heptyl group, an octyl group and a dodecyl group is preferable. More preferably, an alcohol consisting of an aliphatic free radical having 2 to 12 carbon atoms is desirable. Further, an alcohol composed of an alicyclic free radical such as a cyclopentyl group, a cyclohexyl group and a cycloheptyl group can also be used.

As the halogen which is a component of the acid halide, fluorine, chlorine, bromine, iodine, etc. can be used. Of these, chlorine is the most preferable. In the case of polyhalides of polyvalent organic acids, the plurality of halogens may be the same or different.
In addition, aliphatic and aromatic amines can be used as the amine which is a component of the amide. Among these amines, aliphatic amines typified by ammonia, ethylamine and dibutylamine, amines having an aromatic free group typified by aniline and benzylamine in the molecule, and the like can be exemplified as preferable compounds. ..

Examples of the inorganic acid compound that can be used as the electron donor (A1a-4) include carbonic acid, phosphoric acid, silicic acid, sulfuric acid, nitric acid, and the like.
It is desirable to use an ester as the derivative compound of these inorganic acids. Specific examples include tetraethoxysilane (ethyl silicate), tetrabutoxysilane (butyl silicate), and tributyl phosphate.

Examples of the ether compound that can be used as the electron donor (A1a-4) include aliphatic ether compounds typified by dibutyl ether, aromatic ether compounds typified by diphenyl ether, and 2-isopropyl-2-isobutyl-1. , 3-Dimethoxypropane and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are aliphatic polyhydric ethers typified by 1,3-dimethoxypropane having one or two substituents at the 2-position. Examples thereof include compounds, polyvalent ether compounds having an aromatic free group in the molecule represented by 9,9-bis (methoxymethyl) fluorene, and the like.

Ketone compounds that can be used as an electron donor (A1a-4) include aliphatic ketone compounds represented by methyl ethyl ketone, aromatic ketone compounds represented by acetophenone, 2,2,4,6,6- Examples thereof include polyvalent ketone compounds typified by pentamethyl-3,5-heptandione.
Examples of the aldehyde compound that can be used as the electron donor (A1a-4) include aliphatic aldehyde compounds represented by propionaldehyde, aromatic aldehyde compounds represented by benzaldehyde, and the like. ..
Further, examples of the alcohol compound that can be used as the electron donor (A1a-4) include aliphatic alcohol compounds typified by butanol and 2-ethylhexanol, phenols, phenol derivative compounds typified by cresol, glycerin and the like. Examples thereof include aliphatic or aromatic polyhydric alcohol compounds typified by 1,1'-bi-2-naphthol.

Examples of the amine compound that can be used as the electron donor (A1a-4) include aliphatic amine compounds represented by diethylamine and nitrogen-containing fats represented by 2,2,6,6-tetramethyl-piperidine. Cyclic compounds, aromatic amine compounds typified by aniline, polyvalent amine compounds typified by 1,3-bis (dimethylamino) -2,2-dimethylpropane, nitrogen atom-containing aromatic compounds, Etc. can be exemplified.

Further, as a compound that can be used as an electron donor (A1a-4), a compound containing the above-mentioned plurality of functional groups in the same molecule can also be used. Examples of such compounds are 2-benzoyl-carboxylic acid ester compounds having an alkoxy group in the molecule represented by acetate- (2-ethoxyethyl) and ethyl 3-ethoxy-2-t-butylpropionate. Ketoester compounds typified by ethyl benzoate, ketoether compounds typified by (1-t-butyl-2-methoxyethyl) methylketone, N, N-dimethyl-2,2-dimethyl-3-methoxypropylamine Examples thereof include amino ether compounds typified by, and halogeno ether compounds typified by epoxychloropropane.

These electron donors (A1a-4) can be used alone or in combination of a plurality of compounds.
Among these, preferred are diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalic acid diester compounds typified by diheptyl phthalate, phthalic acid dihalide compounds typified by phthaloyl dichloride, and 2-n-butyl-. Malonic acid ester compounds having one or two substituents at the 2-position such as diethyl malonate, one or two substituents or the 2-position and 3 at the 2-position such as 2-n-butyl-diethyl succinate. Succinic acid ester compounds having one or more substituents at each position, 2-positions such as 2-isopropyl-2-isobutyl-1,3-dimethoxypropane and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. An aliphatic polyvalent ether compound typified by 1,3-dimethoxypropane having one or two substituents, and an aromatic free group typified by 9,9-bis (methoxymethyl) fluorene in the molecule. It is a polyvalent ether compound having.
Of these, particularly preferred are organic acid ester compounds, acid halide compounds and ether compounds, and particularly preferred are those selected from the group consisting of phthalic acid diester compounds and phthalic acid dihalide compounds.

The content of the electron donor (A1a-4) in the solid catalyst component (A) for α-olefin polymerization may be 5 to 40 μmol per unit mass of the solid catalyst component (A) for α-olefin polymerization. It may be up to 38 μmol.

1-5. Alkoxysilane compound (A3)
The alkoxysilane compound (A3) contained in the α-olefin polymerization solid catalyst component (A) of the present invention is essential and important to have a specific structure, and can be represented by the following general formula (1). ..
R ¹ R ² _m Si (OR ³ ) _n ... (1)
(Here, R ¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group; R ² represents any free group selected from hydrogen, halogens, hydrocarbon groups and heteroatom-containing hydrocarbon groups. R ³ represents. It is a hydrocarbon group and shows 0 ≦ m ≦ 2, 1 ≦ n ≦ 3, m + n = 3).

2. 2. Method for Producing Solid Catalyst Component (A) for α-olefin Polymerization The method for producing the solid catalyst component for α-olefin polymerization of the present invention is for α-olefin polymerization containing magnesium, titanium, halogen, an electron donor and an alkoxysilane compound. A method for producing the solid catalyst component (A).
It is characterized in that a series of steps of contacting (A2), (A3) and (A4) with the following component (A1) and then washing with a solvent is repeated two or more times.
Component (A1): Solid component containing titanium, magnesium, halogen, and electron donor as essential components Component (A2): Silane compound having an alkenyl group Component (A3): Alkoxysilane compound [However, a silane compound having an alkenyl group Is different. ]
Component (A4): Organoaluminium compound

The solid catalyst component (A) for α-olefin polymerization obtained by the production method of the present invention is a silane compound (A2) having an alkenyl group, an alkoxysilane compound (A3) and an organoaluminum compound with respect to the solid component (A1). (A4) is brought into contact with each other. Further, any component may be contained in any form as long as the effect of the present invention is not impaired.
Each component is described in detail below.

2-1. Solid component (A1)
The solid component (A1) of the present invention contains magnesium (A1a-1), titanium (A1a-2), halogen (A1a-3), and an electron donor (A1a-4) as essential components.
The materials used as magnesium (A1a-1), titanium (A1a-2), halogen (A1a-3), and electron donor (A1a-4) include the above 1. The same as that described in the solid catalyst component (A) for α-olefin polymerization can be used.
The amount ratio of the amount of each component constituting the solid component (A1) of the present invention may be arbitrary as long as the effect of the present invention is not impaired, but generally, the following range is preferable.

The amount of the titanium compound (A1a-2) used is preferably 0.0001 in terms of the molar ratio (the number of moles of the titanium compound / the number of moles of the magnesium compound) with respect to the amount of the magnesium compound (A1a-1) used. It is in the range of about 1,000, more preferably in the range of 0.001 to 100, and particularly preferably in the range of 0.01 to 50.

When a compound that is a halogen source (that is, (A1a-3)) is used in addition to the magnesium compound (A1a-1) and the titanium compound (A1a-2), the amount used is that each of the magnesium compound and the titanium compound is halogen. The molar ratio (number of moles of the halogen source compound / number of moles of the magnesium compound) to the amount of the magnesium compound (A1a-1) used is preferably 0.01, regardless of whether or not the magnesium compound is contained. It is in the range of about 1,000, and particularly preferably in the range of 0.1 to 100.

The amount of the electron donor (A1a-4) used is a molar ratio (number of moles of the electron donor / number of moles of the magnesium compound) to the amount of the magnesium compound (A1a-1) used, and is preferably 0. It is in the range of 001 to 10, and particularly preferably in the range of 0.01 to 5.

The solid component (A1) according to the present invention is obtained by contacting each of the above-mentioned constituent components in the above-mentioned quantitative ratio.
As the contact conditions for each component, it is necessary that oxygen is not present, but any conditions can be used as long as the effects of the present invention are not impaired. Generally, the following conditions are preferable.
The contact temperature is about −50 to 200 ° C., preferably 0 to 150 ° C.
As the contact method, a mechanical method using a rotary ball mill, a vibration mill, or the like, a method of contacting by stirring in the presence of an inert diluent, and the like can be exemplified.

When preparing the solid component (A1), washing with an intermediate and / or finally an inert solvent may be carried out.
Preferred solvent species include aliphatic hydrocarbon compounds such as heptane, aromatic hydrocarbon compounds such as toluene, and halogen-containing hydrocarbon compounds such as 1,2-dichloroethylene and chlorobenzene.

Any method can be used as the method for preparing the solid component (A1) according to the present invention, and more specifically, the methods described as (i) to (vii) below may be exemplified. can. However, the present invention is not limited by the following examples.

(I) Co-grinding method This is a method of supporting a titanium compound on a magnesium compound by co-grinding a magnesium compound containing a halogen represented by magnesium chloride with a titanium compound, and simultaneously or separately with an electron donor. It may be co-ground in the process.
As the mechanical crushing method, any crushing machine such as a rotary ball mill or a vibration mill can be used. Not only a dry pulverization method that does not use a solvent, but also a wet pulverization method that co-pulverizes in the coexistence of an inert solvent can be used.

(Ii) Heat Treatment Method This is a method in which a magnesium compound containing a halogen typified by magnesium chloride and a titanium compound are subjected to contact treatment by stirring in an inert solvent to support the titanium compound on the magnesium compound. The donors may be contacted at the same time or in a separate step.
When a liquid compound such as titanium tetrachloride is used as the titanium compound, the contact treatment can be performed without an inert solvent.
Further, if necessary, an arbitrary component such as a silicon halide compound may be brought into contact at the same time or in a separate step.
Although the contact temperature is not particularly limited, it is often preferable to perform the contact treatment at a relatively high temperature of about 90 ° C to 130 ° C.

(Iii) Dissolution and Precipitation Method In the dissolution and precipitation method, a magnesium compound containing a halogen represented by magnesium chloride is dissolved by contacting it with an electron donor, and the generated solution and a precipitation agent are brought into contact with each other to cause a precipitation reaction. This is a method for forming particles.
Examples of electron donors used for dissolution include alcohol compounds, epoxy compounds, phosphate ester compounds, silicon compounds having an alkoxy group, titanium compounds having an alkoxy group, ether compounds and the like. ..
Examples of precipitates include titanium halide compounds, silicon halide compounds, hydrogen chloride, halogen-containing hydrocarbon compounds, siloxane compounds having a Si—H bond (including polysiloxane compounds), and aluminum. Compounds, etc. can be exemplified.
As a method of contacting the solution and the precipitate, the precipitate may be added to the solution or the solution may be added to the precipitate.
When the titanium compound is not used in either the dissolution or precipitation step, the titanium compound is supported on the magnesium compound by further contacting the particles formed by the precipitation reaction with the titanium compound.
Further, if necessary, the particles formed by the above method may be brought into contact with an arbitrary component such as a titanium halide compound or a silicon halide compound, or may be brought into contact with an electron donor. At this time, the electron donor may be different from that used for dissolution, or may be the same.
The contact order of these arbitrary components is not particularly limited, and they may be contacted as an independent step, or they may be contacted together at the time of dissolution, precipitation, and contact with titanium compounds.
Further, the inert solvent may be present in any of the steps of dissolution, precipitation, and contact with an arbitrary component.

(Iv) Granulation method Similar to the dissolution precipitation method, the granulation method dissolves a magnesium compound containing a halogen represented by magnesium chloride by contacting it with an electron donor, and the resulting solution is mainly physical. It is a method of granulating by a conventional method. The example of the electron donor used for dissolution is the same as the example of the dissolution precipitation method.
Examples of granulation methods include a method of dropping a high-temperature solution into a low-temperature inert solvent, a method of ejecting the solution from a nozzle toward a high-temperature gas phase part to dry it, and a method toward a low-temperature gas phase part. A method of ejecting the solution from a nozzle to cool the solution can be mentioned.
The titanium compound is supported on the magnesium compound by contacting the particles formed by granulation with the titanium compound.
Further, if necessary, it may be brought into contact with an arbitrary component such as a silicon halide compound or an electron donor. At this time, the electron donor may be different from that used for dissolution, or may be the same.
The contact order of these arbitrary components is not particularly limited, and they may be contacted as an independent step, or they may be contacted together at the time of dissolution or contact with a titanium compound.
Further, the inert solvent may be present in any of the steps of dissolution, contact with titanium compounds, and contact with arbitrary components.

(V) Halogenation method of magnesium (Mg) compound The halogenation method of magnesium (Mg) compound is a method of contacting a halogenating agent with a halogen-free magnesium compound to halogenate it, and is an electron donor. May be contacted at the same time or in a separate step.
Examples of the magnesium compound containing no halogen include dialkoxymagnesium compounds, magnesium oxide, magnesium carbonate, magnesium salts of fatty acids, and the like.
When dialkoxymagnesium compounds are used, those prepared in the system by the reaction between metallic magnesium and alcohol can also be used. When this preparation method is used, it is common to form particles by granulation or the like at the stage of a magnesium compound containing no halogen as a starting material.
Examples of the halogenating agent include titanium halide compounds, silicon halide compounds, phosphorus halide compounds, and the like.
When the halogenated titanium compound is not used as the halogenating agent, the halogen-containing magnesium compound formed by halogenation is further brought into contact with the titanium compound to support the titanium compound on the magnesium compound.
Further, if necessary, the particles formed by the above method may be brought into contact with an arbitrary component such as a titanium halide compound or a silicon halide compound, or may be brought into contact with an electron donor.
The contact order of these arbitrary components is not particularly limited, and they may be contacted as an independent step, or they may be contacted together at the time of halogenation of a magnesium compound containing no halogen or contact with titanium compounds. can.
Further, the inert solvent may be present in any of the steps of contact with the titanium halide compounds and contact with the optional component.

(Vi) Precipitation method from an organic magnesium compound A method of contacting a precipitate with a solution of an organic magnesium compound such as a Grignard reagent typified by butylmagnesium chloride, a dialkylmagnesium compound, etc. , Contact treatment may be performed in a separate step.
Examples of the precipitant include titanium compounds, silicon compounds, hydrogen chloride, and the like.
When the titanium compound is not used as the precipitate, the titanium compound is supported on the magnesium compound by further contacting the particles formed by the precipitation reaction with the titanium compound.
Further, if necessary, the particles formed by the above method may be brought into contact with an arbitrary component such as a titanium halide compound or a silicon halide compound, or may be brought into contact with an electron donor.
The contact order of these arbitrary components is not particularly limited, and they may be contacted as an independent step, or they may be contacted together at the time of precipitation or contact with titanium compounds.
Further, the inert solvent may be present in any of the steps of precipitation, contact with titanium compounds, and contact with arbitrary components.

(Vii) Impregnation method A method of impregnating a carrier of an inorganic compound or a carrier of an organic compound with a solution of an organic magnesium compound or a solution of a magnesium compound dissolved in an electron donor.
The examples of the organic magnesium compounds are the same as the examples of the precipitation method from the organic magnesium compounds. The magnesium compound used for dissolving the magnesium compound may or may not contain halogen, and the example of the electron donor is the same as the example of the dissolution precipitation method.
Examples of carriers for inorganic compounds include silica, alumina, magnesia, and the like.
Examples of carriers for organic compounds include polyethylene, polypropylene, polystyrene, and the like.
The carrier particles after the impregnation treatment are immobilized by precipitating the magnesium compound by a physical treatment such as a chemical reaction with a precipitate and drying.
The example of the precipitate is the same as the example of the dissolution precipitation method.
When the titanium compound is not used as the precipitate, the particles thus formed are further brought into contact with the titanium compound to support the titanium compound on the magnesium compound. Further, if necessary, the particles thus formed may be brought into contact with an arbitrary component such as a titanium halide compound or a silicon halide compound, or may be brought into contact with an electron donor.
The contact order of these arbitrary components is not particularly limited, and they may be contacted as an independent step, or they may be contacted together at the time of impregnation, precipitation, drying, and contact with titanium compounds. Further, the inert solvent may be present in any of the steps of impregnation, precipitation, contact with titanium compounds, and contact with arbitrary components.

(Viii) Composite method The methods described in (i) to (vii) above can be combined and used. Examples of combinations include "a method of co-grinding magnesium chloride with an electron donor and then heat-treating it with titanium halide compounds" and "using another electron donor after co-grinding a magnesium chloride compound with an electron donor". "A method of dissolving the dialkoxymagnesium compound with an electron donor and precipitating it by contacting it with titanium halide compounds" and "a method of halogenating the magnesium compound at the same time" , "By contacting carbon dioxide with the dialkoxy magnesium compound, carbonic acid ester magnesium compounds are produced and dissolved at the same time, the formed solution is impregnated into silica, and then the magnesium compound is halogenated by contacting with hydrogen chloride. At the same time, the method of supporting the titanium compound by precipitating and immobilizing the compound and further contacting the halogenated titanium compound with the compound can be mentioned.

2-2. Silicon compound (A2) having an alkenyl group
Examples of the silicon compound (A2) having an alkenyl group used in the present invention include JP-A-2-34707, JP-A-2003-292522, JP-A-2006-169283, and JP-A-2011-74360. The disclosed compounds and the like can be used.
Generally, it is desirable to use a compound represented by the following general formula.
SiR ¹ _n R ² _4-n
(Here, R ¹ is an alkenyl group, R ² is a hydrogen atom, a halogen, an alkyl group or an alkoxy group, and n indicates 1 ≦ n ≦ 4, and when 1 ≦ n ≦ 2. , R ² may be connected to each other to form an annular structure.)

In the formula, R ¹ represents an alkenyl group, and a vinyl group, an allyl group, and a 3-butenyl group are preferable, and a vinyl group and an allyl group are particularly preferable. When the value of n is 2 or more, a plurality of R ^1s may be the same or different.

Further, in the formula, R ² represents a hydrogen atom, a halogen, an alkyl group or an alkoxy group.
Examples of the halogen that can be used as R ² include fluorine, chlorine, bromine, and iodine.
When R ² is an alkyl group, it is generally an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Specific examples of the alkyl group that can be used as ^R2 include methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, texyl group and cyclopentyl. It is desirable to use a group, a cyclohexyl group, or the like.
When R ² is an alkoxy group, it is generally an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Specific examples of the alkoxy group that can be used as R ² include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, and the like. desirable. When the value of n is 2 or less, a plurality of R ^2s may be the same or different. Further, when 1 ≦ n ≦ 2, an annular structure may be formed in which R ^2s are connected to each other.

Specific examples of the silicon compound (A2) having an alkenyl group include vinylsilane, methylvinylsilane, dimethylvinylsilane, trimethylvinylsilane, trichlorovinylsilane, dichloromethylvinylsilane, chlorodimethylvinylsilane, chloromethylvinylsilane, triethylvinylsilane, chlorodiethylvinylsilane, and dichloro. Ethylvinylsilane, dimethylethylvinylsilane, diethylmethylvinylsilane, tripentylvinylsilane, triphenylvinylsilane, diphenylmethylvinylsilane, dimethylphenylvinylsilane, 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 ), divinylsilane, dichlorodivinylsilane, dimethyldivinylsilane, diphenyldivinylsilane, allyltrimethylsilane, allyltriethylsilane, allyltri Vinylsilane, allylmethyldivinylsilane, allyldimethylvinylsilane, allylmethyldichlorosilane, allyltrichlorosilane, allyltribromosilane, diallyldimethylsilane, diallyldiethylsilane, diallyldivinylsilane, diallymethylvinylsilane, diallylmethylchlorosilane, diallyldichlorosilane, diallyl Dibromosilane, triallylmethylsilane, triallylethylsilane, triallylvinylsilane, triallylchlorosilane, triallylbromosilane, tetraallylsilane, di-3-butenyldimethylsilane, di-3-butenylsilane diethylsilane, di- 3-Buthenylsilane Divinylsilane, Di-3-Butenylsilane Methylvinylsilane, Di-3-Butenylsilane Methylchlorosilane, Di-3-Butenylsilane Dichlorosilane, Tri-3-butenylsilane Ethylsilane, Tri- 3-Buthenylsilane Vinylsilane, Tri-3-butenylsilane Chlorosilane, Tri-3-butenylsilanebromosilane, Tetra-3-butenylsilane, 1-methyl-1-vinylsilacyclobutane, 1-methyl-1-vinylsila Cyclopentane, 1-methyl-1-vinylsilacyclohexane, 1,1-divinylsilacyclopentane, 1,1-divinylsilacyclohexane, 1-chloro-1-vinylsilacyclopentane, 1-chloro-1-vinylsilacyclo Hexan, 1-allyl-1-methylsilacyclopentane , 1-allyl-1-methylsilacyclohexane and the like can be exemplified.
Among these, vinylsilane compounds are preferable, and trimethylvinylsilane, trichlorovinylsilane, dimethyldivinylsilane, and 1-methyl-1-vinylsilacyclopentane are particularly preferable.

The amount ratio of the amount of the silicon compound (A2) having an alkenyl group to be used may be arbitrary as long as the effect of the present invention is not impaired, but generally, it is preferably within the following range.
The amount of the silicon compound (A2) having an alkenyl group used is the molar ratio to the titanium component constituting the solid component (A1) (the number of moles of the silicon compound (A2) having an alkenyl group / the titanium atom in the solid component (A1). The number of moles) is preferably in the range of 0.001 to 1,000, and particularly preferably in the range of 0.01 to 100.

The silicon compound (A2) having an alkenyl group used in the present invention usually has a large steric hindrance as compared with an α-olefin monomer, and cannot be polymerized with a Ziegler-Natta catalyst.
However, due to the presence of an organic silyl group with a very strong electron donating property, the charge density of the carbon-carbon double bond is very high, and the coordination to the titanium atom, which is the active center, is very high. It is considered to be fast.
Therefore, the silicon compound having an alkenyl group is coordinated and complexed with the Lewis acid point on the magnesium compound which is the carrier, so that the extraction of the titanium compound into the solvent can be suppressed, and the titanium atom is overreduced by the organic aluminum compound. It is expected to have the effect of preventing the deactivation of active points due to impurities and impurities.

2-3. Alkoxysilane compound (A3)
The alkoxysilane compound (A3) used in the method for producing the solid catalyst component (A) for α-olefin polymerization of the present invention is different from the silane compound (A2) having an alkenyl group.
In the method for producing the solid catalyst component (A) for α-olefin polymerization of the present invention, the component (A3) may be a silicon compound represented by the following general formula (1).
R ¹ R ² _m Si (OR ³ ) _n ... (1)
(Here, R ¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group; R ² represents any free group selected from hydrogen, halogens, hydrocarbon groups and heteroatom-containing hydrocarbon groups. R ³ represents. It is a hydrocarbon group and indicates 0 ≦ m ≦ 2, 1 ≦ n ≦ 3, m + n = 3).

In the formula, R ¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group.
When R ¹ is a hydrocarbon group, it is a hydrocarbon group excluding the alkenyl group.
The hydrocarbon group that can be used as R ¹ is generally one having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ¹ include a linear aliphatic hydrocarbon group represented by an n-propyl group and a branched form represented by an i-propyl group and a t-butyl group. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group typified by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. More preferably, it is desirable to use a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group as R ¹ , and in particular, an i-propyl group, an i-butyl group, a t-butyl group, a texyl group, a cyclopentyl group, and the like. It is desirable to use a cyclohexyl group, etc.
When R ¹ is a heteroatom-containing hydrocarbon group, it is desirable that the heteroatom be selected from nitrogen, oxygen, sulfur, phosphorus or silicon, and in particular nitrogen or oxygen.
As the skeleton structure of the heteroatom-containing hydrocarbon group of R ¹ , it is desirable to select from the examples in the case where R ¹ is a hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.

Further, in the formula, R ² represents an arbitrary free group selected from a hydrogen atom, a halogen, a hydrocarbon group and a hetero atom-containing hydrocarbon group.
Examples of the halogen that can be used as R ² include fluorine, chlorine, bromine, and iodine.
When R ² is a hydrocarbon group, it is a hydrocarbon group excluding the alkenyl group.
The hydrocarbon group that can be used as ^R2 is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ² include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, and a branch represented by an i-propyl group and a t-butyl group. Examples thereof include an alicyclic hydrocarbon group represented by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group represented by a phenyl group. Among them, it is desirable to use a methyl group, an ethyl group, a propyl group, an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group, a texyl group, a cyclopentyl group, a cyclohexyl group and the like.
When R ² is a heteroatom-containing hydrocarbon group, it is desirable to select from the examples when R ¹ is a heteroatom-containing hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.
Further, regardless of the value of m, R ² may be the same as or different from R ¹ .

Further, in the formula, R ³ represents a hydrocarbon group. The hydrocarbon group that can be used as R ³ is generally 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
Specific examples of the hydrocarbon group that can be used as R ³ include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, and a branch represented by an i-propyl group and a t-butyl group. Examples thereof include a aliphatic hydrocarbon group. Of these, a methyl group and an ethyl group are most preferable. When the value of n is 2 or more, a plurality of ^R3s existing may be the same or different.

Preferred examples of the alkoxysilane compound (A3) that can be used in the present invention are t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, and t-butyl-n-propyldimethoxysilane. , Cyclohexylmethyldimethoxysilane, Cyclohexylethyldimethoxysilane, Dicyclopentyldimethoxysilane, Diisopropyldimethoxysilane, Diisobutyldimethoxysilane, Isobutylisopropyldimethoxysilane, n-propylmethyldimethoxysilane, t-butyltriethoxysilane, Bis (diethylamino) dimethoxysilane, Examples thereof include diethylaminotriethoxysilanemethoxysilane and bisperhydroisoquinolinodimethoxysilane.
These alkoxysilane compounds can be used alone or in combination of a plurality of compounds.

The amount ratio of the amount of the alkoxysilane compound (A3) used may be arbitrary as long as the effect of the present invention is not impaired, but generally, it is preferably within the following range.
The amount of the alkoxysilane compound (A3) used is the molar ratio (the number of moles of the alkoxysilane compound (A3) / the number of moles of titanium atoms in the solid component (A1)) to the titanium component constituting the solid component (A1). It is preferably in the range of 0.01 to 1,000, and particularly preferably in the range of 0.1 to 100.

It is considered that the alkoxysilane compound (A3) used in the present invention is coordinated in the vicinity of a titanium atom that can be an active point and controls catalytic performance such as catalytic activity of the active point and regularity of the polymer. ..

2-4. Organoaluminium compound (A4)
As the organoaluminum compound (A4) used in the present invention, the compound disclosed in JP-A-2004-124090 can be used. Generally, it is desirable to use a compound represented by the following general formula.
R ¹ _a AlX _b (OR ² ) _c
(In the formula, R ¹ represents a hydrocarbon group. X represents a halogen or a hydrogen atom. R ² represents a hydrocarbon group or a bridging group by Al. A ≧ 1, 0 ≦ b ≦ 2, 0 ≦ c ≦ 2. a + b + c = 3.)
In the formula, R ¹ is a hydrocarbon group, and it is preferable to use one having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specific examples of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group and the like. Of these, a methyl group, an ethyl group and an isobutyl group are most preferable.
In the formula, X is a halogen or hydrogen atom. Examples of the halogen that can be used as X include fluorine, chlorine, bromine, and iodine. Of these, chlorine is particularly preferred.
In the formula, R ² is a hydrocarbon group or a cross-linking group with Al. When R ² is a hydrocarbon group, R ² can be selected from the same group as in the example of the hydrocarbon group of R ¹ . Further, as the organoaluminum compound (A4), alumoxane compounds typified by methylarmoxane can also be used, in which case R ² represents a cross-linking group due to Al.

Examples of the compound that can be used as the organic aluminum compound (A4) include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum chloride, diethylaluminum ethoxide, methylalmoxane, and the like. Can be mentioned.
Of these, triethylaluminum and triisobutylaluminum are preferable.
As the organoaluminum compound (A4), not only a single compound but also a plurality of compounds can be used in combination.

The amount ratio of the amount of the organoaluminum compound (A4) used may be arbitrary as long as the effect of the present invention is not impaired, but generally, it is preferably within the following range.
The amount of the organic aluminum compound (A4) used is a molar ratio (the number of moles of aluminum atoms / the number of moles of titanium atoms in the solid component (A1)) to the titanium component constituting the solid component (A1), and is preferably 0. It is in the range of 1 to 100, and particularly preferably in the range of 1 to 50.

The organoaluminum compound (A4) used in the present invention is used for the purpose of efficiently supporting the alkoxysilane compound (A3) in the solid catalyst component (A) for α-olefin polymerization.
Therefore, it has a different purpose of use and is distinguished from the organoaluminum compound (B) used as a co-catalyst in the main polymerization described later.

2-5. Compound (A5) having at least two ether bonds
The solid catalyst component (A) for α-olefin polymerization obtained by the production method of the present invention is a silicon compound (A2) having an alkenyl group, an alkoxysilane compound (A3) and an organic substance with respect to the above-mentioned solid component (A1). Although it is formed by contacting the aluminum compound (A4), a compound (A5) having at least two ether bonds may be contacted as an optional component as long as the effect of the present invention is not impaired.
As the compound (A5) having at least two ether bonds that can be used in the present invention, the compounds disclosed in JP-A-3-294302 and JP-A-8-333413 can be used. Generally, it is desirable to use a compound represented by the following formula.
R ³ OC (R ² ) ₂ -C (R ¹ ) ₂ -C (R ² ) -OR ³
(In the formula, R ¹ and R ² represent any free group selected from a hydrogen atom, a hydrocarbon group or a heteroatom-containing hydrocarbon group. R ³ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. .)
Specifically, the compound (A5) having at least two ether bonds is, for example, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isobutyl-. 2-Isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 9,9-bis (methoxymethyl) fluorene And so on.
Further, the compound (A5) having at least two ether bonds can be used not only alone but also in combination with a plurality of compounds. Further, it may be the same as or different from the multivalent ether compound used as the electron donor (A1a-4) which is an essential component in the solid component (A1).

The amount ratio of the amount of the compound (A5) having at least two ether bonds to be used may be arbitrary as long as the effect of the present invention is not impaired, but generally, it is preferably within the following range.
The amount of the compound (A5) having at least two ether bonds used is the molar ratio to the titanium component constituting the solid component (A1) (the number of moles of the compound (A5) having at least two ether bonds / the solid component (A1)). The number of moles of titanium atoms in the compound) is preferably in the range of 0.01 to 10,000, and particularly preferably in the range of 0.5 to 500.

2-6. Method for preparing solid catalyst component (A) for α-olefin polymerization In the production method of the present invention, an alkenyl group is used with respect to the solid component (A1) when preparing the solid catalyst component (A) for α-olefin polymerization. A series of steps of contact treatment of the silicon compound (A2), the alkoxysilane compound (A3), and the organoaluminum compound (A4) having the above-mentioned, and subsequent washing with a solvent are repeated two or more times.
That is, at least the first contact treatment → the first cleaning → the second contact treatment → the second cleaning is performed in this order.
Specifically, first, the solid component (A1) is brought into contact with a silicon compound (A2) having an alkenyl group, an alkoxysilane compound (A3), and an organoaluminum compound (A4) (first contact treatment).
Then, the reaction product containing the obtained component (A1) is washed with a solvent (first washing).
Then, the silicon compound (A2) having an alkenyl group, the alkoxysilane compound (A3), and the organoaluminum compound (A4) are brought into contact with the reaction product containing the obtained component (A1) (second contact). process).
Then, the obtained reaction product is washed with a solvent (second washing).

In the contact treatment, the silicon compound (A2) having an alkenyl group, the alkoxysilane compound (A3), and the organoaluminum compound (A4) are all the same or different compounds used in a plurality of contacts. good.
The solid catalyst component (A) for α-olefin polymerization of the present invention is obtained by contacting each of the above-mentioned constituent components in the above-mentioned quantitative ratio.
In addition, the range of the amount of each component used is shown earlier, but this is the amount used per contact, and from the second time onward, if the amount used once is within the range of the above-mentioned amount used. , You may make contact as many times as you like.

As the contact condition of each component of the solid catalyst component (A) for α-olefin polymerization, it is necessary that oxygen is not present, but any condition can be used as long as the effect of the present invention is not impaired. Generally, the following conditions are preferable.
The contact temperature is about −50 to 200 ° C., preferably −10 to 100 ° C., more preferably 0 to 70 ° C., and particularly preferably 10 ° C. or higher and lower than 50 ° C.

As the contact method, a mechanical method using a rotary ball mill, a vibration mill, or the like, a method of contacting by stirring in the presence of an inert diluent, and the like can be exemplified. Preferably, it is desirable to use a method of contacting by stirring in the presence of an inert diluent.

In the contact treatment, any procedure can be used for the contact procedure of the solid component (A1), the silicon compound (A2) having an alkenyl group, the alkoxysilane compound (A3), and the organoaluminum compound (A4). Specific examples include the following procedures (i) to (iv), and among these, the procedure (i) and the procedure (ii) are preferable.
Procedure (i): A method in which a silicon compound (A2) having an alkenyl group is contacted with a solid component (A1), then an alkoxysilane compound (A3) is contacted, and then an organoaluminum compound (A4) is contacted.
Procedure (ii): A method in which a silicon compound (A2) having an alkenyl group and an alkoxysilane compound (A3) are brought into contact with a solid component (A1), and then an organoaluminum compound (A4) is brought into contact with the solid component (A1).
Procedure (iii): A method in which an alkoxysilane compound (A3) is contacted with a solid component (A1), then a silicon compound (A2) having an alkenyl group is contacted, and then an organoaluminum compound (A4) is contacted.
Procedure (iv): A method of contacting all compounds at the same time.
When a compound (A5) having at least two ether bonds is used as an optional component, it can be contacted in any order in the same manner as described above.

Preferred solvents for cleaning include aliphatic hydrocarbon compounds such as heptane, aromatic hydrocarbon compounds such as toluene, and halogen-containing hydrocarbon compounds such as 1,2-dichloroethylene and chlorobenzene. ..

2-7. Prepolymerization The solid catalyst component (A) for α-olefin polymerization in the present invention may be prepolymerized before being used in the main polymerization. By forming a small amount of polymer around the catalyst in advance prior to the polymerization process, the catalyst becomes more uniform and the amount of fine powder generated can be suppressed.
As the monomer in the prepolymerization, the compound disclosed in JP-A-2004-124090 can be used.
Examples of specific compounds include olefins typified by ethylene, propylene, 1-butene, 3-methylbutene-1,4-methylpentene-1, styrene, α-methylstyrene, allylbenzene, and chlorostyrene. , Etc., and 1,3-butadiene, isoprene, 1,3-pentadiene, 1,5-hexadiene, 2,6-octadien, dicyclopentadiene, 1,3-cyclohexadiene, 1 , 9-Decadien, diene compounds typified by divinylbenzene, and the like.
Among them, ethylene, propylene, 3-methylbutene-1, 4-methylpentene-1, styrene, divinylbenzene and the like are particularly preferable.

When a prepolymerized solid catalyst component (A) for α-olefin polymerization is used, the prepolymerization can be carried out by any procedure in the preparation procedure. For example, after the solid catalyst component (A) for α-olefin polymerization is prepolymerized, the components (A2 to A4) can be brought into contact with each other. Further, when the solid catalyst component (A) for α-olefin polymerization and the components (A2 to A4) are brought into contact with each other, prepolymerization may be performed at the same time.

As the reaction conditions between the solid catalyst component (A) for α-olefin polymerization and the above-mentioned monomer, any conditions can be used as long as the effects of the present invention are not impaired. Generally, the following range is preferable.
On the basis of 1 gram of the solid catalyst component (A) for α-olefin polymerization, the prepolymerization amount of the above-mentioned monomer is in the range of 0.001 to 100 g, preferably 0.1 to 50 g, and more preferably 0. It is preferably in the range of 5 to 10 g.
The reaction temperature during prepolymerization is −150 to 150 ° C., preferably 0 to 100 ° C. Then, it is desirable that the reaction temperature at the time of prepolymerization is lower than the polymerization temperature at the time of main polymerization.
The reaction is generally preferably carried out under stirring, and at that time, an inert solvent such as hexane or heptane can also be present.
The prepolymerization may be performed a plurality of times, and the monomers used at this time may be the same or different. Further, after the prepolymerization, the washing can be performed with an inert solvent such as hexane or heptane.

3. 3. α-olefin polymerization catalyst The α-olefin polymerization catalyst of the present invention is the α-olefin polymerization solid catalyst component (A) or the α-olefin polymerization solid catalyst component (A) obtained by the production method. It is characterized by containing the following component (B).
Component (B): Organoaluminium compound

3-1. Organoaluminium compound (B)
As the organoaluminum compound (B) that can be used in the present invention, the compound disclosed in JP-A-2004-124090 can be used.
Preferably, it can be selected from the same group as the example in the organoaluminum compound (A4) which is a component for preparing the solid catalyst component (A) for α-olefin polymerization.
The organoaluminum compound (B) that can be used as the catalyst for α-olefin polymerization is the same as the organoaluminum compound (A4) that can be used when preparing the solid catalyst component (A) for α-olefin polymerization. May be different.
As the organoaluminum compound (B), not only a single compound but also a plurality of compounds can be used in combination.
The amount of the organoaluminum compound (B) used is the molar ratio to the titanium component constituting the α-olefin polymerization solid catalyst component (A) (the number of moles of the organoaluminum compound (B) / the α-olefin polymerization solid catalyst component (). The number of moles of titanium atoms in A) is preferably in the range of 1 to 5,000, and particularly preferably in the range of 10 to 500.

3-2. Organosilicon compound (C)
In the present invention, the catalyst for α-olefin polymerization may contain an optional component such as an organosilicon compound (C) and a compound (D) having at least two ether bonds as long as the effect of the present invention is not impaired. good.
As the organosilicon compound (C) used as an optional component in the catalyst for α-olefin polymerization of the present invention, the compound disclosed in JP-A-2004-124090 can be used. Preferably, it can be selected from the same group as the example in the alkoxysilane compound (A3) which is a component for preparing the solid catalyst component (A) for α-olefin polymerization.
Further, the organosilicon compound (C) used here may be the same as or different from the alkoxysilane compound (A3) contained in the solid catalyst component (A) for α-olefin polymerization.
Further, when the organosilicon compound (C) is used, the amount used is the molar ratio to the titanium component constituting the solid catalyst component (A) for α-olefin polymerization (the number of moles of the organosilicon compound (C) / α-olefin polymerization). The number of moles of titanium atoms in the solid catalyst component (A)) is preferably in the range of 0.01 to 10,000, and particularly preferably in the range of 0.5 to 500.

3-3. Compound (D) having at least two ether bonds
In the α-olefin polymerization catalyst according to the present invention, the compound (D) having at least two ether bonds used as an optional component is disclosed in JP-A-3-294302 and JP-A-8-333413. Compounds and the like can be used.
Preferably, it can be selected from the same group as in the example of the compound (A5) having at least two ether bonds used in the solid catalyst component (A) for α-olefin polymerization. At this time, a compound (A5) having at least two ether bonds used as an optional component when preparing the α-olefin polymerization solid catalyst component (A), and at least a compound (A5) used as an optional component of the α-olefin polymerization catalyst. The compound (D) having two ether bonds may be the same or different.
As the compound (D) having at least two ether bonds, not only a single compound but also a plurality of compounds can be used in combination.
When the compound (D) having at least two ether bonds is used, the amount used is the molar ratio to the titanium component constituting the solid catalyst component (A) for α-olefin polymerization (the compound (D) having at least two ether bonds). The number of moles of the titanium atom in the solid catalyst component (A) for α-olefin polymerization), preferably in the range of 0.01 to 10,000, and particularly preferably in the range of 0.5 to 500. Is desirable.

3-4. Other Compounds A component other than the above-mentioned organosilicon compound (C) and the compound (D) having at least two ether bonds is used as an optional component of the α-olefin polymerization catalyst as long as the effect of the present invention is not impaired. be able to. For example, the compound (E) having a C (= O) N bond in the molecule disclosed in JP-A-2004-124090 and the sulfite ester compound (F) disclosed in JP-A-2006-225449 can be used. By using it, it is possible to suppress the formation of an amorphous component such as CXS. In this case, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 1-ethyl-2-pyrrolidinone, dimethyl sulfite, diethyl sulfite and the like can be mentioned as preferable examples.
Further, as disclosed in Japanese Patent Application Laid-Open No. 8-66710, an organometallic compound having a metal atom other than Al, such as diethylzinc (G), can also be used.
When the compound (E) having a C (= O) N bond in the molecule, the sulfite ester compound (F) and the diethyl zinc (G) are used, the amount used constitutes the solid catalyst component (A) for α-olefin polymerization. The molar ratio to the titanium component (the number of moles of the optional components (E), (F), (G) / the number of moles of the titanium atom in the solid catalyst component (A) for α-olefin polymerization) is preferably 0.001. It is in the range of about 1,000, and particularly preferably in the range of 0.05 to 500.

4. Method for Producing α-olefin Polymer The method for producing an α-olefin polymer of the present invention is characterized by homopolymerizing or copolymerizing an α-olefin using the α-olefin polymerization catalyst.

4-1. Polymerization of α-olefin The catalyst for α-olefin polymerization of the present invention is used.
As the polymerization of the α-olefin, slurry polymerization using a hydrocarbon solvent, liquid phase no solvent polymerization using substantially no solvent, vapor phase polymerization and the like may be used.
As the polymerization solvent in the case of slurry polymerization, a hydrocarbon solvent such as pentane, hexane, heptane, or cyclohexane is used.
The polymerization method adopted may be any method such as continuous polymerization, batch polymerization or multistage polymerization.
The polymerization temperature is usually about 30 to 200 ° C., preferably 50 to 150 ° C., and hydrogen may be used as the molecular weight adjusting agent at that time.

4-2. α-olefin monomer raw material In the present invention, the α-olefin is represented by the following general formula.
R-CH = CH ₂
(In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms and may have a branching group.)
Specifically, they are α-olefins such as propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. In addition to the homopolymerization of these α-olefins, random copolymerization with a monomer copolymerizable with the α-olefin (for example, ethylene, α-olefins, dienes, styrenes, etc.) can also be performed.
It is also possible to carry out block copolymerization in which homopolymerization is carried out in the first stage and then random copolymerization is carried out in the second stage.
The copolymerizable monomer can be used up to 15% by mass in random copolymerization and up to 50% by mass in block copolymerization.
Of these, α-olefin homopolymerization and block copolymerization are preferable, and propylene homopolymerization and block copolymerization in which the first stage is propylene homopolymerization are most preferable.

The index of the α-olefin polymer polymerized according to the present invention is not particularly limited and can be appropriately adjusted according to various uses.
Generally, the MFR of the α-olefin polymer is preferably in the range of 0.01 to 10,000 g / 10 minutes, and particularly preferably in the range of 0.1 to 1,000 g / 10 minutes. be.

The α-olefin polymer obtained by the production method of the present invention preferably has high stereoregularity.
Here, the stereoregularity of polypropylene is shown. The high degree of stereoregularity of polypropylene can be evaluated by ¹³ C-NMR.
¹³ It is preferable that the mm fraction of the propylene unit 3 chain obtained by C-NMR has a stereoregularity of 96.0% or more.
The mm fraction is the ratio of 3 chains of propylene units in which the direction of the methyl branch in each propylene unit is the same in any 3 chains of propylene units consisting of a head-tail bond in the polymer chain, and the upper limit is 100%. be.
This mm fraction is a value indicating that the three-dimensional structure of the methyl group in the polypropylene molecular chain is isotropically controlled, and the higher the value, the higher the control.
By setting the mm fraction in the range shown below, the flexural modulus, which is an index of the rigidity of the propylene polymer, can be increased.
That is, when the mm fraction is smaller than the value shown below, the mechanical properties tend to decrease, for example, the bending elastic modulus, which is an index of the rigidity of the propylene polymer, decreases.
Therefore, the propylene polymer obtained by the production method of the present invention preferably has a mm fraction of 96.0% or more, more preferably 97.0% or more, and the upper limit is 100% as described above.

The mm fraction of the propylene unit 3 chain can be calculated using the ¹³ C-NMR spectrum.
Spectrum attribution can be made with reference to Polymer Journal, Vol. 16, pp. 717 (1984), Macromolecules, Vol. 8, pp. 687 (1975), and Polymer, Vol. 30, pp. 1350 (1989).
A more specific method for determining the mm fraction is shown below.
Signals derived from the methyl group of the central propylene of a three-chain head-to-tail bond centered on the propylene unit occur in three regions, depending on its configuration.
mm: Approximately 24.0 to approximately 21.1 ppm
mr + rm: about 21.1 to about 20.4 ppm
rr: Approximately 20.4 to approximately 19.7 ppm
The chemical shift range of each region slightly shifts depending on the molecular weight and the copolymer composition, but the above three regions can be easily identified.
Here, mm, mr + rm and rr are represented by the following structural formulas 1- (a) to 1- (c), respectively.

Further, the terminal structure may have the following structural formulas 2- (a) to 2- (d).

Of these, carbon A1, A1', and C2 signals appeared in the mm region, carbon A4', B4', C5', and D3 signals appeared in the mr region, and carbon B2 signals appeared in the rr region, and head-tail binding was performed. It is a signal that is not based on three chains. Therefore, when calculating the mm fraction, carbons A1, A1', A4', B4', B2, C2, and C5'are obtained from the signal area of the mm region, the signal area of the mr region, and the signal area of the rr region, respectively. , D3 based signal area needs to be reduced.
The signal area based on carbon A1, the signal area based on carbon A1', and the signal area based on carbon A4' can be evaluated from the signal area of carbon A2 (resonant at around 25.7 ppm) of structural formula 2- (a).
The signal area based on carbon B2 and the signal area based on carbon B4'are the sum of the signal areas of carbon B1 (resonance near 14.4 ppm) and carbon B3 (resonance near 39.6 ppm) of structural formula 2- (b). It can be evaluated from 1/2 of.
The signal area based on carbon C2 and the signal area based on carbon C5'can be evaluated from carbon C1 (resonance at around 14.1 ppm) of structural formula 2- (c).
The signal area based on carbon D3 can be evaluated from 1/2 of the sum of the signal areas of carbon D5 (resonance near 16.2 ppm) and carbon D2 (resonance near 31.8 ppm) of structural formula 2- (d).

The mm fraction is calculated from the following formula (I).
mm fraction (%) = I _mm × 100 / (I _mm + I rm + _rm + I _rr ) ・ ・ ・ (I)
[In the above formula (I), I _mm , I _{rm + rm} , and I _rr are as follows.
I _rr (signal intensity in the rr region) = I _{20.4 to 19.7-} (I _14.5-14.4 + I _{39.7 to 39.5} ) / 2
I _{rm + rm} (signal intensity in the mr region) = I _{21.1 to 20.4-} (I _14.5-14.4 + I _{39.7 to 39.5} ) / 2-I _{25.8 to 25.7} -I _{14.1 to 14.0-} (I _{16.2 to 16.1} + I _{31.9 to 31.8} ) / 2
I _CH3 (Signal intensity in _CH3 region) = I _{24.0 to 19.7}
I _mm (signal intensity in the mm region) = I _CH3 -I _{rm + rm} -I _rr -2 x I _{25.8 to 25.7} -I _{14.1 to 14.0} ]

The α-olefin polymer polymerized according to the present invention is characterized by having extremely few amorphous components, having high stereoregularity, and having a good odor and hue.
Generally, the preferred range of the cold xylene-soluble component (CXS) as an amorphous component of the α-olefin polymer varies depending on the application. For example, in applications where a hard molded product is preferred, such as for general injection applications, in the case of polypropylene, the cold xylene soluble content (CXS) is preferably 2% by mass or less, more preferably 1.6% by mass or less. The lower limit is 0.1% by mass or more, more preferably 0.2% by mass or more.
Moreover, the polymer particles obtained by the present invention show excellent particle properties. Generally, the particle properties of polymer particles are evaluated by polymer bulk density, particle size distribution, particle appearance, and the like.
The polymer particles obtained by the present invention have a polymer bulk density in the range of 0.35 to 0.55 g / ml, preferably in the range of 0.40 to 0.50 g / ml.

The α-olefin polymer polymerized according to the present invention has extremely few amorphous components and has high stereoregularity, so that it has high density, high rigidity and high heat resistance, and has excellent properties.
In addition, this α-olefin polymer is produced in high yield, and in particular, it is an industrial material such as automobile parts and home appliance parts that are required to have high rigidity and high heat resistance, or a packaging material because it is less sticky. Can be suitably used for the above-mentioned applications.

Next, the present invention will be specifically described with reference to Examples, but the present invention is not restricted by these Examples as long as it does not deviate from the gist thereof. The measurement method in this embodiment is as follows.

(Various physical property measurement methods)
(1) Titanium content:
The sample was accurately weighed, hydrolyzed, and then measured using the colorimetric method. For the sample after prepolymerization, the content was calculated using the mass excluding the prepolymerized polymer.

(2) Phthalate content:
The sample was accurately weighed, the sample was decomposed with sulfuric acid, and then the phthalate ester was extracted into heptane. The concentration of phthalate ester in the obtained heptane solution was determined by comparison with the standard sample using gas chromatography. The content of phthalate ester contained in the sample was calculated from the concentration of phthalate ester in heptane and the mass of the sample. For the sample after prepolymerization, the content was calculated using the mass excluding the prepolymerized polymer.

(3) Alkoxysilane compound content:
The sample was accurately weighed and decomposed with methanol. The concentration of the silicon compound in the obtained methanol solution was determined by comparison with the standard sample using gas chromatography. The content of the silicon compound contained in the sample was calculated from the concentration of the silicon compound in methanol and the mass of the sample. For the sample after prepolymerization, the content was calculated using the mass excluding the prepolymerized polymer.

(4) Polymer bulk density:
The bulk density of the powder sample was measured using a device according to ASTM D1895-69.

(5) MFR:
Evaluation was performed using a melt indexer manufactured by Takara Co., Ltd. under the conditions of 230 ° C. and 21.18N based on JIS-K6921.

(6) Amount of xylene-soluble component at 23 ° C. (CXS: mass%):
The sample (about 5 g) was once completely dissolved in p-xylene (300 ml) at 140 ° C. After that, the mixture was cooled to 23 ° C. and the polymer was precipitated at 23 ° C. for 12 hours. After filtering the precipitated polymer, p-xylene was evaporated from the filtrate. The polymer remaining after evaporation of p-xylene was dried under reduced pressure at 100 ° C. for 2 hours. The dried polymer was weighed to give a CXS value as% by weight with respect to the sample.

(7) mm fraction (3 chains of propylene units):
The mm fraction of the propylene unit 3 chain was calculated using a ¹³ C-NMR spectrum.
¹³ C-NMR measurement conditions:
[Sample preparation and measurement conditions]
200 mg of sample, o-dichlorobenzene / benzene deuterated bromide (C ₆ D ₅ Br) = 4/1 (volume ratio) 2.4 ml, and hexamethyldisiloxane, which is a reference substance for chemical shift, together. The sample was placed in an NMR sample tube having an inner diameter of 10 mmφ, replaced with nitrogen, sealed, and uniformly dissolved with a block heater at 150 ° C.
For the NMR measurement, an AV400 type NMR device of Bruker Biospin Co., Ltd. equipped with a 10 mmφ cryoprobe was used.
¹³ The measurement conditions of C-NMR were the sample temperature of 120 ° C., the pulse angle of 90 °, the pulse interval of 15 seconds, the number of integrations of 512 times, and the measurement by the broadband decoupling method.
The chemical shift was set to 1.98 ppm for the ¹³ C signal of hexamethyldisiloxane, and the chemical shift of the other ¹³ C signals was based on this.

(Example 1)
[Preparation of solid component (A1)]
An autoclave with a capacity of 10 L equipped with a stirrer was sufficiently replaced with nitrogen, and 2 L of purified toluene was introduced.
Here, at room temperature, 200 g of Mg (OEt) ₂ was added as a magnesium source, and 1 L of TiCl ₄ was added as a titanium source and a halogen source.
The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was introduced as an electron donor.
Then, the temperature was raised to 110 ° C. and a 3 hr reaction was carried out. The reaction product was thoroughly washed with purified toluene.
Then, purified toluene was introduced to adjust the total liquid volume to 2 L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and a 2 hr reaction was carried out. The reaction product was thoroughly washed with purified toluene.
Then, purified toluene was introduced to adjust the total liquid volume to 2 L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and a 2 hr reaction was carried out. The reaction product was thoroughly washed with purified toluene. Further, using purified n-heptane, toluene was replaced with n-heptane to obtain a slurry of the solid component (A1).

[Preparation of solid catalyst component (A) for α-olefin polymerization]
An autoclave having a capacity of 20 L equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the slurry of the solid component (A1) was introduced as the solid component (A1). Purified n-heptane was introduced to adjust the concentration of the solid component (A1) to 25 g / L.
50 ml of _SiCl4 was added thereto as a halogen source, and a 1 hr reaction was carried out at 90 ° C. The reaction product was then thoroughly washed with purified n-heptane.
(First contact treatment)
Then, purified n-heptane was introduced to adjust the liquid level to 4 L. Here, 30 ml of dimethyldivinylsilane was used as the component (A2), 30 ml of (i-Pr) ₂ Si (OMe) ₂ was used as the component (A3), and Et ₃ was an n-heptane diluted solution of Et ₃ Al as the component (A4). 80 g of Al was added, and a 2 hr reaction was carried out at 40 ° C.
(First cleaning)
Then, the reaction product containing the obtained component (A1) was thoroughly washed with purified n-heptane.
(Second contact processing)
Then, purified n-heptane was introduced into an autoclave into which the reaction product containing the component (A1) was introduced, and the liquid level was adjusted to 4 L. Here, 30 ml of dimethyldivinylsilane was used as the component (A2), 30 ml of (i-Pr) ₂ Si (OMe) ₂ was used as the component (A3), and Et ₃ was an n-heptane diluted solution of Et ₃ Al as the component (A4). 80 g of Al was added, and a 2 hr reaction was carried out at 40 ° C.
(Second cleaning)
Then, the obtained reaction product was thoroughly washed with purified n-heptane.
Then, a solid catalyst component (A) for α-olefin polymerization was obtained.
Therefore, in Example 1, the series of treatments of the contact treatment of the components (A1), (A2), (A3) and (A4) and the subsequent cleaning was repeated twice (that is, the first contact treatment → The treatment was performed in the order of first cleaning → second contact treatment → second cleaning).

[Prepolymerization]
Using the solid catalyst component (A) for α-olefin polymerization obtained above, prepolymerization was carried out by the following procedure.
Purified n-heptane was introduced into the solid catalyst component (A) for α-olefin polymerization obtained above, and the concentration of the solid catalyst component (A) for α-olefin polymerization was adjusted to 20 g / L. ..
After cooling the slurry to 10 ° C., 10 g of an n-heptane diluted solution of Et ₃ Al as a component (A4) was added as Et ₃ Al, and 210 g of propylene was supplied over 4 hours.
After the supply of propylene was finished, the reaction was continued for another 30 minutes.
The gas phase was then sufficiently replaced with nitrogen and the reaction product was thoroughly washed with purified n-heptane.
The obtained slurry was taken out from the autoclave and vacuum dried to obtain a prepolymerized solid catalyst component (A) for α-olefin polymerization.
The solid catalyst component (A) for α-olefin polymerization after this prepolymerization contained 2.0 g of polypropylene per 1 g.
As a result of analysis, Ti was 189 μmol / g and di-n-butyl phthalate as an electron donor was 38 μmol / g in the portion of the solid catalyst component (A) for α-olefin polymerization after prepolymerization excluding polypropylene. , 400 μmol / g of (i-Pr) ₂ Si (OMe) ₂ was contained as the component (A3).

[Polymerization of propylene]
A stainless steel autoclave having an internal volume of 3.0 L and equipped with a stirring and temperature control device was heated and dried under vacuum, cooled to room temperature, and replaced with propylene.
Then, 550 mg of Et ₃ Al and 8000 ml of hydrogen were introduced as the component (B).
Then, 1000 g of liquid propylene was introduced to adjust the internal temperature to 70 ° C.
Then, 7 mg of the catalyst component (A) for α-olefin polymerization after the above prepolymerization was press-fitted to polymerize propylene.
After 1 hour, 10 ml of ethanol was press-fitted to terminate the polymerization.
The polymer was dried and weighed. The results are shown in Table 1.

(Example 2)
In Example 1, a series of treatments of the contact treatment of the components (A1), (A2), (A3) and (A4) and the subsequent cleaning was repeated three times (that is, the first contact treatment → the first cleaning → The treatment was carried out in the same manner as in Example 1 except that the treatment was performed in the order of the second contact treatment → the second cleaning → the third contact treatment → the third cleaning).
The portion of the solid catalyst component (A) for α-olefin polymerization after prepolymerization excluding polypropylene contains 170 μmol / g of Ti, 18 μmol / g of di-n-butyl phthalate as an electron donor, and the component (A3). As (i-Pr) ₂ Si (OMe) ₂ , 410 μmol / g was contained. The results are shown in Table 1.

(Example 3)
In Example 2, the same procedure as in Example 2 was carried out except that the amount of Et ₃ Al used as the component (A4) was changed from 80 g to 32 g in [Preparation of solid catalyst component (A) for α-olefin polymerization]. rice field.
In the portion of the solid catalyst component (A) for α-olefin polymerization after prepolymerization excluding polypropylene, Ti was 180 μmol / g, di-n-butyl phthalate as an electron donor was 31 μmol / g, and the component (A3). As a result, (i-Pr) ₂ Si (OMe) ₂ was contained at 253 μmol / g. The results are shown in Table 1.

(Comparative Example 1)
[Preparation of solid component (A1)]
As the solid component (A1), the solid component (A1) described in Example 1 of JP-A-2008-88347 was used.
[Preparation of solid catalyst component (A) for α-olefin polymerization, prepolymerization, polymerization of propylene]
And, except that in Example 1 of this specification, the contact treatment of the components (A1), (A2), (A3) and (A4) and the subsequent washing a series of treatments were performed only once. The same work was performed in the same manner as in Example 1 of the book.
The portion of the solid catalyst component (A) for α-olefin polymerization after prepolymerization excluding polypropylene contains 209 μmol / g of Ti, 105 μmol / g of di-n-butyl phthalate as an electron donor, and the component (A3). As a result, (i-Pr) ₂ Si (OMe) ₂ was contained at 465 μmol / g. The results are shown in Table 1.

(Comparative Example 2)
In Example 1, no cleaning was performed during the two contact treatments of the components (A1), (A2), (A3) and (A4) (that is, the first contact treatment → the second contact treatment → the second. The treatment was carried out in the same manner as in Example 1 except that the treatments were carried out in the order of washing in 1.).
The portion of the solid catalyst component (A) for α-olefin polymerization after prepolymerization excluding polypropylene contains 240 μmol / g of Ti, 78 μmol / g of di-n-butyl phthalate as an electron donor, and the component (A3). As a result, (i-Pr) ₂ Si (OMe) ₂ was contained in an amount of 380 μmol / g. The results are shown in Table 1.
As shown in Table 1, in Comparative Example 2, it can be seen that the electron donor content exceeds 40 μmol / g. It is presumed that the extraction efficiency of the electron donor deteriorated because the cleaning (intermediate cleaning) between the two contact treatments was not performed.

(Example 4)
[Preparation of solid component (A1)]
As the solid component (A1), the solid component (A1) described in Example 1 of JP-A-2001-40028 was used. Specifically, the solid component (A1) was obtained by the following method.
200 ml of dehydrated and deoxidized n-heptane was introduced into a fully nitrogen-substituted flask.
Next, 0.4 mol of MgCl ₂ was introduced as a magnesium source and 0.8 mol of Ti ( _On —C 4H ₉ ) ₄ was introduced as a titanium source, and the mixture was 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 (20 centistokes) was introduced as a polymer silicon compound, and the reaction was carried out for 3 hours.
The solid component produced was washed with n-heptane.
Next, 50 ml of dehydrated and deoxidized n-heptane was introduced into a flask fully substituted with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms.
Next, 25 ml of n-heptane was mixed with _0.4 mol of SiC as a halogen source, introduced into a flask at 30 ° C. over 30 minutes, and reacted at 70 ° C. for 3 hours.
After completion of the reaction, the cells were washed with n-heptane.
Then, 0.024 mol of phthalic acid chloride as an electron donor was mixed with 25 ml of n-heptane, introduced into a flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour.
After completion of the reaction, the cells were thoroughly washed with n-heptane.
Then, 0.4 mol of _SiCl4 was introduced as a halogen source and reacted at 80 ° C. for 6 hours.
After completion of the reaction, the solid component (A1) was sufficiently washed with n-heptane. The titanium content of this product was 1.8% by mass.

[Preparation of solid catalyst component (A) for α-olefin polymerization]
An autoclave having a capacity of 20 L equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the solid component (A1) described in Example 1 of JP-A-2001-40028 was introduced.
(First contact treatment)
Purified n-heptane was introduced to adjust the concentration of the solid component (A1) to 20 g / L.
Here, 20 ml of dimethyldivinylsilane as the component (A2), 25 ml of t-Bu (Me) Si (OMe) ₂ as the component (A3), and Et ₃ Al as an n-heptane diluted solution of Et ₃ Al as the component (A4). 42 g of Al was added, and a 2 hr reaction was carried out at 30 ° C.
(First cleaning)
The reaction product was then thoroughly washed with purified n-heptane.
A series of treatments of the contact treatment of the components (A1), (A2), (A3) and (A4) and the subsequent washing was repeated twice.
[Prepolymerization, polymerization of propylene]
The prepolymerization and the polymerization of propylene were carried out in the same manner as in Example 1.
The portion of the solid catalyst component (A) for α-olefin polymerization after prepolymerization excluding polypropylene contains 230 μmol / g of Ti, 7 μmol / g of di-n-butyl phthalate as an electron donor, and the component (A3). As a result, t-Bu (Me) Si (OMe) ₂ was contained in an amount of 356 μmol / g. The results are shown in Table 1.

(Comparative Example 3)
[Preparation of solid component (A1)]
As in Example 4, the solid component (A1) described in Example 1 of JP-A-2001-40028 was used as the solid component (A1).
[Preparation of solid catalyst component (A) for α-olefin polymerization]
(First contact treatment)
Next, 50 ml of dehydrated and deoxidized n-heptane was introduced into a fully nitrogen-substituted flask, 4 grams of the solid component (A1) obtained above was introduced, and Al (i-C ₄ H) was introduced as the (A4) component. ₉ ) 2.94 g of ₃ (TIBA) was contacted at 30 ° C. for 2 hours. That is, the component (A2) and the component (A3) were not brought into contact with each other.
(First cleaning)
After the contact was completed, it was thoroughly washed with n-heptane.
(Second contact processing)
Next, 30 g of (t-C ₄ H ₉ ) Si (CH ₃ ) (OCH ₃ ) ₂ 0.5 ml as a component (A3) and 1.69 g of Al (C ₂ H ₅ ) ₃ (TEA) as a component (A4). It was contacted at ° C for 2 hours. That is, the component (A2) was not contacted.
(Second cleaning)
After the contact was completed, the mixture was thoroughly washed with n-heptane to obtain a solid catalyst component (A) for α-olefin polymerization mainly composed of magnesium chloride. The titanium content of this product was 1.2% by mass.
[Prepolymerization, polymerization of propylene]
The prepolymerization and the polymerization of propylene were carried out in the same manner as in Example 1.
The portion of the solid catalyst component (A) for α-olefin polymerization after prepolymerization excluding polypropylene contains 250 μmol / g of Ti, 70 μmol / g of di-n-butyl phthalate as an electron donor, and the component (A3). 231 μmol / g of t-Bu (Me) Si (OMe) ₂ was contained. The results are shown in Table 1.

As is clear from Table 1, when Examples and Comparative Examples are compared and examined, polypropylene having a small amount of xylene-soluble component (CXS) at 23 ° C. and high stereoregularity can be obtained by the catalyst for α-olefin polymerization of the present invention. be able to.
Specifically, by comparing Examples 1 to 4 and Comparative Examples 1 to 3, the solid component (A1), the silane compound (A2) having an alkenyl group, the alkoxysilane compound (A3), and the organoaluminum compound (A3) By performing a series of treatments of contact treatment with A4) and subsequent cleaning multiple times, the content of di-n-butyl phthalate used as an electron donor contained in the catalyst component (A) is significantly reduced. You can see that it was possible.
Further, by comparing Example 1 and Comparative Example 2, the amount of the 23 ° C. xylene-soluble component (CXS) of the polymer obtained by the polymerization was washed by washing during the contact treatment at the time of preparing the catalyst component (A). By comparing Examples 2 to 3 with Example 1, the polymer obtained by polymerization was increased by increasing the series of treatments of contact treatment and subsequent cleaning from 2 times to 3 times. It can be seen that the amount of the xylene-soluble component (CXS) at 23 ° C. was further reduced.
Further, by comparing Examples 1 and 3 with Comparative Example 1, a three-dimensional structure of the polymer obtained by polymerization was carried out by performing a series of contact treatments and subsequent washings a plurality of times at the time of preparation of the catalyst component (A). It can be seen that the regularity (mm fraction) could be improved.
Therefore, the catalyst for α-olefin polymerization used in the examples is a catalyst having an extremely small amount of CXS (amount of xylene-soluble component at 23 ° C.) and can obtain a polymer having high stereoregularity, and is compared with the comparative example. It can be said that excellent results have been obtained.

The α-olefin polymerization catalyst of the present invention has high catalytic performance such as stereoregularity, particle properties, and catalytic activity, and in particular, produces an α-olefin polymer having few amorphous components. It can be industrially highly available.

Claims (5)

A method for producing a solid catalyst component (A) for α-olefin polymerization, which comprises magnesium, titanium, halogen, an electron donor and an alkoxysilane compound.
A series of steps of contacting (A2), (A3) and (A4) with the following component (A1) and then washing with a solvent is repeated two or more times, and the content of the electron donor is 5 to 40 μmol. A method for producing an α-olefin polymerization solid catalyst component , which comprises obtaining the α-olefin polymerization solid catalyst component (A) at / g .
Component (A1): Solid component containing titanium, magnesium, halogen, and electron donor as essential components Component (A2): Silane compound having an alkenyl group Component (A3): Alkoxysilane compound [However, a silane compound having an alkenyl group Is different. ]
Component (A4): Organoaluminium compound The method for producing a solid catalyst component for α-olefin polymerization according to claim 1 , wherein the component (A2) is a vinylsilane compound. The method for producing a solid catalyst component for α-olefin polymerization according to claim 1 or 2 , wherein the component (A3) is a silicon compound represented by the following general formula (1).
R ¹ R ² _m Si (OR ³ ) _n ... (1)
(Here, R ¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group; R ² represents any free group selected from hydrogen, halogens, hydrocarbon groups and heteroatom-containing hydrocarbon groups. R ³ represents. It is a hydrocarbon group and indicates 0 ≦ m ≦ 2, 1 ≦ n ≦ 3, m + n = 3). For α-olefin polymerization, which comprises the solid catalyst component (A) for α-olefin polymerization obtained by the production method according to any one of claims 1 to 3 and the following component (B). Method of manufacturing a catalyst.
Component (B): Organoaluminium compound A method for producing an α-olefin polymer, which comprises homopolymerizing or copolymerizing an α-olefin using the α-olefin polymerization catalyst obtained by the production method according to claim 4 .