JP5892032B2 - Method for producing catalyst component for α-olefin polymerization, method for producing catalyst for α-olefin polymerization, and method for producing α-olefin polymer - Google Patents

Description

  The present invention relates to a catalyst component for α-olefin polymerization, a method for producing a catalyst component for α-olefin polymerization, a catalyst for α-olefin polymerization, and a method for producing an α-olefin polymer, and more specifically, contacting a specific phenol compound. An α-olefin polymerization catalyst component obtained by contacting an α-olefin polymerization solid catalyst component obtained by treatment with a silicon compound having an alkenyl group, an organosilicon compound component, and an organoaluminum compound. By using α-olefin polymerization, an α-olefin polymer with extremely low amorphous components, high stereoregularity, high density and high rigidity, and less sticky components can be obtained in high yield. Α-Olefin Polymerization Catalyst Component, α-Olefin Polymerization Catalyst Component Production Method, α-Olefin Polymerization Catalyst and It The present invention relates to a method for producing an α-olefin polymer.

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 household appliances as molded products, and textile materials and Widely used in various applications such as building materials.
In this way, because of the very wide range of applications, polyolefins continue to seek improvements and improvements in various properties from the viewpoint of their applications. In order to meet those demands, mainly improvements in polymerization catalysts Technical development by has been deployed.

Ziegler-based catalysts using transition metal compounds and organometallic compounds have greatly increased the polymerization activity of olefins and realized industrial production. After that, improvements in polymer properties due to 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 was developed, and further, the catalyst activity and stereoregularity were enhanced by using an electron donating compound. A catalyst (for example, refer to Patent Documents 1 to 3), and thereafter, a proposal has been made to further add a specific organosilicon compound to the catalyst component to further improve the catalytic activity and stereoregularity ( (See Patent Document 4). In addition to specific organosilicon compounds, the catalytic activity and stereoregularity are further improved by using a silicon compound with a special structure having an alkenyl group such as a vinyl group or an allyl group as a molecular weight regulator. Proposals have also been made to improve performance such as improving the response of hydrogen used (see, for example, Patent Documents 5 to 7). Furthermore, a proposal has been made to reduce the amorphous component by using a specific amide compound or a sulfite ester combined with an organosilicon compound as an external donor (see Patent Documents 8 and 9). Moreover, many improved techniques are disclosed, such as improving activity and regularity by using a phenol compound as an electron-donating compound with respect to a specific solid catalyst (for example, refer patent documents 10-12). Yes.

  However, as far as the present inventors know, in any of these catalyst systems, improvement of various properties such as stereoregularity and high crystallization of the α-olefin polymer to be produced is still sufficient. In each application field, various properties need to be improved. For example, in the field of automotive parts materials, high rigidity and high density are required as molded products, and particularly high crystallinity, that is, amorphous that dissolves in cold xylene. Further improvement with respect to the reduction of components is desired, and in the field of packaging materials, further improvement of stickiness is strongly demanded.

JP 58-138706 A JP-A-57-59909 JP 58-147409 A JP-A-62-187707 Japanese Patent Laid-Open No. 03-234707 Japanese Patent Application Laid-Open No. 07-2923 JP 2006-169283 A JP 2004-124090 A JP 2006-225449 A Japanese Patent Laid-Open No. 07-173210 Japanese Patent Application Laid-Open No. 11-071421 JP 2001-329012 A

  The object of the present invention is to further increase the rigidity and density in order to meet the demand for further performance improvement from a wide range of application fields in the above-mentioned state of the art in the field of polyolefin materials and catalysts for olefin polymerization. The present invention provides a catalyst capable of producing an α-olefin polymer having reduced stereogenic components, improved stereoregularity or having less sticky components, and a method for producing an α-olefin polymer using the catalyst. is there.

In view of the above problems, the present inventors have made a general thought about the properties and chemical structures of various catalyst components in Ziegler catalysts in order to solve the basic and universal problems in Ziegler catalysts. In addition, various investigations were conducted on various catalyst components and production conditions, and with regard to the active points of the catalyst, diligent studies were conducted on the catalyst components and production conditions involved in stereoregularity and monomer involvement.
As a result, a specific phenol compound is contact-treated with a solid catalyst component containing magnesium, titanium, halogen, and an electron donating compound as essential components, and further, a silicon compound having an alkenyl group, an organosilicon compound component, and an organoaluminum compound. A polymerization catalyst has been found that is excellent in molding processability and is capable of obtaining an extremely high crystalline olefin polymer in a high yield by performing the contact treatment. That is, the present inventors have reduced the amorphous component by a selective coordination and extraction to a catalytic active point where a specific phenol compound forms an amorphous component, and this method is very balanced. Based on these findings, the present inventors have completed the present invention.

That is, according to the first invention of the present invention, a phenol compound represented by the following general formula (1) is previously added to the solid catalyst component (A1a) containing magnesium, titanium, halogen and an electron donating compound as essential components. Α-olefin polymerization characterized in that the following components (A2), (A3) and (A4) are further contact-treated to the α-olefin polymerization solid catalyst component (A1) obtained by subjecting (A1b) to contact treatment A method for producing a catalyst component is provided.
Component (A2): Silicon compound having alkenyl group Component (A3): Organosilicon compound Component (A4): Organoaluminum compound

(In the formula, R ¹ is a tertiary hydrocarbon group having 4 or more carbon atoms and may be the same or different. R ² is a hydrogen atom or a hydrocarbon group, and each is the same. May be different.)

According to the second invention of the present invention, in the first invention, the phenol compound (A1b) is represented by the following general formula (2) : Is provided.

(In the formula, R ¹ is a tertiary hydrocarbon group having 4 to 20 carbon atoms, which may be the same or different.)

According to the third invention of the present invention, the α-olefin polymerization catalyst component (A) produced by the production method of the α-olefin polymerization catalyst component according to the first or second invention, and the following components ( There is provided a method for producing an α-olefin polymerization catalyst characterized in that B) is contact- treated .
Component (B): Organoaluminum compound

According to a fourth aspect of the present invention, there is provided a method for producing an α-olefin polymerization catalyst , characterized in that, in the third aspect , the following component (C) is further contact- treated .
Component (C): Organosilicon compound

According to a fifth aspect of the present invention, there is used an α-olefin polymerization catalyst produced by the method for producing an α-olefin polymerization catalyst according to the third or fourth aspect of the invention. A method for producing a polymer is provided.

As described above, the present invention relates to an α-olefin polymerization catalyst component and the like, and preferred embodiments thereof include the following.
(1) In the first invention, the electron donating compound is a phthalic acid ester compound, a phthalic acid halide compound, a malonic acid ester compound, a succinic acid ester compound, an aliphatic polyvalent ether compound or a polyvalent ether compound. A catalyst component for polymerizing α-olefin.
(2) In the first or second invention, the phenol compound (A1b) is 2,6-di-t-butylphenol, 2,6-di- (1,1-dimethylpropyl) phenol, 2,6-di -(1,1-dimethylbutyl) phenol, 2,6-di- (1-methylcyclohexyl) phenol or 2,6-di- (1-ethyl-1-methylpropyl) phenol -Catalyst component for olefin polymerization.

  The α-olefin polymerization catalyst of the present invention has high catalytic activity and excellent yield during polymerization, and the α-olefin polymer polymerized by the α-olefin polymerization catalyst of the present invention is an amorphous component. Is extremely small, has high stereoregularity, and produces less sticky components.

FIG. 4 is a flowchart for helping and clarifying the catalyst of the present invention.

  Hereinafter, the present invention will be described in detail for each item.

I. α-Olefin Polymerization Catalyst In the present invention, the α-olefin polymerization catalyst component (A) and the organoaluminum compound (B) are used as the α-olefin polymerization catalyst. In this case, an optional component such as an organosilicon compound (C) and / or a compound (D) having at least two ether bonds can be used as long as the effects of the present invention are not impaired.

1. α-Olefin Polymerization Catalyst Component (A)
The α-olefin polymerization catalyst component (A) used in the present invention comprises an alkenyl group-containing silicon compound (A2), organosilicon compound (A3), and organoaluminum with respect to the α-olefin polymerization solid catalyst component (A1). The compound (A4) is contacted. In addition, any component may be included in any form as long as the effects of the present invention are not impaired.

1-1. Solid catalyst component for α-olefin polymerization (A1)
The solid catalyst component (A1) for α-olefin polymerization used in the present invention is essentially composed of magnesium (A1a-1), titanium (A1a-2), halogen (A1a-3) and electron donating compound (A1a-4). A specific phenol compound (A1b) is contact-treated with the solid catalyst component (A1a). In addition, the α-olefin polymerization solid catalyst component (A1) may contain any component in any form as long as the effects of the present invention are not impaired.
Below, each component is explained in full detail.

1-1-1. Solid catalyst component (A1a)
The solid catalyst component (A1a) used in the present invention comprises magnesium (A1a-1), titanium (A1a-2), halogen (A1a-3) and an electron donating compound (A1a-4) as essential components. is there. Moreover, you may include arbitrary components in arbitrary forms in the range which does not impair the effect of this invention.

(1) Magnesium (A1a-1)
Arbitrary things can be used as a magnesium compound used as a magnesium source used with a solid catalyst ingredient (A1a) concerning the present invention. Typical examples thereof include compounds disclosed in JP-A-3-234707.
In general, magnesium halide compounds represented by magnesium chloride, alkoxymagnesium compounds represented by diethoxymagnesium, metal magnesium, oxymagnesium compounds represented by magnesium oxide, and magnesium hydroxide Hydroxymagnesium compounds, Grignard compounds typified by butylmagnesium chloride, organic magnesium compounds typified by butyloctylmagnesium, magnesium salts of inorganic and organic acids typified by magnesium carbonate and magnesium stearate, and the like 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), and the like can be used.
Of these, magnesium chloride, diethoxymagnesium, metallic magnesium and butylmagnesium chloride are particularly preferred.

(2) Titanium (A1a-2)
Arbitrary things can be used as a titanium compound used as a titanium source used with a solid catalyst ingredient (A1a) concerning the present invention. Typical examples include compounds disclosed in JP-A-3-234707.
Regarding the valence of titanium, a titanium compound having any valence of tetravalent, trivalent, divalent, and zero valent can be used, preferably tetravalent and trivalent titanium compounds, more preferably tetravalent. It is desirable to use the titanium compound.

Specific examples of tetravalent titanium compounds include titanium halide compounds typified by titanium tetrachloride, alkoxy titanium compounds typified by tetrabutoxy titanium, tetrabutoxy titanium dimer (BuO) ₃ Ti—O—Ti ( Examples thereof include condensation compounds of alkoxy titanium having a Ti—O—Ti bond typified by OBu) ₃ and organometallic titanium compounds typified by dicyclopentadienyl titanium dichloride. Of these, titanium tetrachloride and tetrabutoxy titanium are particularly preferred.
Specific examples of the trivalent titanium compound include titanium halide compounds represented by titanium trichloride. Titanium trichloride may be a compound produced by any known method such as a hydrogen reduction type, a metal aluminum reduction type, a metal titanium reduction type, or an organoaluminum reduction type.
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 or a compound whose average composition formula is a mixed formula 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.

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

(4) Electron donating compound (A1a-4)
Representative examples of the electron donating compound (A1a-4) used in the solid catalyst component (A1a) according to the present invention include compounds disclosed in JP-A-2004-124090. In general, organic acids and inorganic acids and their derivatives (esters, acid anhydrides, acid halides, amides) compounds, ether compounds, ketone compounds, aldehyde compounds, alcohol compounds, amine compounds, etc. It is desirable to use

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

Examples of the organic acid derivative compound that can be used as the electron-donating compound (A1a-4) include the above-mentioned organic acid esters, acid anhydrides, acid halides, amides, and the like.
Aliphatic and aromatic alcohols can be used as the alcohol that is a constituent of the ester. Among these alcohols, alcohols composed of aliphatic free radicals having 1 to 20 carbon atoms such as ethyl group, butyl group, isobutyl group, heptyl group, octyl group and dodecyl group are preferable. More preferably, an alcohol composed of an aliphatic radical having 2 to 12 carbon atoms is desirable. In addition, an alcohol having an alicyclic free group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group can also be used.

Fluorine, chlorine, bromine, iodine, or the like can be used as the halogen that is a constituent element of the acid halide. Of these, chlorine is most preferred. 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 that is a component of the amide. Among these amines, ammonia, aliphatic amines typified by ethylamine and dibutylamine, amines having aromatic free radicals typified by aniline and benzylamine, and the like can be exemplified as preferable compounds. .

Examples of the inorganic acid compound that can be used as the electron donating compound (A1a-4) include carbonic acid, phosphoric acid, silicic acid, sulfuric acid, and nitric acid.
As derivatives of these inorganic acids, it is desirable to use esters. Specific examples include tetraethoxysilane (ethyl silicate), tetrabutoxysilane (butyl silicate), and tributyl phosphate.

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

Examples of the ketone compound that can be used as the electron donating compound (A1a-4) include aliphatic ketone compounds typified by methyl ethyl ketone, aromatic ketone compounds typified by acetophenone, 2, 2, 4, 6, 6 Examples thereof include polyvalent ketone compounds represented by pentamethyl-3,5-heptanedione.
Examples of aldehyde compounds that can be used as the electron-donating compound (A1a-4) include aliphatic aldehyde compounds typified by propionaldehyde, aromatic aldehyde compounds typified by benzaldehyde, and the like. it can.
Furthermore, examples of alcohol compounds that can be used as the electron-donating compound (A1a-4) include aliphatic alcohol compounds typified by butanol and 2-ethylhexanol, aromatic alcohols typified by benzyl alcohol, and glycerin. Examples thereof include aliphatic polyhydric alcohol compounds.

  Nitrogen-containing compounds that can be used as the electron-donating compound (A1a-4) include aliphatic amine compounds typified by diethylamine and nitrogen typified by 2,2,6,6-tetramethyl-piperidine. Containing alicyclic compounds, aromatic amine compounds typified by aniline, nitrogen atom-containing aromatic compounds typified by pyridine, and 1,3-bis (dimethylamino) -2,2-dimethylpropane Examples thereof include polyvalent amine compounds.

  Furthermore, as a compound that can be used as the electron-donating compound (A1a-4), a compound containing a plurality of the above functional groups in the same molecule can also be used. Examples of such compounds include ester compounds having an alkoxy group in the molecule, such as acetic acid- (2-ethoxyethyl) and ethyl 3-ethoxy-2-t-butylpropionate, and 2-benzoyl-benzoic acid. Ketoester compounds represented by ethyl, ketoether compounds represented by (1-t-butyl-2-methoxyethyl) methylketone, represented by N, N-dimethyl-2,2-dimethyl-3-methoxypropylamine Aminoether compounds, and halogenoether compounds typified by epoxy chloropropane.

  These electron donating compounds (A1a-4) can be used not only alone but also in combination with a plurality of compounds. Of these, preferred are diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalic acid ester compounds typified by diheptyl phthalate, phthalic acid halide compounds typified by phthaloyl dichloride, 2-n- Malonic acid ester compounds having one or two substituents at the 2-position such as butyl-diethyl malonate, one or two substituents at the 2-position such as 2-n-butyl-diethyl succinate, or 2 Succinic acid ester compounds having one or more substituents at each of the 3-position and 2-isopropyl-2-isobutyl-1,3-dimethoxypropane or 2-isopropyl-2-isopentyl-1,3-dimethoxypropane Aliphatic polyhydric ether compounds represented by 1,3-dimethoxypropane having one or two substituents at the 2-position , Polyvalent ether compounds having 9,9-bis (methoxymethyl) aromatic radicals represented by fluorene in the molecule, and the like.

(5) Preparation of solid catalyst component (A1a) The amount ratio of each component constituting the solid catalyst component (A1a) of the present invention can be any as long as the effects of the present invention are not impaired. In general, the following range is preferable.

  The amount of titanium compounds (A1a-2) used is preferably a molar ratio (number of moles of titanium compound / number of moles of magnesium compound) to the amount of magnesium compound (A1a-1) used, preferably 0. It is in the range of 0.0001 to 1,000, more preferably in the range of 0.001 to 100, and particularly preferably in the range of 0.01 to 50.

  In the case of using a halogen source compound (that is, (A1a-3)) in addition to the magnesium compound (A1a-1) and the titanium compound (A1a-2), the amount used is the magnesium compound and the titanium compound. Regardless of whether or not each of them contains a halogen, the molar ratio (number of moles of the compound serving as the halogen source / number of moles of the magnesium compound) with respect to the amount of the magnesium compounds (A1a-1) used, Preferably it is in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100.

  The amount of the electron-donating compound (A1a-4) used is preferably a molar ratio (number of moles of electron-donating compound / number of moles of magnesium compound) with respect to the amount of magnesium compound (A1a-1) used. It is in the range of 0.001 to 10, particularly preferably in the range of 0.01 to 5.

The solid catalyst component (A1a) according to the present invention is obtained by contacting the components constituting the above in the above quantitative ratio.
Although it is necessary for the contact condition of each component not to make oxygen exist, arbitrary conditions can be used in the range which does not impair the effect of this invention. In general, the following conditions are preferred.
The contact temperature is about −50 to 200 ° C., preferably 0 to 150 ° C. Examples of the contact method include a mechanical method using a rotating ball mill and a vibration mill, and a method of contacting by stirring in the presence of an inert diluent.

In preparing the solid catalyst component (A1a), washing may be performed with an inert solvent in the middle and / or finally.
Examples of preferable 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.

  As a method for preparing the solid catalyst component (A1a) according to the present invention, any method can be used. Specifically, the methods described as the following (i) to (viii) are exemplified. Can do. However, this invention is not restrict | limited at all by the following illustration.

(I) Co-grinding method This is a method of supporting a titanium compound on a magnesium compound by co-grinding a magnesium compound containing halogen typified by magnesium chloride with the titanium compound, or simultaneously with an electron-donating compound, or You may grind | pulverize in another process. As the mechanical pulverization method, an arbitrary pulverizer such as a rotating ball mill or a vibration mill can be used. Not only a dry pulverization method without using a solvent but also a wet pulverization method in which co-pulverization is performed in the presence of an inert solvent can be used.

(Ii) Heat treatment method A contact treatment is performed by stirring a magnesium compound containing a halogen represented by magnesium chloride and a titanium compound in an inert solvent, and the titanium compound is supported on the magnesium compound. The donating compound may be contact-treated 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. Moreover, you may contact arbitrary components, such as a silicon halide compound, simultaneously or in another process as needed. The contact temperature is not particularly limited, but it is often preferable to perform the contact treatment at a relatively high temperature of about 90 ° C to 130 ° C.

(Iii) Dissolution Precipitation Method The dissolution precipitation method involves dissolving a halogen-containing magnesium compound represented by magnesium chloride by bringing it into contact with an electron-donating compound, and bringing the resulting solution into contact with a precipitant to effect a precipitation reaction. It is a method of forming particles by waking up.
Examples of electron donating compounds 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. it can. Examples of the precipitating agent include titanium halide compounds, silicon halide compounds, hydrogen chloride, halogen-containing hydrocarbon compounds, siloxane compounds having a Si—H bond (including polysiloxane compounds), aluminum Examples thereof include compounds.
As a method for contacting the dissolving solution with the precipitating agent, the precipitating agent may be added to the dissolving solution, or the dissolving solution may be added to the precipitating agent. In both steps of dissolution and precipitation, when the titanium compound is not used, the titanium compound is supported on the magnesium compound by further bringing the particles formed by the precipitation reaction into contact with the titanium compound. If necessary, the particles thus formed may be brought into contact with an optional component such as a titanium halide compound or a silicon halide compound, or may be brought into contact with an electron donating compound. At this time, the electron-donating compound may be different from that used for dissolution, or may be the same. The order of contact of these optional components is not particularly limited, and may be contacted as an independent process, or may be contacted together during dissolution, precipitation, or contact with titanium compounds. Further, an inert solvent may be present in any step of dissolution, precipitation, and contact with an arbitrary component.

(Iv) Granulation method As in the case of the dissolution precipitation method, the granulation method dissolves a halogen-containing magnesium compound represented by magnesium chloride by bringing it into contact with an electron-donating compound, and the resulting solution is mainly used. It is a method of granulating by a physical method. Examples of the electron donating compound used for dissolution are the same as those of the dissolution precipitation method.
Examples of granulation techniques include a method in which a high-temperature solution is dropped into a low-temperature inert solvent, a method in which the solution is sprayed from a nozzle toward a high-temperature gas phase, and a method in which the solution is directed to a low-temperature gas phase. And a method of cooling the solution by ejecting it from a nozzle. The titanium compound is supported on the magnesium compound by bringing particles formed by granulation into contact with the titanium compound. Furthermore, you may make it contact with arbitrary components, such as a halogenated silicon compound and an electron-donating compound, as needed. In this case, the electron-donating compound may be different from that used for dissolution, or may be the same. There is no restriction | limiting in particular about the contact order of these arbitrary components, You may make it contact as an independent process, and can also contact together in the case of melt | dissolution or contact with a titanium compound. Further, an inert solvent may be present in any of the steps of dissolution, contact with titanium compounds, and contact with an arbitrary component.

(V) Magnesium (Mg) Compound Halogenation Method The magnesium (Mg) compound halogenation method is a method in which a halogenating agent is brought into contact with a magnesium compound not containing a halogen, and is electron-donating. The compounds may be contact-treated at the same time or in a separate step.
Examples of magnesium compounds not containing halogen include dialkoxy magnesium compounds, magnesium oxide, magnesium carbonate, magnesium salts of fatty acids, and the like. When dialkoxymagnesium compounds are used, those prepared in the system by reaction of magnesium metal 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, which is a starting material.
Examples of the halogenating agent include titanium halide compounds, halogenated silicon compounds, and halogenated phosphorus compounds. When a halogenated titanium compound is not used as the halogenating agent, the titanium compound is supported on the magnesium compound by further contacting the halogen-containing magnesium compound formed by halogenation with the titanium compound. If necessary, the particles thus formed may be brought into contact with an optional component such as a titanium halide compound or a silicon halide compound, or may be brought into contact with an electron donating compound. The order of contact of these optional components is not particularly limited, and may be contacted as an independent process, or may be contacted together when halogenated magnesium compound is not halogenated or contacted with titanium compounds. it can. Further, an inert solvent may be present in any step of halogenation, contact with titanium compounds, and contact with an optional component.

(Vi) Precipitation method from organomagnesium compound This is a method in which a precipitant is brought into contact with a solution of an organomagnesium compound such as a Grignard reagent typified by butylmagnesium chloride and a dialkylmagnesium compound. Or you may contact-process at another process.
Examples of the precipitating agent include titanium compounds, silicon compounds, hydrogen chloride, and the like. When the titanium compound is not used as the precipitating agent, the titanium compound is supported on the magnesium compound by further bringing the particles formed by the precipitation reaction into contact with the titanium compound. If necessary, the particles thus formed may be brought into contact with an optional component such as a titanium halide compound or a silicon halide compound, or may be brought into contact with an electron donating compound. There is no restriction | limiting in particular about the contact order of these arbitrary components, You may make it contact as an independent process, and can also contact together in the case of precipitation and contact with titanium compounds. Further, an inert solvent may be present in any of the steps of precipitation, contact with titanium compounds, and contact with an arbitrary component.

(Vii) Impregnation method In this method, an inorganic compound carrier or an organic compound carrier is impregnated with a solution of an organic magnesium compound or a solution obtained by dissolving a magnesium compound with an electron-donating compound.
Examples of organomagnesium compounds are the same as examples of precipitation methods from organomagnesium compounds. The magnesium compound used for dissolving the magnesium compound may or may not contain halogen, and examples of the electron donating compound are the same as those of the dissolution precipitation method. Examples of the inorganic compound carrier include silica, alumina, magnesia, and the like. Examples of the organic compound carrier include polyethylene, polypropylene, polystyrene, and the like. The carrier particles after the impregnation treatment are fixed by depositing a magnesium compound by a chemical reaction with a precipitation agent or a physical treatment such as drying. Examples of the precipitating agent are the same as those of the dissolution precipitation method. When a titanium compound is not used as a precipitating agent, the titanium compound is supported on the magnesium compound by further contacting the particles thus formed with the titanium compound. If necessary, the particles thus formed may be brought into contact with an optional component such as a titanium halide compound or a silicon halide compound, or may be brought into contact with an electron donating compound. The order of contacting these optional components is not particularly limited, and may be contacted as an independent process, or may be contacted together during impregnation, precipitation, drying, and contact with titanium compounds. Further, an inert solvent may be present in any step of impregnation, precipitation, contact with titanium compounds, and contact with an optional component.

(Viii) Combined method The methods described in (i) to (vii) above can also be used in combination. Examples of combinations are “method of heat treatment with titanium halide compounds after co-grinding magnesium chloride with electron donating compound”, “another electron donating property after co-grinding magnesium chloride compound with electron donating compound Method of dissolving using compound, and further depositing using a precipitating agent ”,“ dissolving dialkoxymagnesium compound with electron donating compound and bringing it into contact with titanium halide compounds at the same time ”Method of converting to carbon dioxide” by contacting carbon dioxide with a dialkoxymagnesium compound to simultaneously produce carbonate ester magnesium compounds, impregnating the formed solution into silica, and then contacting with magnesium chloride to form magnesium. Precipitation fixation at the same time as halogenating compounds And it can be exemplified a method of carrying a titanium compound ", and by further contacted with titanium halide compounds.

1-1-2. Phenol compound having a specific structure (A1b)
In the solid catalyst component (A1) for α-olefin polymerization according to the present invention, the phenol compound (A1b) used for the contact treatment of the solid catalyst component (A1a) according to the present invention must have a specific structure. And can be represented by the following general formula (1).

(In the formula, R ¹ is a tertiary hydrocarbon group having 4 or more carbon atoms and may be the same or different. R ² is a hydrogen atom or a hydrocarbon group, and each is the same. May be different.)

The feature of the present invention is that the specific phenol compound (A1b) shown above is contacted with the solid catalyst component (A1a).
The phenol compound is considered to have a very fast coordination to the titanium atom, which is the active center, because the oxygen atom has a high charge density. Accordingly, it is expected that a titanium compound can be extracted into a solvent by coordination / complexation with a titanium compound on a magnesium compound as a carrier.
On the other hand, in the specific phenol compound (A1b) disclosed in the present invention, the structure located in the vicinity of the oxygen atom is made bulky, thereby forming a structure that is easily coordinated and complexed with a titanium compound with less steric hindrance. To be considered. As a result, it is considered that a titanium compound that is an active site with less steric hindrance and low steric restriction ability is extracted, and amorphous components are reduced.

Based on such an inventive concept, the present invention is based on the specific phenol compound (A1b) represented by the general formula (1). Among them, what is important is to make the substituent located in the vicinity of the oxygen atom bulky. Due to this bulky structure, the titanium compound has a high steric hindrance with respect to oxygen atoms and has a high steric hindrance and cannot be coordinated or complexed. It may be preferable to extract compounds preferentially.
Therefore, although the specific phenol compound (A1b) shown above is an electron donating compound, the purpose of use is different from the electron donating compound (A1a-4) which is an essential component of the solid catalyst component (A1a), Differentiated.

Hereinafter, the structure of each substituent of the general formula (1) will be described in detail.
In general formula (1), R ¹ represents a tertiary hydrocarbon group having 4 or more carbon atoms. R ¹ is a tertiary hydrocarbon group having 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, specifically, t-butyl group, 1,1-dimethyl-propyl group, 1,1-dimethyl group. A butyl group, 1-methylcyclohexyl group, 1-ethyl-1-methylpropyl group, 1-adamantyl group and the like can be mentioned. Of these, t-butyl, 1,1-dimethylpropyl, and 1,1-dimethylbutyl are preferred. Two R ¹ may be the same or different.

In the formula (1), ^{R 2} is a hydrogen atom or a hydrocarbon group. When R ² is a hydrocarbon group, it generally has 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 branched aliphatic hydrocarbon group represented by a methyl group or an ethyl group, a branch represented by an i-propyl group or a t-butyl group. And an alicyclic hydrocarbon group represented by a cycloaliphatic hydrocarbon group, a cyclopentyl group and a cyclohexyl group. Among these, 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, or the like. Two or more R ² may be the same or different. If R ² is an aromatic hydrocarbon group is preferably a substituent such as no aromatic hydrocarbon group having a substituent having 6 to 20 carbon atoms, more preferably 6 to 12. Specific examples include a phenyl group, a biphenyl group, an indenyl group, and a fluorenyl group, and a phenyl group, a biphenyl group, and an indenyl group are particularly preferable.

  Of these, a structure having no substituent at the 3, 4, and 5 positions as represented by the following general formula (2) is preferable.

(In the formula, R ¹ is a tertiary hydrocarbon group having 4 to 20 carbon atoms, which may be the same or different.)

Specifically, the following phenol compounds can be exemplified.
(1) 2,6-di-t-butylphenol,
(2) 2,6-di- (1,1-dimethylpropyl) phenol,
(3) 2,6-di- (1,1-dimethylbutyl) phenol,
(4) 2,6-di- (1-methylcyclohexyl) phenol,
(5) 2,6-di- (1-ethyl-1-methylpropyl) phenol,
(6) 2,6-di- (1-adamantyl) phenol,
(7) 2,6-di-tert-butyl-4-methylphenol,
Etc. Two or more kinds of these phenol compounds can be used.

  Among these phenol compounds, 2,6-di-t-butylphenol, 2,6-di- (1,1-dimethylpropyl) phenol, 2,6-di- (1,1-dimethylbutyl) phenol, 2 , 6-di- (1-methylcyclohexyl) phenol, 2,6-di- (1-ethyl-1-methylpropyl) phenol are preferred, especially 2,6-di-t-butylphenol, 2,6-di -(1,1-dimethylpropyl) phenol is preferred.

1-1-3. Preparation of α-olefin polymerization solid catalyst component (A1) The amount ratio of each component constituting the α-olefin polymerization solid catalyst component (A1) according to the present invention is within a range that does not impair the effects of the present invention. In general, the following range is preferred.

  The amount of the phenol compound (A1b) having the above specific structure is not particularly limited, but a preferable range is a molar ratio with respect to the titanium component constituting the solid catalyst component (A1) (the number of moles of the phenol compound (A1b)). / Number of moles of titanium atoms) in the range of 0.1 to 1.5, and more preferably in the range of 0.3 to 1.0.

The solid catalyst component (A1) for α-olefin polymerization according to the present invention is obtained by contacting the components constituting the above in the above quantitative ratio.
Although it is necessary for the contact condition of each component not to make oxygen exist, arbitrary conditions can be used in the range which does not impair the effect of this invention. In general, the following conditions are preferred.
The contact temperature is about −50 to 200 ° C., preferably 0 to 150 ° C. Examples of the contact method include a mechanical method using a rotating ball mill and a vibration mill, and a method of contacting by stirring in the presence of an inert diluent.

In the preparation of the solid catalyst component (A1) for α-olefin polymerization, it is essential to finally wash with an inert solvent.
Examples of preferable 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.

1-2. Silicon compound having alkenyl group (A2)
Examples of the silicon compound (A2) having an alkenyl group used in the present invention include compounds disclosed in JP-A-2-34707, JP-A-2003-292522, JP-A-2006-169283, and JP-A-2011-74360. Etc. can be used.
In general, it is desirable to use a compound represented by the following general formula.
SiR ¹¹ _n R ¹² _4-n
(Here, R ¹¹ is an alkenyl group, R ¹² is a hydrogen atom, a halogen, an alkyl group, or an alkoxy group, and n represents 1 ≦ n ≦ 4. When 1 ≦ n ≦ 2, , R ² may be linked to form a cyclic structure.)

In the formula, R ¹¹ represents an alkenyl group, preferably a vinyl group, an allyl group, or a 3-butenyl group, and particularly preferably a vinyl group or an allyl group. When the value of n is 2 or more, the plurality of R ¹ may be the same or different.
In the formula, R ¹² 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 ¹² 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 R ¹² 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 ¹² 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 ¹² include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group. desirable. When the value of n is 2 or less, the plurality of R ¹² may be the same or different. Further, when 1 ≦ n ≦ 2, a cyclic structure in which R ¹² are connected to each other may be formed.

Specifically, the silicon compound (A2) having an alkenyl group includes vinyl silane, methyl vinyl silane, dimethyl vinyl silane, trimethyl vinyl silane, trichloro vinyl silane, dichloro methyl vinyl silane, chloro dimethyl vinyl silane, chloro methyl vinyl silane, triethyl vinyl silane, chloro diethyl vinyl silane, dichloro. Ethyl vinyl silane, dimethyl ethyl vinyl silane, diethyl methyl vinyl silane, tripentyl vinyl silane, triphenyl vinyl silane, diphenyl methyl vinyl silane, dimethyl phenyl vinyl silane, 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, dichlorodifluoromethane vinylsilane Dimethyldivinylsilane, diphenyldivinylsilane, allyltrimethylsilane, allyltriethylsilane, allyltrivinylsilane, allylmethyldivinylsilane, allyldimethylvinylsilane, allylmethyldichlorosilane, allyltrichlorosilane, allyltribromosilane, diallyldimethylsilane, diallyldiethylsilane Diallyldivinylsilane, diallylmethylvinylsilane, diallylmethylchlorosilane, diallyldichlorosilane, diallyldibromosilane, triallylmethylsilane, triallylethylsilane, triallylvinylsilane, triallylchlorosilane, triallylbromosilane, tetraallylsilane, di-3 -Butenyldimethylsilane, di-3-butenylsilane diethylsilane, di-3-butenylsilane Nylsilane, di-3-butenylsilane methyl vinyl silane, di-3-butenyl silane methyl chlorosilane, di-3-butenyl silane dichlorosilane, tri-3-butenyl silane ethyl silane, tri-3-butenyl silane vinyl silane , Tri-3-butenylsilane chlorosilane, tri-3-butenylsilane bromosilane, tetra-3-butenylsilane, 1-methyl-1-vinylsilacyclobutane, 1-methyl-1-vinylsilacyclopentane, 1-methyl -1-vinylsilacyclohexane, 1,1-divinylsilacyclopentane, 1,1-divinylsilacyclohexane, 1-chloro-1-vinylsilacyclopentane, 1-chloro-1-vinylsilacyclohexane, 1-allyl -1-methylsilacyclopentane, 1-allyl-1-methylsilaic Examples include rohexane and the like.
Among these, vinylsilane compounds are preferable, and trimethylvinylsilane, trichlorovinylsilane, dimethyldivinylsilane, and 1-methyl-1-vinylsilacyclopentane are particularly preferable.

  The amount ratio of the silicon compound (A2) having an alkenyl group may be any as long as it does not impair the effects of the present invention, but is generally preferably within the following range. The silicon compound (A2) having an alkenyl group is used in a molar ratio with respect to the titanium component constituting the solid catalyst component (A1) for α-olefin polymerization (number of moles of silicon compound (A2) having an alkenyl group / α-olefin. The number of moles of titanium atoms in the solid catalyst component for polymerization is preferably in the range of 0.001 to 1,000, particularly preferably in the range of 0.01 to 100.

  The silicon compound (A2) having an alkenyl group, which is an essential component in the present invention, usually has a larger steric hindrance than an α-olefin monomer and cannot be polymerized with a Ziegler-Natta catalyst. However, since there is an organic silyl group with a very strong electron donating property, the charge density of the carbon-carbon double bond portion 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 coordinates and complexed with the Lewis acid point on the magnesium compound as a carrier, so that extraction of the titanium compound into the solvent can be suppressed, and the excess of titanium atoms by the organoaluminum compound can be suppressed. The effect of preventing the deactivation of active sites due to reduction or impurities is expected.

1-3. Organosilicon compound (A3)
As the organosilicon compound (A3) used in the present invention, compounds disclosed in JP-A No. 2004-124090 can be used.
In general, it is desirable to use a compound represented by the following general formula.
R ²¹ R ²² _m Si (OR ²³ ) _3-m
(Wherein R ²¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group, R ²² represents hydrogen, halogen, a hydrocarbon group or a heteroatom-containing hydrocarbon group, and R ²³ represents a hydrocarbon group. Yes, m represents 1 ≦ m ≦ 3.)

In the formula, R ²¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group.
When R ²¹ is a hydrocarbon group, it is a hydrocarbon group excluding an alkenyl group. The hydrocarbon group that can be used as R ²¹ 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 ²¹ include a branched aliphatic hydrocarbon group represented by an n-propyl group, a branched chain 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 ²¹ , and in particular, i-propyl group, i-butyl group, t-butyl group, texyl group, cyclopentyl group, It is desirable to use a cyclohexyl group or the like.
When R ²¹ is a heteroatom-containing hydrocarbon group, the heteroatom is preferably selected from nitrogen, oxygen, sulfur, phosphorus or silicon, and particularly preferably nitrogen or oxygen. The skeleton structure of the hetero atom-containing hydrocarbon group R ^21, it is desirable to select from the example when R ²¹ is a hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.

In the formula, R ²² represents a hydrogen atom, a halogen, a hydrocarbon group, or a heteroatom-containing hydrocarbon group.
Examples of the halogen that can be used as R ²² include fluorine, chlorine, bromine, and iodine. Further, when R ²² is a hydrocarbon group, it is a hydrocarbon group excluding an alkenyl group. The hydrocarbon group that can be used as R ²² is generally one having 1 to 20 carbon atoms, preferably one having 1 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ²² include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, a branch represented by an i-propyl group and a t-butyl group. And an aliphatic hydrocarbon group typified by a cycloaliphatic hydrocarbon group, a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. Among these, 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, or the like.
In addition, when R ²² is a heteroatom-containing hydrocarbon group, it is desirable to select from the examples when R ²¹ is a heteroatom-containing hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.
When the value of m is 2, two R ²² may be the same or different. Regardless of the value of m, R ²² may be the same as or different from R ²¹ .

In the formula, R ²³ represents a hydrocarbon group. The hydrocarbon group that can be used as R ²³ is generally one having 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 ²³ include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, a branch represented by an i-propyl group and a t-butyl group. And an aliphatic hydrocarbon group. Of these, a methyl group and an ethyl group are most preferable. When the value of m is 2 or more, a plurality of R ²³ may be the same or different.

Preferred examples of the organosilicon compound (A3) used in the present invention include t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, t-butyl-n-propyldimethoxysilane, and cyclohexylmethyl. Dimethoxysilane, cyclohexylethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isobutylisopropyldimethoxysilane, n-propylmethyldimethoxysilane, t-butyltriethoxysilane, bis (diethylamino) dimethoxysilane, diethylaminotriethoxy Examples thereof include silane methoxy silane and bisperhydroisoquinolinodimethoxy silane.
These organosilicon compounds can be used not only alone but also in combination with a plurality of compounds.

The amount ratio of the organosilicon compound (A3) used may be any as long as the effects of the present invention are not impaired, but generally it is preferably within the following range.
The amount of the organosilicon compound (A3) used is the molar ratio to the titanium component constituting the α-olefin polymerization solid catalyst component (A1) (number of moles of organosilicon compound (A3) / solid catalyst component for α-olefin polymerization). The number of moles of titanium atoms) is preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100.

  The organic silicon compound (A3), which is an essential component in the present invention, is coordinated in the vicinity of a titanium atom that can be an active site, and is considered to control the catalytic performance such as the catalytic activity of the active site and the regularity of the polymer. ing.

1-4. Organoaluminum compound (A4)
As the organoaluminum compound (A4) used in the present invention, compounds disclosed in JP-A No. 2004-124090 can be used. In general, it is desirable to use a compound represented by the following general formula.
R ³¹ _a AlX _b (OR ³² ) _c
(In the formula, R ³¹ represents a hydrocarbon group. X represents a halogen atom or a hydrogen atom. R ³² 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 ³¹ is a hydrocarbon group, preferably 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 ³¹ include methyl group, ethyl group, propyl group, butyl group, isobutyl group, hexyl group, octyl group, and the like. Among these, a methyl group, an ethyl group, and an isobutyl group are most preferable.
In formula, X is a halogen or a hydrogen atom. Examples of halogen that can be used as X include fluorine, chlorine, bromine, iodine, and the like. Of these, chlorine is particularly preferred.
In the formula, R ³² is a hydrocarbon group or a bridging group by Al. When R ³² is a hydrocarbon group, R ² can be selected from the same group as exemplified for the hydrocarbon group of R ³¹ . Further, as the organoaluminum compound (A4), alumoxane compounds typified by methylalumoxane can be used, in which case R ³² represents a cross-linking group of Al.

Examples of compounds that can be used as the organoaluminum compound (A4) include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum chloride, diethylaluminum ethoxide, methylalumoxane, 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 organoaluminum compound (A4) used may be any as long as the effects of the present invention are not impaired, but generally it is preferably within the following range.
The amount of the organoaluminum compound (A4) used is the molar ratio of the titanium component constituting the α-olefin polymerization solid catalyst component (A1) (the number of moles of aluminum atoms / the number of titanium atoms in the solid catalyst component for α-olefin polymerization). The number of moles) is preferably in the range of 0.1 to 100, particularly preferably in the range of 1 to 50.

  The organoaluminum compound (A4), which is an essential component in the present invention, is used for the purpose of efficiently supporting the organosilicon compound (A3) in the catalyst component (A). Therefore, the purpose of use differs from the organoaluminum compound (B) used as a co-catalyst at the time of the main polymerization.

1-5. Compound (A5) having at least two ether bonds
The catalyst component (A) for α-olefin polymerization of the present invention is obtained by contacting a silicon compound (A2), an organosilicon compound (A3), and an organoaluminum compound (A4) having an alkenyl group with respect to the aforementioned component (A1). However, the compound (A5) having at least two ether bonds may be contacted as an optional component as long as the effects of the present invention are not impaired.
As the compound (A5) having at least two ether bonds that can be used in the present invention, compounds disclosed in JP-A-3-294302 and JP-A-8-333413 can be used. In general, it is desirable to use a compound represented by the following formula.
_{^{R 43 O-C (R 42}} ) 2 -C (R 41) 2 -C (R 42) -OR 43
(In the formula, R ⁴¹ and R ⁴² represent any free radical selected from a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. R ⁴³ 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 Etc.
In addition, 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 polyvalent ether compound used as the electron donating compound (A1a-4) which is an optional component in the solid catalyst component (A1) for α-olefin polymerization.

  The amount ratio of the compound (A5) having at least two ether bonds may be any as long as the effects of the present invention are not impaired, but in general, it is preferably within the following range. The amount of the compound (A5) having at least two ether bonds is the molar ratio to the titanium component constituting the solid catalyst component (A1) for α-olefin polymerization (the number of moles of the compound (A5) having at least two ether bonds). / Number of moles of titanium atoms in the solid catalyst component for α-olefin polymerization), preferably in the range of 0.01 to 10,000, particularly preferably in the range of 0.5 to 500.

1-6. Preparation Method of α-Olefin Polymerization Catalyst Component (A) The α-olefin polymerization catalyst component (A) of the present invention is a silicon compound having an alkenyl group with respect to the α-olefin polymerization solid catalyst component (A1) ( A2), an organosilicon compound (A3) and an organoaluminum compound (A4) are brought into contact with each other. Under the present circumstances, you may contact other arbitrary components, such as a compound (A5) which has an at least 2 ether bond, by arbitrary methods in the range which does not impair the effect of this invention.
The contact condition of each component of the solid catalyst component (A) for α-olefin polymerization needs to be free of oxygen, but any condition can be used as long as the effects of the present invention are not impaired. In general, the following conditions are preferred.
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 to 60 ° C. Examples of the contact method include a mechanical method using a rotating ball mill and a vibration mill, and a method of contacting by stirring in the presence of an inert diluent. Preferably, it is desirable to use a method of contacting with stirring in the presence of an inert diluent.

Regarding the contact procedure of the solid catalyst component (A1) for α-olefin polymerization, the silicon compound (A2) having an alkenyl group, the organosilicon compound (A3) and the organoaluminum compound (A4), any procedure can be used. Specific examples include the following procedures (i) to (iv), and among them, the procedures (i) and (ii) are preferable.
Procedure (i): Contacting the α-olefin polymerization solid catalyst component (A1) with the silicon compound (A2) having an alkenyl group, and then contacting the organosilicon compound (A3), the organoaluminum compound (A4) How to contact.
Procedure (ii): A method of contacting the organoaluminum compound (A4) after bringing the silicon compound (A2) and organosilicon compound (A3) having an alkenyl group into contact with the solid catalyst component (A1) for α-olefin polymerization.
Procedure (iii): The organosilicon compound (A3) is contacted with the solid catalyst component (A1) for α-olefin polymerization, and then the silicon compound (A2) having an alkenyl group is contacted. How to contact.
Procedure (iv): Method of contacting all compounds simultaneously.
When the compound (A5) having at least two ether bonds is used as an optional component, it can be contacted in any order as described above.

Furthermore, the silicon compound (A2), the organosilicon compound (A3) and the organoaluminum compound (A4) having an alkenyl group are brought into contact with the solid catalyst component (A1) for α-olefin polymerization any number of times. You can also. At this time, any of the silicon compound (A2), the organosilicon compound (A3), and the organoaluminum compound (A4) having an alkenyl group may be the same or different from each other. Moreover, although the range of the usage amount of each component was shown previously, this is the usage amount to be brought into contact with each time, and when it is used a plurality of times, the single usage amount is within the above-mentioned usage amount range. If it exists, you may make it contact many times.
In preparing the α-olefin polymerization catalyst component (A), washing with an inert solvent may be performed in the middle and / or finally. Examples of preferable 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.

1-7. Prepolymerization The solid catalyst component (A1) or catalyst component (A) for α-olefin polymerization in the present invention may be prepolymerized before being used in the main polymerization. Prior to the polymerization process, a small amount of polymer is generated around the catalyst in advance, so that the catalyst becomes more uniform and the generation amount of fine powder can be suppressed.
As the monomer in the prepolymerization, compounds disclosed in JP-A No. 2004-124090 can be used.
Specific examples of the compound include olefins represented by ethylene, propylene, 1-butene, 3-methylbutene-1, 4-methylpentene-1, and the like, styrene, α-methylstyrene, allylbenzene, and chlorostyrene. Styrene-like compounds typified by, and the like, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,5-hexadiene, 2,6-octadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,9 -Diene compounds represented by decadiene, divinylbenzene, and the like.
Of these, ethylene, propylene, 3-methylbutene-1, 4-methylpentene-1, styrene, divinylbenzenes, and the like are particularly preferable.

  In the case of using a prepolymerized solid catalyst component (A1) for α-olefin polymerization, prepolymerization can be carried out by any procedure in the preparation procedure. For example, after prepolymerizing the solid catalyst solid component (A1) for α-olefin polymerization, the optional components (A2 to A4) can be contacted. Furthermore, when the α-olefin polymerization solid catalyst component (A1) and the optional components (A2 to A4) are brought into contact with each other, preliminary polymerization may be performed simultaneously.

Arbitrary conditions can be used for the reaction conditions of the solid catalyst component (A1) for α-olefin polymerization or the catalyst component (A) for α-olefin polymerization and the above monomer as long as the effects of the present invention are not impaired. In general, the following range is preferable.
On the basis of 1 gram of α-olefin polymerization solid catalyst component (A1) or α-olefin polymerization catalyst component (A), the prepolymerization amount of the monomer is in the range of 0.001 to 100 g, preferably The range of 0.1 to 50 g, more preferably 0.5 to 10 g is desirable. The reaction temperature at the time of prepolymerization is −150 to 150 ° C., preferably 0 to 100 ° C. And it is desirable to make the reaction temperature at the time of preliminary polymerization lower than the polymerization temperature at the time of main polymerization. In general, the reaction is preferably carried out with stirring, and 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. Moreover, it can wash | clean with inert solvents, such as hexane and heptane, after preliminary polymerization.

2. Organoaluminum compound (B)
In the present invention, an organoaluminum compound (B) is used as the α-olefin polymerization catalyst in addition to the α-olefin polymerization catalyst component (A).
As said organoaluminum compound (B), the compound etc. which were disclosed by Unexamined-Japanese-Patent No. 2004-124090 can be used. Preferably, it can select from the same group as the illustration in the organoaluminum compound (A4) which is a component at the time of preparing a catalyst component (A). The organoaluminum compound (A4) that can be used when preparing the catalyst component (A) and the organoaluminum compound (B) that can be used as the catalyst component may be the same or 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 catalyst component (A) (number of moles of organoaluminum compound (B) / α-olefin polymerization catalyst component (A)). The number of moles of titanium atoms in the composition is preferably in the range of 1 to 50,000, particularly preferably in the range of 10 to 5,000.

3. Organosilicon compound (C)
In the present invention, the α-olefin polymerization catalyst component (A) and the organoaluminum compound (B) are used as the α-olefin polymerization catalyst. In this case, optional components such as the organosilicon compound (C) and the compound (D) having at least two ether bonds can be used as long as the effects of the present invention are not impaired.
In the catalyst of the present invention, as the organosilicon compound (C) used as an optional component, compounds disclosed in JP-A No. 2004-124090 can be used. Preferably, it can select from the same group as the illustration in the organosilicon compound (A3) which is a component at the time of preparing the catalyst component (A) for α-olefin polymerization.
Moreover, the organosilicon compound (C) used here may be the same as or different from the organosilicon compound (A3) contained in the α-olefin polymerization catalyst component (A).
Furthermore, when using the organosilicon compound (C), the amount used is the molar ratio to the titanium component constituting the catalyst component (A) for α-olefin polymerization (number of moles of organosilicon compound (C) / for α-olefin polymerization). The number of moles of titanium atoms in the catalyst component (A) is preferably in the range of 0.01 to 10,000, particularly preferably in the range of 0.5 to 500.

4). Compound (D) having at least two ether bonds
In the catalyst according to the present invention, as the compound (D) having at least two ether bonds used as an optional component, compounds disclosed in JP-A-3-294302 and JP-A-8-333413 are used. Can do. Preferably, it can be selected from the same group as exemplified in the compound (A5) having at least two ether bonds used in the catalyst component (A) for α-olefin polymerization. At this time, the compound (A5) having at least two ether bonds used as an optional component in preparing the catalyst component (A) for α-olefin polymerization and the compound having at least two ether bonds used as an optional component of the catalyst (D) 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 a molar ratio to the titanium component constituting the catalyst component (A) (the number of moles of the compound (D) having at least two ether bonds / α- The number of moles of titanium atoms in the catalyst component for olefin polymerization (A)) is preferably in the range of 0.01 to 10,000, particularly preferably in the range of 0.5 to 500.

5. Other compounds As long as the effects of the present invention are not impaired, components other than the organosilicon compound (C) and the compound (D) having at least two ether bonds can be used as optional components of the catalyst. For example, a compound (E) having a C (═O) N bond in the molecule disclosed in JP-A No. 2004-124090 or a sulfite compound (F) disclosed in JP-A No. 2006-225449 is used. By using it, the production | generation of an amorphous component like CXS can be suppressed. In this case, preferred examples include tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 1-ethyl-2-pyrrolidinone, dimethyl sulfite, diethyl sulfite and the like.
Further, as disclosed in JP-A-8-66710, an organometallic compound having a metal atom other than Al, such as diethyl zinc (G), can also be used.
The amount used in the case of using the compound (E) having a C (═O) N bond in the molecule, the sulfite compound (F) and diethyl zinc (G) constitutes the α-olefin polymerization catalyst component (A). The molar ratio to the titanium component (number of moles of optional components (E), (F), (G) / number of moles of titanium atoms in the α-olefin polymerization catalyst component (A)), preferably 0.001 to 1. Within the range of 1,000, particularly preferably within the range of 0.05 to 500.

II. Polymerization of α-olefin Polymerization of α-olefin using the catalyst for α-olefin polymerization of the present invention includes slurry polymerization using a hydrocarbon solvent, liquid phase solventless polymerization or gas phase polymerization using substantially no solvent, etc. Applies to As a polymerization solvent in the case of slurry polymerization, hydrocarbon solvents such as pentane, hexane, heptane and cyclohexane are used.
The polymerization method employed 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. At that time, hydrogen can be used as a molecular weight regulator.

III. α-Olefin Monomer Raw Material The α-olefin polymerized using the α-olefin polymerization catalyst of the present invention 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 branched group.)

Specifically, α-olefins such as propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. In addition to homopolymerization of these α-olefins, random copolymerization with monomers (for example, ethylene, α-olefins, dienes, styrenes, etc.) copolymerizable with α-olefins can also be performed. Further, block copolymerization in which homopolymerization in the first stage and random copolymerization in the second stage can be performed. The copolymerizable monomer can be used up to 15% by weight in random copolymerization and up to 50% by weight 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.

IV. α-Olefin Polymer 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.
In general, the MFR of the α-olefin polymer is preferably within a range of 0.01 to 10,000 g / 10 minutes, and particularly preferably within a range of 0.1 to 1,000 g / 10 minutes. is there.
The α-olefin polymer polymerized according to the present invention is characterized by having very few amorphous components, high stereoregularity, and good odor and hue.
The preferred range of the cold xylene solubles (CXS) as the amorphous component of the α-olefin polymer is different depending on the application. For example, in applications where hard molded bodies are preferred, such as general injection applications, in the case of polypropylene, the cold xylene solubles (CXS) is preferably 1% by weight or less, more preferably in the range of 0.1 to 1% by weight. More preferably, the content is in the range of 0.2 to 0.6% by weight.
Further, the polymer particles obtained by the present invention exhibit excellent particle properties. In general, the particle properties of polymer particles are evaluated by polymer bulk density, particle size distribution, particle appearance, and the like.
The polymer particles obtained according to 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 very few amorphous components and high stereoregularity, and therefore has high density, high rigidity and heat resistance, and excellent properties.
In addition, this α-olefin polymer is produced with a high yield, and in particular, industrial materials such as automobile parts and home appliance parts that require high rigidity and high heat resistance, or packaging materials because they are less sticky. It can use suitably for the use of.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to these Examples. The measuring method of each physical property value in the present invention is shown below.

(1) MFR:
Evaluation was performed under the conditions of 230 ° C. and 21.18 N (2.16 kg) based on JIS K6921 using a melt indexer manufactured by Takara.
(2) Polymer bulk density:
The bulk density of the powder sample was measured using an apparatus according to ASTM D1895-69.
(3) CXS:
The sample (about 5 g) was completely dissolved once in 140 ° C. p-xylene (300 ml). Thereafter, the mixture was cooled to 23 ° C., and a polymer was precipitated at 23 ° C. for 12 hours. After the precipitated polymer was filtered off, 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 polymer after drying was weighed, and the value of CXS was obtained as the weight% with respect to the sample.
(4) Ti content:
The sample was accurately weighed, hydrolyzed, and measured using a colorimetric method. About the sample after prepolymerization, content was calculated using the weight remove | excluding prepolymerized polymer.
(5) Silicon compound content:
The sample was accurately weighed and decomposed with methanol. The silicon compound concentration in the obtained methanol solution was determined by comparison with a 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 weight of the sample. About the sample after prepolymerization, content was computed using the weight remove | excluding prepolymerized polymer.

[Example 1]
(1) Preparation of α-olefin polymerization solid catalyst component (A1) A 500 ml round bottom flask equipped with a stirrer was sufficiently replaced with nitrogen, 105 ml of purified toluene was introduced, 10 g of MgCl ₂ and epoxychloropropane 10 g and 26 g of tributyl phosphate were introduced and reacted at 50 ° C. for 2 hours to obtain a uniform solution.
Next, 3.8 g of phthalic anhydride was introduced while the uniform solution was kept at 50 ° C., and reacted for 1 hour. Subsequently, 95 ml of purified toluene was introduced, cooled to −25 ° C., and 118 ml of TiCl ₄ was introduced and held for 4 hours. The solution was then heated to 80 ° C. over 3 hours to precipitate the solid component.
Next, 3.9 g of diisobutyl phthalate was added, and the reaction was performed at 80 ° C. for 1 hour. The reaction product was thoroughly washed with purified toluene. Further, purified toluene was introduced to adjust the total liquid volume to 190 ml. 20 ml of TiCl ₄ was added, the temperature was raised to 105 ° C., and the reaction was carried out for 1 hour. After removing the filtrate, the temperature was raised to 110 ° C. and the treatment was performed for 30 minutes.
This treatment with TiCl ₄ was repeated three times. Thereafter, the reactive organism was thoroughly washed with purified hexane. The obtained slurry was extracted from the flask and vacuum dried to obtain a solid catalyst component. When this solid catalyst component was analyzed, the Ti content was 1.4 wt%.
Next, a 500 ml round bottom flask equipped with a stirrer was sufficiently replaced with nitrogen, 200 ml of purified n-heptane was introduced, 10 g of the solid catalyst component synthesized above, 2,6-di-t-butylphenol 0.3g was introduce | transduced and reaction was performed at 90 degreeC for 2 hours.
The reaction product was sufficiently washed with purified n-heptane, and the resulting slurry was extracted from the flask and vacuum dried to obtain a solid catalyst component (A1) for α-olefin polymerization. When the solid catalyst component (A1) for α-olefin polymerization was analyzed, the Ti content was 1.0 wt%.

(2) Preparation of α-olefin polymerization catalyst component (A) A 500 ml round bottom flask equipped with a stirrer was sufficiently substituted with nitrogen, 50 ml of purified n-heptane was introduced, and α-prepared above. 4 g of the solid catalyst component (A1) for olefin polymerization was introduced. Purified n-heptane was introduced, and the concentration of the solid catalyst component (A1) for α-olefin polymerization was adjusted to 60 g / L. Here, 1 dimethyl divinyl silane as the component (A2) 1.0 ml, of diisopropyl dimethoxy silane as the component (A3) 0.8 ml, the n- heptane dilution of _Et 3 Al as the component (A4) as _Et 3 Al. 7g was added and reaction was performed at 30 degreeC for 2 hours.
The reaction product was thoroughly washed with purified n-heptane. The obtained slurry was extracted from the flask and vacuum-dried to obtain a polymerization catalyst component (A) for α-olefin. This polymerization catalyst component (A) for α-olefin contained 0.9 wt% Ti and 4.3 wt% diisopropyldimethoxysilane.

(3) Polymerization of propylene A stainless steel autoclave having an internal volume of 3.0 L having a stirring and temperature control device was heated and dried under vacuum, cooled to room temperature and substituted with propylene, and then triethylaluminum (Et as component (B)) ₃ Al) and 550 mg of hydrogen and 2000 ml of hydrogen were introduced, and then 1000 g of liquid propylene was introduced, the internal temperature was adjusted to 70 ° C., and 7 mg of the above α-olefin polymerization catalyst component (A) was injected. Propylene was polymerized.
After 1 hour, 10 ml of ethanol was injected to terminate the polymerization. The polymer was dried and weighed. The results are shown in Table 1.

[Example 2]
The preparation of the solid catalyst component (A1) for α-olefin polymerization in Example 1 was performed in exactly the same manner except that the amount of 2,6-di-t-butylphenol used was 1.3 g.
The polymerization of propylene was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
The preparation of the α-olefin polymerization catalyst component (A) in Example 1 was performed in exactly the same manner except that t-butylmethyldimethoxysilane was used instead of diisopropyldimethoxysilane.
The polymerization of propylene was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Example 4]
Preparation of the α-olefin polymerization catalyst component (A) in Example 1 was carried out in the same manner except that dicyclopentyldimethoxysilane was used instead of diisopropyldimethoxysilane.
The polymerization of propylene was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
The preparation of the solid catalyst component (A1) for α-olefin polymerization in Example 1 was performed in the same manner except that the contact treatment of 2,6-di-t-butylphenol was not performed.
The polymerization of propylene was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
(Propylene polymerization)
A stainless steel autoclave with an internal volume of 3.0 L having a stirring and temperature control device is heated and dried under vacuum, cooled to room temperature and substituted with propylene, and then 550 mg of triethylaluminum as component (B) and as component (C) After 85 mg of diisopropyldimethoxysilane and 2000 ml of hydrogen were introduced, and then 1000 g of liquid propylene was introduced and the internal temperature was adjusted to 70 ° C., 7 mg of the solid catalyst component (A1) for polymerization of α-olefin of Example 2 was obtained. Injected to polymerize propylene.
After 1 hour, 10 ml of ethanol was injected to terminate the polymerization. The polymer was dried and weighed. The results are shown in Table 1.

[Comparative Example 3]
The preparation of the α-olefin polymerization catalyst component (A1) in Example 1 was carried out in the same manner except that 0.3 g of 2,6-diisopropylphenol was used instead of 2,6-di-t-butylphenol. It was.
The polymerization of propylene was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 4]
Except that 0.2 g of 2,6-dimethylphenol was used instead of 2,6-di-t-butylphenol in the preparation of the solid catalyst component (A1) for α-olefin polymerization of Example 1, it was exactly the same. went.
The polymerization of propylene was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Example 5]
(1) Preparation of α-olefin polymerization solid catalyst component (A1) 10 g of Mg (OEt) ₂ was introduced into a 500-ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen. Purified toluene was introduced here, and the solid component concentration was adjusted to 100 g / L.
Next, 50 ml of TiCl ₄ was added, the temperature was raised to 90 ° C., and 2.5 ml of di-n-butyl phthalate was further introduced. Thereafter, the temperature was raised to 110 ° C. and the reaction was carried out for 3 hours. The reaction product was thoroughly washed with purified toluene.
Subsequently, purified toluene was introduced to adjust the total liquid volume to 100 ml. 50 ml of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was carried out for 2 hours. The reaction product was thoroughly washed with purified toluene.
Subsequently, purified toluene was introduced to adjust the total liquid volume to 100 ml. 50 ml of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was carried out for 2 hours. The reaction product was thoroughly washed with purified toluene.
Furthermore, toluene was substituted with n-heptane using purified n-heptane. The obtained slurry was extracted from the flask and vacuum dried to obtain a solid catalyst component. When this solid catalyst component was analyzed, the Ti content was 2.8 wt%.
Next, a 500 ml round bottom flask equipped with a stirrer was sufficiently replaced with nitrogen, 200 ml of purified n-heptane was introduced, 10 g of the solid catalyst component synthesized above, 2,6-di-t-butylphenol 0.6 g was introduced and reacted at 90 ° C. for 2 hours. The reaction product was sufficiently washed with purified n-heptane, and the resulting slurry was extracted from the flask and vacuum dried to obtain a solid catalyst component (A1) for α-olefin polymerization. When the solid catalyst component (A1) for α-olefin polymerization was analyzed, the Ti content was 2.1 wt%.

(2) Preparation of α-olefin polymerization catalyst component (A) A 500 ml round bottom flask equipped with a stirrer was sufficiently substituted with nitrogen, 50 ml of purified n-heptane was introduced, and α-prepared above. 4 g of the solid catalyst component (A1) for olefin polymerization was introduced. Purified n-heptane was introduced, and the concentration of the solid catalyst component (A1) for α-olefin polymerization was adjusted to 60 g / L.
Here, 1 dimethyl divinyl silane as the component (A2) 1.0 ml, of diisopropyl dimethoxy silane as the component (A3) 0.8 ml, the n- heptane dilution of _Et 3 Al as the component (A4) as _Et 3 Al. 7g was added and reaction was performed at 30 degreeC for 2 hours.
The reaction product was thoroughly washed with purified n-heptane. The obtained slurry was extracted from the flask and vacuum-dried to obtain a polymerization catalyst component (A) for α-olefin.
This polymerization catalyst component (A) for α-olefin contained 1.2 wt% Ti and 5.2 wt% diisopropyldimethoxysilane.
The polymerization of propylene was carried out in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 5]
The polymerization of propylene of Comparative Example 2 was performed in exactly the same manner except that the α-olefin polymerization solid catalyst component (A1) of Example 5 was used. The results are shown in Table 2.

As is clear from Tables 1 and 2, by comparing Examples 1 to 5 and Comparative Examples 1 to 5, Examples 1 to 5 of the present invention have a general catalytic performance such as polymerization activity and bulk density. The CXS component was maintained at a high level, and the CXS component was reduced as compared with the comparative example. Thus, it can be said that the catalyst of the present invention is a very well balanced catalyst.
Specifically, by comparing Example 1 with Comparative Example 1, it can be seen that the CXS component is reduced by contacting the phenol compound (A1b) with the solid catalyst component (A1a). Further, by comparing Example 2 and Comparative Example 2, contact treatment with an alkenyl group-containing silicon compound, organosilicon compound, or organoaluminum compound as a solid catalyst component results in high activity and further reduces CXS. ing. In Examples 3 and 4, evaluation was performed using an organosilicon compound (A3) having a structure different from that in Example 1, but it can be seen that there is a CXS reduction effect as well.
Furthermore, in Comparative Examples 3 and 4, evaluation was performed using a phenol compound having a structure different from that in Example 1. Since the phenolic compounds of Comparative Examples 3 and 4 have small substituents near the oxygen atom, the amount of titanium extracted is large, and the activity and CXS are inferior.
Further, in Example 5 and Comparative Example 5, a solid catalyst component (A1a) having a production method different from that in Example 1 was used, and in the same manner as in the above-described results, a phenol compound having a specific structure was used. It can be seen that the CXS component is reduced by contact treatment of the silicon compound, the organosilicon compound, and the organoaluminum compound having a group.
Therefore, the catalyst of each example of the present invention is a catalyst having an extremely small number of CXS components while maintaining basic performance such as catalyst activity at a high level, and excellent results are obtained as compared with each comparative example. It can be said that. Thus, the rationality and significance of the configuration of the present invention and the superiority over the prior art are demonstrated.

  The α-olefin polymerization catalyst of the present invention has high performance in all of the catalyst performance such as stereoregularity, particle properties, and catalytic activity, and in particular, produces an α-olefin polymer with few amorphous components. Can be used industrially.

Claims (5)

Α-olefin polymerization obtained by previously subjecting a solid catalyst component (A1a) containing magnesium, titanium, halogen and an electron donating compound as essential components to a phenol compound (A1b) represented by the following general formula (1). The following component (A2), (A3) and (A4) are further contact-treated with the solid catalyst component (A1) for use in the production method of the catalyst component for α-olefin polymerization.
Component (A2): Silicon compound having alkenyl group Component (A3): Organosilicon compound Component (A4): Organoaluminum compound

(In the formula, R ¹ is a tertiary hydrocarbon group having 4 or more carbon atoms and may be the same or different. R ² is a hydrogen atom or a hydrocarbon group, and each is the same. May be different.) The method for producing an α-olefin polymerization catalyst component according to claim 1, wherein the phenol compound (A1b) is represented by the following general formula (2).

(In the formula, R ¹ is a tertiary hydrocarbon group having 4 to 20 carbon atoms, which may be the same or different.) The α-olefin polymerization catalyst component (A) produced by the method for producing an α-olefin polymerization catalyst component according to claim 1 or 2 is contact- treated with the following component (B): α- A method for producing an olefin polymerization catalyst.
Component (B): Organoaluminum compound Furthermore, the following component (C) is contact- processed , The manufacturing method of the catalyst for alpha-olefin polymerization of Claim 3 characterized by the above-mentioned.
Component (C): Organosilicon compound The manufacturing method of the alpha-olefin polymer characterized by using the catalyst for alpha-olefin polymerization manufactured with the manufacturing method of the catalyst for alpha-olefin polymerization of Claim 3 or 4 .

Images