JP2007119514A - α-Olefin Polymerization Catalyst Component, α-Olefin Polymerization Catalyst, and Method for Producing α-Olefin Polymer - Google Patents

Abstract

（式（１）中、Ｒ^１およびＲ^２は炭素数１つ以上の脂肪族炭化水素基、芳香族炭化水素基またはヘテロ原子含有炭化水素基を表す。）
【選択図】なしAn object of the present invention is to provide an α-olefin polymerization catalyst component exhibiting sufficient performance in all catalyst performance such as stereoregularity and catalytic activity, and a method for producing an α-olefin polymer using the catalyst component.
SOLUTION: It contains titanium, magnesium, halogen, an electron donating compound, and a furan compound represented by the following formula (1), and a molar ratio of the electron donating compound to the furan compound (the number of moles of the electron donating compound). / Number of moles of furan compound) is in the range of 0.01 to 1.0, a catalyst component for α-olefin polymerization, a catalyst for α-olefin polymerization, and a method for producing an α-olefin polymer.
[Chemical 1]

(In Formula (1), R ¹ and R ² represent an aliphatic hydrocarbon group having 1 or more carbon atoms, an aromatic hydrocarbon group, or a heteroatom-containing hydrocarbon group.)
[Selection figure] None

Description

  The present invention relates to an α-olefin polymerization catalyst component, an α-olefin polymerization catalyst, and a method for producing an α-olefin polymer using the same. More specifically, the present invention relates to an α-olefin polymerization catalyst component having high stereoregularity and extremely high catalytic activity, an α-olefin polymerization catalyst, and a method for producing an α-olefin polymer using the same.

Polyolefins such as polyethylene and polypropylene are the most important plastic materials as industrial materials, such as packaging materials and electrical materials as films and sheets, industrial materials such as automobile parts and household appliances as molded products, and textile materials and construction. Widely used in various applications such as materials.
In this way, the applications are so wide and diverse that polyolefins continue to seek improvements in various properties from the viewpoint of their applications. In order to meet these demands, mainly by improving the polymerization catalyst. Technology development has been deployed.

For example, Ziegler-based catalysts using transition metal compounds and organometallic compounds have greatly enhanced the polymerization activity of olefins and realized industrial production, but subsequently improved the physical properties of polymers due to molecular weight distribution and α -Various performance improvements have been made, including improvements in olefin stereoregularity.
Specifically, a catalyst using a solid catalyst component containing titanium and a halogen as an essential component with a magnesium compound as a catalyst support was developed, and the catalytic activity and stereoregularity were further improved by using an electron donating compound. There has also been proposed a catalyst (for example, see Patent Document 1), and thereafter, various organic silicon compounds are newly added to the catalyst component to further improve catalytic activity and stereoregularity (for example, patents). See references 2 and 3.)
In addition, as a proposal to use an electron-donating compound other than a silicon compound, dibenzofuran and its derivatives are allowed to coexist to improve hydrogen responsiveness (for example, see Patent Document 4), or an ether compound is converted into an electron for a specific catalyst system. Many improved techniques, such as improving catalyst activity by using as a donating compound (for example, refer patent document 5 and 6), are disclosed.

However, as far as the present inventors know, none of the catalyst performances such as stereoregularity and catalytic activity of the α-olefin polymer produced in any of these catalyst systems show sufficient performance. Development of an improved technology is desired.
JP 58-138706 (Claims, page 2, lower left column) JP-A-62-187707 (Claims, first page and lower right column on first page) Japanese Patent Laid-Open No. 03-2234707 (claims, first page, second page, upper right column) JP 2002-249507 A (summary) JP 2003-105019 A (summary) JP 2003-261612 A (summary)

  In the state of the prior art, the present invention realizes a catalyst exhibiting sufficient performance in all catalyst performance such as stereoregularity and catalytic activity, and a method for producing an α-olefin polymer using such a catalyst component. It is an object of the invention.

  In order to solve the above-mentioned basic and universal problems in Ziegler catalysts in response to the above-mentioned problems, the present inventors have generally considered the properties and chemical structures of various catalyst components in Ziegler catalysts. Thoughts and searches were conducted, and various catalyst components were studied and experimented repeatedly, and catalyst components related to stereoregularity and monomer involvement with respect to the active sites of the catalyst were searched. As a result, it has been newly found that the stereoregularity and catalytic activity of the polymer are remarkably improved when a specific furan compound is employed and contact treatment is performed in the solid component of the Ziegler catalyst. That is, a furan compound is basically brought into contact with a Ziegler solid component composed of a tetravalent titanium compound, a magnesium compound, a halogen, and an electron donating compound to form a catalyst component, and optionally vinylsilane. A combination of a solid catalyst component in contact with a compound, an organosilicon compound and an organoaluminum compound, and an organoaluminum compound is used as a Ziegler-type catalyst. When an α-olefin is polymerized in the presence of the catalyst, an α-olefin polymer having extremely high stereoregularity, that is, excellent crystallinity can be produced. A polymer having very high crystallinity and significantly improved polymerization efficiency. It found that is, the present invention has been completed.

  That is, according to the first invention of the present invention, titanium, magnesium, halogen, an electron donating compound, and a furan compound represented by the following formula (1) are contained, and the moles of the electron donating compound and the furan compound. A catalyst component for α-olefin polymerization is provided, wherein the ratio (number of moles of electron donating compound / number of moles of furan compound) is in the range of 0.05 to 1.0.

（式（１）中、Ｒ^１およびＲ^２は炭素数１つ以上の脂肪族炭化水素基、芳香族炭化水素基またはヘテロ原子含有炭化水素基を表す。）

(In Formula (1), R ¹ and R ² represent an aliphatic hydrocarbon group having 1 or more carbon atoms, an aromatic hydrocarbon group, or a heteroatom-containing hydrocarbon group.)

According to the second invention of the present invention, the following components (B), (C) and (D) are brought into contact with the α-olefin polymerization catalyst component (A) of the first invention. A catalyst component for α-olefin polymerization is provided.
(B) Vinylsilane compound (C) Organosilicon compound (D) Organoaluminum compound

Further, according to the third invention of the present invention, the α-olefin polymerization catalyst component (A) of the first invention or the α-olefin polymerization catalyst component (A ′) of the second invention and the following component (E The catalyst for α-olefin polymerization is provided.
(E) Organoaluminum compound

According to a fourth aspect of the present invention, there is provided an α-olefin polymerization catalyst comprising the α-olefin polymerization catalyst of the third aspect and the following component (F).
(F) Organosilicon compound

  According to a fifth aspect of the present invention, the α-olefin is polymerized in the presence of any one of the first to fourth α-olefin polymerization catalyst components or the α-olefin polymerization catalyst. A method for producing an α-olefin polymer is provided.

The catalyst component for α-olefin polymerization of the present invention, the catalyst for α-olefin polymerization, is a catalyst having remarkably high catalytic activity. When α-olefin is polymerized in the presence of the catalyst, the stereoregularity is very high. That is, an α-olefin polymer having excellent crystallinity can be produced.
The most characteristic feature of the catalyst component for α-olefin polymerization of the present invention is obtained by bringing a specific furan compound into contact with a solid component of a conventional Ziegler catalyst. This does not necessarily mean that the furan compound remains in the catalyst component. In the present invention, a surprising and new catalytic function in which both the stereoregularity and the catalytic activity of a polymer are improved by bringing a specific furan compound into contact with a solid component of a conventional Ziegler catalyst as a catalyst component. Although the reason for the occurrence of is not yet clear, the planar structure of the furan compound and the balance of the substituents of an appropriate size are coordinated directly or in the vicinity of the titanium atom that is the active species of the catalyst supported on MgCl _2. By doing so, it is thought that the carrying state and electronic state of the titanium atoms were changed. As a result, the stereoregularity is affected, and as a result, the insertion of the monomer to be polymerized into the active site is facilitated, whereby the polymerization reaction is more likely to occur and the catalytic activity is improved. Guessed.

  The present invention relates to α-olefin polymerization comprising titanium (A-1), magnesium (A-2), halogen (A-3), electron donating compound (A-4), and furan compound (A-5). Catalyst component (A), α-olefin polymerization catalyst component (A), (B) vinyl silane compound, (C) organosilicon compound, and (D) organoaluminum compound, and (G) at least The α-olefin polymerization catalyst component (A ′), the α-olefin polymerization catalyst component (A) or the α-olefin polymerization catalyst component (A ′) contacted with the compound having an ether bond is combined with (E) organic An α-olefin polymerization catalyst blended with an aluminum compound, and, if necessary, (F) an organosilicon compound, (H) a compound having at least an ether bond, and the like. Or method for producing α- olefin polymer using a α- olefin polymerization catalyst. Hereinafter, the present invention will be described in detail.

1. α-Olefin Polymerization Catalyst Component (A)
(1) Component (A) (A-1) Titanium Any titanium compound can be used as a titanium source of titanium used in the catalyst component for α-olefin polymerization of the present invention. Representative examples include compounds disclosed in JP-A-3-234707. With respect to the valence of titanium, a titanium compound having any valence of tetravalent, trivalent, divalent, and zero 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.

(A-2) Magnesium Any magnesium compound can be used as the magnesium source. Representative examples 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, organometallic magnesium compounds typified by butyloctylmagnesium, magnesium salts of inorganic and organic acids typified by magnesium carbonate and magnesium stearate, In addition, a compound in which a mixture thereof or an average composition formula thereof is a mixed formula thereof (for example, a compound such as Mg (OEt) _m Cl _2-m ; 0 <m <2) can be used. Of these, magnesium chloride, diethoxymagnesium, metallic magnesium and butylmagnesium chloride are particularly preferred.

(A-3) Halogen As the halogen, fluorine, chlorine, bromine, iodine, and a mixture thereof can be used. Of these, chlorine is particularly preferred. The halogen is generally supplied from the above-described 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.

(A-4) Electron-donating compound As typical examples of the electron-donating compound, compounds disclosed in JP-A No. 2004-124090 can be given. 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 include aromatic polyvalent carboxylic acid compounds represented by phthalic acid, aromatic carboxylic acid compounds represented by benzoic acid, and 2-n-butyl-malon. One or two substituents such as malonic acid or 2-n-butyl-succinic acid having one or two substituents at the 2-position such as acid, or one at each of the 2- and 3-positions Aliphatic polycarboxylic acid compounds represented by succinic acid having the above substituents, aliphatic carboxylic acid compounds represented by propionic acid, aromatics and aliphatics represented by benzenesulfonic acid and methanesulfonic acid Examples of the 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 include esters, acid anhydrides, acid halides, amides, and the like of the above organic acids.
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, etc. 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.
Aliphatic and aromatic amines can be used as the amine that is a constituent 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 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 include aliphatic ether compounds represented by dibutyl ether, aromatic ether compounds represented by diphenyl ether, 2-isopropyl-2-isobutyl-1,3-dimethoxy Aliphatic polyvalent ether compounds typified by 1,3-dimethoxypropane having one or two substituents at the 2-position, such as propane and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 9 , 9-bis (methoxymethyl) fluorene, polyvalent ether compounds having an aromatic free radical in the molecule, and the like. Preferred examples of the polyvalent ether compounds can be selected from the examples of the compound (G) having at least two ether bonds described later.
In addition, although the furan compound represented by General formula (1) used for this invention is also contained in a broad sense ether compound, this invention is a furan compound represented by General formula (1) as a polymerization catalyst component (A). In combination with other electron donors.

Examples of the ketone compound that can be used as the electron donating compound include aliphatic ketone compounds typified by methyl ethyl ketone, aromatic ketone compounds typified by acetophenone, 2,2,4,6,6-pentamethyl-3, Examples thereof include polyvalent ketone compounds represented by 5-heptanedione.
Examples of the aldehyde compound that can be used as the electron-donating compound include aliphatic aldehyde compounds represented by propionaldehyde, aromatic aldehyde compounds represented by benzaldehyde, and the like.
Examples of alcohol compounds that can be used as electron donating compounds include aliphatic alcohol compounds represented by butanol and 2-ethylhexanol, phenol derivative compounds represented by phenol and cresol, glycerin and 1,1′-bis. Examples thereof include aliphatic or aromatic polyhydric alcohol compounds represented by 2-naphthol.
Examples of amine compounds that can be used as electron donating compounds include aliphatic amine compounds typified by diethylamine, nitrogen-containing alicyclic compounds typified by 2,2,6,6-tetramethyl-piperidine, and aniline. Aromatic atom compounds typified by nitrogen, nitrogen atom-containing aromatic compounds typified by pyridine, polyvalent amine compounds typified by 1,3-bis (dimethylamino) -2,2-dimethylpropane, etc. Can be illustrated.

  As a compound that can be used as an electron-donating compound, 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 typified by ethyl, ketoether compounds typified by (1-t-butyl-2-methoxyethyl) methylketone, aminos typical of N, N-dimethyl-2,2-dimethyl-3-methoxypropylamine Examples include ether compounds and halogeno ether compounds typified by epoxy chloropropane.

  These electron donating compounds can be used alone or in combination with a plurality of compounds. Among these, preferred are phthalate compounds represented by diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, phthalate halide compounds represented 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.

(A-5) Furan Compound The furan compound used in the present invention is selected from compounds represented by the following formula (1).

（式（１）中、Ｒ^１およびＲ^２は炭素数１つ以上の脂肪族炭化水素基、芳香族炭化水素基またはヘテロ原子含有炭化水素基を表す。）

(In Formula (1), R ¹ and R ² represent an aliphatic hydrocarbon group having 1 or more carbon atoms, an aromatic hydrocarbon group, or a heteroatom-containing hydrocarbon group.)

In the formula, the aliphatic hydrocarbon group represented by R ¹ or R ² is a substituent having a small structure such as an alkyl group or a cycloalkyl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Preferably there is. Specifically, methyl group, ethyl group, vinyl group, allyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, i-hexyl Group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. Among them, methyl group and ethyl group are preferable.
The aromatic hydrocarbon group represented by R ¹ or R ² is preferably a substituent such as an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms having no substituent. 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.
Heteroatoms that can be contained in R ¹ and R ² are nitrogen, oxygen, silicon, phosphorus, and sulfur, and nitrogen and oxygen are more preferable. Specific examples of the hydrocarbon group containing a hetero atom include a methoxymethyl group, an ethoxymethyl group, a phenoxymethyl group, and a dimethylaminomethyl group.

Specific compounds include 2,5-dimethylfuran, 2,5-diethylfuran, 2,5-dipropylfuran, 2,5-diisopropylfuran, 2,5-dicyclopentylfuran, 2,5-diphenylfuran. And furan compounds. Two or more of these furan compounds can be used.
Among these furan compounds, 2,5-dimethylfuran, 2-methyl-5-phenylfuran and 2,5-diphenylfuran are particularly preferable, and 2,5-dimethylfuran is most preferable.

(2) Preparation method of (alpha) -olefin polymerization catalyst component (A) The amount ratio of the usage-amount of each component which comprises the (alpha) -olefin polymerization catalyst component (A) in this invention is the following range.
The amount of titanium compounds used is a molar ratio (number of moles of titanium compound / number of moles of magnesium compound) with respect to the amount of magnesium compound used, and is preferably in the range of 0.0001 to 1,000. In particular, the range of 0.01 to 10 is desirable. When a halogen source compound is used in addition to the magnesium compound and the titanium compound, the amount used is the same as the magnesium compound used regardless of whether the magnesium compound and the titanium compound contain halogen or not. The molar ratio (number of moles of the halogen source compound / number of moles of the magnesium compound) to the amount used is preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100. The inside is desirable.
The amount of the electron donor used in preparing the α-olefin polymerization catalyst component (A) is a molar ratio (number of moles of electron donor / number of moles of magnesium compound) with respect to the amount of magnesium compound used. Preferably it is in the range of 0.001 to 10, particularly preferably in the range of 0.01 to 5.
The amount of furan compound used in preparing the α-olefin polymerization catalyst component (A) is preferably a molar ratio (number of moles of furan compound / number of moles of magnesium compound) to the amount of magnesium compound used. It is in the range of 0.001 to 10, particularly preferably in the range of 0.01 to 5. The molar ratio of the electron-donating compound and furan compound used in preparing the α-olefin polymerization catalyst component (A) (number of moles of electron-donating compound / number of moles of furan compound) is 0.05 to 1.0. Range, preferably in the range of 0.1 to 0.7. When the molar ratio of the electron donating compound and the furan compound is smaller than the above range, that is, when the furan compound is too much, the yield during the production of the catalyst is deteriorated and the catalyst activity tends to be lowered. On the other hand, when this molar ratio is larger than the above range, that is, when the amount of the furan compound is too small, the desired effect by the furan compound cannot be obtained.

As the contact conditions for the above-mentioned components constituting the α-olefin polymerization catalyst component (A) in the present invention, any conditions can be used as long as the effects of the present invention are not impaired. preferable.
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 solvent.

  Further, when the α-olefin polymerization catalyst component (A) is prepared, it may be washed with an inert solvent in the middle and / or finally. Preferred examples of the 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.

  In addition, although arbitrary methods can be used as a preparation method of (alpha) -olefin polymerization catalyst component (A) in this invention, the method demonstrated as following (i)-(vii) is illustrated. I can do it. In addition, this invention is not restrict | limited at all by the following illustration.

(I) Co-grinding method A method of supporting a titanium compound on a magnesium compound by co-grinding a magnesium compound containing a halogen typified by magnesium chloride with the titanium compound. If necessary, co-pulverization may be performed simultaneously with an optional component such as an electron donor or in a separate step. 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 method in which a magnesium compound containing a halogen typified by magnesium chloride and a titanium compound are stirred in an inert solvent to carry out contact treatment, and the titanium compound is supported on the magnesium compound. When a liquid compound such as titanium tetrachloride is used as the titanium compound, the contact treatment can be performed without an inert solvent. Optionally, optional components such as an electron donor and a silicon halide compound may be contacted simultaneously or in a separate step. 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 A magnesium compound containing a halogen represented by magnesium chloride is dissolved by bringing it into contact with an electron donor, and the resulting solution is brought into contact with a precipitant to cause a precipitation reaction to form particles. How to do. Examples of electron donors used for dissolution include alcohol compounds, epoxy compounds, phosphate ester compounds, silicon compounds having an alkoxy group, titanium compounds having an alkoxy group, and ether compounds. . Examples of the precipitating agent include titanium halide compounds, silicon halide compounds, hydrogen chloride, halogen-containing hydrocarbon compounds, siloxane compounds having Si-H bonds (including polysiloxane compounds), aluminum compounds , Etc. can be illustrated. 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. When the titanium compound is not used in either the dissolution or precipitation process, 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. Furthermore, if necessary, the particles thus formed may be brought into contact with an optional component such as a halogenated titanium compound or a halogenated silicon compound, or may be brought into contact with an electron donor. At this time, the electron donor may be different from or different from that used for dissolution. 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, precipitation, and 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 In the same manner as the dissolution precipitation method, a magnesium compound containing a halogen represented by magnesium chloride is dissolved by contacting with an electron donor, and the resulting solution is granulated mainly by a physical method. how to. The example of the electron donor used for dissolution is the same as that 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 donor, as needed. At this time, the electron donor may be different from or different from that used for dissolution. There is no restriction | limiting in particular about the contact order of these arbitrary components, You may 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) Method of halogenating Mg compound A method of halogenating a magnesium compound containing no halogen by bringing a halogenating agent into contact therewith. 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 halogen-containing magnesium compound formed by halogenation is further brought into contact with the titanium compound, whereby the titanium compound is supported on the magnesium compound. Furthermore, if necessary, the particles thus formed may be brought into contact with an optional component such as a halogenated titanium compound or a halogenated silicon compound, or may be brought into contact with an electron donor. 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 containing no halogen or in contact with titanium compounds. . 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 an organic magnesium compound A method in which a precipitation agent is brought into contact with a solution of an organic magnesium compound such as a Grignard reagent typified by butyl magnesium chloride or a dialkyl magnesium compound. Examples of the precipitating agent include titanium compounds, silicon compounds, hydrogen chloride, and the like. When a 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. Furthermore, if necessary, the particles thus formed may be brought into contact with an optional component such as a halogenated titanium compound or a halogenated silicon compound, or may be brought into contact with an electron donor. There is no restriction | limiting in particular about the contact order of these arbitrary components, You may 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 A method of impregnating a support of an inorganic compound or a support of an organic compound with a solution of an organic magnesium compound or a solution obtained by dissolving a magnesium compound with an electron donating compound. Examples of the organomagnesium compounds are the same as those of the precipitation method from the organomagnesium compounds. The magnesium compound used for dissolving the magnesium compound may or may not contain halogen. Examples of the electron donor 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. Furthermore, if necessary, the particles thus formed may be brought into contact with an optional component such as a halogenated titanium compound or a halogenated silicon compound, or may be brought into contact with an electron donor. There is no restriction | limiting in particular about the contact order of these arbitrary components, You may contact as an independent process, and can also contact together in the case of an 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) Composite 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, a method of carrying a titanium compound by further contacted with titanium halide compounds ", and the like.

2. α-Olefin Polymerization Catalyst Component (A ′)
The α-olefin polymerization catalyst component (A ′) of the present invention comprises the above α-olefin polymerization catalyst component (A), (B) a vinylsilane compound, (C) an organosilicon compound, (D) an organoaluminum compound, Accordingly, (G) it is brought into contact with a compound having at least two ether bonds.

(1) Component (B) Vinylsilane Compound As the vinylsilane compound (B) used in the present invention, at least one hydrogen atom of monosilane (SiH ₄ ) is a vinyl group, and some of the remaining hydrogen atoms are A halogen (preferably Cl), an alkyl group (preferably a hydrocarbon group having 1 to 12 carbon atoms), an aryl group (preferably a phenyl group), an alkoxy group (preferably an alkoxy group having 1 to 12 carbon atoms), etc. It shows the replaced structure.
More _{specifically, CH 2 = CH-SiH 3} , CH 2 = CH-SiH 2 (CH 3), CH 2 = CH-SiH (CH 3) 2, CH 2 = CH-Si (CH 3) 3, _{CH 2 = CH-SiCl 3,} CH 2 = CH-SiCl 2 (CH 3), CH 2 = CH-SiCl (CH 3) 2, CH 2 = CH-SiH (Cl) (CH 3), CH 2 = CH _{-Si (C 2 H 5) 3} , CH 2 = CH-SiCl (C 2 H 5) 2, CH 2 = CH-SiCl 2 (C 2 H 5), CH 2 = CH-Si (CH 3) 2 ( _{C 2 H 5), CH 2} = CH-Si (CH 3) (C 2 H 5) 2, CH 2 = CH-Si (n-C 4 H 9) 3, CH 2 = CH-Si (C 6 H _{5) 3, CH 2 = CH} -Si (CH 3) (C 6 H 5) 2, _{CH 2 = CH-Si (CH} 3) 2 (C 6 H 5), CH 2 = CH-Si (CH 3) 2 (C 6 H 4 CH 3), (CH 2 = CH) (CH 3) 2 Si _{-O-Si (CH 3) 2} (CH = CH 2), (CH 2 = CH) 2 SiH 2, (CH 2 = CH) 2 SiCl 2, (CH 2 = CH) 2 Si (CH 3) 2, _{(CH 2 = CH) 2 Si} (C 6 H 5) 2 and the like can be exemplified.

(C) Organosilicon compound As the organosilicon compound (C) that can be used in the present invention, compounds disclosed in JP-A-2004-124090 can be used. In general, it is desirable to use a compound represented by the following formula (2).
R ¹ R ² _a Si (OR ³ ) _b (2)
(In the formula, R ¹ represents a hydrocarbon group or a hetero atom-containing hydrocarbon group. R ² represents an arbitrary radical selected from hydrogen, halogen, a hydrocarbon group, and a hetero atom-containing hydrocarbon group. R ³ represents Represents a hydrocarbon group, 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, a + b = 3)

In the formula (2), the hydrocarbon group that can be used as R ¹ is generally one having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ¹ include a linear aliphatic hydrocarbon group typified by an n-propyl group, a branched chain typified 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 alicyclic hydrocarbon group as R ¹ , 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 ¹ is a heteroatom-containing hydrocarbon group, the heteroatom is preferably selected from nitrogen, oxygen, sulfur, phosphorus and silicon, and particularly preferably nitrogen or oxygen. The skeleton structure of the hetero atom-containing hydrocarbon group of R ^1, it is desirable to select from the example of R ¹ is a hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.

In formula (2), R ² represents hydrogen, halogen, a hydrocarbon group or a heteroatom-containing hydrocarbon group. Examples of the halogen that can be used as R ² include fluorine, chlorine, bromine, iodine, and the like. 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 linear aliphatic hydrocarbon group typified by a methyl group or an ethyl group, a branch represented by an i-propyl group or 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.
When R ² is a heteroatom-containing hydrocarbon group, it is desirable to select from the examples when R ¹ is a heteroatom-containing hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.
In Formula (2), when the value of a is 2, two R ² may be the same or different. Regardless of the value of a, R ² may be the same as or different from R ¹ .

In formula (2), R ³ represents a hydrocarbon group. The hydrocarbon group that can be used as R ³ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ³ include a linear aliphatic hydrocarbon group represented by a methyl group or an ethyl group, a branch represented by an i-propyl group or a t-butyl group. And the like, and the like. Of these, a methyl group and an ethyl group are most preferable. When the value of b is 2 or more, a plurality of R ³ may be the same or different.

Preferred examples of the organosilicon compound (C) that can be used in the present invention include t-Bu (Me) Si (OMe) ₂ , t-Bu (Me) Si (OEt) ₂ , t-Bu (Et) Si. (OMe) ₂ , t-Bu (n-Pr) Si (OMe) ₂ , c-Hex (Me) Si (OMe) ₂ , c-Hex (Et) Si (OMe) ₂ , c-Pen ₂ Si (OMe) ) ₂ , i-Pr ₂ Si (OMe) ₂ , i-Bu ₂ Si (OMe) ₂ , i-Pr (i-Bu) Si (OMe) ₂ , n-Pr (Me) Si (OMe) ₂ , TexylSi (OMe) ₃ , t-BuSi (OEt) ₃ , (Et ₂ N) ₂ Si (OMe) ₂ , Et ₂ N—Si (OEt) ₃ ,

And so on.
These organosilicon compounds can be used alone or in combination with a plurality of compounds.

(D) Organoaluminum compound As the organoaluminum compound (D) that can be 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 formula (3).
R ⁴ _c AlX _d (OR ⁵ ) _e (3)
(In the formula, R ⁴ represents a hydrocarbon group. X represents a halogen or hydrogen. R ⁵ represents a hydrocarbon group or a bridging group by Al. C ≧ 1, 0 ≦ d ≦ 2, 0 ≦ e ≦ 2. , C + d + e = 3.)

In formula (3), R ⁴ 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 ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group. Of these, a methyl group, an ethyl group, and an isobutyl group are most preferable.
In formula (3), X is halogen or hydrogen. Examples of halogen that can be used as X include fluorine, chlorine, bromine, iodine, and the like. Of these, chlorine is particularly preferred.
In formula (3), R ⁵ is a hydrocarbon group or a crosslinking group by Al. When R ⁵ is a hydrocarbon group, R ⁵ can be selected from the same group as exemplified for the hydrocarbon group of R ⁴ . Moreover, it is also possible to use alumoxane compounds represented by methylalumoxane as the organoaluminum compound (SD ′), in which case R ⁵ represents a cross-linking group of Al.

Specific examples of compounds that can be used as the organoaluminum compound (D) 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 (D), not only a single compound but also a plurality of compounds can be used in combination.

(G) Compound having at least two ether bonds The compound (G) having at least two ether bonds that can be used in the present invention is disclosed in JP-A-3-294302 and JP-A-8-333413. The compound etc. which can be used can be used. In general, it is desirable to use a compound represented by the following formula (4).
_{^{R 8 O-C (R 7}} ) 2 -C (R 6) 2 -C (R 7) 2 -OR 8 ... (4)
(In the formula, R ⁶ and R ⁷ represent any free radical selected from hydrogen, a hydrocarbon group, and a hetero atom-containing hydrocarbon group. R ⁸ represents a hydrocarbon group or a hetero atom-containing hydrocarbon group.)

In formula (4), R ⁶ represents any free radical selected from hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. The hydrocarbon group that can be used as R ⁶ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ⁶ include a linear aliphatic hydrocarbon group typified by an n-propyl group, a branched chain typified 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 alicyclic hydrocarbon group as R ⁶ , and in particular, i-propyl group, i-butyl group, i-pentyl group, cyclopentyl group, cyclohexyl group, It is desirable to use etc.
Two R ⁶ may combine to form one or more rings. In this case, a cyclopolyene structure having 2 or 3 unsaturated bonds in the ring structure can be taken. Further, it may be condensed with other cyclic structures. Regardless of whether monocyclic, polycyclic, or condensed, one or more hydrocarbon groups may be present as substituents on the ring. Substituents on the ring are generally those having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples include linear aliphatic hydrocarbon groups typified by n-propyl groups, branched aliphatic hydrocarbon groups typified by i-propyl groups and t-butyl groups, cyclopentyl groups, and cyclohexyl groups. And alicyclic hydrocarbon groups, and aromatic hydrocarbon groups typified by phenyl groups.
In formula (4), R ⁷ represents any free radical selected from hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. Specifically, R ⁷ can be selected from the examples of R ⁶ . Preferably it is hydrogen.
In formula (4), R ⁸ represents a hydrocarbon group or a hetero atom-containing hydrocarbon group. Specifically, R ⁸ can be selected from the examples when R ⁶ is a hydrocarbon group. Preferably, it is a hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group. Most preferred is a methyl group.
When R ⁶ to R ⁸ are hetero atom-containing hydrocarbon groups, the hetero atom is preferably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon. Further, regardless of whether R ⁶ to R ⁸ are a hydrocarbon group or a heteroatom-containing hydrocarbon group, they may optionally contain a halogen. When R ⁶ to R ⁸ contain a hetero atom and / or halogen, the skeleton structure is preferably selected from the examples in the case of a hydrocarbon group. Further, the eight substituents R ⁶ to R ⁸ may be the same as or different from each other.

Preferred examples of the compound (G) having at least two ether bonds that can be used in the present invention include 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2,2-dipropyl -1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimeth Cyclopropane, 9,9-bis (methoxymethyl) fluorene, 9,9-bis (methoxymethyl) -1,8-dichlorofluorene, 9,9-bis (methoxymethyl) -2,7-dicyclopentylfluorene, 9, 9-bis (methoxymethyl) -1,2,3,4-tetrahydrofluorene, 1,1-bis (1′-butoxyethyl) cyclopentadiene, 1,1-bis (α-methoxybenzyl) indene, 1,1 -Bis (phenoxymethyl) -3,6-dicyclohexylindene, 1,1-bis (methoxymethyl) benzonaphthene, 7,7-bis (methoxymethyl) -2,5-nobornadinene, and the like. Among them, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl Particularly preferred are -1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, and 9,9-bis (methoxymethyl) fluorene.
These compounds (G) having at least two ether bonds can be used alone or in combination with a plurality of compounds. Moreover, it may be the same as or different from the polyvalent ether compound used as the electron donating compound which is an optional component in the α-olefin polymerization catalyst component (A).

(2) Preparation Method of α-Olefin Polymerization Catalyst Component (A ′) The α-olefin polymerization catalyst component (A ′) used in the present invention is an α-olefin polymerization catalyst component (A), a vinylsilane compound (B), An organic silicon compound (C) and an organoaluminum compound (D) are brought into contact with each other. At this time, other optional components such as the compound (G) having at least two ether bonds may be contacted by any method as long as the effects of the present invention are not impaired. Arbitrary conditions can be used for the contact conditions of each structural component of the catalyst component (A ′) for α-olefin polymerization 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 or 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.

The amount ratio of each component constituting the α-olefin polymerization catalyst component (A ′) in the present invention may be any ratio within a range not impairing the effects of the present invention. Within the range of is preferable.
The amount of the vinylsilane compound (B) used is preferably a molar ratio (number of moles of vinylsilane compound (B) / number of moles of titanium atoms) with respect to the titanium component constituting the catalyst component (A) for α-olefin polymerization. It is in the range of 001 to 1,000, particularly preferably in the range of 0.01 to 100.
The amount of the organosilicon compound (C) used is the molar ratio with respect to the titanium component constituting the α-olefin polymerization catalyst component (A) (number of moles of organosilicon compound (C) having an alkoxy group / number of moles of titanium atoms). ), Preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100.
When the organoaluminum compound (D) is used as an optional component, the amount used is the atomic ratio of aluminum to the titanium component constituting the α-olefin polymerization catalyst component (A) (number of moles of aluminum atoms / number of moles of titanium atoms). And preferably in the range of 0.1 to 100, particularly preferably in the range of 1 to 50.
When the compound (G) having at least two ether bonds is used as an optional component, the amount used is the molar ratio to the titanium component constituting the solid component (A) (the number of moles of the compound (G) having at least two ether bonds). / Mol number of titanium atoms), preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100.

As for the contact procedure of the solid component (A), the vinylsilane compound (B), and the organosilicon compound (C), any procedure can be used. Specifically, the following (i) to (iii): Procedures can be listed.
Procedure (i): A method of bringing the organosilane compound (C) into contact with the catalyst component (A) for α-olefin polymerization after contacting the vinylsilane compound (B).
Procedure (ii): A method of bringing the vinylsilane compound (B) into contact with the catalyst component (A) for α-olefin polymerization after contacting the organosilicon compound (C).
Procedure (iii): A method in which all compounds are contacted simultaneously.
Among these, the procedure (i) and the procedure (iii) are preferable.

  Further, any of the vinylsilane compound (B) and the organosilicon compound (C) can be brought into contact with the α-olefin polymerization catalyst component (A) any number of times. At this time, both the vinylsilane compound (B) and the organosilicon compound (C) may be the same or different from each other.

Moreover, regarding the contact of the organoaluminum compound (D), it can be brought into contact in an arbitrary order in the same manner as described above, but preferred contact orders include the following procedures (iv) to (vi). .
Step (iv): A method in which the vinylsilane compound (B) is contacted with the α-olefin polymerization catalyst component (A), then the organosilicon compound (C) is contacted, and the organoaluminum compound (D) is further contacted.
Procedure (v): A method in which the vinylsilane compound (B) and the organosilicon compound (C) are contacted with the catalyst component (A) for α-olefin polymerization, and then the organoaluminum compound (D) is contacted.
Procedure (vi): A method in which all compounds are contacted simultaneously.
The organoaluminum compound (D) can be contacted a plurality of times as described above. At this time, the organoaluminum compound (D) used a plurality of times may be the same or different.

  Even when the compound (G) having at least two ether bonds and / or other compounds are used as optional components, they can be contacted in any order as described above.

  In preparing the α-olefin polymerization catalyst component (A ′), washing may be performed with an inert solvent in the middle and / or finally. Preferred examples of the 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.

3. α-Olefin Polymerization Catalyst The α-olefin polymerization catalyst of the present invention includes an α-olefin polymerization catalyst component (A) or an α-olefin polymerization catalyst component (A ′), an organoaluminum compound (E), and Accordingly, a polymerization catalyst is formed by using an organosilicon compound (F) and a compound (H) having at least two ether bonds in combination.

(1) Component (E) Organoaluminum Compound As the organoaluminum compound (E) that can be used in the α-olefin polymerization catalyst of the present invention, compounds disclosed in JP-A No. 2004-124090 are used. I can do it. Preferably, it can select from the same group as the illustration in the organoaluminum compound (D) which is an arbitrary component at the time of preparing the catalyst component (A ′) for α-olefin polymerization. At this time, the organoaluminum compound (D) that can be used as an optional component in preparing the α-olefin polymerization catalyst component (A ′) is the same as the organoaluminum compound (E) that can be used as an essential component of the catalyst. Or different.
As the organoaluminum compound (E), not only a single compound but also a plurality of compounds can be used in combination.

  The amount of the organoaluminum compound (E) used in the α-olefin polymerization catalyst is the molar ratio of the organoaluminum compound (E) to the titanium component constituting the α-olefin polymerization catalyst component (A) or (A ′). Number / number of moles of titanium atoms), preferably in the range of 1 to 5,000, particularly preferably in the range of 10 to 500.

  In the present invention, there is no particular limitation on the mode in which the α-olefin polymerization catalyst component (A) or (A ′) and the organoaluminum compound (E) are used in combination. The polymerization catalyst component (A) or (A ′) and the organoaluminum compound (E) are allowed to coexist.

(F) Organosilicon compound As the organosilicon compound (F) that can be used as an optional component in the α-olefin polymerization catalyst of the present invention, compounds disclosed in JP-A-2004-124090 can be used. . Preferably, it can select from the same group as the illustration in the organosilicon compound (C) which can be used in the catalyst component (A ′) for α-olefin polymerization. In this case, the organosilicon compound (C) that can be used as an essential component in preparing the α-olefin polymerization catalyst component (A ′) is the same as the organosilicon compound (F) that can be used as an optional component of the catalyst. Or different.
As the organosilicon compound (F), not only a single compound but also a plurality of compounds can be used in combination.

  In the present invention, when the organosilicon compound (F) is used, it is usually allowed to coexist in the polymerization reaction layer with the α-olefin polymerization catalyst component (A) or (A ′) and the organoaluminum compound (E).

(H) Compound having at least two ether bonds As the compound (H) having at least two ether bonds that can be used as an optional component in the catalyst for α-olefin polymerization of the present invention, JP-A-3-294302 and The compounds disclosed in JP-A-8-333413 can be used. Preferably, it can be selected from the same group as exemplified in the compound (G) having at least two ether bonds used in the α-olefin polymerization catalyst component (A ′). At this time, the compound (G) having at least two ether bonds that can be used as an optional component when preparing the α-olefin polymerization catalyst component (A ′) and at least two that can be used as an optional component of the catalyst. The compounds (H) having an ether bond may be the same or different.
As the compound (H) having at least two ether bonds, not only a single compound but also a plurality of compounds can be used in combination.

  In the present invention, when the compound (H) having at least two ether bonds is used, the α-olefin polymerization catalyst component (A) or (A ′), the organoaluminum compound (E), and Coexist.

(I) Other compounds As long as the effects of the present invention are not impaired, the component (I) other than the organosilicon compound (F) and the compound (H) having at least two ether bonds is used as an optional component of the catalyst. I can do it. For example, as disclosed in JP-A No. 2004-124090, by using a compound having a C (═O) N bond in the molecule, an amorphous component such as cold xylene solubles (CXS) can be obtained. Generation can be suppressed. In this case, preferred examples include tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 1-ethyl-2-pyrrolidinone and the like.
A compound having a C (═O) N bond in the molecule can use not only a single compound but also a plurality of compounds.
An organometallic compound having a metal atom other than aluminum, such as diethyl zinc, can also be used.

Although the usage-amount of the arbitrary component in the catalyst of this invention may be arbitrary in the range which does not impair the effect of this invention, generally the inside of the following range is preferable.
When the organosilicon compound (F) is used, the amount used is the molar ratio of the α-olefin polymerization catalyst component (A) or (A ′) to the titanium component constituting the number of moles of the organosilicon compound (F) / mol of titanium atoms. Number), preferably in the range of 0.01 to 50,000, particularly preferably in the range of 0.5 to 500.
When the compound (H) having at least two ether bonds is used, the amount used is a molar ratio to the titanium component constituting the α-olefin polymerization catalyst component (A) or (A ′) (compound having at least two ether bonds). The number of moles of (H) / number of moles of titanium atoms) is preferably in the range of 0.01 to 50,000, and particularly preferably in the range of 0.5 to 500.
The amount used in the case of using a compound having a C (═O) N bond in the molecule is a molar ratio to the titanium component constituting the α-olefin polymerization catalyst component (A) or (A ′) (C (= O) The number of moles of the compound having an N bond / the number of moles of titanium atoms) is preferably in the range of 0.001 to 5,000, particularly preferably in the range of 0.05 to 500.

(2) Prepolymerization The α-olefin polymerization catalyst of the present invention may be one obtained by prepolymerizing the α-olefin polymerization catalyst component (A) or (A ′) before use in the main polymerization. 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, etc., and 1,3-butadiene, isoprene, 1,3-pentadiene, 1,5-hexadiene, 2,6-octadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1 , 9-decadiene, divinyl benzenes, 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 component as the α-olefin polymerization catalyst component (A) or (A ′), the prepolymerization is carried out by an arbitrary procedure in the preparation procedure of the α-olefin polymerization catalyst component (A ′). I can do it. For example, after pre-polymerizing the α-olefin polymerization catalyst component (A), the vinylsilane compound (B) and the organosilicon compound (C) can be contacted. In addition, after the α-olefin polymerization catalyst component (A), the vinylsilane compound (B), and the organosilicon compound (C) are contacted, prepolymerization can be performed. Furthermore, when the α-olefin polymerization catalyst component (A), the vinylsilane compound (B), and the organosilicon compound (C) are contacted, prepolymerization may be performed simultaneously.

Arbitrary conditions can be used for the reaction conditions of the α-olefin polymerization catalyst component (A ′) or α-olefin polymerization catalyst component (A) and the monomer as long as the effects of the present invention are not impaired. In general, the following range is preferable.
The amount of prepolymerization is within the range of 0.001 to 100 g, preferably 0.1 to 50 g, based on 1 gram of α-olefin polymerization catalyst component (A ′) or α-olefin polymerization catalyst component (A), More preferably, it is in the range of 0.5 to 10 g. As a method for supplying the monomer, any method can be used, such as a method for maintaining the monomer in the reaction tank at a constant speed, a constant pressure state or a constant concentration, a combination thereof, or a stepwise change. The reaction temperature during the 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. The prepolymerization time is preferably in the range of 5 minutes to 24 hours. 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. After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst, but may be dried if necessary.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

4). α-Olefin Polymerization The α-olefin polymerization using the novel catalyst of the present invention is applied to slurry polymerization using a hydrocarbon solvent, liquid phase solventless polymerization or gas phase polymerization using substantially no solvent. 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.

The α-olefin polymerized in the catalyst system of the present invention is represented by the general formula R ⁹ —CH═CH ₂ (wherein R ⁹ 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, copolymerization with monomers (for example, ethylene, α-olefins, dienes, styrenes, etc.) copolymerizable with α-olefins can also be performed. These copolymerizable monomers can be used up to 15% by weight in random copolymerization and up to 50% by weight in block copolymerization.

5. 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 applications. In general, the MFR of the α-olefin polymer is preferably in the range of 0.01 to 10,000 g / 10 minutes, and particularly preferably in the range of 0.1 to 1,000 g / 10 minutes. . The amount of cold xylene solubles (CXS), which is an amorphous component, generally varies in preferred range depending on the application. For applications where high rigidity is preferred, such as injection molding applications, the amount of CXS is preferably in the range of 0.01 to 3.0% by weight, particularly preferably 0.05 to 1.5% by weight. In the range of 0.1 to 1.0% by weight is particularly desirable.
Here, the values of MFR and CXS are values measured by the methods defined in the following examples.

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.
Here, the value of the polymer bulk density is a value measured by the method defined in the following examples.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited only to these examples. In addition, the measuring method of the physical property used by an Example and a comparative example is as follows.

1. Method of measuring physical properties (1) MFR
Evaluation was performed under the conditions of 230 ° C. and 21.18 N based on JIS-K6921 using a melt indexer manufactured by Takara.
(2) Polymer bulk density It measured using the 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% by weight based on the sample.
(4) Density Using the extruded strand obtained at the time of MFR measurement, the density gradient tube method was used in accordance with JIS-K7112 D method.

Example 1
(1) Preparation of α-olefin polymerization catalyst component (A) 200 ml of dehydrated and deoxygenated n-heptane was introduced into a fully nitrogen-substituted flask, and then 0.16 mol of MgCl ₂ and Ti (O-n- 0.3 mol of C ₄ H ₉ ) ₄ was introduced, 0.03 mol of 2,5-dimethylfuran was further introduced, and the mixture was reacted at 90 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., then 23 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 4 hours. The resulting solid component was washed with n-heptane.
Next, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, and 0.06 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 0.1 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 90 ° C. for 2 hours. After completion of the reaction, washing with n-heptane was performed. Next, 0.006 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Then, 2.5 mol of TiCl ₄ was introduced and reacted at 110 ° C. for 2 hours. After completion of the reaction, the mixture was thoroughly washed with n-heptane, and 2.5 mol of TiCl _{4 was} further introduced and reacted at 90 ° C. for 2 hours. After completion of the reaction, the mixture was sufficiently washed with n-heptane to obtain an α-olefin polymerization catalyst component (A).
(2) Preparation of α-olefin polymerization catalyst component (A ′) 4 g of the above component (A) slurry was introduced as a component (A) into a sufficiently nitrogen-substituted flask. Thereafter, purified n-heptane was introduced to adjust the concentration of the component (A) to 20 g / L. Here, 1.5 g of trimethyl vinyl silane 1.0 ml, organosilicon compound (C) as t-Bu (Me) Si ( OMe) 2 1.2ml, an n- heptane dilution of _Et 3 Al as _Et 3 Al The mixture was added and reacted at 30 ° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane.
Next, purified n-heptane was introduced into the slurry, and the concentration of the component (A) was adjusted to 20 g / L. After cooling the slurry to 15 ° C., the n- heptane dilution of _Et 3 Al 0.5 g was added as _Et 3 Al, were fed slowly propylene 9g. After the supply of propylene was completed, the reaction was further continued for 10 minutes. Next, the gas phase was sufficiently replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. Thereafter, vacuum drying was performed to obtain an α-olefin polymerization catalyst component (A ′). This component (A ′) contained 2.0 g of polypropylene per 1 g of the solid component. As a result of analysis, 1.2 wt% of Ti was contained in the component (A ′) excluding polypropylene.
(3) Polymerization of propylene A stainless steel autoclave having an internal volume of 3.0 liters having a stirring and temperature control device was sufficiently heated and dried, and then cooled to room temperature. After thoroughly purging the autoclave with propylene, an organoaluminum compound (E) as _Et 3 Al of n- heptane diluent was 550mg added as _Et 3 Al. Next, 5,000 ml of hydrogen and 1,000 g of propylene were sequentially introduced into the autoclave. After adjusting the internal temperature of the autoclave to 75 ° C., 7 mg (excluding the prepolymerized polymer) of the α-olefin polymerization catalyst component (A ′) prepared above was injected to initiate polymerization. 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)
(1) Preparation of α-olefin polymerization catalyst component (A) 200 ml of dehydrated and deoxygenated n-heptane was introduced into a fully nitrogen-substituted flask, and then 0.16 mol of MgCl ₂ and Ti (O-n- 0.3 mol of C ₄ H ₉ ) ₄ was introduced and reacted at 90 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., then 23 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 4 hours. The resulting solid component was washed with n-heptane.
Next, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, and 0.06 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 0.1 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 90 ° C. for 2 hours. After completion of the reaction, washing with n-heptane was performed. Next, 0.006 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Subsequently, 0.04 mol of 2,5-dimethylfuran was introduced and reacted at 90 ° C. for 2 hours. After completion of the reaction, washing with n-heptane was performed. Then, 2.5 mol of TiCl ₄ was introduced and reacted at 110 ° C. for 2 hours. After completion of the reaction, the mixture was thoroughly washed with n-heptane, and 2.5 mol of TiCl _{4 was} further introduced and reacted at 90 ° C. for 2 hours. After completion of the reaction, the mixture was sufficiently washed with n-heptane to obtain an α-olefin polymerization catalyst component (A).
(2) Preparation of α-olefin polymerization catalyst component (A ′) 4 g of the above component (A) slurry was introduced as a solid component (A) into a sufficiently nitrogen-substituted flask. Thereafter, purified n-heptane was introduced to adjust the concentration of the solid component (A) to 20 g / L. Here, 1.5 g of trimethyl vinyl silane 1.0 ml, organosilicon compound (C) as t-Bu (Me) Si ( OMe) 2 1.2ml, an n- heptane dilution of _Et 3 Al as _Et 3 Al The mixture was added and reacted at 30 ° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane.
Next, purified n-heptane was introduced into the slurry, and the concentration of the component (A) was adjusted to 20 g / L. After cooling the slurry to 15 ° C., the n- heptane dilution of _Et 3 Al 0.5 g was added as _Et 3 Al, were fed slowly propylene 9g. After the supply of propylene was completed, the reaction was further continued for 10 minutes. Next, the gas phase was sufficiently replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. Thereafter, vacuum drying was performed to obtain an α-olefin polymerization catalyst component (A ′). This component (A ′) contained 2.0 g of polypropylene per 1 g of the solid component. As a result of analysis, 1.3 wt% of Ti was contained in the component (A ′) excluding polypropylene.
(3) Polymerization of propylene A stainless steel autoclave having an internal volume of 3.0 liters having a stirring and temperature control device was sufficiently heated and dried, and then cooled to room temperature. After thoroughly purging the autoclave with propylene, an organoaluminum compound (E) as _Et 3 Al of n- heptane diluent was 550mg added as _Et 3 Al. Next, 5,000 ml of hydrogen and 1,000 g of propylene were sequentially introduced into the autoclave. After adjusting the internal temperature of the autoclave to 75 ° C., 7 mg (excluding the prepolymerized polymer) of the α-olefin polymerization catalyst component (A ′) prepared above was injected to initiate polymerization. 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 3)
Implemented except that 2,5-diphenylfuran was used instead of 2,5-dimethylfuran used in Example 1 and 80 mg of t-Bu (Me) Si (OMe) ₂ was introduced as component (F) during polymerization. Performed exactly as in Example 1. The results are shown in Table 1.

Example 4
In place of 2,5-dimethylfuran used in Example 2, 2,5-diphenylfuran was used, and 90 mg of (C ₆ H ₁₁ ) CH ₃ Si (OCH ₃ ) ₂ was introduced as a component (F) during polymerization. Except for this, the same procedure as in Example 2 was performed. The results are shown in Table 1.

(Example 5)
Example except that α-olefin polymerization catalyst component (A) prepared in Example 2 was used at the time of propylene polymerization and 110 mg of (c-Pen) ₂ Si (OMe) ₂ was introduced as component (F) at the time of polymerization. Performed exactly as in 2. The results are shown in Table 1.

(Comparative Example 1)
The procedure was the same as in Example 1 except that 2,5-dimethylfuran used in Example 1 was not used. The results are shown in Table 2.

(Comparative Example 2)
The same procedure as in Example 1 was performed except that dibutyl ether was used instead of 2,5-dimethylfuran used in Example 1. The results are shown in Table 2.

(Comparative Example 3)
The same procedure as in Example 1 was performed except that dibenzofuran was used instead of 2,5-dimethylfuran used in Example 1. The results are shown in Table 2.

(Comparative Example 4)
The same procedure as in Example 2 was performed except that furan was used instead of 2,5-dimethylfuran used in Example 2. The results are shown in Table 2.

(Comparative Example 5)
The same procedure as in Example 5 was performed except that dibenzofuran was used instead of 2,5-dimethylfuran used in Example 5. The results are shown in Table 2.

(Comparative Example 6)
The same procedure as in Example 2 was performed except that the amount of 2,5-dimethylfuran used in Example 2 was 0.12 mol. The results are shown in Table 2.

By comparing each of Examples 1 to 5 and Comparative Examples 1 to 6 in Tables 1 and 2, in the present invention, the catalyst activity, polymer bulk density, cold xylene solubles (CXS), density, etc. are covered. It is clear that superior results are obtained compared to the comparative example.
Specifically, Examples 1 and 2 have higher catalytic activity and lower CXS than Comparative Examples 1 to 4. Polymer bulk density and density are comparable. In Examples 3 and 4, by using the organosilicon compound (F), although there is a slight decrease in activity compared to Examples 1 and 2, CXS is reduced. Example 5 has higher catalytic activity and polymer bulk density, and CXS and density are the same as those of Comparative Example 5. Therefore, it can be said that the results obtained in Examples are superior to those in the Comparative Examples over the catalyst performance, stereoregularity, and particle properties.

  The catalyst component for α-olefin polymerization of the present invention, the catalyst for α-olefin polymerization has high catalytic activity, and the α-olefin polymer obtained using this novel catalyst is excellent in stereoregularity and particle properties, Can be used in various fields.

FIG. 3 is a flowchart for helping and clarifying the catalyst of the present invention.

Claims (5)

It contains titanium, magnesium, halogen, an electron donating compound, and a furan compound represented by the following formula (1), and a molar ratio of the electron donating compound to the furan compound (number of moles of electron donating compound / furan compound The catalyst component for α-olefin polymerization, wherein the number of moles) is in the range of 0.05 to 1.0.

(In Formula (1), R ¹ and R ² represent an aliphatic hydrocarbon group having 1 or more carbon atoms, an aromatic hydrocarbon group, or a heteroatom-containing hydrocarbon group.) An α-olefin polymerization catalyst component, wherein the following components (B), (C) and (D) are brought into contact with the α-olefin polymerization catalyst component (A) according to claim 1.
(B) Vinylsilane compound (C) Organosilicon compound (D) Organoaluminum compound The α-olefin polymerization catalyst component (A) according to claim 1 or the α-olefin polymerization catalyst component (A ′) according to claim 2 and the following component (E): Polymerization catalyst.
(E) Organoaluminum compound An α-olefin polymerization catalyst comprising the α-olefin polymerization catalyst according to claim 3 and the following component (F).
(F) Organosilicon compound   The manufacturing method of the alpha-olefin polymer characterized by superposing | polymerizing alpha-olefin in presence of the catalyst component for alpha-olefin polymerization of Claims 1-4, or the catalyst for alpha-olefin polymerization.

Images