JP2001294610A - Solid catalytic component for polymerizing alpha-olefin, catalyst for polymerizing alpha-olefin, and method for producing alpha-olefinic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high activity catalyst for polymerizing an α-olefin and also to provide an efficient method for producing an α-olefinic polymer. SOLUTION: A solid catalyst component for polymerizing an α-olefin is obtained by bringing a solid reaction product obtained through the reduction of a titanium compound represented by general formula [I] (wherein a is a number of 2 to 20; R2 is a 1-20C hydrocarbon group; and X2s are each a halogen atom or a 1-20C oxyhydrocarbon group) with an organomagnesium compound into contact with an electron donative compound and/or organic acid halide and a compound having Ti-halogen bond in the presence of an organosilicon compound having Si-O bond. A catalyst for polymerizing an α-olefin obtained by using a solid catalyst component, an organoaluminum and an electron donative compound, and a method for producing an α-olefinic polymer in the presence of a catalyst are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art As a method for producing an .alpha.-olefin polymer such as propylene and butene-1, there are known the following methods of the periodic table.
It is well known to use a so-called Ziegler-Natta catalyst comprising a solid catalyst component prepared using a Group 6 transition metal compound and an organic metal compound of Groups 1, 2, and 13.

When an α-olefin polymer is produced, an amorphous polymer is usually produced in addition to a stereoregular α-olefin polymer having high industrial value. This amorphous polymer has little industrial value and greatly affects the mechanical properties of an α-olefin polymer when processed into an injection-molded product, film, fiber, or other processed product. In addition, the production of the amorphous polymer causes a loss of the raw material monomer, and at the same time, requires a production facility for removing the amorphous polymer, resulting in an extremely disadvantageous industrial view. Therefore, the catalyst for producing the α-olefin polymer has no such amorphous polymer, or
Even if it is, it is desirable that it is very slight.

[0004] In addition, a catalyst residue comprising a transition metal component and an organometallic component usually remains in the obtained α-olefin polymer. Since this catalyst residue causes problems in various points such as the stability and processability of the α-olefin polymer, deashing equipment for removing and stabilizing the catalyst residue is often required. This disadvantage can be improved by increasing the catalytic activity expressed by the weight of the produced α-olefin polymer per catalyst weight, and by realizing a sufficient catalytic activity, the equipment for removing the catalyst residue is also required. This is unnecessary, and the production cost of the α-olefin polymer can be reduced.

[0005] By using a supported solid catalyst component obtained by supporting a tetravalent titanium halide on a magnesium halide, an organoaluminum compound as a co-catalyst, and an organosilicon compound as a third polymerization component, α
It is known that high stereoregular polymerization of olefins can be realized (JP-A-57-63310, JP-A-5-63310).
8-83006, JP-A-61-78803).

A solid product obtained by reducing a titanium compound with an organomagnesium compound in the presence of an organosilicon compound and an ester compound is treated with an ester compound, and then treated with a mixture of an ether compound and titanium tetrachloride or an ether compound. Even when a combination of a trivalent titanium compound-containing solid catalyst component obtained by treating with a mixture of titanium tetrachloride and an ester compound, an organoaluminum compound as a co-catalyst, and an electron-donating compound as a third polymerization component is used. It is known that high stereoregular polymerization of olefins can be realized (JP-A-7-216017).

Further, a mixture of an ether compound and titanium tetrachloride and an organic acid halide compound are added in this order to a solid product obtained by reducing a titanium compound with an organic magnesium compound in the presence of an organosilicon compound and an ester compound. After the treatment, obtained by treating with a mixture of an ether compound and titanium tetrachloride, or a mixture of an ether compound and titanium tetrachloride and an ester compound, a trivalent titanium compound-containing solid catalyst component, and a cocatalyst organoaluminum compound It is known that high stereoregularity polymerization of α-olefin can be realized even in combination with an electron-donating compound as the third component of polymerization (Japanese Patent Application Laid-Open No. 10-21).
No. 2319).

In each case, although no extraction and no decalcification processes can be realized, further improvements are desired. Specifically, in order to reduce the production cost of the α-olefin polymer, it is desired to realize a further highly active polymerization. Furthermore, in applications where high rigidity of the polymer is desired, such as in the field of injection molding, a high stereoregularity polymer directly produces high rigidity quality, so that a high stereoregularity polymerization ability is required. There is an urgent need for a catalyst having high activity polymerization ability without sacrificing.

[0009]

Under such circumstances,
The problem to be solved by the present invention, that is, an object of the present invention is to provide a solid catalyst component for α-olefin polymerization and a catalyst for α-olefin polymerization having high active polymerization ability, and an efficient α-olefin polymer. It is to provide a manufacturing method of.

[0010]

According to the present invention, a titanium compound () represented by the following general formula (I) is converted to an organomagnesium compound () in the presence of an organosilicon compound () having a Si--O bond. A solid product (e) obtained by reducing with an electron-donating compound (b) and / or an organic acid halide (c) and a compound (d) having a Ti-halogen bond. In the presence of a solid catalyst component for α-olefin polymerization, and an organosilicon compound () and an ester compound () having a Si—O bond, a titanium compound () represented by the following general formula [I]
Is reduced with an organomagnesium compound (), a solid product (e), an electron donating compound (b) and / or
Alternatively, the present invention relates to a solid catalyst component for α-olefin polymerization obtained by contacting an organic acid halide (c) with a compound (d) having a Ti-halogen bond. The present invention also provides an α-olefin polymerization catalyst obtained using the solid catalyst component (A), the organoaluminum (B), and the electron donating compound (C), and an α-olefin polymerization catalyst. The present invention relates to a method for producing an α-olefin polymer in which α-olefin is homopolymerized or copolymerized. (In the formula, a represents a number of 2 to 20, and R ² has 1 carbon atom.
Represents up to 20 hydrocarbon groups. X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, and all X ² may be the same or different. )

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. (A) Solid catalyst component The solid catalyst component of the present invention is obtained by converting a titanium compound () represented by the following general formula [I] into an organomagnesium compound in the presence of an organosilicon compound () having a Si-O bond. ), And a solid product (e) obtained by reduction with an electron-donating compound (b) and / or an organic acid halide (c).
And a compound (d) having a Ti-halogen bond, a solid catalyst component for α-olefin polymerization obtained by contact treatment,
Alternatively, it is obtained by reducing a titanium compound () represented by the following general formula [I] with an organomagnesium compound () in the presence of an organosilicon compound () and an ester compound () having a Si—O bond. Α-olefin polymerization solid obtained by contacting the solid product (e), the electron donating compound (b) and / or the organic acid halide (c), and the compound (d) having a Ti-halogen bond It is a catalyst component. (In the formula, a represents a number of 2 to 20, and R ² has 1 carbon atom.
Represents up to 20 hydrocarbon groups. X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, and all X ² may be the same or different. )

(B) Electron-donating compound The electron-donating compound used for preparing the solid catalyst component in the present invention includes ethers (diethers), ketones, aldehydes, carboxylic acids, organic acids and inorganic acids. Esters, organic acid or inorganic acid acid amides, oxygen-containing electron donating compounds such as acid anhydrides, and nitrogen-containing electron donating compounds such as ammonia, amines, nitriles, and isocyanates. it can. Among these electron donating compounds, esters of organic acids and / or
Or ethers, more preferably carboxylic esters (b1) and / or ethers (b2).

Examples of the carboxylic acid esters (b1) include mono- and polyvalent carboxylic acid esters,
Examples thereof include a saturated aliphatic carboxylic acid ester, an unsaturated aliphatic carboxylic acid ester, an alicyclic carboxylic acid ester, and an aromatic carboxylic acid ester.
Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, butyl benzoate, methyl toluate, and toluyl. Ethyl acrylate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Examples thereof include ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, and diphenyl phthalate.

Among these carboxylic esters, unsaturated aliphatic carboxylic esters such as methacrylic esters and maleic esters and aromatic carboxylic esters such as benzoic esters and phthalic esters are preferably used. Particularly preferred are aromatic polycarboxylic esters, and most preferred are dialkyl phthalates.

Examples of ethers (b2) include dial
Kill ether and general formula(However, R^Five ~ R⁸ Is independently 1 to 2 carbon atoms
0 linear, branched or alicyclic alkyl group,
Or an aralkyl group,⁶ And R ⁷ Haso
Each may be independently a hydrogen atom. )
And ether compounds.
Species or two or more species are suitably used.

Specific examples include dimethyl ether, diethyl ether, di-n-butyl ether, methyl ethyl ether, methyl-n-butyl ether, methyl cyclohexyl ether, 2,2-diisobutyl-1,3-dimethoxypropane, and 2-isopropyl- 2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane,
-Isopropyl-2-3,7-dimethyloctyl-1,
3-dimethoxypropane, 2,2-diisopropyl-
1,3-dimethoxypropane, 2-isopropyl-2-
Cyclohexylmethyl-1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3 -Dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-
2-cyclopentyl-1,3-dimethoxypropane,
Examples thereof include 2,2-dicyclopentyl-1,3-dimethoxypropane and 2-heptyl-2-pentyl-1,3-dimethoxypropane, and one or more of these are suitably used. . Ethers (b2)
Is particularly preferably a dialkyl ether, and most preferably di-n-butyl ether. In addition,
n-Butyl ether may be simply described as dibutyl ether or butyl ether.

(C) Organic acid halide The organic acid halide used for the preparation of the solid catalyst component of the present invention is preferably a mono- or polyvalent carboxylic acid halide, and examples thereof include aliphatic carboxylic acid halides. Alicyclic carboxylic acid halides and aromatic carboxylic acid halides can be mentioned. Specific examples include acetyl chloride, propionic chloride, butyric chloride, valeric chloride, acrylic chloride, methacrylic chloride, benzoic chloride, toluic chloride, anisic chloride, succinic chloride, malonic chloride, and maleic chloride. , Itaconic acid chloride, phthalic acid chloride and the like.

Of these organic acid halides, aromatic carboxylic acid chlorides such as benzoic acid chloride, toluic acid chloride and phthalic acid chloride are preferred, and aromatic dicarboxylic acid dichloride is more preferred, and phthalic acid chloride is particularly preferred. Can be

(D) Compound Having a Ti-Halogen Bond The compound having a Ti-halogen bond used for preparing the solid catalyst component of the present invention is preferably a compound of the general formula Ti
During ^{_{(OR 9) b X 4 4}} -b ( wherein, R ⁹ represents a hydrocarbon group having a carbon number of 1 to 20, X ⁴ represents a halogen atom, b is 0
≤b <4. ) Is a titanium compound. Specific examples of R ⁹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl,
alkyl groups such as tert-amyl group, hexyl group, heptyl group, octyl group, decyl group and dodecyl group, aryl groups such as phenyl group, cresyl group, xyler group and naphthyl group; allyl groups such as propenyl group; And the like. Among them, those having 2 to 1 carbon atoms
An alkyl group having 8 or an aryl group having 6 to 18 carbon atoms is preferred. Particularly, a linear alkyl group having 2 to 18 carbon atoms is preferable. It is also possible to use a titanium compound having two or more different OR ⁹ groups.

Examples of the halogen atom represented by X ⁴ include a chlorine atom, a bromine atom and an iodine atom. Among them, a chlorine atom gives a preferable result.

[0021] b of the general formula _{^{Ti (OR 9) b X 4}} 4-b in the titanium compound represented by a number satisfying 0 ≦ b <4, preferably in number satisfying 0 ≦ b ≦ 2 And particularly preferably b = 0.

Specifically, the general formula Ti (OR ⁹ ) _b X _4-b
As the titanium compound represented by, titanium tetrachloride, titanium tetrabromide, titanium tetrahalide such as titanium tetraiodide,
Methoxytitanium trichloride, ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, ethoxytitanium tribromide, etc. And dialkoxytitanium dihalides such as diethoxytitanium dibromide, and most preferably titanium tetrachloride.

(E) Solid product The solid product (e) used in the present invention is a Si-O
It is a solid product obtained by reducing a titanium compound () represented by the following general formula [I] with an organomagnesium compound () in the presence of an organosilicon compound () having a bond. At this time, an ester compound ()
Is preferable because the activity and the stereoregular polymerization ability are further improved. (In the formula, a represents a number of 2 to 20, and R ² has 1 carbon atom.
Represents up to 20 hydrocarbon groups. X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, and all X ² may be the same or different. )

Organosilicon compound having Si--O bond
() Is preferably represented by the following general formula.
Is included. Si (OR^Ten)_tR¹¹ _4-t R¹²(R¹³ _TwoSiO)_uSiR¹⁴ _ThreeOr (R^Fifteen _TwoSiO)_v Where R^TenRepresents a hydrocarbon group having 1 to 20 carbon atoms,
R¹¹, R¹², R¹³, R ¹⁴And R^FifteenAre independent of each other,
Represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom
You. t represents an integer satisfying 0 <t ≦ 4, and u represents 1 to 1.
000 represents an integer, and v represents an integer of 2 to 1000.

Specific examples of such organosilicon compounds include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxy-diisopropylsilane. , Tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane,
Dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisilohexane, hexaethyldisilohexane, hexapropyldi Examples include siloxane, octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, and phenylhydropolysiloxane.

[0026] a preferred general formula Si (OR ¹⁰⁾ alkoxysilane compound represented by _t R ¹¹ _{4 -t} Among these organosilicon compounds, in which case t is preferably 1
It is a number that satisfies ≦ t ≦ 4, particularly preferably tetraalkoxysilane with t = 4, and most preferably tetraethoxysilane.

The titanium compound () is a titanium compound represented by the following general formula [I]. (In the formula, a represents a number of 2 to 20, and R ² has 1 carbon atom.
Represents up to 20 hydrocarbon groups. X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, and all X ² may be the same or different. )

Specific examples of R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, decyl, dodecyl and the like. Aryl groups such as alkyl group, phenyl group, cresyl group, xylyl group, and naphthyl group; cycloalkyl groups such as cyclohexyl group and cyclopentyl group; allyl groups such as propenyl group; and aralkyl groups such as benzyl group. Among these groups, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. Especially 2 carbon atoms
~ 18 linear alkyl groups are preferred.

Examples of the halogen atom for X ² include a chlorine atom, a bromine atom and an iodine atom. Particularly, a chlorine atom is preferred. The hydrocarbon oxy group having 1 to 20 carbon atoms in X ² is a hydrocarbon oxy group having a hydrocarbon group having 1 to 20 carbon atoms similar to R ² . X ² is particularly preferably an alkoxy group having a linear alkyl group having 2 to 18 carbon atoms.

In the titanium compound represented by the general formula [I], a represents a number of 2 to 20, preferably 2 ≦ a ≦
This is a number that satisfies 5.

Specific examples of the titanium compound include:
Tetraisopropyl polytitanate (a mixture in the range of a = 2 to 10), tetra-n-butyl polytitanate (a
= A mixture in the range of 2 to 10), tetra-n-hexylpolytitanate (a = a mixture in the range of 2 to 10), and tetra-n-octyl polytitanate (a mixture in the range of a = 2 to 10). . Further, a condensate of a tetraalkoxytitanium obtained by reacting a small amount of water with the tetraalkoxytitanium can also be mentioned.

More preferred as the titanium compound ()
Is a titanium compound represented by the above general formula [I].
a is a titanium compound wherein a is 2 or 4; Even more preferred
Or tetra-n-butyl polytitanate,
Tetra-n-butyl titanium dimer or tetra-
N-butyl titanium tetramer is preferably used.
You. In addition, other than the titanium compound (), the general formula Ti
(OR^Two)_qX^Three _4-q(Where R ^TwoRepresents 1 to 20 carbon atoms
X represents a hydrocarbon group.^ThreeRepresents a halogen atom, and q represents 0 <q ≦ 4.
Represents a number that satisfies )
Both can be used.

The organomagnesium compound () is
Any type of organic magnesium having a carbon-carbon bond
Compound. In particular, the general formula R¹⁶MgX^Five(Wherein, Mg
Represents a magnesium atom, R¹⁶Is a char having 1 to 20 carbon atoms
A hydride group represented by X^FiveRepresents a halogen atom. )
Grignard compound represented by the general formula R¹⁷R¹⁸Mg (Formula
In the formula, Mg represents a magnesium atom, R¹⁷And R¹⁸Is it
Each represents a hydrocarbon group having 1 to 20 carbon atoms. )
Preferred use of dihydrocarbyl magnesium
Is done. Where R¹⁷And R¹⁸May be the same or different
No. R¹⁶~ R ¹⁸Specific examples of
Group, ethyl group, propyl group, isopropyl group, butyl
Group, sec-butyl group, tert-butyl group, isoamido
Group, hexyl group, octyl group, 2-ethylhexyl
Group, phenyl group, benzyl group, etc.
Alkyl group, aryl group, aralkyl group, alkenyl group
Is mentioned. Especially R¹⁶MgX^FiveGrignard represented by
Use of ether compounds in ether solution is a catalyst performance point
Is preferred.

A hydrocarbon-soluble complex of the above-mentioned organomagnesium compound and an organic metal that solubilizes the organomagnesium compound in hydrocarbon can also be used. Examples of organometallic compounds include Li, Be, B, Al or Z
n.

As the ester compound (), a mono- or polyvalent carboxylic acid ester is used, and examples thereof include a saturated aliphatic carboxylic acid ester, an unsaturated aliphatic carboxylic acid ester, an alicyclic carboxylic acid ester and an aromatic carboxylic acid ester. Carboxylic acid esters can be mentioned. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, ethyl benzoate, butyl benzoate, toluyl Methyl acrylate, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate Methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, diphenyl phthalate and the like. it can.

Of these ester compounds, unsaturated aliphatic carboxylic acid esters such as methacrylic acid ester and maleic acid ester and aromatic carboxylic acid esters such as phthalic acid ester are preferable, and dialkyl phthalate is particularly preferable. .

The solid product (e) is prepared in the presence of the organosilicon compound () or the titanium compound () in the presence of the organosilicon compound () and the ester compound ().
Is reduced with an organomagnesium compound ().

The titanium compound (), the organosilicon compound () and the ester compound () are preferably used after being dissolved or diluted in a suitable solvent. Examples of such a solvent include aliphatic hydrocarbons such as hexane, heptane, octane, and decane; aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin; diethyl ether; dibutyl ether; Ether compounds such as isoamyl ether and tetrahydrofuran are exemplified.

The reduction reaction temperature is usually -50 to 70 ° C, preferably -30 to 50 ° C, and particularly preferably -25 to 35 ° C.
Temperature range. The reaction time is not particularly limited, but is usually about 30 minutes to 6 hours. After that, another 20-1
The post-reaction may be carried out at a temperature of 20 ° C.

At the time of the reduction reaction, it is also possible to coexist a porous carrier such as an inorganic oxide or an organic polymer to impregnate the solid product with the porous carrier. Known porous carriers may be used. SiO ₂ , Al
Porous inorganic oxides represented by ₂ O ₃ , MgO, TiO ₂ , ZrO ₂ , or polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol-
Methyl dimethacrylate copolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene Organic porous polymers such as copolymers, polyvinyl chloride, polyethylene, and polypropylene can be used. Of these, organic porous polymers are preferably used,
Among them, a styrene-divinylbenzene copolymer or an acrylonitrile-divinylbenzene copolymer is particularly preferred.

The porous carrier has a pore radius of 200 to 2000.
細孔 preferably has a pore volume of 0.3 cc / g or more,
More preferably, the pore volume is 0.4 cc / g or more, and the pore volume in the range is preferably 35% or more, more preferably 40% of the pore volume at a pore radius of 35 to 75000 °.
That is all. If the pore volume of the porous carrier is small, the catalyst component may not be effectively immobilized, which is not preferable. Further, the pore volume of the porous carrier is 0.3 cc / g.
Even if it is above, if it does not sufficiently exist in the pore radius of 200 to 2000 °, it may not be possible to effectively immobilize the catalyst component, which is not preferable.

The amount of the organosilicon compound () used is usually Si / Ti = 1 to 500, preferably 1 in terms of the atomic ratio of silicon atoms to titanium atoms in the titanium compound ().
To 300, particularly preferably 3 to 100. Further, the amount of the organomagnesium compound () used is usually (Ti + Si) /Mg=0.1 to 10, preferably 0.2 to 5.0, particularly in the atomic ratio of the sum of titanium atoms and silicon atoms and magnesium atoms. Preferably it is in the range of 0.5 to 2.0. In the solid catalyst component (A), Mg / Ti
The amounts of the titanium compound (), the organosilicon compound (), and the organomagnesium compound () are determined so that the molar ratio of is within the range of 1 to 51, preferably 2 to 31, and particularly preferably 4 to 26. You may. The amount of the optional ester compound () used is usually an ester compound / Ti = 0.5 to 100, preferably 1 to 60, particularly preferably 1 to 60, in a molar ratio of the ester compound to the titanium atom of the titanium compound (). It is in the range of 2 to 30.

The solid product obtained by the reduction reaction is usually subjected to solid-liquid separation and washed several times with an inert hydrocarbon solvent such as hexane and heptane. The solid product (e) thus obtained contains a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group, and generally shows amorphous or extremely weak crystallinity. From the viewpoint of catalyst performance, an amorphous structure is particularly preferable.

(A) Preparation of Solid Catalyst Component The solid catalyst component (A) for α-olefin polymerization of the present invention comprises:
It is obtained by subjecting the above solid product (e), an electron donating compound (b) and / or an organic acid halide (c) to a contact treatment with a compound (d) having a Ti-halogen bond.
All of these contact treatments are usually performed under an atmosphere of an inert gas such as nitrogen or argon.

As a specific method of the contact treatment for obtaining the solid catalyst component, a method of contact-treating (e) with (b) and / or (c), and further contacting with (d), (E) contacting a mixture of (b) and / or (c) with (d), and then contacting with (d); and (e) contacting (d) with (d) (B) and / or
Or a method of contacting with (c), after contacting (e) and (d), (b) and / or
Alternatively, a method of performing contact treatment with (c) and further performing contact treatment with (d) may be mentioned, and each contact treatment may be repeated several times.

As the solid catalyst component (A) used in the present invention, a solid component obtained by contacting (e) and (b), (b) and (d) are contact-treated. A solid product obtained by contacting (e), (b), (d), and (c), and a solid component obtained by contacting (b) with (d). The solid product obtained by contacting (e) and (b) is more preferably
A solid product obtained by contacting with a mixture of (b) and (d), or (e), (b), (d) and (c), followed by (b) and ( a solid product obtained by contacting the mixture with d).

As the solid catalyst component (A) used in the present invention, it is particularly preferable to contact (e) and (b1) and then contact with a mixture of (b1), (b2) and (d). And then contacting the solid product obtained by contacting with the mixture of (b2) and (d), and the mixture of (b2), (d) and (c) to (e), (B1) contact treatment with a mixture of (b2) and (d), and further (b)
2) A solid product obtained by contacting twice with a mixture of (d) or a mixture of (b2) and (d) with (e), followed by (c) After that, (b
This is a solid product obtained by subjecting a mixture of (1), (b2) and (d) to a contact treatment, and further contacting a mixture of (b2) and (d) twice.

The contact treatment can be carried out by any method known in the art, such as a slurry method or a mechanical pulverizing means such as a ball mill, in which each component can be brought into contact. Occurs and the particle size distribution may be widened, which is not preferable from an industrial viewpoint. Therefore, it is preferable that both are brought into contact in the presence of the diluent. After the contact treatment, the next treatment can be performed as it is, but it is preferable to perform a cleaning treatment with a diluent in order to remove surplus substances.

The diluent is preferably inert to the components to be treated, such as aliphatic hydrocarbons such as pentane, hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; cyclohexane; Alicyclic hydrocarbons such as cyclopentane, and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene can be used. The amount of the diluent used in the contact treatment is usually 0.1 ml to 1000 ml per 1 g of the solid product (e) per one-step contact treatment. It is preferably 1 ml to 100 ml per gram. Further, the amount of the diluent used in one washing operation is almost the same. The number of times of the washing operation in the washing process is usually 1 to 5 times per one-stage contact process.

The temperature of the contact treatment and / or the washing treatment is usually from -50 to 150 ° C., preferably from 0 to 150 ° C.
The temperature is 140 ° C, more preferably 60 to 135 ° C. The contact treatment time is not particularly limited, but is preferably set to 0.1.
It is 5 to 8 hours, more preferably 1 to 6 hours. The washing operation time is not particularly limited, but is preferably 1
To 120 minutes, more preferably 2 to 60 minutes.

The amount of the electron donating compound (b) used is usually 0.1 to 5 per mol of titanium atom in the solid product (e).
0 mol, preferably 0.3 to 30 mol, more preferably 0.5 to 20 mol.

The amount of the organic acid halide (c) to be used is usually 1 to 500 per mol of titanium atom in the solid product (e).
Mol, preferably 3 to 200 mol, more preferably 5 mol
１００100 mol. The amount of the organic acid halide (c) used per mole of magnesium atoms in the solid product (e) is usually 0.01 to 1.0 mol, preferably 0.0 to 1.0 mol.
3 to 0.5 mol. If the amount of (b) or (c) is excessively large, the particles may be disintegrated.

Compound (d) having Ti-halogen bond
Is usually used in an amount of 10 to 10000 mol, preferably 30 to 5000 mol, more preferably 100 to 300 mol, per 1 mol of titanium atom contained in the solid product (e).
0 mol. When a compound having a Ti-halogen bond is used, it is preferable to use the electron-donating compound (b) together. In that case, the amount of the compound (d) having a Ti-halogen bond to 1 mol of the electron donating compound (b) is usually 1 to 100 mol, preferably 1.5 to 75 mol, more preferably 2 to 50 mol. It is.

When the contact treatment is carried out by using each compound a plurality of times, the amount of each compound described above represents the amount of each compound used once and each type of compound.

The solid catalyst component obtained by the above method is usually
After solid-liquid separation, it is washed several times with an inert hydrocarbon solvent such as hexane or heptane, and then used for polymerization. After solid-liquid separation, a large amount of a halogenated hydrocarbon solvent such as monochlorobenzene or an aromatic hydrocarbon solvent
After washing at least once at a temperature of 120 ° C. and further repeating several times with an aliphatic hydrocarbon solvent such as hexane, it is preferable to use for polymerization in view of catalytic activity and stereoregular polymerization ability.

(B) Organoaluminum Compound The organoaluminum compound used in the present invention has at least one Al-carbon bond in the molecule.
Typical ones are shown below by a general formula. R ¹⁹ _w AlY _3-w R ²⁰ R ²¹ Al—O—AlR ²² R ²³ (wherein, R ^{19 to} R ²³ represent a hydrocarbon group having 1 to 20 carbon atoms, and Y represents a halogen atom, a hydrogen atom or an alkoxy group. Represents a group, and w is a number satisfying 2 ≦ w ≦ 3.) Specific examples of such an organoaluminum compound include trialkylaluminums such as triethylaluminum, triisobutylaluminum and trihexylaluminum, diethylaluminum hydride, and diisobutyl. Dialkylaluminum hydride such as aluminum hydride, dialkylaluminum halide such as diethylaluminum chloride, mixture of trialkylaluminum and dialkylaluminum halide such as a mixture of triethylaluminum and diethylaluminum chloride, Chill di alumoxane, an alkyl alumoxane such as tetrabutyl di alumoxane can be exemplified.

Of these organoaluminum compounds,
Trialkylaluminum, a mixture of a trialkylaluminum and a dialkylaluminum halide, or an alkylalumoxane is preferable, and particularly, triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride or tetraethyldialumoxane is preferable.

(C) Electron Donating Compound The electron donating compound (C) used at the time of polymerization in the present invention.
Include oxygen-containing electron-donating compounds such as ethers (diethers), ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, acid amides of organic or inorganic acids, and acid anhydrides. Nitrogen-containing electron donating compounds such as ammonia, amines, nitriles and isocyanates. Among these electron donating compounds, preferred are esters or diethers of inorganic acids, and more preferred are those of the general formula R ³ _r Si (O
R ⁴ ) _{4-r wherein} R ³ represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and R ⁴ represents 1 to 20 carbon atoms.
And r represents a number satisfying 0 ≦ r <4. All R ³ and all R ⁴ may be the same or different. The alkoxysilicon compound represented by the general formula R ²⁴ R ²⁵ S is particularly preferable.
An alkoxysilicon compound represented by i (OR ²⁶ ) ₂ is used. Here, in the formula, R ²⁴ is a hydrocarbon group having 3 to 20 carbon atoms in which the carbon atom adjacent to Si is secondary or tertiary, and specifically, isopropyl, sec-
Butyl group, tert-butyl group, branched alkyl group such as tert-amyl group, cyclobutyl group, cyclopentyl group, cycloalkyl group such as cyclohexyl group, cycloalkenyl group such as cyclopentenyl group, phenyl group, tolyl group And an aryl group. In the formula, R ²⁵
Is a hydrocarbon group having 1 to 20 carbon atoms, specifically, a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, and a sec.
Branched alkyl groups such as -butyl group, tert-butyl group and tert-amyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; cycloalkenyl groups such as cyclopentenyl group; aryl such as phenyl group and tolyl group. And the like. Further, in the formula, R ²⁶ is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms.

Specific examples of the alkoxysilicon compound used as the electron donating compound (C) include:
Diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane,
tert-butylmethyldimethoxysilane, tert-
Butylethyldimethoxysilane, tert-butyl-n
-Propyldimethoxysilane, tert-butyl-n-
Butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyln-propyldimethoxysilane, t
ert-amyl-n-butyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutylisobutyldimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyl Dimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl Sil-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, Diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyldiethoxysilane, ter
t-butyl-n-propyldiethoxysilane, tert
-Butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyl Examples thereof include diethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.

[Polymerization of olefin] α used in the present invention
-Olefin is an α-olefin having 3 or more carbon atoms, and specific examples of such α-olefin include propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, and decene-1. And branched monoolefins such as 3-methylbutene-1, 3-methylpentene-1, and 4-methylpentene-1, and vinylcyclohexane.
One type of these α-olefins may be used, or two or more types may be used in combination. Among these α-olefins, it is preferable to perform homopolymerization using propylene or butene-1, or to perform copolymerization using a mixed olefin containing propylene or butene-1 as a main component. It is particularly preferable to carry out homopolymerization by use of propylene or to carry out copolymerization using a mixed olefin containing propylene as a main component. In the copolymerization in the present invention, two or more olefins selected from ethylene and the above-mentioned α-olefin can be used as a mixture. Further, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used for the copolymerization. Then, heteroblock copolymerization in which polymerization is carried out in two or more stages can be easily performed.

The catalyst of the present invention is an α-olefin polymerization catalyst obtained by bringing the above-mentioned solid catalyst component (A), organoaluminum (B) and electron-donating compound (C) into contact. The contact here means the catalyst component (A) to
Any method may be used as long as (C) comes into contact and a catalyst is formed, and the components (A) to (C) may be mixed in advance with or without dilution with a solvent, or may be mixed separately. For example, a method in which the mixture is supplied to a polymerization tank and brought into contact in the polymerization tank. As a method of supplying each catalyst component to the polymerization tank, it is preferable to supply each catalyst component in an inert gas such as nitrogen or argon without moisture. Each catalyst component may be supplied by contacting any two members in advance.

In the present invention, olefin polymerization can be carried out in the presence of the above-mentioned catalyst. However, prior to carrying out such polymerization (main polymerization), preliminary polymerization described below may be carried out.

The prepolymerization is usually carried out by supplying a small amount of olefin in the presence of the solid catalyst component (A) and the organoaluminum compound (B), and is preferably carried out in a slurry state. Solvents used for slurrying include propane, butane, isobutane, pentane, isopentane,
Inert hydrocarbons such as hexane, heptane, octane, cyclohexane, benzene, toluene can be mentioned. Further, in forming the slurry, a liquid olefin can be used instead of part or all of the inert hydrocarbon solvent.

The amount of the organoaluminum compound used in the prepolymerization can be selected from a wide range, usually from 0.5 to 700 mol, per mol of titanium atom in the solid catalyst component. Preferably, 1 to 200 mol is particularly preferred.

The amount of the olefin to be prepolymerized is
Usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 1000 g per 1 g of the solid catalyst component.
200 g.

The slurry concentration for performing the prepolymerization is 1 to
500 g-solid catalyst component / liter-solvent is preferred,
Particularly, 3 to 300 g-solid catalyst component / liter-solvent is preferable. The prepolymerization temperature is preferably from -20 to 100C, particularly preferably from 0 to 80C. The partial pressure of the olefin in the gas phase during the prepolymerization is 0.01 to 20 kg / c.
m ² is preferable, and 0.1 to 10 kg / cm ² is particularly preferable. However, the olefin which is liquid at the pressure and temperature of the prepolymerization is not limited to this. Further, the prepolymerization time is not particularly limited, but is usually preferably from 2 minutes to 15 hours.

In carrying out the prepolymerization, the solid catalyst component (A), the organoaluminum compound (B) and the olefin are supplied by contacting the solid catalyst component (A) with the organoaluminum compound (B). Any method may be used, such as a method of supplying an olefin after the contact, or a method of supplying the organoaluminum compound (B) after the solid catalyst component (A) is brought into contact with the olefin. Further, as a method for supplying the olefin, any method of sequentially supplying the olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of initially supplying a predetermined amount of the olefin at all is used. good. It is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight of the obtained polymer.

Further, when the solid catalyst component (A) is preliminarily polymerized with a small amount of olefin in the presence of the organoaluminum compound (B), if necessary, the electron donating compound (C) may be used.
May coexist. The electron donating compound used is
Part or all of the above electron donating compound (C). The amount used is generally 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.1 to 400 mol, per 1 mol of titanium atoms contained in the solid catalyst component (A).
The amount is usually from 0.003 to 5 mol, preferably from 0.005 to 3 mol, particularly preferably from 0.01 to 2 mol, based on the organoaluminum compound (B).

The method of supplying the electron donating compound (C) during the prepolymerization is not particularly limited, and it may be supplied separately from the organoaluminum compound (A) or may be supplied in contact with the organic aluminum compound in advance. The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

After the pre-polymerization as described above, or without the pre-polymerization, the α-constituent comprising the solid catalyst component (A), the organoaluminum compound (B) and the electron donating compound (C) is used. The main polymerization of α-olefin can be carried out in the presence of an olefin polymerization catalyst.

The amount of the organoaluminum compound used in the main polymerization can be generally selected from a wide range such as 1 to 1000 mol per 1 mol of titanium atom in the solid catalyst component (A). A range is preferred.

The electron donating compound (C) used at the time of the main polymerization is usually 0.1 to 2,000 mol, preferably 0.3 to 2000 mol per 1 mol of titanium atom contained in the solid catalyst component (A). To 1000 mol, particularly preferably 0.5 to
The amount is 800 mol, usually 0.001 to 5 mol, preferably 0.005 to 3 mol, particularly preferably 0.01 to 1 mol, based on the organic aluminum compound.

The main polymerization can be carried out usually at -30 to 300 ° C, but preferably at 20 to 180 ° C. Although there is no particular limitation on the polymerization pressure, it is generally from normal pressure to 100 kg in view of industrial and economical aspects.
/ Cm ² , preferably about ² to 50 kg / cm ² . As the polymerization system, any of a batch system and a continuous system can be used. Further, slurry polymerization or solution polymerization using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, or octane, bulk polymerization using an olefin liquid at the polymerization temperature as a medium, or gas phase polymerization is also possible.

At the time of the main polymerization, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

[0075]

EXAMPLES The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not particularly limited by the following Examples. In the examples, methods for evaluating various physical properties of the polymer are as follows.

(1) 20 ° C. xylene soluble part (hereinafter referred to as CXS)
After dissolving 1 g of the polymer in 200 ml of boiling xylene, the solution was gradually cooled to 50 ° C., then immersed in ice water, cooled to 20 ° C. with stirring, left at 20 ° C. for 3 hours, and precipitated. The polymer obtained was separated by filtration. The weight percentage of the polymer remaining in the filtrate was defined as CXS (unit =%).
It can be said that the smaller the value of CXS, the higher the stereoregularity of polypropylene.

(2) Intrinsic viscosity (hereinafter abbreviated as [η]): Measured at 135 ° C. in a tetralin solvent.

(3) Bulk density: JIS K-6721-1
It was measured according to 966.

(4) The composition analysis of a solid sample such as a solid catalyst component was carried out as follows. That is,
Titanium atom content, after decomposing solid sample with dilute sulfuric acid,
An excess amount of aqueous hydrogen peroxide was added thereto, and the characteristic absorption at 410 nm of the obtained liquid sample was measured using a Hitachi Double Beam Spectrophotometer Model U-2001, and determined by a calibration curve prepared separately. . The alkoxy group content was determined by decomposing a solid sample with water, and then determining the amount of alcohol corresponding to the alkoxy group in the obtained liquid sample by using a gas chromatography internal standard method, and converting the content to an alkoxy group content. The carboxylate content was determined by decomposing a solid sample with water, extracting a soluble component with a saturated hydrocarbon solvent, and determining the amount of the carboxylate in the extract by gas chromatography internal standard method.

Example 1 (1) Synthesis of Solid Product (e) After a 500 ml flask equipped with a stirrer and a dropping funnel was purged with nitrogen, 270 ml of hexane and 5.8 ml of tetrabutoxytitanium dimer (Ti atom 21.9 mmol), 2.5 ml of diisobutyl phthalate (9.3
Mmol) and 74 ml of tetraethoxysilane (3
29 mmol) to give a homogeneous solution. Next, n-
172 ml of a di-n-butyl ether solution of butylmagnesium chloride (manufactured by Organic Synthetic Chemicals, n-butylmagnesium chloride concentration 2.1 mmol / ml)
While maintaining the temperature in the flask at 5 ° C., the solution was gradually dropped from the dropping funnel over 3 hours. After completion of the dropwise addition, the mixture was further stirred at 5 ° C. for 30 minutes, and further stirred at 35 ° C. for 1.5 hours. Then, after cooling to room temperature, solid-liquid separation was performed.
After repeating washing three times with 00 ml, toluene 200
ml was added. A part of the solid product slurry was sampled and subjected to composition analysis. The solid product contained 1.64% by weight of titanium atoms and 0.06% of phthalate.
It contained 7% by weight, 38.5% by weight of ethoxy groups and 3.63% by weight of butoxy groups. The slurry concentration was 0.149 g / ml.

(2) Synthesis of solid catalyst component After a 100 ml flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen, 54 ml of the solid product slurry obtained in the above (1) was charged, and the supernatant was added. 7.1 ml of liquid
Was extracted and stirred at 105 ° C. for 1 hour. After cooling to 95 ° C, 6.9 ml (25.8 mmol) of diisobutyl phthalate was added, and a contact treatment was performed at 95 ° C for 30 minutes.
Then, solid-liquid separation was performed at the same temperature, and toluene
Was performed twice. After washing, 10 ml of toluene was added, and 0.8 ml (4.73 mmol) of butyl ether was added.
And a mixture of 0.45 ml (1.68 mmol) of diisobutyl phthalate and 16 ml (0.146 mol) of titanium tetrachloride were subjected to a contact treatment at 105 ° C. for 3 hours. After the completion, the solid-liquid separation was carried out at the same temperature, and the mixture was washed twice with 40 ml of toluene at the same temperature. Then, 10 ml of toluene and 0.8 ml of butyl ether (4.7
A mixture of 3 mmol) and 8 ml (0.0728 mol) of titanium tetrachloride was added, and a contact treatment was performed at 105 ° C. for 1 hour. After the completion, solid-liquid separation was carried out at the same temperature, washing was carried out three times with 40 ml of toluene at the same temperature, followed by washing with 40 ml of hexane three times at room temperature, and further drying under reduced pressure to obtain 6.47 g of a solid catalyst component. . The solid catalyst component contained 1.70% by weight of titanium atoms and 9.79% of phthalic acid esters.
% By weight, 0.08% by weight of an ethoxy group, and 0.11% by weight of a butoxy group.

(3) Polymerization of Propylene A 3-liter stirred stainless steel autoclave was purged with argon, and 2.6 mmol of triethylaluminum was used as the component (B), 0.26 mmol of cyclohexylethyldimethoxysilane was used as the component (C), and (A) ) The solid catalyst component synthesized in (2) above as the component
8.5 mg was charged, and hydrogen equivalent to a partial pressure of 0.33 kg / cm ² was added. Next, 780 g of liquefied propylene was charged, and the temperature of the autoclave was raised to 80 ° C.
Polymerization was carried out at 0 ° C. for 1 hour. After completion of the polymerization, unreacted monomers were purged. The resulting polymer was dried under reduced pressure at 60 ° C. for 2 hours to obtain 328 g of polypropylene powder. Therefore, the yield of polypropylene per gram of the solid catalyst component (hereinafter abbreviated as PP / cat) is PP / cat = 3
8,590 (g / g). The ratio of the component soluble in xylene at 20 ° C. in the total polymer yield was CXS =
0.64 (wt%), the intrinsic viscosity of the polymer is [η] = 2.
18 (dl / g) and bulk density was 0.371 (g / ml).

Example 2 (1) Synthesis of Solid Product (e) In Example 1 (1), the tetrabutoxytitanium dimer was changed to 4.9 ml (22.1 mmol of titanium atom) of tetrabutoxytitanium tetramer. A solid product was synthesized in the same manner as in Example 1 (1) except for the above.
The solid product contained 1.40% by weight of a titanium atom, 0.10% by weight of a phthalate, 38.5% by weight of an ethoxy group, and 3.42% by weight of a butoxy group. The slurry concentration was 0.149 g / ml.

(2) Synthesis of solid catalyst component The procedure of Example 1 (2) was repeated except that the solid product slurry obtained in the above (1) was used as the solid product slurry. The operation was performed to synthesize a solid catalyst component. The solid catalyst component contained 1.61% by weight of a titanium atom, 11.1% by weight of a phthalate, 0.53% by weight of an ethoxy group, and 0.08% by weight of a butoxy group.

(3) Polymerization of propylene Polymerization of propylene was carried out in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (2) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Comparative Example 1 (1) Synthesis of Solid Product In Example 1 (1), 7.5 ml of tetrabutoxytitanium dimer was used instead of tetrabutoxytitanium dimer.
22.0 mmol), and a solid product was synthesized in the same manner as in Example 1 (1). The solid product contained 2.11% by weight of a titanium atom, 0.24% by weight of a phthalate, 39.3% by weight of an ethoxy group, and 3.15% by weight of a butoxy group. The slurry concentration was 0.143 g / ml.

(2) Synthesis of solid catalyst component The procedure of Example 1 (2) was repeated except that the solid product slurry obtained in the above (1) was used as the solid product slurry. The operation was performed to synthesize a solid catalyst component. The solid catalyst component contained 2.04% by weight of a titanium atom, 13.8% by weight of a phthalate, 0.47% by weight of an ethoxy group, and 0.08% by weight of a butoxy group.

(3) Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (2) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Example 3 (1) Synthesis of solid product (e) Example 1 was the same as Example 1 (1) except that the amount of diisobutyl phthalate was changed to 5.0 ml (18.7 mmol). A solid product was synthesized in the same manner as in (1). The solid product contained 1.61% by weight of titanium atoms, 0.26% by weight of phthalic esters, and 34.4% of ethoxy groups.
It contained 9% by weight and 3.24% by weight of a butoxy group. The slurry concentration was 0.150 g / ml.

(2) Synthesis of solid catalyst component The procedure of Example 1 (2) was repeated, except that the solid product slurry obtained in the above (1) was used as the solid product slurry. The operation was performed to synthesize a solid catalyst component. The solid catalyst component contained 1.61% by weight of a titanium atom, 12.0% by weight of a phthalate, 0.42% by weight of an ethoxy group, and 0.12% by weight of a butoxy group.

(3) Polymerization of propylene Polymerization of propylene was carried out in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (2) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Example 4 (1) Synthesis of Solid Product (e) In Example 3 (1), the tetrabutoxytitanium dimer was changed to 4.9 ml (22.1 mmol of titanium atom) of tetrabutoxytitanium tetramer. A solid product was synthesized in the same manner as in Example 3 (1) except for the above.
The solid product contained 1.39% by weight of a titanium atom, 33.7% by weight of an ethoxy group, and 3.08% by weight of a butoxy group, and did not contain a phthalate ester. The slurry concentration was 0.134 g / ml.

(2) Synthesis of solid catalyst component The procedure of Example 1 (2) was repeated except that the solid product slurry obtained in (1) was used as the solid product slurry. The operation was performed to synthesize a solid catalyst component. The solid catalyst component contained 1.62% by weight of a titanium atom, 10.5% by weight of a phthalate, 0.46% by weight of an ethoxy group, and 0.06% by weight of a butoxy group.

(3) Polymerization of propylene Polymerization of propylene was carried out in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (2) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Comparative Example 2 (1) Synthesis of Solid Product In Example 3 (1), tetrabutoxytitanium dimer was replaced with 7.5 ml of tetrabutoxytitanium (titanium atom).
22.0 mmol) to synthesize a solid product in the same manner as in Example 3 (1). The solid product contained 1.78% by weight of a titanium atom, 0.26% by weight of a phthalate, 36.1% by weight of an ethoxy group, and 2.94% by weight of a butoxy group. The slurry concentration was 0.148 g / ml.

(2) Synthesis of solid catalyst component The procedure of Example 1 (2) was repeated except that the solid product slurry obtained in the above (1) was used as the solid product slurry. The operation was performed to synthesize a solid catalyst component. The solid catalyst component contained 1.96% by weight of a titanium atom, 14.6% by weight of a phthalate, 0.38% by weight of an ethoxy group, and 0.06% by weight of a butoxy group.

(3) Polymerization of propylene Polymerization of propylene was carried out in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (2) was used as the solid catalyst component. The polymerization results are shown in Table 1.

[Example 5] (1) Synthesis of solid product (e) Example 1 was repeated except that the amount of diisobutyl phthalate was changed to 7.5 ml (28.0 mmol) in Example 1 (1). A solid product was synthesized in the same manner as in (1). 1.43% by weight of titanium atoms, 0.2% by weight of phthalates and 32.7% of ethoxy groups in the solid product.
%, Butoxy group 2.98% by weight.
The slurry concentration was 0.142 g / ml.

(2) Synthesis of solid catalyst component The procedure of Example 1 (2) was repeated except that the solid product slurry obtained in the above (1) was used as the solid product slurry. The operation was performed to synthesize a solid catalyst component. The solid catalyst component contained 1.77% by weight of a titanium atom, 9.56% by weight of a phthalate, 0.45% by weight of an ethoxy group, and 0.09% by weight of a butoxy group.

(3) Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (2) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Example 6 (1) Synthesis of Solid Product (e) In Example 5 (1), the tetrabutoxytitanium dimer was changed to 4.9 ml (22.1 mmol of titanium atom) of tetrabutoxytitanium tetramer. A solid product was synthesized in the same manner as in Example 5 (1) except for the above.
The solid product contained 1.39% by weight of a titanium atom, 0.08% by weight of a phthalate, 32.0% by weight of an ethoxy group, and 2.88% by weight of a butoxy group. The slurry concentration was 0.140 g / ml.

(2) Synthesis of solid catalyst component The procedure of Example 1 (2) was repeated except that the solid product slurry obtained in the above (1) was used as the solid product slurry. The operation was performed to synthesize a solid catalyst component. The solid catalyst component contained 1.72% by weight of a titanium atom, 10.1% by weight of a phthalate, 0.43% by weight of an ethoxy group, and 0.10% by weight of a butoxy group.

(3) Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (2) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Comparative Example 3 (1) Synthesis of Solid Product In Example 5 (1), 7.5 ml of tetrabutoxytitanium dimer was used instead of titanium butoxytitanium dimer.
22.0 mmol), except that the operation was performed in the same manner as in Example 5 (1) to synthesize a solid product. The solid product contained 1.62% by weight of a titanium atom, 0.42% by weight of a phthalate, 34.8% by weight of an ethoxy group, and 2.93% by weight of a butoxy group. The slurry concentration was 0.145 g / ml.

(2) Synthesis of solid catalyst component The procedure of Example 1 (2) was repeated except that the solid product slurry obtained in the above (1) was used as the solid product slurry. The operation was performed to synthesize a solid catalyst component. The solid catalyst component contained 1.64% by weight of a titanium atom, 12.2% by weight of a phthalate, 0.38% by weight of an ethoxy group, and 0.08% by weight of a butoxy group.

(3) Polymerization of propylene Polymerization of propylene was carried out in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (2) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Example 7 (1) Synthesis of Solid Catalyst Component A 100-ml flask equipped with a stirrer, a dropping funnel, and a thermometer was purged with nitrogen, and then obtained in the same manner as in Example 1 (1). 48.8 ml of the obtained solid product slurry was added, 22.3 ml of the supernatant was withdrawn, and 0.8 ml (4.73 mmol) of butyl ether and titanium tetrachloride 1
A mixture with 6 ml (0.146 mol) was added and then
1.6 ml of phthalic acid chloride (11.1 mmol:
(0.20 ml / 1 g solid product), and the mixture was heated to 115 ° C. and stirred for 3 hours. After completion, the mixture was subjected to solid-liquid separation at the same temperature, and then washed twice with 40 ml of toluene at the same temperature. After washing, a mixture of 10 ml of toluene, 0.45 ml (1.68 mmol) of diisobutyl phthalate, 0.8 ml (4.73 mmol) of butyl ether and 8 ml (0.073 mol) of titanium tetrachloride was added, and 115 The contact treatment was carried out at a temperature of 1 hour. After completion, solid-liquid separation was performed at the same temperature.
Washing was performed twice. Next, a mixture of 10 ml of toluene, 0.8 ml (4.73 mmol) of butyl ether and 8 ml (0.073 mol) of titanium tetrachloride was added, and 1
The contact treatment was performed at 15 ° C. for 1 hour. After completion, the solid-liquid separation was performed at the same temperature, and the solid was washed three times with 40 ml of toluene at the same temperature. In the solid catalyst component, 1.93% by weight of a titanium atom, 9.12% by weight of a phthalate, and 0.04% of an ethoxy group were contained.
% By weight, and 0.19% by weight of a butoxy group.

(2) Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (1) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Comparative Example 4 (1) Synthesis of Solid Catalyst Component In Example 7 (2), a solid product slurry obtained by the same operation as Comparative Example 1 (1) was used as the solid product slurry. A solid catalyst component was synthesized in the same manner as in Example 7 (2), except for the difference. The solid catalyst component contained 2.00% by weight of titanium atoms and 9.2% of phthalic acid esters.
It contained 6% by weight, 0.04% by weight of ethoxy groups and 0.16% by weight of butoxy groups.

(2) Polymerization of propylene Polymerization of propylene was carried out in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (1) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Example 8 (1) Synthesis of Solid Catalyst Component In Example 7 (2), a solid product slurry obtained by the same operation as in Example 3 (1) was used as the solid product slurry. A solid catalyst component was synthesized in the same manner as in Example 7 (2), except for the difference. The solid catalyst component contained 1.97% by weight of titanium atoms and 9.0% of phthalic acid esters.
It contained 0% by weight, 0.04% by weight of ethoxy groups and 0.20% by weight of butoxy groups.

(2) Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (1) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Comparative Example 5 (1) Synthesis of Solid Catalyst Component In Example 7 (2), a solid product slurry obtained by operating in the same manner as in Comparative Example 2 (1) was used as the solid product slurry. A solid catalyst component was synthesized in the same manner as in Example 7 (2), except for the difference. In the solid catalyst component, 1.85% by weight of titanium atom and 6.7% of phthalic acid ester were contained.
It contained 1% by weight, 0.03% by weight of ethoxy groups and 0.21% by weight of butoxy groups.

(2) Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (1) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Example 9 (1) Synthesis of Solid Catalyst Component In Example 7 (2), a solid product slurry obtained by the same operation as in Example 5 (1) was used as the solid product slurry. A solid catalyst component was synthesized in the same manner as in Example 7 (2), except for the difference. In the solid catalyst component, 1.84% by weight of titanium atom and 7.7 of phthalic acid ester were contained.
It contained 1% by weight, 0.03% by weight of ethoxy groups and 0.18% by weight of butoxy groups.

(2) Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (1) was used as the solid catalyst component. The polymerization results are shown in Table 1.

Example 10 (1) Synthesis of Solid Catalyst Component In Example 7 (2), a solid product slurry obtained by the same operation as in Example 6 (1) was used as the solid product slurry. A solid catalyst component was synthesized in the same manner as in Example 7 (2), except for the difference. In the solid catalyst component, 1.83% by weight of titanium atom and 6.2% of phthalate were contained.
It contained 4% by weight, 0.03% by weight of ethoxy groups and 0.13% by weight of butoxy groups.

(2) Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1 (3) except that the solid catalyst component obtained in the above (1) was used as the solid catalyst component. The polymerization results are shown in Table 1.

[0119]

[Table 1]

[0120]

As described above, according to the present invention,
A solid catalyst component for α-olefin polymerization and a catalyst for α-olefin polymerization having high active polymerization ability are provided, and an efficient method for producing an α-olefin polymer is provided. Since the α-olefin polymerization catalyst of the present invention can realize high active polymerization ability without sacrificing high stereoregular polymerization ability, its industrial utility value is extremely large.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Front page of the continued F-term (reference) 4J028 AA02A AB02A AC03A AC04A AC05A AC06A BA01B BA02A BB00A BB01B BC05A BC06A BC15B BC16B BC25B BC27B BC34A CB27A CB27B CB52A CB52B CB53A CB53B CB54A CB54B CB58A CB58B CB62A CB62B CB68A CB68B EB04 EB05 EB07 EB08 EB09 EB10 EB26 EC01 EC02 FA09 GA04 GA09 GA21 GB01

Claims (11)

[Claims] 1. A solid product obtained by reducing a titanium compound () represented by the following general formula [I] with an organic magnesium compound () in the presence of an organic silicon compound () having a Si—O bond. (E), an electron donating compound (b) and / or an organic acid halide (c),
A solid catalyst component for α-olefin polymerization, which is obtained by contacting a compound (d) having a halogen bond with a compound (d). (In the formula, a represents a number of 2 to 20, and R ² has 1 carbon atom.
Represents up to 20 hydrocarbon groups. X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, and all X ² may be the same or different. ) 2. A titanium compound () represented by the following general formula [I] is reduced with an organomagnesium compound () in the presence of an organosilicon compound () and an ester compound () having a Si—O bond. Product (e), an electron-donating compound (b) and / or an organic acid halide (c), and a compound (d) having a Ti-halogen bond. And α
-A solid catalyst component for olefin polymerization. (In the formula, a represents a number of 2 to 20, and R ² has 1 carbon atom.
Represents up to 20 hydrocarbon groups. X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, and all X ² may be the same or different. ) 3. A solid component obtained by contacting a solid product (e) with an electron donating compound (b), an electron donating compound (b), and a compound (d) having a Ti-halogen bond. 3) The solid catalyst component for polymerization of α-olefins according to claim 1 or 2, which is obtained by contacting 4. A solid component obtained by contacting a solid product (e), an electron donating compound (b), a compound (d) having a Ti-halogen bond and an organic acid halide (c), The solid catalyst component for α-olefin polymerization according to claim 1 or 2, wherein the solid catalyst component is obtained by contacting an electron-donating compound (b) with a compound (d) having a Ti-halogen bond. 5. A compound (d) having a Ti-halogen bond with a carboxylic acid ester (b1), an ether (b2) and a carboxylic acid ester (b1) after contacting the solid product (e) with a carboxylic acid ester (b1). The α-olefin according to claim 1 or 2, wherein the α-olefin is obtained by subjecting the mixture to a contact treatment with a mixture of an ether (b2) and a compound (d) having a Ti-halogen bond. Solid catalyst component for polymerization. 6. A solid product (e) is added with a mixture of an ether (b2), a compound (d) having a Ti-halogen bond and an organic acid halide (c), and is subjected to a contact treatment. (B1) and ethers (b2) and Ti-
It is obtained by contacting with a mixture of a compound (d) having a halogen bond and further contacting twice with a mixture of an ether (b2) and a compound (d) having a Ti-halogen bond. The solid catalyst component for α-olefin polymerization according to claim 1 or 2. 7. A mixture of an ether (b2) and a compound (d) having a Ti-halogen bond is added to the solid product (e), followed by contact treatment with an organic acid halide (c). Acid esters (b1) and ethers (b
2) and a mixture of the compound (d) having a Ti-halogen bond with a mixture of ethers (b2) and Ti-
3. It is obtained by contacting twice with a mixture with a compound (d) having a halogen bond.
The solid catalyst component for α-olefin polymerization according to the above. 8. The solid catalyst component for α-olefin polymerization according to claim 1, wherein a in formula (I) is 2 or 4. 9. An α-character obtained by contacting the solid catalyst component (A) according to any one of claims 1 to 8, an organoaluminum (B), and an electron-donating compound (C). Olefin polymerization catalyst. 10. An electron-donating compound (C) comprising R ³ _r Si (O
R ⁴ ) _4-r (wherein, R ³ represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, and r is 0 ≦ r <represents a number satisfying 4. all of R ³ and all R ⁴ are according to claim 9, wherein it is alkoxy silicon compounds represented by the may be the same or different.) Α-olefin polymerization catalyst. 11. A method for producing an α-olefin polymer, comprising homopolymerizing or copolymerizing an α-olefin using the α-olefin polymerization catalyst according to claim 9 or 10.