JP2003105021A - alpha-OLEFIN POLYMERIZATION SOLID CATALYST COMPONENT, alpha-OLEFIN POLYMERIZATION CATALYST AND PROCESS FOR PRODUCING alpha- OLEFIN POLYMER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an α-olefin polymerization solid catalyst component and an α-olefin polymerization catalyst which have highly active polymerizability, and a process for efficiently producing an α-olefin polymer. SOLUTION: The α-olefin polymerization solid catalyst component can be obtained by subjecting (a) a solid product to be obtained by reducing (2) a titanium compound to be represented by formula [I] (wherein a is a number of 2-20; R<2> is a 1-20C hydrocarbon group; and X<2> is a halogen atom or a 1-20C hydrocarbon oxy group, and all X may be the same or different) with (3) an organomagnesium compound in the presence of (1) an organosilicon compound having an Si-O bond, (b) an organic acid halide, (c) a halogenated compound, and (d) a phthalic acid ester compound having a 7C hydrocarbon oxy group to contact treatment. Other aspects are also disclosed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid catalyst component for α-olefin polymerization, an α-olefin polymerization catalyst, and an α-olefin polymerization catalyst.
-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 or butene-1, the periodic table No. 4 to No.
It is well known to use so-called Ziegler-Natta catalysts which consist of a solid catalyst component prepared with a Group 6 transition metal compound and a Group 1, 2, 13 organometallic compound.

When producing an α-olefin polymer, an amorphous polymer is usually produced as a by-product in addition to a stereoregular α-olefin polymer which is industrially useful. This amorphous polymer has a low industrial utility value and exerts a great adverse effect on the mechanical properties when the α-olefin polymer is processed into an injection-molded product, a film, a fiber, or other processed products for use. In addition, the production of the amorphous polymer causes a loss of the raw material monomer, and at the same time requires a manufacturing facility for removing the amorphous polymer, which causes a great disadvantage from an industrial viewpoint. Therefore, the catalyst for producing the α-olefin polymer has no formation of such an amorphous polymer, or
Even if there is, it is desirable that it is extremely small.

In addition, a catalyst residue consisting of a transition metal component and an organic metal 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, a deashing facility for removing and stabilizing the catalyst residue is often required. This drawback can be ameliorated by increasing the catalyst activity represented by the weight of the α-olefin polymer produced per weight of the catalyst, and by realizing sufficient catalyst activity, the equipment for removing the catalyst residue is also provided. It becomes unnecessary and the production cost of the α-olefin polymer can be reduced.

By using a combination of a supported solid catalyst component obtained by supporting a tetravalent titanium halide on magnesium halide, an organoaluminum compound as a cocatalyst, and an organosilicon compound as a third component for polymerization, α
It is known that highly stereoregular polymerization of olefins can be realized (Japanese Patent Laid-Open Nos. 57-63310 and 5).
8-83006, and JP-A-61-78803).

The 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 a mixture of ether compound and titanium tetrachloride or an ether compound. In the 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 cocatalyst, and an electron donating compound as a polymerization third component, α It is known that highly stereoregular polymerization of olefins can be realized (JP-A 7-216017).

Furthermore, 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 added in the order of a mixture of an ether compound and titanium tetrachloride and an organic acid halide compound. After the treatment, a trivalent titanium compound-containing solid catalyst component obtained by treatment with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound, and a promoter organoaluminum compound It is known that highly stereoregular polymerization of α-olefin can be realized even in combination with an electron-donating compound as the third component of the polymerization (Japanese Patent Laid-Open No. 10-21).
2319).

[0008] In any case, there is a level at which a non-extracting and non-decalcifying process can be realized, but further improvement is desired. Specifically, in order to reduce the production cost of the α-olefin polymer, it is desired to realize even higher activity polymerization. Furthermore, in applications where high rigidity of the polymer is desired, such as in the field of injection molding, the high stereoregularity of the polymer directly produces the quality of high rigidity. The advent of a catalyst having a high activity polymerization ability without sacrificing is urgently desired.

[0009]

Under the present circumstances,
The problem to be solved by the present invention, that is, the 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 activity 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 added to an organomagnesium compound () in the presence of an organosilicon compound () having a Si--O bond. A solid product (a) obtained by reduction with an organic acid halide (b), a halogenated compound (c), and a phthalate compound (d) having a hydrocarbon oxy group having 7 carbon atoms. Solid catalyst component for α-olefin polymerization obtained by catalytic treatment; and Si-
In the presence of the organosilicon compound () having an O bond and the ester compound (), the titanium compound () represented by the following general formula [I] is added to the organomagnesium compound ().
A solid product (a) obtained by reduction with, an organic acid halide (b), a halogenated compound (c), and 7 carbon atoms.
The present invention relates to a solid catalyst component for α-olefin polymerization obtained by subjecting the phthalate compound (d) having a hydrocarbon oxy group to a contact treatment. The present invention also provides these solid catalyst components (A), organoaluminum (B),
And α obtained by bringing the electron-donating compound (C) into contact with
The present invention relates to an olefin polymerization catalyst and a method for producing an α-olefin polymer in which an α-olefin is homopolymerized or copolymerized using the α-olefin polymerization catalyst. (In the formula, a represents a number of 1 to 20, and R ² has 1 carbon atom.
Represents a hydrocarbon group of 20. 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 comprises a titanium compound () represented by the following general formula [I] in the presence of an organosilicon compound () having a Si—O bond, and an organomagnesium compound (). ) A solid product (a) obtained by reduction with an organic acid halide (b), a halogenated compound (c), and a phthalate compound (d) having a hydrocarbon oxy group having 7 carbon atoms. Is a solid catalyst component for α-olefin polymerization obtained by contacting with. (In the formula, a represents a number of 2 to 20, and R ² has 1 carbon atom.
Represents a hydrocarbon group of 20. 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) Phthalic acid ester compound having a hydrocarbon oxy group having 7 carbon atoms 7 carbon atoms used for preparing a solid catalyst component in the present invention
The phthalate compound (b) having a hydrocarbon oxy group is preferably a phthalate compound represented by the following general formula [II]. (In the formula, R represents a hydrocarbon group having 7 carbon atoms, and each R may be the same or different.)

R is a linear n-heptyl group, a branched 2-methylhexyl group, a 3-methylhexyl group, 4
-Methylhexyl group, 5-methylhexyl group, 2,3-
Dimethylpentyl group, 2,4-dimethylpentyl group, 2
-Ethylpentyl group, 3-ethylpentyl group, cyclic cycloheptyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group,
2,3-cyclopentyl group, 2,4-cyclopentyl group, 3,4-cyclopentyl group, 2-ethylcyclopentyl group, 3-ethylcyclopentyl group, 4-ethylcyclopentyl group and the like, among which branched hydrocarbons are mentioned. It is preferable to contain a group. R may be the same or different, and may be a mixture of phthalic acid esters having different molecular structures.

(A) Solid Product The solid product (a) used in the present invention is Si-O.
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, the ester compound () as an optional component
It is preferable to coexist with the above because the polymerization 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 a hydrocarbon group of 20. 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
Examples of () include those represented by the following general formula.
To be Si (OR^Ten)_tR¹¹ _4-t R¹²(R¹³ ₂SiO)_uSiR¹⁴ ₃, Or (R¹⁵ ₂SiO)_v R here^TenRepresents a hydrocarbon group having 1 to 20 carbon atoms,
R¹¹, R¹², R¹³, R ¹⁴And R¹⁵Each independently,
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 is 1 to 1
Represents an integer of 000, 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, Hexapropyldiphenylsilane Examples thereof include siloxane, octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, phenylhydropolysiloxane and the like.

[0017] a alkoxysilane compounds preferred are represented by the general formula _{^{Si (OR 10) t R 11}} 4 -t Among these organosilicon compounds, in which case t is preferably 1
It is a number that satisfies ≦ t ≦ 4, and tetraalkoxysilane having t = 4 is particularly preferable, and tetraethoxysilane is most preferable.

The titanium compound () is a titanium compound represented by the following general formula [I]. (In the formula, a represents a number of 1 to 20, and R ² has 1 carbon atom.
Represents a hydrocarbon group of 20. 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 group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, decyl group and dodecyl group. Examples thereof include an alkyl group, a phenyl group, a cresyl group, a xylyl group, an aryl group such as a naphthyl group, a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group, an allyl group such as a propenyl group, and an aralkyl group such as a benzyl group. Of 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 straight chain alkyl groups are preferred.

Examples of the halogen atom for X ² include chlorine atom, bromine atom and iodine atom. A chlorine atom is particularly preferable. 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 . Particularly preferably, X ² is an alkoxy group having a linear alkyl group having 2 to 18 carbon atoms.

In the titanium compound represented by the above general formula [I], a represents a number of 1 to 20, preferably 1≤a≤.
It is a number that satisfies 5.

Specific examples of the titanium compound will be given below.
Tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetra-iso-propoxy titanium, tetra-n-butoxy titanium, tetra-iso
-Butoxy titanium, n-butoxy titanium trichloride, di-n-butoxy titanium dichloride, tri-n-
Butoxy titanium chloride, di-n-tetraisopropyl polytitanate (a = 2-10 mixture), tetra-n-butyl polytitanate (a = 2-10 mixture), tetra-n-hexyl polytitanate (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). Moreover, the condensate of tetraalkoxy titanium obtained by reacting tetraalkoxy titanium with a small amount of water can be mentioned.

The titanium compound () is preferably a titanium compound represented by the general formula [I] wherein a is 1, 2 or 4. Particularly preferred is tetra-n-butoxytitanium, tetra-n-butyltitanium dimer or tetra-n-butyltitanium tetramer. The titanium compound () can be used in a mixed state of plural kinds.

The organic magnesium compound () is
Any type of organic magnesia having a sium-carbon bond
It is a compound. Especially the general formula R¹⁶MgX^Five(In the formula, Mg
Is a magnesium atom, R¹⁶Is charcoal having 1 to 20 carbon atoms
A hydrogenated group, X^FiveRepresents a halogen atom. )
Grignard compound or general formula R¹⁷R¹⁸Mg (formula
Inside, Mg is magnesium atom, R¹⁷And R¹⁸Is it
Each represents a hydrocarbon group having 1 to 20 carbon atoms. )
Dihydrocarbyl magnesium used is suitable
To be done. Where R¹⁷And R¹⁸Can be the same or different
Yes. R¹⁶~ R ¹⁸Examples 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
Groups having 1 to 20 carbon atoms such as groups, phenyl groups, benzyl groups, etc.
Alkyl group, aryl group, aralkyl group, alkenyl group
Is mentioned. Especially R¹⁶MgX^FiveRepresented by Grignard
Of the catalytic performance is the use of a ruthenium compound in an ether solution
Is preferred.

It is also possible to use a hydrocarbon-soluble complex of the above-mentioned organomagnesium compound and an organometal which solubilizes the organomagnesium compound in hydrocarbon. Examples of the organometallic compound include Li, Be, B, Al or Z
The compound of n is mentioned.

As the ester compound (), mono- or polyvalent carboxylic acid esters are used, examples of which include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic compounds. Mention may be made of carboxylic acid esters. 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, methyl toluate, toluyl. Ethyl acid, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-phthalate n-octyl,
Examples thereof include di (2-ethylhexyl) phthalate, diisodecyl phthalate, dicyclohexyl phthalate, and diphenyl phthalate.

Among these ester compounds, unsaturated aliphatic carboxylic acid esters such as methacrylic acid ester and maleic acid ester or aromatic carboxylic acid esters such as phthalic acid ester are preferred, and dialkyl ester of phthalic acid is particularly preferred. .

The solid product (a) is a titanium compound () in the presence of the organosilicon compound () or in the presence of the organosilicon compound () and the ester compound ().
Is obtained by reduction with an organomagnesium compound ().

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

The reduction reaction temperature is usually -50 to 70 ° C, preferably -30 to 50 ° C, particularly preferably -25 to 35 ° C.
The temperature range is ° C. The reaction time is not particularly limited, but is usually about 30 minutes to 6 hours. After that, 20 more
The post reaction may be carried out at a temperature of 120 ° C.

It is also possible to allow a porous carrier such as an inorganic oxide or an organic polymer to coexist during the reduction reaction and impregnate the porous product with the solid product. A known porous carrier may be used. SiO ₂ , Al
₂ O ₃ , MgO, TiO ₂ , ZrO _{2 and} other porous inorganic oxides, or polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol-
Methyl dimethacrylate copolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethylmethacrylate, methylmethacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene Examples thereof include copolymers, polyvinyl chloride, polyethylene, and organic porous polymers such as polypropylene. Of these, preferably an organic porous polymer is used,
Among them, a styrene-divinylbenzene copolymer or an acrylonitrile-divinylbenzene copolymer is particularly preferable.

The porous carrier has a pore radius of 200 to 2000.
The pore volume in Å is preferably 0.3 cc / g or more,
It is more preferably 0.4 cc / g or more, and the pore volume in this range is preferably 35% or more, more preferably 40% of the pore volume at a pore radius of 35 to 75000Å.
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. In addition, the pore volume of the porous carrier is 0.3 cc / g
Even if the above is the case, the catalyst component may not be effectively immobilized unless it is sufficiently present in the pore radius of 200 to 2000Å, which is not preferable.

The amount of the organosilicon compound () used is an atomic ratio of silicon atoms to titanium atoms in the titanium compound (), and usually Si / Ti = 1 to 500, preferably 1
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, in terms of the sum of titanium atoms and silicon atoms and the atomic ratio of magnesium atoms. It is preferably in the range of 0.5 to 2.0. Further, in the solid catalyst component (A), Mg / Ti
The amount of the titanium compound (), the organosilicon compound (), and the organomagnesium compound () used is determined so that the molar ratio of the compound is in the range of 1 to 51, preferably 2 to 31, and particularly preferably 4 to 26. May be. The amount of the ester compound () used as an optional component is a molar ratio of the ester compound to the titanium atom of the titanium compound (), and is usually ester compound / Ti = 0.05 to 100, preferably 0.1 to 60, particularly It is preferably in the range of 0.2 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, heptane or toluene. The solid product (a) thus obtained contains a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group, and generally exhibits amorphous or extremely weak crystallinity. From the viewpoint of catalytic performance, an amorphous structure is particularly preferable.

(B) Organic Acid Halide The organic acid halide (c) used in the preparation of the solid catalyst component of the present invention is preferably a mono- or polyvalent carboxylic acid halide, examples of which are aliphatic carboxylic acids. Examples thereof include acid halides, alicyclic carboxylic acid halides, and aromatic carboxylic acid halides. Specific examples include acetyl chloride, propionyl chloride, butyric acid chloride, valeric acid chloride, acrylic acid chloride, methacrylic acid chloride, benzoic acid chloride, toluic acid chloride, anisic acid chloride, succinic acid chloride, malonic acid chloride, maleic acid chloride. , Itaconic acid chloride, phthalic acid chloride and the like.

Among these organic acid halides, aromatic carboxylic acid chlorides such as benzoic acid chloride, toluic acid chloride and phthalic acid chloride are preferable, more preferably aromatic dicarboxylic acid dichloride, and particularly preferably phthalic acid chloride. To be

(C) Halogenated Compound The halogenated compound is preferably a compound capable of substituting a halogen atom for the hydrocarbyloxy group in the solid product (a). Among them, halogen compounds of Group 4 elements,
A halogen compound of a Group 13 element or a halogen compound of a Group 14 element is preferable.

As the halogen compound of the group 4 element, a general formula M (OR ⁹ ) _b X ⁴ _4-b (wherein M represents a group 4 element, R ⁹ is a carbon atom having 1 to 20 carbon atoms) Represents a hydrogen group, X ⁴
Represents a halogen atom, and b represents a number satisfying 0 ≦ b <4. ) A halogen compound represented by Specific examples of M include titanium, zirconium and hafnium, with titanium being preferred. Specific examples of R ⁹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group. , Alkyl groups such as decyl group and dodecyl group, phenyl group, cresyl group, xylel group,
Examples thereof include an aryl group such as a naphthyl group, an allyl group such as a propenyl group, and an aralkyl group such as a benzyl group. Among these, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. Particularly, a linear alkyl group having 2 to 18 carbon atoms is preferable. It is also possible to use halogen compounds of Group 4 elements 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, chlorine atom gives particularly preferable results.

A _fourth represented by the general formula M (OR ⁹ ) _b X ⁴ _4-b
B of the halogen compound of the group element is a number satisfying 0 ≦ b <4, preferably 0 ≦ b ≦ 2,
Particularly preferably, b = 0.

Specifically, examples of the titanium compound represented by the general formula M (OR ⁹ ) _b X _4-b include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and other tetrahalogenated titanium, and methoxy. Titanium trichloride, ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, trihalogenated alkoxy titanium such as ethoxy titanium tribromide, dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, diphenoxy titanium dichloride, Examples thereof include dihalogenated dialkoxytitanium such as diethoxytitanium dibromide, zirconium compounds and hafnium compounds corresponding thereto. Most preferably titanium tetrachloride

As the halogen compound of the group 13 element or the group 14 element, a compound represented by the general formula MR _ma X _a (in the formula, M is a first group)
Group 3 or Group 14 atom, R has 1 to 20 carbon atoms
X represents a halogen atom, and m represents a valence of M. The compound represented by a is preferably a number satisfying 0 <a ≦ m). Examples of the group 13 atom include B, Al, Ga, In and Tl, and B or A
1 is preferable, and Al is more preferable. Examples of the atom of Group 14 include C, Si, Ge, Sn, and Pb,
Si, Ge or Sn is preferable, and Si or Sn is more preferable.

M is the valence of M, for example, m = 4 when M is Si. a represents a number satisfying 0 <a ≦ m, and when M is Si, a is preferably 3 or 4.
Examples of the halogen atom represented by X include F, Cl, Br and I, with Cl being preferred.

Specific examples of R include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, decyl group and dodecyl group. And other alkyl groups, phenyl groups, tolyl groups, cresyl groups, xylyl groups, naphthyl groups and other aryl groups, cyclohexyl groups, cyclopentyl groups and other cycloalkyl groups, propenyl groups and other alkenyl groups, benzyl groups and other aralkyl groups, etc. Can be mentioned. Preferred R is an alkyl group or an aryl group, and particularly preferred R is a methyl group, an ethyl group, a normal propyl group, a phenyl group or a paratolyl group.

Specific examples of the halogen compound of the Group 13 element include trichloroboron, methyldichloroboron, ethyldichloroboron, phenyldichloroboron, cyclohexyldichloroboron, dimethylchloroboron, methylethylchloroboron, trichloroaluminum and methyldichloroaluminum. , Ethyldichloroaluminum, phenyldichloroaluminum, cyclohexyldichloroaluminum, dimethylchloroaluminum, diethylchloroaluminum, methylethylchloroaluminum, ethylaluminum sesquichloride, gallium chloride, gallium dichloride, trichlorogallium, methyldichlorogallium, ethyldichlorogallium, phenyldichloro Gallium, cyclohexyldichlorogallium, dimethyl Chlorogallium, methyl ethyl chlorogallium, indium chloride, indium trichloride, methyl indium dichloride, phenyl indium dichloride, dimethyl indium chloride, thallium chloride, thallium trichloride, methyl thallium dichloride, phenyl thallium dichloride, dimethyl thallium chloride, and the like, The compound which changed chloro of these compound names into fluoro, bromo, or iodo is also mentioned.

Specific examples of the halogen compound of Group 14 element include tetrachloromethane, trichloromethane, dichloromethane, monochloromethane, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1. , 2,2-Tetrachloroethane, tetrachlorosilane, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, normal butyltrichlorosilane, phenyltrichlorosilane, benzyltrichlorosilane, paratolyltrichlorosilane, cyclohexyltrichlorosilane, dichlorosilane Chlorosilane, methyldichlorosilane, ethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, monochlorosilane, tri Tylchlorosilane, triphenylchlorosilane, tetrachlorogermane, trichlorogermane, methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane, dichlorogermane, dimethyldichlorogermane, diethyldichlorogermane, diphenyldichlorogermane, monochlorogermane, trimethylchlorogermane, triethylchloro Germane, tri-n-butylchlorogermane, tetrachlorotin, methyltrichlorotin, n-butyltrichlorotin, dimethyldichlorotin, di-n-butyldichlorotin, diisobutyldichlorotin, diphenyldichlorotin,
Examples thereof include divinyldichlorotin, methyltrichlorotin, phenyltrichlorotin, dichlorolead, methylchlorolead, phenylchlorolead, and compounds in which chloro in these compound names is changed to fluoro, bromo, or iodo.

As the halogenated compound (c), tetrachlorotitanium, methyldichloroaluminum, ethyldichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane or tetrachlorotin is used as a polymerization active. From the viewpoint of, it is particularly preferable.
As the halogenated compound (c), only one kind of the above compounds may be used, or plural kinds thereof may be used.

(E) Electron Donor In the preparation of the solid catalyst component of the present invention, the number of carbon atoms is 7
In addition to the phthalic acid ester compound (d) having a hydrocarbon oxy group, the electron donor (e) can be used for the contact treatment. It is particularly preferable to use it as a mixture with the halogenated compound (c) from the viewpoint of high stereoregularity polymerization ability. As the electron donor (e), ethers, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, acid amides of organic acids or inorganic acids,
Examples thereof include oxygen-containing electron-donating compounds such as acid anhydrides, and nitrogen-containing electron-donating compounds such as ammonia, amines, nitriles, and isocyanates. Of these electron-donating compounds, organic acid esters and / or ethers are preferable, and carboxylic acid esters (e1) and / or ethers (e) are more preferable.
2).

Examples of the carboxylic acid esters (e1) include mono- and polyvalent carboxylic acid esters,
Examples thereof include saturated aliphatic carboxylic acid ester, unsaturated aliphatic carboxylic acid ester, alicyclic carboxylic acid ester, and 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, methyl toluate, toluyl. Ethyl acid, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-phthalate
Examples thereof include n-hexyl, di-n-octyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, dicyclohexyl phthalate, and diphenyl phthalate.

Among these carboxylic acid esters, unsaturated aliphatic carboxylic acid esters such as methacrylic acid ester and maleic acid ester or aromatic carboxylic acid esters such as benzoic acid ester and phthalic acid ester are preferably used. Aromatic polycarboxylic acid esters are particularly preferred, and phthalic acid dialkyl esters are most preferred.

Examples of ethers (e2) include dial
Kill ether and general formula (However, R^Five ~ R⁸ Each independently has 1 to 2 carbon atoms
0 straight-chain, branched or alicyclic alkyl group, ant
Group or aralkyl group, and R⁶ And R ⁷ Haso
Each may independently be a hydrogen atom. ) Represented by
There may be mentioned ether compounds, one of these
One kind or two or more kinds are preferably 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, 2-isopropyl- 2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2
-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,
2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,3-dimethoxypropane and the like can be mentioned, and one or more of these are preferably used. . Ethers (e2)
Is particularly preferably dialkyl ether, and most preferably di-n-butyl ether. In addition,
The n-butyl ether may be simply referred to as dibutyl ether or butyl ether.

(A) Preparation of Solid Catalyst Component The solid catalyst component (A) of the present invention is the above solid component (a).
With an organic acid halide (b) and a halogenated compound (c)
And an electron donor (d) as the case requires. All of these contact treatments are usually performed in an atmosphere of an inert gas such as nitrogen or argon.

Specific methods of the contact treatment for obtaining the solid catalyst component are as follows: (a) is charged with (b), (c), and (d) (arrangement order is arbitrary), and the contact treatment is carried out, A method of introducing a mixture of (b), (c) and (d) into (a) and subjecting it to contact treatment; (a) a mixture of (b) and (c) and (d) Method of charging (contact order) with (charging order is arbitrary), Method of charging with (a), (b), and (d) (charging order is arbitrary) to (c), and (c) And (d) into a mixture of (a) and (b)
Method of charging (contacting order is arbitrary) and performing contact treatment: (a) and (d) in a mixture of (b) and (c)
Method of charging (contacting treatment is arbitrary), (b), (c), and (d) (charging order is arbitrary) to (a), and after contact treatment, further (c) The method of contact-treating with :-( a) is charged with (b) and (c) (arrangement order is arbitrary), and after contact-treatment, (c) and (d) are further added.
(B) and (c) (arrangement order is arbitrary) are added to (a), contact treatment is performed, and then a mixture of (c) and (d) is further added. Contact treatment with (b) and (c) (arrangement order is arbitrary) into (a), contact treatment is performed, and then contact treatment is performed with (c) and (d) (arrangement order is arbitrary) In addition, (b) and (c) (arrangement order is arbitrary) are added to (a), and contact treatment is performed, and then (c) and (d). And a method of performing contact treatment with (c) one or more times, and any of these (c) is a mixture of (c) and (e). Can be mentioned.

Of these, (a) was charged with (b) and a mixture of (c) and (e) (arbitrary order of charging),
After the contact treatment, it is preferable to carry out the contact treatment with the mixture of (c), (d) and (e), and further to carry out the contact treatment once or more with the mixture of (c) and (e). , A mixture of (c) and (e2), and (b) in that order, and after contact treatment, contact treatment with a mixture of (c), (d) and (e2), and ( A method in which the mixture is treated with the mixture of c) and (e2) one or more times is particularly preferable.

The contact treatment can be carried out by any known method capable of bringing the respective components into contact with each other, such as a slurry method or mechanical crushing means such as a ball mill. However, when the mechanical crushing is carried out, a large amount of fine powder is added to the solid catalyst component. It may occur and the particle size distribution may become broad, which is not preferable from an industrial viewpoint. Therefore, it is preferable to contact them in the presence of a diluent. Further, after the contact treatment, the following operation can be carried out as it is, but it is preferable to carry out a washing treatment with a diluent in order to remove an excess.

The diluent is preferably inert to the components to be treated, and 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 component (a) per one-step contact treatment. Preferably 1
It is 1 ml to 100 ml per g. Further, the amount of the diluent used in one washing operation is about the same. The number of times of the washing operation in the washing treatment is usually 1 to 5 times per one-step contact treatment.

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

The amount of the phthalate compound (d) having a hydrocarbon oxy group having 7 carbon atoms is usually 0.01 to 100 mmol, preferably 0.05 to 50, based on 1 g of the solid component (a). Mmol, and more preferably 0.1 to 20 mmol. The amount of the organic acid halide (b) used is usually 0.1 to 1 with respect to 1 g of the solid component (a).
The amount is 00 mmol, preferably 0.3 to 50 mmol, and more preferably 0.5 to 20 mmol. The amount of the organic acid halide (b) used is generally 0.01 to 1.0 mol, and preferably 0.03 to 0.5 mol, per 1 mol of magnesium atom in the solid component (a).

The amount of the halogenated compound (c) used is usually 0.5 to 1000 mmol, preferably 1 to 200 mmol, and more preferably 2 to 100 mmol based on 1 g of the solid product (a). When the halogenated compound (c) is used, it is preferable to use the electron donor (d) together. In that case, the amount of (c) used is usually 1 to 100 mol, preferably 1.5 to 75 mol, and more preferably 2 to 50 mol, relative to 1 mol of (d).

The amount of the electron donor (e) used is usually 0.01 to 100 mmol, preferably 0.05 to 50 mmol, and more preferably 0.1 to 20 mmol based on 1 g of the solid component (a). is there. When the amount of (d) or (e) used is excessively large, particle disintegration may occur.

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

The obtained solid catalyst component may be used for polymerization in a slurry state in combination with an inert diluent, or may be used for polymerization as a fluid powder obtained by drying. Examples of the drying method include a method of removing volatile components under reduced pressure and a method of removing volatile components under the flow of an inert gas such as nitrogen or argon. Drying temperature is 0-200
C. is preferable, and 50 to 100.degree. C. is more preferable. The drying time is preferably 0.01 to 20 hours, more preferably 0.5 to 10 hours.

The solid catalyst component (A) according to the present invention is an α-olefin polymerization catalyst obtained by bringing an organoaluminum compound (B) and, if necessary, an electron donating compound (C) into contact with each other. -Used in the polymerization of olefins.

(B) Organoaluminum Compound The organoaluminum compound (B) used for forming the olefin polymerization catalyst has at least one Al-carbon bond in the molecule. A typical one is shown below by a general formula. During ^{_{R 19 w AlY 3-w R}} 20 R 21 Al-O-AlR 22 R 23 ( wherein, R ¹⁹ to R ²³ is a hydrocarbon group having a carbon number of 1 to 20, Y is a halogen atom, a hydrogen atom or an alkoxy Represents a group, and w is a number satisfying 2 ≦ w ≦ 3.)

Specific examples of the organoaluminum compound include trialkylaluminums such as triethylaluminum, triisobutylaluminum and trihexylaluminum, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, and dialkylaluminum halides such as diethylaluminum chloride. Examples thereof include a mixture of trialkylaluminum and dialkylaluminum halide such as a mixture of triethylaluminum and diethylaluminum chloride, and alkylalumoxane such as tetraethyldialumoxane and tetrabutyldialumoxane.

Of these organoaluminum compounds,
Preference is given to trialkylaluminum, mixtures of trialkylaluminium and dialkylaluminium halides or alkylalumoxanes, especially triethylaluminum, triisobutylaluminum, mixtures of triethylaluminum and diethylaluminium chloride or tetraethyldialumoxane.

(C) Electron donating compound Used as needed to form olefin polymerization catalysts
The electron-donating compound (C) to be used is an oxygen-containing compound.
Compounds, nitrogen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds
Among them are oxygen-containing compounds or nitrogen-containing compounds.
Compounds are preferred. As the oxygen-containing compound, alkoxy
Silicon, ethers, esters, ketones, etc. are listed.
Especially alkoxy silicons or ethers
Is preferred. As the alkoxy silicons, general formula R
³ _rSi (OR^Four)_4-r  (In the formula, R ³Has 1 to 2 carbon atoms
0 hydrocarbon group, hydrogen atom- or hetero atom-containing substituent
Represents R^FourRepresents a hydrocarbon group having 1 to 20 carbon atoms
Where r represents a number satisfying 0 ≦ r <4. All R³Oh
And all R^FourAre the same or different
Good. ) Alkoxy silicon compounds represented by
Used well. R³Is a hydrocarbon group, a methyl group,
Linear such as tyl, propyl, butyl, pentyl, etc.
Alkyl group, isopropyl group, sec-butyl group, te
branched chain amides such as rt-butyl group, tert-amyl group, etc.
Such as alkyl group, cyclopentyl group, cyclohexyl group, etc.
Cycloalkyl such as cycloalkyl group and cyclopentenyl group
Examples include aryl groups such as kenyl group, phenyl group and tolyl group.
You can Above all, silicon source of alkoxy silicon compound
The carbon atom directly bonded to the child is secondary or tertiary carbon
R ³It is preferable to have at least one. R³Is hete
In the case of an atom-containing substituent, the heteroatom is oxygen
Child, nitrogen atom, sulfur atom, and phosphorus atom. Concrete
Dimethylamino group, methylethylamino group, diene
Cylamino group, ethyl n-propylamino group, di-n-propyl group
Ropyramino group, pyrrolyl group, pyridyl group, pyrrolidini
Group, piperidyl group, perhydroindolyl group, perhi
Droisoindolyl group, perhydroquinolyl group, perhi
Droisoquinolyl group, perhydrocarbazolyl group, per
Hydroacridinyl group, furyl group, pyranyl group, perhi
Examples thereof include a drofuryl group and a thienyl group.
B atom directly converted to silicon atom of alkoxy silicon compound
Substituents capable of chemical bonding are preferred.

Specific examples of the alkoxy silicon compound include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane and ter.
t-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, tert-butyl-
n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl npropyldimethoxysilane, tert-amyl-n-butyldimethoxysilane,
Isobutyl isopropyldimethoxysilane, tert-
Butylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutylisobutyldimethoxysilane,
Cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, Cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyl Silane, phenyl -
tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-
Butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane,
tert-amylmethyldiethoxysilane, tert-
Amylethyldiethoxysilane, tert-amyl-n
-Propyldiethoxysilane, tert-amyl-n-
Butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane, bis (perhydroxy) Norino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) methyldimethoxysilane, (perhydroisoquinolino) methyldimethoxysilane , (Perhydroquinolino) ethyldimethoxysilane, (perhydroisoquinolino) ethyldimethoxysilane, (perhydroquinolino) (n-propyl) dimethoxy Run, (perhydroisoquinolino)
Examples thereof include (n-propyl) dimethoxysilane, ((perhydroquinolino) (tert-butyl) dimethoxysilane, and (perhydroisoquinolino) (tert-butyl) dimethoxysilane.

The ethers include electron donors (e2)
And the cyclic ether compound. The cyclic ether compound is a heterocyclic compound having at least one —C—O—C— bond in the ring system. Specific examples of the cyclic ether compound include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, 2,5-dimethoxytetrahydrofuran, tetrahydropyran, hexamethylene oxide, 1,3-dioxepane, 1,3-dioxane,
1,4-dioxane, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3
-Dioxolane, 4-methyl-1,3-dioxolane,
2,4-dimethyl-1,3-dioxolane, furan,
2,5-dimethylfuran or s-trioxane may be mentioned. Among them, at least one -COC is included in the ring system.
Cyclic ether compounds having a —O—C— bond are preferred.

Examples of the nitrogen-containing compound include 2,6-substituted piperidines such as 2,6-dimethylpiperidine and 2,2,6,6-tetramethylpiperidine, 2,5-substituted piperidines, N, N, N. Examples thereof include substituted methylenediamines such as ', N'-tetramethylmethylenediamine and N, N, N', N'-tetraethylmethylenediamine, and substituted imidazolidines such as 1,3-dibenzylimidazolidine. Of these, 2,6-substituted piperidines are preferable.

[Olefin Polymerization] In the production of an α-olefin using the solid catalyst component obtained by the present invention, the α-olefin is an α-olefin having 3 or more carbon atoms. Specific examples of such an α-olefin As propylene, butene-1, pentene-1, hexene-1,
Linear monoolefins such as heptene-1, octene-1, and decene-1, branched monoolefins such as 3-methylbutene-1, 3-methylpentene-1, and 4-methylpentene-1, vinylcyclohexane And so on. 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 carry out homopolymerization using propylene or butene-1, or to carry out copolymerization using a mixed olefin containing propylene or butene-1 as a main component. It is particularly preferable that the homopolymerization is performed by using the above method or the copolymerization is performed using a mixed olefin containing propylene as a main component. Further, in the copolymerization in the present invention, two or more kinds of olefins selected from ethylene and the above α-olefins can be mixed and used. Further, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used for the copolymerization. And, heteroblock copolymerization in which the polymerization is carried out in two or more stages can be easily carried out.

The catalyst using the solid catalyst component obtained according to the present invention is the solid catalyst component (A), the organoaluminum (B), and, if necessary, the electron donating compound (C).
Is a catalyst for α-olefin polymerization obtained by contacting with. The term "contact" as used herein may be any means as long as the catalyst components (A) to (C) come into contact with each other to form a catalyst, and the components (A) to (C) may be diluted with a solvent in advance or may be diluted. A method of mixing (C) and bringing them into contact with each other, a method of separately supplying them to the polymerization tank and bringing them into contact with each other in the polymerization tank, and the like can be adopted. As a method of supplying each catalyst component to the polymerization tank,
It is preferable to supply in an inert gas such as nitrogen or argon without water. Each catalyst component may be supplied by contacting any two of them in advance.

The olefin can be polymerized in the presence of the above-mentioned catalyst, but the following prepolymerization may be carried out before such polymerization (main polymerization).

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

The amount of the organoaluminum compound used in the prepolymerization can be selected within a wide range, usually 0.5 to 700 mol, per mol of titanium atom in the solid catalyst component, but 0.8 to 500 mol is preferable. It is preferably 1 to 200 mol and particularly preferably 1 to 200 mol.

The amount of olefin prepolymerized is
It is usually 0.01 to 1000 g, preferably 0.05 to 500 g, and particularly preferably 0.1 to 1 g of the solid catalyst component.
It is 200 g.

The slurry concentration during the prepolymerization is from 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 -20 to 100 ° C, particularly preferably 0 to 80 ° C. 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, but this is not the case for olefins that are liquid at the pressure and temperature of prepolymerization. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is suitable.

When carrying out the prepolymerization, the solid catalyst component (A), the organoaluminum compound (B) and the olefin can be supplied by contacting the solid catalyst component (A) with the organoaluminum compound (B). After that, any method such as a method of supplying an olefin and a method of contacting the solid catalyst component (A) with the olefin and then supplying an organoaluminum compound (B) may be used. Further, as the olefin supply method, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure or a method of initially supplying all of a predetermined amount of olefin may be used. good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the obtained polymer.

Furthermore, when preliminarily polymerizing the solid catalyst component (A) with a small amount of olefin in the presence of the organoaluminum compound (B), the electron donating compound (C) may be added, if necessary.
May coexist. The electron-donating compound used is
It is a part or all of the above electron donating compound (C). The amount used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, and particularly preferably 0.1 to 400 mol, based on 1 mol of the titanium atom contained in the solid catalyst component (A).
It is from 03 to 100 mol, and is usually from 0.003 to 5 mol, preferably from 0.005 to 3 mol, and particularly preferably from 0.01 to 2 mol, based on the organoaluminum compound (B).

The electron donating compound (C) may be supplied separately from the organoaluminum compound (A) in the prepolymerization, or may be supplied in contact with it in advance. The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

After prepolymerization as described above or without prepolymerization, α-comprising the above solid catalyst component (A), organoaluminum compound (B) and electron donating compound (C). 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 selected within a wide range, such as 1 to 1000 mol, per 1 mol of titanium atom in the solid catalyst component (A). Ranges are preferred.

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

The main polymerization can be carried out usually at -30 to 300 ° C, but 20 to 180 ° C is preferable. The polymerization pressure is not particularly limited, but is generally atmospheric pressure to 100 kg in terms of being industrial and economical.
/ Cm ² , preferably a pressure of about ² to 50 kg / cm ² . The polymerization system may be either batch system or continuous system. Further, slurry polymerization or solution polymerization with an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, octane, bulk polymerization or gas phase polymerization using a liquid olefin as a medium at the polymerization temperature is also possible.

At the time of main polymerization, it is possible to add a chain transfer agent such as hydrogen for controlling the molecular weight of the polymer.

[0087]

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

(1) 20 ° C. xylene soluble part (hereinafter referred to as CXS
1 g of the polymer is dissolved in 200 ml of boiling xylene, then gradually cooled to 50 ° C., then immersed in ice water, cooled to 20 ° C. with stirring, and left standing at 20 ° C. for 3 hours, followed by precipitation. The polymer obtained was filtered off. 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 solid samples such as solid catalyst components was carried out as follows. That is,
Titanium atom content, after decomposing a solid sample with dilute sulfuric acid,
To this, an excess of hydrogen peroxide solution was added, and the characteristic absorption at 410 nm of the obtained liquid sample was measured using a Hitachi double-beam spectrophotometer U-2001 type, and determined by a calibration curve prepared separately. . The alkoxy group content was obtained by decomposing a solid sample with water, and determining the amount of alcohol corresponding to the alkoxy group in the obtained liquid sample using a gas chromatography internal standard method, and converting the content into an alkoxy group content. The carboxylic acid ester content was obtained by decomposing a solid sample with water, extracting soluble components with a saturated hydrocarbon solvent, and determining the amount of carboxylic acid ester in the extract by a gas chromatography internal standard method.

[Example 1] (1) Synthesis of solid product (a) Hexane 12 was added to a reactor equipped with a stirrer substituted with nitrogen.
43 liters, tetraethoxysilane 350 kg and tetrabutoxy titanium 38.8 kg were added and stirred. Next, 900 liters of a solution of butylmagnesium chloride in dibutyl ether (concentration: 2.1 mol / liter) was added dropwise to the above stirring mixture over 5 hours while maintaining the temperature of the reactor at 17 ° C. After completion of the dropping, the mixture was stirred at 20 ° C. for 1 hour and then filtered, and the obtained solid was toluene 11
Washing with 00 liters was repeated 3 times, and toluene was added to make a slurry. When the composition analysis of this solid product was conducted, 2.09% by weight of titanium atom, 36.9% by weight of ethoxy group and 3.1 of butoxy group were found in the solid product.
It was contained in an amount of 4% by weight. The slurry concentration is 0.2
It was 76 g-solid component / ml-slurry.

(2) Synthesis of solid catalyst component After replacing a 100 ml flask equipped with a stirrer, a dropping funnel and a thermometer with nitrogen, 29.0 ml of the solid product slurry obtained in the above (1) was charged. , Supernatant liquid 2.5
1 ml of titanium tetrachloride and 0.8 g of dibutyl ether were added to the slurry, keeping the slurry at about 40 ° C.
A mixture of 1.6 ml of phthalic acid chloride (hereinafter sometimes abbreviated as OPC) and 1.6 ml of toluene was added thereto at a constant rate (0.08 ml-OPC / g). -Solid product / min). After the dropping was completed, the reaction mixture was stirred at 115 ° C. for 3 hours. After that, solid-liquid separation was performed at the same temperature, and washing was performed 3 times with 40 ml of toluene at 115 ° C. After washing, add toluene so that the volume of the slurry becomes 26.5 ml,
It was set to 105 ° C. There dibutyl ether 0.8m
1, a mixture of 0.61 ml of diheptyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd., a mixture of branched isomers) and 16 ml of titanium tetrachloride was added and stirred at 105 ° C. for 1 hour. afterwards,
Solid-liquid separation was performed at the same temperature, and 40 ml of toluene was washed twice at 105 ° C. Next, the volume of the slurry is 26.5 m.
Toluene was added to adjust the temperature to 1 and the temperature was adjusted to 105 ° C. 0.8 ml of dibutyl ether and 16 titanium tetrachloride
A mixture of ml was added and the mixture was stirred at 105 ° C for 1 hour. After that, solid-liquid separation was performed at the same temperature, and toluene was added at 105 ° C.
It was washed twice with ml. Furthermore, the volume of the slurry is 2
Toluene was added to 6.5 ml and the temperature was adjusted to 105 ° C. A mixture of 0.8 ml of dibutyl ether and 16 ml of titanium tetrachloride was added thereto, and the mixture was stirred at 105 ° C for 1 hour. After that, solid-liquid separation was performed at the same temperature, and washing was performed at 105 ° C. three times with 40 ml of toluene and three times at room temperature with 40 ml of hexane. This is dried under reduced pressure to obtain a solid catalyst component 7.
27 g was obtained. In the solid catalyst component, titanium atoms are 1.
The content was 95% by weight, 10.18% by weight of phthalic acid ester, 0.06% by weight of ethoxy group, and 0.11% by weight of butoxy group.

(3) Polymerization of propylene A stainless steel autoclave having an internal volume of 3 liters was replaced with argon, and 2.6 mmol of triethylaluminum as the component (B), 0.26 mmol of cyclohexylethyldimethoxysilane as the component (C), and Solid catalyst component synthesized in (2) above as component (A)
5.50 mg was charged and hydrogen corresponding to a partial pressure of 0.033 MPa 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 the polymerization was completed, unreacted monomers were purged. The produced polymer was dried under reduced pressure to obtain 328 g of polypropylene powder. The yield of polypropylene per 1 g of the solid catalyst component (hereinafter abbreviated as PP / cat) was PP / cat = 59600 (g / g). In addition, the proportion of components soluble in xylene at 20 ° C. in the total polymer yield is CXS = 0.44 (wt%), the intrinsic viscosity of the polymer is [η] = 2.20 (dl / g), and the bulk density is Was 0.462 (g / ml).

Comparative Example 1 (1) Synthesis of Solid Catalyst Component Example 1 except that diheptyl phthalate was not used.
It was synthesized according to (2). The solid catalyst component contained 2.04% by weight of titanium atom, 8.51% by weight of phthalic acid ester, 0.08% by weight of ethoxy group and 0. 0% of butoxy group.
The content was 22% by weight.

(2) Polymerization of Propylene Polymerization was carried out according to Example 1 (3) except that 4.87 mg of the solid catalyst component obtained in (1) was charged to obtain 232 g of polypropylene powder. Yield of polypropylene per gram of solid catalyst component (hereinafter abbreviated as PP / cat)
Was PP / cat = 47600 (g / g), which was lower than that when diheptyl phthalate was used. In addition, the proportion of components soluble in 20 ° C xylene in the total polymer yield is CXS = 0.63 (wt%), the intrinsic viscosity of the polymer is [η] = 2.50 (dl / g), and the bulk density is Is 0.46
It was 0 (g / ml).

Comparative Example 2 (1) Synthesis of solid catalyst component Synthesis was carried out according to Example 1 (2) except that 0.45 ml of diisobutyl phthalate was used instead of diheptyl phthalate. The solid catalyst component contained 2.10% by weight of titanium atoms, 12.07% by weight of phthalates, 0.05% by weight of ethoxy groups, and 0.14% by weight of butoxy groups.

(2) Polymerization of Propylene Polymerization was carried out according to Example 1 (3) except that 6.30 mg of the solid catalyst component obtained in (1) was charged to obtain 284 g of polypropylene powder. Yield of polypropylene per gram of solid catalyst component (hereinafter abbreviated as PP / cat)
Was PP / cat = 45100 (g / g), which was lower than that when diheptyl phthalate was used. The ratio of the components soluble in xylene at 20 ° C. in the total polymer yield is CXS = 0.59 (wt%), the intrinsic viscosity of the polymer is [η] = 2.35 (dl / g), and the bulk density is Is 0.45
It was 1 (g / ml).

Example 2 (1) Synthesis of solid product (a) In a reactor equipped with a stirrer substituted with nitrogen, 14.5 kg of diisobutyl phthalate, 670 liters of hexane, 349 kg of tetraethoxysilane and titanium tetrabutoxytitanium. 38 kg was charged and stirred. Next, 900 liters of a solution of butylmagnesium chloride in dibutyl ether (concentration: 2.1 mol / liter) was added dropwise to the above stirring mixture over 5 hours while maintaining the temperature of the reactor at 8 ° C. After completion of dropping, the mixture was stirred at 8 ° C. for 1 hour and at 20 ° C. for 1 hour and then filtered, and the obtained solid was washed 3 times with 1100 liters of toluene, and toluene was added to form a slurry. When the composition of this solid product was analyzed, the solid product contained 1.90% by weight of titanium atoms, 34.8% by weight of ethoxy groups and 3.0% by weight of butoxy groups. The slurry concentration was 0.160 g-solid component / ml-slurry.

(2) Synthesis of solid catalyst component Synthesis was carried out according to Example 1 (2) except that 50 ml of the solid product slurry synthesized in (1) was charged and 23.5 ml of the supernatant liquid was extracted and used. The solid catalyst component contained 1.80% by weight of titanium atom, 9.11% by weight of phthalic acid ester, 0.04% by weight of ethoxy group and 0.12% by weight of butoxy group.

(3) Polymerization of Propylene Polymerization was carried out according to Example 1 (3) except that 4.73 mg of the solid catalyst component obtained in (1) was charged to obtain 330 g of polypropylene powder. Yield of polypropylene per gram of solid catalyst component (hereinafter abbreviated as PP / cat)
Was PP / cat = 69800 (g / g). In addition, the proportion of components soluble in xylene at 20 ° C. in the total polymer yield is CXS = 0.44 (wt%), the intrinsic viscosity of the polymer is [η] = 2.18 (dl / g), and the bulk density is Is 0.43
It was 1 (g / ml).

Comparative Example 3 (1) Synthesis of solid catalyst component Synthesis was carried out according to Example 2 (2) except that 0.45 ml of diisobutyl phthalate was used instead of diheptyl phthalate. The solid catalyst component contained 1.85% by weight of titanium atom, 10.9% by weight of phthalic acid ester, 0.04% by weight of ethoxy group and 0.10% by weight of butoxy group.

(2) Polymerization of Propylene Polymerization was carried out according to Example 1 (3) except that 5.15 mg of the solid catalyst component obtained in (1) was charged to obtain 291 g of polypropylene powder. Yield of polypropylene per gram of solid catalyst component (hereinafter abbreviated as PP / cat)
Was PP / cat = 56500 (g / g), which was lower than that when diheptyl phthalate was used. In addition, the proportion of components soluble in xylene at 20 ° C. in the total polymer yield is CXS = 0.37 (wt%), the intrinsic viscosity of the polymer is [η] = 2.17 (dl / g), and the bulk density is Is 0.43
It was 6 (g / ml).

[0104]

As described above, according to the present invention,
A solid catalyst component for α-olefin polymerization and a catalyst for α-olefin polymerization having a high activity polymerization ability are provided, and an efficient method for producing an α-olefin polymer is provided. The α-olefin polymerization catalyst of the present invention can realize high activity polymerization ability without sacrificing high stereoregularity polymerization ability, and therefore has a great industrial utility value.

Continued front page    F-term (reference) 4J028 AA01A AA02A AB01A AB02A                       AC02A AC03A AC04A AC05A                       AC06A AC07A AC24A AC25A                       BA01B BB01B BC04A BC06A                       BC14B BC16B BC17B BC18B                       BC20B BC24B CB27A CB27C                       CB42A CB42C CB43A CB44A                       CB52A CB53A CB53C CB54A                       CB58A CB62A CB62C CB66A                       CB68A CB74C CB75C CB79A                       CB81C CB86C CB91A CB92A                       CB92C CB93A CB93C DA00                       EA01 EA02 EB01 EB02 EB03                       EB04 EB05 EB07 EB08 EB09                       EC01 EC02 GB01

Claims (6)

[Claims] 1. 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 Si--O bond. Α-obtained by subjecting the compound (a), the organic acid halide (b), the halogenated compound (c), and the phthalate compound (d) having a hydrocarbon oxy group having 7 carbon atoms to each other. Solid catalyst component for olefin polymerization. (In the formula, a represents a number of 1 to 20, and R ² has 1 carbon atom.
Represents a hydrocarbon group of 20. 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 () having a Si—O bond and an ester compound (). The solid product (a) thus obtained, the organic acid halide (b), the halogenated compound (c), and the phthalate compound (d) having a hydrocarbon oxy group having 7 carbon atoms are subjected to contact treatment. The obtained solid catalyst component for α-olefin polymerization. (In the formula, a represents a number of 1 to 20, and R ² has 1 carbon atom.
Represents a hydrocarbon group of 20. 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. The solid product (a) according to claim 1 or 2.
And an organic acid halide (b) and a halogenated compound (c)
After contacting with, the halogenated compound (c) is contacted with the phthalic acid ester compound (d) having a hydrocarbon oxy group having 7 carbon atoms, and further contacted with the halogenated compound (c) one or more times. The solid catalyst component for α-olefin polymerization according to claim 1, which is obtained by treatment. (In the formula, a represents a number of 1 to 20, and R ² has 1 carbon atom.
Represents a hydrocarbon group of 20. 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. ) 4. An α-olefin polymerization catalyst obtained by bringing the solid catalyst component (A) according to any one of claims 1 to 3 into contact with an organoaluminum (B) and an electron donating compound (C). 5. The electron donating compound (C) is R ³ _r Si (OR
⁴ ) _4-r (In the formula, 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 that satisfies 4.
All R ³ and all R ⁴ may be the same or different. The catalyst for α-olefin polymerization according to claim 4, which is an alkoxysilicon compound represented by the formula (4). 6. A method for producing an α-olefin polymer, wherein an α-olefin is homopolymerized or copolymerized using the catalyst for α-olefin polymerization according to claim 4 or 5.