JP2001342213A - Olefin polymerization catalyst and method for producing olefin polymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin polymerization catalyst capable of giving an olefin polymer with a low content of low-molecular weight component, and to provide a method for producing such an olefin polymer. SOLUTION: This olefin polymerization catalyst is prepared by mutually contacting (I) a solid catalytic component containing at least titanium atom, magnesium atom and halogen atom, (II) an organoaluminum compound and (III) an oxygen-containing compound with such a structure that two or more hydrocarbyloxy groups are bound to the identical carbon atom. The other objective method for producing an olefin polymer comprises using the above catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer.

[0002]

2. Description of the Related Art The presence of a low molecular weight component in an olefin polymer is not preferable for the transparency, impact resistance, blocking property, etc. of a film made of the olefin polymer. desirable.

In recent years, catalytic performance has been improved by using a solid catalyst component obtained by combining a specific magnesium compound and a specific titanium compound (JP-B-46-34092, JP-B-47-41676). JP, JP-B-55-23561, JP-B-57-24
361).

Further, in the polymerization of propylene, it has been disclosed that a highly crystalline propylene polymer can be obtained by using an oxygen-containing electron donor such as an ester as an internal donor of a solid catalyst component (Japanese Patent Publication No. Sho 52). -3
No. 9431, Japanese Patent Publication No. 52-36786, Japanese Patent Publication No. 1-28049, Japanese Patent Publication No. 3-43283, etc.).

[0005]

However, the olefin polymer obtained by the former catalyst (Japanese Patent Publication No. 46-34092, etc.) is not satisfactory in terms of blocking properties, and the latter catalyst (Special Features) No.52-39431
In the case where the olefin polymer is used for copolymerization of ethylene and an α-olefin, the obtained olefin polymer is not satisfactory in terms of blocking properties. JP-A-11-80
JP-A-234, JP-A-11-322833 and the like disclose an olefin polymerization catalyst capable of producing an olefin polymer having a low content of a low-molecular-weight component, which is an index of blocking property. However, in order to further improve the quality of the olefin polymer, it is required to further reduce the content of low molecular weight components. Under these circumstances, the problem to be solved by the present invention, that is, an object of the present invention is to provide an olefin polymerization catalyst capable of producing an olefin polymer having a low low molecular weight component content, and an olefin having a low low molecular weight component content. An object of the present invention is to provide a method for producing a polymer.

[0006]

The present invention relates to a solid catalyst component (I) containing at least a titanium atom, a magnesium atom and a halogen atom, and an organoaluminum compound (I).
I) and an olefin polymerization catalyst obtained by contacting an oxygen-containing compound (III) having a structure in which two or more hydrocarbyloxy groups are bonded to the same carbon atom. The present invention also relates to a method for producing an olefin polymer using the olefin polymerization catalyst. Hereinafter, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION [Oxygen-Containing Compound] The oxygen-containing compound (III) used in the present invention is a compound having a structure in which two or more hydrocarbyloxy groups are bonded to the same carbon atom. The hydrocarbyloxy group here is preferably an alkoxy group, an aralkyloxy group or an aryloxy group, more preferably an alkoxy group, and particularly preferably a methoxy group. As the oxygen-containing compound (III) used in the present invention, a compound having a structure in which two such hydrocarbyloxy groups are bonded to the same carbon atom is preferable.

[0008] More preferred as the oxygen-containing compound (III)
Or a compound having the following structure:(Where R¹ And R^Two Are each independently a hydrogen atom
Or a hydrocarbon group having 1 to 20 carbon atoms;¹ And R
^Two May combine with each other to form a ring. R ^Three And
And R^Four Is independently a hydrocarbon having 1 to 20 carbon atoms
Elementary group. )

The hydrocarbon group as R ¹ , R ² , R ³ or R ⁴ is preferably an alkyl group, an aryl group or an aralkyl group.

The alkyl group referred to herein is preferably an alkyl group having 1 to 20 carbon atoms, for example, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, n-octyl group, n-decyl Group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc., more preferably methyl group, ethyl group, n-propyl Group, isopropyl group, n-butyl group, tert-butyl group, isobutyl group, cyclopentyl group or cyclohexyl group.

All of these alkyl groups may be substituted with halogen atoms such as fluorine, chlorine, bromine and iodine. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,
Perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group,
Perchloropentadecyl group, perchloroeicosyl group,
Perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl, perbromoeicosyl and the like.

The aryl group has 6 to 20 carbon atoms.
Are preferred, for example, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6
-Xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-
Trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5
-Trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethyl Phenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n- Examples include an octylphenyl group, an n-decylphenyl group, an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is more preferable. All of these aryl groups are a fluorine atom,
A part thereof may be substituted with a halogen atom such as a chlorine atom, a bromine atom and an iodine atom.

The aralkyl group may have 7 to 2 carbon atoms.
An aralkyl group of 0 is preferred, for example, a benzyl group, (2
-Methylphenyl) methyl group, (3-methylphenyl)
Methyl group, (4-methylphenyl) methyl group, (2,3
-Dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3
(4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3 6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group,
(2,4,6-trimethylphenyl) methyl group, (2,4
3,4,5-tetramethylphenyl) methyl group, (2,
3,4,6-tetramethylphenyl) methyl group, (2,
3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) Methyl group, (sec-butylphenyl) methyl group, (ter
t-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group,
(N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group,
Examples thereof include (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group and the like, and more preferably benzyl group. Any of these aralkyl groups may be partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ¹ or R ² is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, cyclopentyl group or cyclohexyl group.
When R ¹ and R ² are bonded to each other to form a ring, the ring structure is preferably a cycloheptane structure or a cyclohexane ring structure. R ³ or R ⁴ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

Specific examples of the oxygen-containing compound (III) include dimethoxymethane, diethoxymethane, dinormal propoxymethane, diisopropoxymethane, dinormal butoxymethane, diphenoxymethane, 1,1-dimethoxyethane, 1-dimethoxypropane, 1,1-
Dimethoxybutane, propionaldehyde dimethyl acetal, 2-methyl-1,1-dimethoxypropane,
2,2-dimethyl-1,1-dimethoxypropane, 3-
Methyl-1,1-dimethoxypropane, 3,3-dimethyl-1,1-dimethoxypropane, 1,1-dimethoxybutane, 1,1-dimethoxypentane, normal octylaldehyde dimethyl acetal, benzaldehyde dimethyl acetal, phenylacetaldehyde dimethyl acetal 2,2-dimethoxypropane, 2,2-dimethoxybutane, 3-methyl-2,2-dimethoxybutane, 3,3-dimethyl-2,2-dimethoxybutane,
2,2-dimethoxypentane, 2,2-dimethoxyoctane, 2,2-dimethoxydecane, 3,3-dimethoxypentane, 4-methyl-3,3-dimethoxypentane,
4,4-dimethyl-3,3-dimethoxypentane, 2,
4-dimethyl-3,3-dimethoxypentane, 2,2
4,4-tetramethyl-3,3-dimethoxypentane,
3,3-dimethoxyhexane, 5-methyl-3,3-dimethoxyhexane, 5,5-dimethyl-3,3-dimethoxyhexane, 3,3-dimethoxypentane, 3,3-
Dimethoxydecane, diphenyldimethoxymethane, dicyclopentyldimethoxymethane, dicyclohexyldimethoxymethane, 1-phenyl-1,1-dimethoxyethane, 1-cyclopentyl-1,1-dimethoxyethane,
1-cyclohexyl-1,1-dimethoxyethane, 1-
Cyclohexyl-1,1-dimethoxypropane, 1-cyclohexyl-2-methyl-1,1-dimethoxypropane, 1-cyclohexyl-2,2-dimethyl-1,1-
Dimethoxypropane, trimethoxymethane, 1,1,1
-Trimethoxyethane, 1,1,2-trimethoxyethane, 1,1,1-trimethoxypropane, 1,1,2-
Trimethoxypropane, 1,1,3-trimethoxypropane, 1,1,1-trimethoxypentane, 1,1,
2,2-tetramethoxyethane, 1,1,3,3-tetramethoxypropane, 2-methyl-1,1,3,3-tetramethoxypropane, 2,2-dimethyl-1,1,1
3,3-tetramethoxypropane, 1,1-dimethoxycyclobutane, 1,1-dimethoxycyclopentane,
Examples thereof include 1,1-dimethoxycyclohexane, 1,1,2-trimethoxycyclohexane, 1,1,2,2-tetramethoxycyclohexane, 1,1,3,3-tetramethoxycyclohexane and the like.

Oxygen-containing compound (III) used in the present invention
As an acetal of a saturated aliphatic ketone or a saturated aliphatic aldehyde and an alcohol is more preferable, an acetal of a saturated aliphatic ketone or a saturated aliphatic aldehyde and methanol is particularly preferable, and among them, dimethoxymethane, 1,1-dimethoxyethane, Propionaldehyde dimethyl acetal, normal octyl aldehyde dimethyl acetal, 2,2-dimethoxypropane, 3,3
-Dimethoxyhexane or 1,1-dimethoxycyclohexane is preferred.

The amount of the oxygen-containing compound (III) used is usually
It can be selected from a wide range of 1 mol to 2000 mol per 1 mol of titanium atom in the solid catalyst component (I), and particularly preferably 5 mol to 1000 mol. The amount of the oxygen-containing compound (III) to be used with respect to the organoaluminum compound (II) can be generally selected in a wide range from 0.001 mol to 10 mol per 1 mol of aluminum atoms of the organoaluminum compound (II). , Especially 0.01 mol ~
A range of 5 moles is preferred.

[Solid Catalyst Component] As the solid catalyst component (I) containing at least a titanium atom, a magnesium atom and a halogen atom used in the present invention, any known solid catalyst containing a titanium atom, a magnesium atom and a halogen atom can be used. Ingredients can be used.

Examples of such a solid catalyst component containing a titanium atom, a magnesium atom and a halogen atom include, for example, JP-B-46-34092 and JP-B-47-41.
676, JP-B-55-23561, JP-B-57-24361, JP-B-52-39431, JP-B-52-36786, and JP-B1-280.
No. 49, Japanese Patent Publication No. 3-43283, Japanese Unexamined Patent Publication No.
80044, JP-A-55-52309, JP-A-58-21405, JP-A-61-18180
7, JP-A-63-142008, JP-A-5-142008
-339319, JP-A-54-148093, JP-A-4-227604, JP-A-6-293
No. 3, JP-A-64-6006, and JP-A-6-1
JP-A-79720, JP-B-7-116252, JP-A-8-134124, JP-A-9-31119, JP-A-11-228628, JP-A-11-112
Examples thereof include solid catalyst components described in JP-A-80234 and JP-A-11-322833. Among them, a solid catalyst component containing an electron donor in addition to a titanium atom, a magnesium atom and a halogen atom is preferred.

Specifically, a method of contact-treating a magnesium halide compound and a titanium compound, a method of contact-treating a magnesium halide compound, an electron donor and a titanium compound, and a method of treating a magnesium halide compound and a titanium compound with an electron-donating solvent , A method of impregnating the carrier substance with a carrier material, a method of contact-treating a dialkoxymagnesium compound with a titanium halide compound and an electron donor, a solid catalyst component precursor containing a magnesium atom, a titanium atom and a hydrocarbyloxy group And a solid catalyst component obtained by, for example, a method of subjecting the catalyst to a contact treatment with a halogen compound having a halogenating ability and an electron donor.

In particular, a method of contact-treating a solid catalyst precursor (C) containing a magnesium atom, a titanium atom and a hydrocarbyloxy group with a halogenated compound (A) having a halogenating ability and an electron donor (B). Are preferred. The solid catalyst component precursor (C) referred to here is a solid component containing a magnesium atom, a titanium atom and a hydrocarbyloxy group. Specifically, an organosilicon compound having a Si-O bond () disclosed in JP-A-11-80234
Is represented by the general formula Ti (OR ¹ ) _a X _4-a (wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a is 0 <a ≦ 4 A solid product obtained by reducing a titanium compound () represented by the formula (1) with an organomagnesium compound (), or a Si—O bond disclosed in Japanese Patent Publication No. 4-57685. Organosilicon compound () and porous carrier ()
Is represented by the general formula Ti (OR ¹ ) _a X _4-a (wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a is 0 <a ≦ 4 And a solid product obtained by reducing the titanium compound () represented by the formula (1) with an organomagnesium compound ().

Specific examples of R ^{1 in} the general formula Ti (OR ¹ ) _a X _4-a include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl and the like. , An alkyl group such as heptyl group, octyl group, decyl group and dodecyl group, an aryl group such as phenyl group, cresyl group, xylyl group and naphthyl group, a cycloalkyl group such as cyclohexyl group and cyclopentyl group, and an alkenyl group such as propenyl group. And an aralkyl group such as a benzyl group. It is also possible to use a titanium compound having two or more different (OR ¹ ) groups. Among these groups, 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.

Examples of the halogen atom represented by X include a chlorine atom, a bromine atom and an iodine atom. Particularly chlorine atoms give favorable results.

The value of a in the general formula Ti (OR ¹ ) _a X _4-a is a number satisfying 0 <a ≦ 4, preferably 2 ≦ a.
It is a number satisfying ≦ 4, and particularly preferably a = 4.

As _a method for synthesizing the titanium compound represented by the general formula Ti (OR ¹ ) _a X _4-a , _a known method can be used. For example, a method of reacting Ti (OR ¹ ) ₄ and TiX ₄ at a predetermined ratio, or a method of reacting TiX ₄ with a corresponding alcohol (eg, R ¹ OH) in a predetermined amount can be used.

As the organosilicon compound () having a Si—O bond, preferably represented by the general formula Si (OR ³ )
_{^{b R 4 4-b, R}} 5 (R 6 2 SiO) c SiR 7 3 or (R ⁸ ₂ Si
O) Those represented by _d can be exemplified. Here, R ³ is a hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. , B is a number satisfying 0 <b ≦ 4, c is an integer of 1 to 1000, and d is 2 to 10
It is an integer of 00.

Specific examples of such organosilicon compounds include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetra-isopropoxysilane and di-isopropoxy-silane. Di-isopropylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triphen Ethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octaethyltrisiloxane, Le polysiloxane, diphenyl polysiloxane, methyl hydropolysiloxane, phenyl hydropolysiloxane like.

[0028] a preferred general formula _{^{Si (OR 3) b R 4}} 4-b alkoxysilane compound represented among these organic silicon compounds, in which case b is preferably 1 ≦
The number satisfies b ≦ 4, and a tetraalkoxysilane compound with b = 4 is particularly preferable.

As the organomagnesium compound (),
Any type of organomagnesium compound having a magnesium-carbon bond can be used. In particular, the general formula R
A Grignard compound represented by ⁹ MgX (where Mg represents a magnesium atom, R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen atom) or a compound represented by the general formula R
(Wherein, Mg is a magnesium atom, respectively R ¹⁰ and R ¹¹ represents a hydrocarbon group having a carbon number of 1 to 20) ¹⁰ R ¹¹ Mg dihydrocarbyl magnesium compound represented by is preferably used. Wherein R ¹⁰ and R ¹¹ may be the same or different. Specific examples of R ^{9 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isoamyl group, a hexyl group, an octyl group, and a 2-ethylhexyl group. , A phenyl group, a benzyl group and the like, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group and an alkenyl group. In particular, it is preferable to use a Grignard compound represented by R ⁹ MgX in an ether solution from the viewpoint of catalytic performance.

A hydrocarbon-soluble complex of the above-described 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 porous carrier (), a known carrier may be used. SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , ZrO ₂
And the like, 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 copolymer, polyvinyl chloride, Organic porous polymers such as polyethylene and polypropylene can be mentioned. Among these, an organic porous polymer is preferably used, and 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 material 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.

As a method of the reduction reaction of the titanium compound by the organomagnesium compound, a method of adding the organomagnesium compound () to a mixture of the titanium compound () and the organosilicon compound (), or the reverse method can be mentioned. At this time, a porous carrier () may coexist.

The titanium compound () and the organosilicon compound () are preferably dissolved or diluted in a suitable solvent before use.

Examples of such a solvent include aliphatic hydrocarbons such as hexane, heptane, octane and decane, toluene,
Examples thereof include aromatic hydrocarbons such as xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decalin; and ether compounds such as diethyl ether, dibutyl ether, diisoamyl ether, and tetrahydrofuran.

The temperature of the reduction reaction is usually -50 to 70 ° C, preferably -30 to 50 ° C, particularly preferably -25 to 35 ° C.
Temperature range. The lowering time is not particularly limited, but is usually about 30 minutes to 6 hours. After completion of the reduction reaction, a post-reaction may be further performed at a temperature of 20 to 120 ° C.

The amount of the organosilicon compound () used is usually the ratio of 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. The amount of the organomagnesium compound () used is usually represented by the sum of titanium atoms and silicon atoms and the atomic ratio of magnesium atoms (T
i + Si) /Mg=0.1 to 10, preferably 0.2 to
5.0, particularly preferably 0.5 to 2.0.
In the solid catalyst component, the molar ratio of Mg / Ti is 1 to 51, preferably 2 to 31, and particularly preferably 4 to 2.
The amounts of the titanium compound (), the organosilicon compound (), and the organomagnesium compound () may be determined so as to fall within the range of 6.

The solid product obtained by the reduction reaction is usually separated into solid and liquid, and washed several times with an inert hydrocarbon solvent such as hexane and heptane. The solid catalyst component precursor (C) 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.

As the halogen compound (A) having a halogenating ability, a compound capable of replacing the hydrocarbyloxy group of the solid catalyst precursor (C) with a halogen atom is preferable. Of these, a halogen compound of a Group 4 element, 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 halogen compound of titanium is preferable.
Specifically, titanium halide, titanium halide alkoxide, titanium halide amide and the like can be mentioned.

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

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

Specific examples of R include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, decyl, dodecyl and the like. Aryl groups such as phenyl group, tolyl group, cresyl group, xylyl group, naphthyl group, cycloalkyl group such as cyclohexyl group and cyclopentyl group, alkenyl group such as propenyl group, and aralkyl group such as benzyl group. No. 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 compounds of Group 13 elements include trichloroboron, methyldichloroboron, ethyldichloroboron, phenyldichloroboron, cyclohexyldichloroboron, dimethylchloroboron, methylethylchloroboron, trichloroaluminum, 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, Compounds in which chloro in these compound names is changed to fluoro, bromo, or iodo are also included.

Specific examples of the halogen compounds of Group 14 elements 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, di Chlorosilane, methyldichlorosilane, ethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, monochlorosilane, trichlorosilane Tylchlorosilane, triphenylchlorosilane, tetrachlorogermane, trichlorogermane, methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane, dichlorogermane, dimethyldichlorogermane, diethyldichlorogermane, diphenyldichlorogermane, monochlorogermane, trimethylchlorogermane, triethylchloro Germane, trinormalbutylchlorogermane, tetrachlorotin, methyltrichlorotin, normalbutyltrichlorotin, dimethyldichlorotin, dinormalbutyldichlorotin, diisobutyldichlorotin, diphenyldichlorotin,
Examples thereof include divinyldichlorotin, methyltrichlorotin, phenyltrichlorotin, dichlorolead, methylchlorolead, and phenylchlorolead, and compounds in which chloro of these compounds is changed to fluoro, bromo, or iodo.

As the halogen compound (A), in particular, tetrachlorotitanium, methyldichloroaluminum, ethyldichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane,
Alternatively, tetrachlorotin is preferred from the viewpoint of polymerization activity. As the halogen compound (A), only one type may be used, or a plurality of types may be used.

Examples of the electron donor (B) include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers,
Examples include oxygen-containing electron donors such as acid amides and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates. Among these electron donors, preferably, esters of organic acids or ethers
Ters are used.

The esters of organic acids are preferably mono- or polyvalent carboxylic esters, such as saturated aliphatic carboxylic esters, unsaturated aliphatic carboxylic esters, alicyclic carboxylic esters, and aromatic carboxylic esters. Can be mentioned.

Specifically, methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, benzoic acid Butyl, methyl toluate, 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,
Examples thereof include di-2-ethylhexyl phthalate, di-n-octyl phthalate, and diphenyl phthalate.

As the ethers, preferred are dialkyl ethers and general formulas (Wherein, each of R ^{22 to} R ²⁵ is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group;
R ²² or R ²³ may be a hydrogen atom). In particular,
Dimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, methyl butyl ether, methyl cyclohexyl ether, 2,2-dimethyl-1,
3-dimethoxypropane, 2,2-diethyl-1,3-
Dimethoxypropane, 2,2-dinorbutyl-1,1,
3-dimethoxypropane, 2,2-diisobutyl-1,
3-dimethoxypropane, 2-ethyl-2-butyl-
1,3-dimethoxypropane, 2-normalpropyl-
2-cyclopentyl-1,3-dimethoxypropane,
2,2-dimethyl-1,3-diethoxypropane, 2-
Normal propyl-2-cyclohexyl-1,3-diethoxypropane and the like can be mentioned.

As the electron donor (B), esters of organic acids are particularly preferred, dialkyl esters of aromatic dicarboxylic acids are particularly preferred, and dialkyl esters of phthalic acid are most preferred. As the electron donor (B), only one type may be used, or a plurality of types may be used.

Halogen compound (A) and electron donor (B)
The contact treatment of the solid catalyst component precursor (C) can be carried out by any known method such as a slurry method or a mechanical pulverization means such as a ball mill, which can bring the two into contact with each other. A large amount of fine powder is generated in the catalyst component and the particle size distribution tends to be widened, which is not preferable from an industrial viewpoint. Therefore, it is preferable that both are brought into contact by the slurry method in the presence of the medium. As a medium,
It 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; and alicyclic carbons such as cyclohexane and cyclopentane. Halogenated hydrocarbons such as hydrogen, 1,2-dichloroethane and monochlorobenzene can be used. Among them, aliphatic hydrocarbons are preferred in terms of polymerization activity. The amount of the medium used is not particularly limited, but the presence of an excessive amount of the medium is not preferable from the viewpoint of catalyst performance and catalyst productivity. Normal,
0.1 ml to 10 g per 1 g of the solid catalyst component precursor (C)
00 ml, preferably 0.5 ml to 20 ml,
Particularly preferably, it is 1 ml to 5 ml.

After the contact treatment, the next treatment can be carried out as it is, but it is preferable to carry out an arbitrary number of washing operations with a detergent in order to remove unreacted reagents. The detergent is preferably inert to the component to be treated, and the same compounds as those exemplified above as the medium can be used. The amount of the detergent used is usually 0.1 ml to 1000 ml per 1 g of the solid catalyst component precursor (C). It is preferably 1 ml to 100 ml per gram.

The contact treatment and / or washing temperature is usually −
The temperature is 50 to 150 ° C, preferably 0 to 140 ° C, and more preferably 60 to 135 ° C. The contact treatment time is not particularly limited, but is preferably 0.5 to 8 hours, and more preferably 1 to 6 hours. The washing time is not particularly limited, but is preferably 1 to 120 minutes, and more preferably 2 to 60 minutes.

The specific method for bringing the halogen compound (A) and the electron donor (B) into contact with the solid catalyst component precursor (C) is not particularly limited, but (C), (A) and ( A method in which B) is simultaneously subjected to contact treatment, and a method in which (A) and (B) are successively subjected to contact treatment with respect to (C) are exemplified. (C), (A) and (B) can be simultaneously contact-treated by a method in which a mixture obtained by previously mixing (A) and (B) is charged into (C) and subjected to contact treatment; (B) and (A) and (B) are successively charged and (A) and (B) are subjected to contact treatment. A method in which A) and (B) are simultaneously charged and a contact treatment is performed may be exemplified. As a method of sequentially contacting (A) and (B) with (C), (A) is charged into (C), contact treatment is performed, and then cleaning treatment is performed. A method in which (B) is put into an object to perform contact processing, and (B) is applied to (C).
, A cleaning process is performed after the contact process is performed, and a method of performing the contact process by supplying (A) to the cleaned product can be exemplified. Preferably, (C), (A) and (B) are contacted simultaneously.

After the contact treatment of (C), (A) and (B), the resulting treated solid can be further contacted with (A) and / or (B). As a method of bringing the halogen compound (A) and the electron donor (B) into contact with the solid catalyst component precursor (C), particularly preferably,
(A) and (B) are sequentially charged into (C) to perform a contact treatment, and then a cleaning treatment is performed. ) To (A)
After the contact treatment is performed by charging a mixture of (A) and (B), a cleaning process is performed, and (A) is charged into the cleaned product to perform the contact process. After the contact treatment is performed by sequentially charging B), a cleaning treatment is performed, and the contact treatment is performed by sequentially supplying (A) and (B) to the cleaned product. A method in which a mixture of (A) and (B) is charged to perform a contact treatment, followed by a cleaning treatment, and a mixture of (A) and (B) is charged to the washed material to perform a contact treatment. , (A) and (B) are sequentially charged into (C) to carry out the contact treatment. (C) is charged into (A) to carry out the contact treatment, and then the cleaning treatment is carried out. A method in which (B) is charged into the processed material to perform the contact treatment, and a cleaning process is performed after the (B) is charged into (C) and the contact processing is performed, and the cleaned processed material is obtained. After (A) and (B) are successively charged to perform the contact treatment, a further washing treatment is performed, and (A) and (B) are sequentially charged to the washed material to carry out the contact treatment. How to do, or (B) to (C)
, A contact treatment is carried out, a washing treatment is carried out, a mixture of (A) and (B) is put into the washed treatment material, a contact treatment is carried out, and further a washing treatment is carried out. This is a method in which a mixture of (A) and (B) is charged into a cleaning treatment product to perform a contact treatment. As (A) and (B) used a plurality of times by these methods, the same one may be used each time or a different one may be used.

The amount of the halogen compound (A) used in one contact treatment is usually 0.1 to 1000 mmol, preferably 0.3 to 1 g per 1 g of the solid catalyst component precursor (C).
５００500 mmol, particularly preferably 0.5-300 mmol.

The amount of the electron donor (B) used in one contact treatment is usually 0.1 to 1000 mmol, preferably 0.3 to 50 mmol per 1 g of the solid catalyst component precursor (C).
0 mmol, particularly preferably 0.5 to 300 mmol.

Halogen compound (A), electron donor (B)
When the solid catalyst component precursor (C) is brought into contact with the halogen compound (A), the molar ratio of the electron donor (B) to the halogen compound (A) is preferably 0.01 to 200, preferably 0.1 to 200.
100.

The obtained solid catalyst component may be used for polymerization in a slurry state in the presence of an inert diluent, or may be used for polymerization as a free-flowing powder after appropriate drying. .

[Preliminary Polymerization Treatment] In the present invention, the solid catalyst component (I) can be used as it is in the polymerization (main polymerization) reaction. I ') may be prepared first and used in the main polymerization. The prepolymerization treatment is performed, for example, by bringing the solid catalyst component (I) and the organoaluminum compound (II) into contact with an olefin. As the olefin used in the prepolymerization treatment, ethylene, propylene, 1-
Butene. Preliminary polymerization can be either homopolymerization or copolymerization.

In order to obtain a highly crystalline prepolymer (a polymer obtained by the prepolymerization treatment), a known electron donor or hydrogen may be used together. As such an electron donor, an organic compound having a Si-OR bond (R represents a hydrocarbon group having 1 to 20 carbon atoms) can be preferably used.

When the solid catalyst component of the present invention is preliminarily polymerized, it is preferable that the solid catalyst component is slurried. As the solvent, an aliphatic hydrocarbon such as butane, pentane, hexane, heptane or the like may be used. Examples thereof include aromatic hydrocarbons such as toluene and xylene.

The slurry concentration is usually from 0.001 to 0.
5 g solid catalyst component / ml solvent, especially 0.01 to 0.3 g
Solid catalyst components / ml solvent are preferred. Further, it is preferable to use the organoaluminum compound in such a ratio that the Al / Ti atomic ratio is 0.1 to 100, particularly 0.5 to 50.

The temperature of the prepolymerization treatment is usually from -30 to 80.
° C, especially -10 ° C to 50 ° C. The amount of the prepolymer is usually 0.1 to 300 g, preferably 0.5 to 50 g, per 1 g of the solid catalyst component.

The obtained prepolymerized solid catalyst component (I ')
May be used for the polymerization in a slurry state in the presence of an inert diluent, or may be used for the polymerization as a free-flowing powder after appropriate drying.

[Organoaluminum Compound] The organoaluminum compound (II) used in the present invention has at least one Al-carbon bond in the molecule, and a typical example thereof is represented by the general formula R ¹² _r AlY _{3. -r} and R ¹³ R ¹⁴ Al- (O
—AlR ¹⁵ ) _d R ¹⁶ . here,
^{R 1 2, R 13, R} 14, R 15 and R ¹⁶ each, 1-8 hydrocarbon group carbon atoms, Y represents a halogen atom, a hydrogen atom or an alkoxy group. r is a number satisfying 2 ≦ r ≦ 3. d is a number satisfying 1 ≦ d ≦ 30.

Specific examples of the organoaluminum compound include trialkylaluminums such as triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, diethylaluminum hydride, dinormal butylaluminum hydride, diisobutylaluminum hydride and the like. Alkyl aluminum dihalides such as dialkyl aluminum hydride, ethyl aluminum dichloride, normal butyl aluminum dichloride, isobutyl aluminum dichloride, dialkyl aluminum halides such as diethyl aluminum chloride, di normal butyl aluminum chloride, diisobutyl aluminum chloride, trialkyl aluminum and dialkyl aluminum Mixtures Umuharaido, tetraethyldialumoxane, tetrabutyl di alumoxane, polymethyl alumoxane, and alkyl alumoxanes of polyethyl alumoxane like. Of these organoaluminum compounds, trialkylaluminum, a mixture of a trialkylaluminum and a dialkylaluminum halide, or an alkylalumoxane is preferable, and particularly, triethylaluminum, tri-n
-Butyl aluminum, triisobutyl aluminum,
Trihexyl aluminum, a mixture of triethyl aluminum and diethyl aluminum chloride, or tetraethyl dialumoxane is preferred.

The amount of the organoaluminum compound (II) used is usually from 1 to 10 per mole of titanium atom in the solid catalyst component.
Although it can be selected in a wide range such as 000 mol, a range of 5 to 5000 mol is particularly preferable. The organoaluminum compound (II) may be used as it is, or may be used as a solution with an inert diluent.

[Production of Olefin Polymer] The olefin polymerization catalyst of the present invention is a catalyst obtained by contacting the solid catalyst component (I), the organoaluminum compound (II) and the oxygen-containing compound (III). The term “contact” used herein means any method as long as the catalyst components (I) to (III) come into contact with each other to form a catalyst. The catalyst component (I) may be diluted with a solvent or not diluted beforehand. To (III) and a method of separately contacting them in a polymerization reaction tank and bringing them into contact in the polymerization reaction tank.

The method for supplying the solid catalyst component (I), the organoaluminum compound (II) and the oxygen-containing compound (III) to the polymerization reactor is described below. An inert gas such as nitrogen or argon; It is preferable to supply in a state without moisture. (I),
(II) and (III) may be supplied individually, or may be supplied by contacting two or more in advance.

The polymerization reaction can be carried out by a known method such as ordinary gas phase polymerization and slurry polymerization. The conditions of the polymerization reaction are usually lower than the temperature at which the obtained polymer melts, preferably lower than 130 ° C, more preferably 20 to 110 ° C, particularly preferably 40 to 100 ° C, and normal pressure to 5 MPa.
It is preferable to carry out in the range of the pressure. For the purpose of adjusting the melt fluidity of the obtained polymer, polymerization can be carried out by adding hydrogen as a molecular weight regulator. Further, the polymerization method may be either a continuous type or a batch type.

The process for producing the olefin polymer of the present invention comprises:
This is a method for producing an olefin polymer using the olefin polymerization catalyst. Examples of the olefin polymer include a homopolymer of an olefin and a copolymer of an olefin and an addition-polymerizable monomer other than the olefin, and the like.
It is suitable for producing an ethylene polymer having a polyethylene crystal structure. As the ethylene polymer, ethylene and α
-Copolymers with olefins (linear low density polyethylene) are preferred.

The α-olefin referred to herein includes propylene, 1-butene, 1-pentene, 1-hexene,
-Methyl-1-pentene, 4-methyl-1-pentene, and the like, and 1-butene, 1-hexene, or 4-
Methyl-1-pentene is preferred.

[0074]

The present invention will be described below with reference to examples.
The present invention is not limited by these examples. The properties of solids (hereinafter, sometimes simply referred to as solid components) such as polymers and solid catalyst components in the examples were measured by the following methods.

(1) The content of the repeating unit derived from α-olefin in the copolymer of ethylene and α-olefin was determined by using an infrared spectrophotometer (1600 series manufactured by PerkinElmer). It was determined from the characteristic absorption of the olefin using a calibration curve and was expressed as the number of short-chain branches per 1000 C (SCB).

(2) The flow rate (FR) is ASTM
It was determined by measuring at 190 ° C. according to D1238.

(3) The outflow ratio (FRR) was adopted as a measure of the melt fluidity. The FRR is a ratio of the outflow amount when a load of 21.60 kg is applied to the outflow amount when a load of 2.160 kg is applied in the method of measuring the flow rate (FR), that is, FRR = (21.60 kg load)
At this time) (outflow at a load of 2.160 kg). Generally, it is known that the FRR value increases as the molecular weight distribution of the polymer increases.

(4) The content of the low molecular weight component was evaluated by the value (CXS) in which the amount soluble in cold xylene at 25 ° C. was expressed in terms of weight percentage (wt%). In general, the larger the SCB, the more C
XS also increases.

(5) The Ti content is determined by decomposing a solid component with dilute sulfuric acid, adding an excess of hydrogen peroxide solution, and measuring the characteristic absorption at 410 nm using a Hitachi Double Beam Spectrophotometer U-2001. And a calibration curve. The alkoxy group content was determined by decomposing a solid component with water, and then measuring the corresponding alcohol amount using a gas chromatography internal standard method.

Example 1 (1) Synthesis of Solid Catalyst Component Precursor In a reactor equipped with a stirrer purged with nitrogen, hexane 800 was added.
One liter, 349 kg of tetraethoxysilane and 38 kg of tetrabutoxytitanium were charged and stirred. next,
852 of a solution of butylmagnesium chloride in dibutyl ether (concentration: 2.1 mol / l) was added to the stirred mixture.
One liter was added dropwise over 5 hours while maintaining the temperature of the reactor at 5 ° C. After completion of the dropwise addition, the mixture was stirred at 8 ° C. for 1 hour and further at 20 ° C. for 1 hour, and then filtered.
Washing with 100 liters was repeated three times, and toluene was added to form a slurry. When 50 ml of the slurry was collected and the solvent was removed, 8.15 g of a solid component was contained therein. The precursor of the solid catalyst component was Ti: 2.09 wt.
%, Ethoxy group: 38.8 wt%, butoxy group: 2.9
wt%.

(2) Synthesis of solid catalyst component After replacing a 200-ml flask equipped with a stirrer with nitrogen, the solid catalyst component precursor 2 obtained in the above (1) was replaced with nitrogen.
A slurry containing 1.0 g was charged into the flask and subjected to solid-liquid separation. The obtained solid was washed three times with 100 ml of heptane, and heptane was added to the washed solid so that the total volume of the slurry became 122 ml. Internal volume 40 with stirrer
After replacing the 0 ml autoclave with nitrogen,
Transfer the heptane slurry of the solid catalyst component precursor,
After charging 11.0 ml of tetrachlorosilane (hereinafter sometimes referred to as SiCl ₄ ), 16.1 ml of di (2-ethylhexyl) phthalate (hereinafter sometimes abbreviated as DEHP) is continuously charged, and 105 ° C. For 3 hours. After the autoclave was cooled to room temperature, the stirred mixture was transferred to a 200 ml-volume flask purged with nitrogen. The stirred mixture was subjected to solid-liquid separation, and the obtained solid was washed three times with 105 ml of toluene at 105 ° C., and 105 ml of toluene was added again. After the temperature was raised to 70 ° C., 10.5 ml of titanium tetrachloride (hereinafter sometimes referred to as TiCl ₄ ) was added, and the mixture was stirred at 105 ° C. for 1 hour. Next, solid-liquid separation was performed, and the obtained solid was subjected to 105
The washing with 105 ml of toluene was repeated 6 times at ℃, and the washing with 105 ml of hexane was further repeated twice at room temperature, and the washed solid was dried under reduced pressure to obtain a solid catalyst component. The solid catalyst component contained Ti: 1.0 wt%.

(3) Polymerization An autoclave with an internal volume of 3 liters equipped with a stirrer was sufficiently dried, evacuated, charged with 400 g of butane and 350 g of 1-butene, and heated to 70 ° C. Next, the partial pressure of hydrogen was 0.4 MPa, and the partial pressure of ethylene was 1.2 MPa.
Was added. Triethyl aluminum 5.7m
mol, 3,3-dimethoxyhexane 0.57 mmol
1) 17.4 mg of the solid catalyst component obtained in the above (2) was press-fitted with argon to initiate polymerization. After that, while continuously supplying ethylene, keeping the total pressure constant, 70 ° C
For 3 hours. After the completion of the polymerization reaction, unreacted monomers were purged to obtain 160 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of the polymer produced per unit of catalyst (polymerization activity) was 9,200 g polymer / g solid catalyst component. For this polymer, SCB: 2
1.0, FR: 0.56, FRR: 22.7, CXS:
It was 10.3 wt%.

Example 2 (1) Polymerization Example 1 (3) was repeated except that 3,3-dimethoxyhexane was replaced by 0.57 mmol of 2,2-dimethoxypropane and 14.1 mg of a solid catalyst component. 1 (3)
Polymerization was carried out in the same manner as in
4 g were obtained. The inner wall of the autoclave and the stirrer
The polymer hardly adhered. The amount of polymer produced per unit of catalyst (polymerization activity) was 1700 g polymer /
g solid catalyst component. For this polymer, SC
B: 21.1, FR: 0.36, FRR: 24.3, C
XS: 9.0 wt%.

Example 3 (1) Polymerization In Example 1 (3), 3,3-dimethoxyhexane was replaced by 0.57 mmol of 1,1-dimethoxycyclohexane.
The polymerization was carried out in the same manner as in Example 1 (3) except that the amount of the solid catalyst component was changed to 11.1 mg, to obtain 53 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. Amount of polymer produced per unit of catalyst (polymerization activity)
Was 4800 g polymer / g solid catalyst component. For this polymer, SCB: 21.5, FR: 0.46, F
RR: 19.9, CXS: 9.7 wt%.

Example 4 (1) Polymerization In Example 1 (3), 3,3-dimethoxyhexane was changed to 0.57 mmol of 1,1-dimethoxyethane, and the amount of the solid catalyst component was reduced to 21.3 mg. Polymerization was carried out in the same manner as in Example 1 (3), except for changing, to obtain 66 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer.
The amount of polymer produced per unit of catalyst (polymerization activity) was 31.
It was 00 g polymer / g solid catalyst component. About this polymer, SCB: 19.1, FR: 0.61, FRR:
22.3, CXS: 7.4 wt%.

Example 5 (1) Polymerization In Example 1 (3), 3,3-dimethoxyhexane was replaced with propionaldehyde dimethyl acetal 0.57 m
The polymerization was carried out in the same manner as in Example 1 (3) except that the amount was changed to 1 mol, and the amount of the solid catalyst component was changed to 16.6 mg, to obtain 108 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of polymer produced per unit of catalyst (polymerization activity) was 6,500 g polymer / g solid catalyst component. About this polymer, SCB: 16.0, FR:
0.78, FRR: 21.5, CXS: 4.2 wt%.

Example 6 (1) Polymerization In Example 1 (3), 3,3-dimethoxyhexane was replaced with normal octyl aldehyde dimethyl acetal 0.1.
The amount was changed to 57 mmol and the amount of the solid catalyst component was 17.2 m
The polymerization was carried out in the same manner as in Example 1 (3) except that the amount was changed to g, to obtain 103 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of polymer produced per unit of catalyst (polymerization activity) was 5,990 g polymer / g solid catalyst component. For this polymer, SCB: 17.3, F
R: 0.87, FRR: 21.7, CXS: 5.9 wt
%Met.

Example 7 (1) Polymerization In Example 1 (3), 3,3-dimethoxyhexane was replaced with benzaldehyde dimethyl acetal 0.057 mm
ol, and the polymerization was carried out in the same manner as in Example 1 (3) except that the amount of the solid catalyst component was changed to 11.5 mg, to obtain 54.7 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of polymer produced per unit of catalyst (polymerization activity) was 4,760 g polymer / g solid catalyst component. About this polymer, SCB: 15.9, FR:
0.67, FRR: 21.8, CXS: 4.3 wt%.

Comparative Example 1 (1) Polymerization Example 1 (3) was repeated except that 3,3-dimethoxyhexane was not used and the amount of the solid catalyst component was changed to 9.8 mg. The polymerization was carried out in the same manner as in the above) to obtain 140 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The production amount (polymerization activity) of the polymer per catalyst unit amount was 14000 g polymer / g solid catalyst component.
About this polymer, SCB: 20.9, FR: 1.1
2, FRR: 23.0, CXS: 11.1 wt%, and the amount of CXS with respect to SCB was larger than that when an oxygen-containing compound was used.

Comparative Example 2 (1) Polymerization In Example 1 (3), the amount of butane was changed to 380 g, the amount of 1-butene was changed to 370 g, and 3,3-dimethoxyhexane was not used. , The amount of the solid catalyst component is 11.
Polymerization was carried out in the same manner as in Example 1 (3) except that the amount was changed to 2 mg, to obtain 222 g of a polymer having good powder properties.
The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of the polymer produced per unit of catalyst (polymerization activity) was 19,800 g polymer / g solid catalyst component. For this polymer, SCB: 12.
3, FR: 1.27, FRR: 24.5, CXS: 13
wt%, compared with the case where an oxygen-containing compound is used.
The amount of CXS to SCB was large.

Comparative Example 3 (1) Polymerization In Example 1 (3), the amount of butane was changed to 450 g, the amount of 1-butene was changed to 300 g, and 3,3-dimethoxyhexane was not used. 13. the amount of the solid catalyst component;
Polymerization was carried out in the same manner as in Example 1 (3) except that the amount was changed to 3 mg, to obtain 245 g of a polymer having good powder properties.
The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of the polymer produced per unit of catalyst (polymerization activity) was 17,100 g polymer / g solid catalyst component. About this polymer, SCB: 19.
1, FR: 1.34, FRR: 24.5, CXS: 9.
1 wt%, and the CXS amount with respect to SCB was larger than that in the case where an oxygen-containing compound was used.

Comparative Example 4 (1) Polymerization In Example 1 (3), the amount of butane was changed to 480 g, the amount of 1-butene was changed to 270 g, and 3,3-dimethoxyhexane was not used. , The amount of the solid catalyst component is 7.1
Polymerization was carried out in the same manner as in Example 1 (3) except that the amount was changed to mg, to obtain 105 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of polymer produced per unit of catalyst (polymerization activity) was 15000 g polymer / g solid catalyst component. For this polymer, SCB: 15.9,
FR: 0.69, FRR: 25.5, CXS: 5.4w
t%, compared with the case where an oxygen-containing compound is used.
The amount of CXS with respect to CB was large.

Comparative Example 5 (1) Polymerization In Example 1 (3), 3,3-dimethoxyhexane was replaced with normal propylmethyldimethoxysilane (0.57 m).
The polymerization was carried out in the same manner as in Example 1 (3) except that the amount was changed to mol, and the amount of the solid catalyst component was changed to 16.1 mg, to obtain 71 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of the polymer produced per unit of catalyst (polymerization activity) was 4100 g polymer / g solid catalyst component.
About this polymer, SCB: 13.6, FR: 0.9
6, FRR: 22.0, CXS: 5.9 wt%,
Compared with the case where the oxygen-containing compound was used, the CXS amount with respect to SCB was larger.

Comparative Example 6 (1) Polymerization In Example 1 (3), 3,3-dimethoxyhexane was changed to 0.57 mmol of dimethoxymethylsilane.
Polymerization was carried out in the same manner as in Example 1 (3) except that the amount of the solid catalyst component was changed to 26.5 mg, to obtain 33 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of polymer produced per unit of catalyst (polymerization activity) was 1300.
g polymer / g solid catalyst component. About this polymer, SCB: 17.5, FR: 0.58, FRR: 2
0.8, CXS: 7.3 wt%, and the CXS amount with respect to SCB was larger than that in the case where an oxygen-containing compound was used.

Comparative Example 7 (1) Polymerization In Example 1 (3), 3,3-dimethoxyhexane was changed to 2,2-diisobutyl-1,3-dimethoxypropane 0.57 mmol to obtain a solid catalyst component. The amount is 16.
Polymerization was carried out in the same manner as in Example 1 (3) except that the amount was changed to 5 mg, to obtain 71 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of polymer produced per unit of catalyst (polymerization activity) was 4,300 g polymer / g solid catalyst component. For this polymer, SCB: 22.2, F
R: 1.68, FRR: 23.4, CXS: 16.0w
t%, compared with the case where an oxygen-containing compound is used.
The amount of CXS with respect to CB was large.

[0096]

As described in detail above, according to the present invention, an olefin polymerization catalyst capable of producing an olefin polymer having a low content of low molecular weight components, and an olefin polymer having a low content of low molecular weight components are provided. A manufacturing method is provided. According to the present invention, there is also provided a method for producing an olefin polymer having good particle properties with almost no adhesion to a polymerization reaction tank. In the production of an olefin polymer, a large amount of adhesion of the olefin polymer or the like to the polymerization reaction tank causes various obstacles in the operation of the production process of the olefin polymer and causes a decrease in operation efficiency. Should be as small as possible. And, regarding the particle properties of the obtained olefin polymer powder, from the viewpoint of operation stability and operation efficiency,
A polymer powder having a high bulk density, a narrow particle size distribution and good fluidity is desirable. Further, according to the present invention, a catalyst for olefin polymerization having a sufficiently high activity and a method for producing a sufficiently efficient olefin polymer are also provided.

[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.

Continued on the front page F term (reference) 4J028 AA01A AB01A AC06A BA01A BA01B BB00A BB01B BC04A BC05A BC06A BC07A BC15B BC16B CB29C EA01 EB02 EB04 EB05 EB08 EB09 EB10 FA01 FA02 FA04

Claims (7)

[Claims] The present invention relates to a solid catalyst component (I) containing at least a titanium atom, a magnesium atom and a halogen atom, an organoaluminum compound (II), and a structure in which two or more hydrocarbyloxy groups are bonded to the same carbon atom. An olefin polymerization catalyst obtained by contacting an oxygen-containing compound (III) having the same. 2. The oxygen-containing compound (III) has the following structure:
The catalyst for olefin polymerization according to claim 1, which is a compound having
Medium.(Where R¹ And R^Two Are each independently a hydrogen atom
Or a hydrocarbon group having 1 to 20 carbon atoms;¹ And R
^Two May combine with each other to form a ring. R ^Three And
And R^Four Is independently a hydrocarbon having 1 to 20 carbon atoms
Elementary group. ) 3. The olefin polymerization catalyst according to claim 1, wherein the oxygen-containing compound (III) is an acetal of a saturated aliphatic ketone or a saturated aliphatic aldehyde and an alcohol. 4. A solid catalyst component (I) containing at least a titanium atom, a magnesium atom and a halogen atom,
The olefin polymerization catalyst according to any one of claims 1 to 3, further comprising an electron donor. 5. The catalyst for olefin polymerization according to claim 4, wherein the electron donor is an ester of an organic acid. 6. A method for producing an olefin polymer using the catalyst for olefin polymerization according to any one of claims 1 to 5. 7. The method for producing an olefin polymer according to claim 6, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.