JP2002105116A - METHOD FOR PRODDING STEREOREGULAR alpha-OLEFIN POLYMER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a more efficient method for producing a stereoregular α-olefin polymer using a single-site catalyst. SOLUTION: This method for producing the stereoregular α-olefin polymer comprises bringing (A) modified particles obtained by bringing (a) dried particles into contact with (b) an organometallic compound, then bringing the resultant product into contact with (c) a compound having a functional group having an active hydrogen or a proton-nondonating Lewis basic functional group and an electron attractive group into contact with an α-olefin and subsequently bringing the resultant contact product into contact with (B) a transition metal compound having the stereoregular polymerizability of the α-olefin and (C) an organometallic compound and polymerizing the α-olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for efficiently producing a stereoregular α-olefin polymer.

[0002]

2. Description of the Related Art Stereoregular α-olefin polymers have been mainly produced using multi-site catalysts such as conventional solid catalysts, but recently, single-stranded polymers obtained using metallocene complexes having a specific structure have been developed. It is known that a stereoregular α-olefin polymer can be produced even with a site catalyst.

For example, a production example of a highly stereoregular isotactic propylene polymer using a metallocene complex in which two 1-3 substituted η ⁵ -cyclopentadienyl groups are bridged (Japanese Patent No. 2587251, Japanese Patent No. 262766
No. 9 and Japanese Patent No. 2668732) are known. It has also been reported that a syndiotactic propylene polymer can be obtained by using an oxypyridene (cyclopentadienyl) (fluorenyl) zirconium dichloride, which is a Cs-symmetric metallocene complex, and an aluminum oxy compound (J. Am. Che
m. Soc., 1988, 110, 6255.).

[0004]

However, with these known methods of using single-site catalysts, the method for producing an α-olefin polymer has not been sufficiently efficient. In view of such circumstances, a problem to be solved by the present invention, that is, an object of the present invention is to provide a more efficient method for producing a stereoregular α-olefin polymer using a single-site catalyst.

[0005]

According to the present invention, there is provided a method comprising bringing dried particles (a) into contact with an organometallic compound (b), and then contacting a functional group having active hydrogen or a non-proton-donating Lewis basic functional group. , And the modified particles (A) obtained by contacting the compound (c) having an electron-withdrawing group with the α-olefin, and then contacting the obtained contact product with the stereoregularity of the α-olefin. The present invention relates to a method for producing a stereoregular α-olefin polymer in which an α-olefin is polymerized by bringing a transition metal compound (B) and an organometallic compound (C) having an ionic polymerization ability into contact with each other.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. (A) Dry Particles The modified particles used in the present invention are prepared by bringing the dried particles (a) into contact with the organometallic compound (b), and then contacting the active hydrogen-containing functional group or the aprotic donor. The particles are obtained by bringing a compound (c) having a Lewis basic functional group and an electron-withdrawing group into contact, and the particles (a) used here are dried and substantially contain water. Aluminoxane is not substantially produced by contact with the trialkylaluminum. The fact that aluminoxane is not substantially formed by contact with a trialkylaluminum is described in Example 1 (1) of the present specification.
A solid component obtained using the particles under the same conditions as in Example 1 was used.
When the polymerization was carried out under the same conditions as in Example 1 (3) without using the treatment (2), it can be confirmed that no polymer was formed.

As the particles (a), those generally used as a carrier are preferably used. A porous substance having a uniform particle size is preferable, and an inorganic substance or an organic polymer is suitably used. From the viewpoint of the particle size distribution of the obtained polymer, the particle (a) preferably has a volume-based geometric standard deviation of the particle diameter of the particle (a) of 2.5 or less, more preferably 2.0 or less, and still more preferably. Is 1.7 or less.

Inorganic substance usable in the particles (a) of the present invention
Examples of the quality include inorganic oxides and magnesium compounds.
It is possible to use clay and clay minerals as long as they do not interfere.
is there. These may be used as a mixture. Inorganic oxidation
As a specific example of the material, SiO 2_Two, Al_TwoO_Three, MgO, Z
rO_Two, TiO _Two, B_TwoO_Three, CaO, ZnO, BaO, T
hO_TwoAnd mixtures thereof, for example, SiO 2_Two-M
gO, SiO_Two-Al_TwoO_Three, SiO_Two-TiO_Two, SiO_Two
-V_TwoO _Five, SiO_Two−Cr_TwoO_Three, SiO_Two-TiO_Two-M
gO etc. can be illustrated. These inorganic oxides
Among the SiO_TwoAnd / or Al_TwoO_ThreeIs preferred
No. The inorganic oxide contains a small amount of Na_TwoCO_Three, K_Two
CO_Three, CaCO_Three, MgCO_Three, Na_TwoSO_Four, Al_Two(S
O_Four)_Three, BaSO_Four, KNO_Three, Mg (NO_Three)_Two, Al
(NO_Three)_Three, Na_TwoO, K_TwoO, Li_TwoCarbonate such as O, sulfuric acid
Acid salts, nitrates and oxide components may be contained.

Examples of the magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride and the like. Alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium; phenoxy magnesium and dimethyl Allyloxymagnesium such as phenoxymagnesium; lau Magnesium phosphate, and the like can be exemplified carboxylates of magnesium such as magnesium stearate. Of these, magnesium halide or alkoxymagnesium is preferred, and magnesium chloride or butoxymagnesium is more preferred.

As the clay or clay mineral, kaolin,
Bentonite, kibushi clay, gairome clay, allophane,
Hisingelite, Vylophilite, Talc, Plum group,
Montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, halloysite and the like. Among these, smectite, montmorillonite, hectorite, laponite and saponite are preferred, and montmorillonite and hectorite are more preferred.

These inorganic substances need to be dried to substantially remove water, and are preferably dried by heat treatment. The heat treatment is usually performed at a temperature of 100 to 1,500.
C., preferably at 100 to 1,000.degree. C., more preferably at 200 to 800.degree. After heating,
For example, a method of flowing a dried inert gas (for example, nitrogen or argon or the like) at a constant flow rate for several hours or more,
Alternatively, a method of reducing the pressure for several hours may be mentioned, but the method is not limited.

These inorganic substances need to be dried to substantially remove water, and are preferably dried by a heat treatment. The heat treatment is usually carried out at a temperature of 100 to 1500 ° C., preferably 100 to 1,000 ° C., and more preferably 200 to 8 ° C.
Performed at 00 ° C. The heating time is not particularly limited, but is preferably from 10 minutes to 50 hours, more preferably from 1 hour to 30 hours. Further, during the heating, for example, a method of flowing a dried inert gas (for example, nitrogen or argon) at a constant flow rate or a method of reducing the pressure may be used, but the method is not limited thereto.

As the organic polymer which can be used for the particles (a) of the present invention, any organic polymer may be used, and a mixture of plural kinds of organic polymers may be used. The organic polymer is preferably an organic polymer having a functional group reactive with the organometallic compound (b). Examples of such a functional group include a functional group having an active hydrogen and a non-proton-donating Lewis basic functional group. A polymer having a non-proton donating Lewis basic functional group is preferred.

The functional group having active hydrogen is not particularly limited as long as it has active hydrogen. Specific examples thereof include a primary amino group, a secondary amino group, an imino group, an amide group, a hydrazide group, an amidino group. , Hydroxy, hydroperoxy, carboxyl, formyl, carbamoyl, sulfonic, sulfinic, sulfenic, thiol, thioformyl, pyrrolyl, imidazolyl,
Examples include a piperidyl group, an indazolyl group, and a carbazolyl group. Preferably, a primary amino group, a secondary amino group,
It is an imino group, an amide group, an imide group, a hydroxy group, a formyl group, a carboxyl group, a sulfonic acid group or a thiol group. Particularly preferred are a primary amino group, a secondary amino group, an amide group and a hydroxy group. In addition, these groups may be substituted by a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

The non-proton donating Lewis basic functional group is not particularly limited as long as it has a Lewis base moiety having no active hydrogen atom, and specific examples thereof include a pyridyl group, an N-substituted imidazolyl group, N-substituted indazolyl group, nitrile group, azide group, N-substituted imino group, N,
N-substituted amino group, N, N-substituted aminooxy group, N,
N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl group, carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group,
Examples include an N, N-substituted carbamoyl group, a thioalkoxy group, a substituted sulfinyl group, a substituted sulfonyl group, and a substituted sulfonic acid group. Preferred is a heterocyclic group, and more preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and most preferred is a pyridyl group. In addition, these groups may be substituted by a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

The amount of the functional group having an active hydrogen or the non-proton-donating Lewis basic functional group is not particularly limited, but is preferably 0.01 to 50 mmol as a molar amount of the functional group per unit gram of the polymer. / G,
More preferably, it is 0.1 to 20 mmol / g.

The polymer having such a functional group is, for example,
By homopolymerizing a monomer having an active hydrogen-containing functional group or an aprotic donating Lewis basic functional group and one or more polymerizable unsaturated groups, or another monomer having a polymerizable unsaturated group It can be obtained by copolymerizing with a monomer. At this time, it is preferable to further copolymerize together a crosslinkable polymerizable monomer having two or more polymerizable unsaturated groups.

Examples of the monomer having an active hydrogen-containing functional group or an aprotic donating Lewis basic functional group and one or more polymerizable unsaturated groups include the above active hydrogen-containing functional group and one or more polymerizable unsaturated groups. Examples of the monomer include a monomer having a polymerizable unsaturated group, or a monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups. Examples of such a polymerizable unsaturated group include an alkenyl group such as a vinyl group and an allyl group, and an alkynyl group such as an ethyne group. Examples of the monomer having an active hydrogen-containing functional group and one or more polymerizable unsaturated groups include a vinyl group-containing primary amine,
Vinyl group-containing secondary amine, vinyl group-containing amide compound,
Examples thereof include vinyl group-containing hydroxy compounds.
Specific examples include N- (1-ethenyl) amine, N-
(2-propenyl) amine, N- (1-ethenyl) -N
-Methylamine, N- (2-propenyl) -N-methylamine, 1-ethenylamide, 2-propenylamide,
N-methyl- (1-ethenyl) amide, N-methyl-
(2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-buten-1-ol and the like. Specific examples of the monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole, vinyl (N-substituted) indazole Can be mentioned.

Examples of the other monomer having a polymerizable unsaturated group include ethylene, α-olefin, aromatic vinyl compound and the like. Specific examples include ethylene, propylene, butene-1, hexene-1, 4-hexene. Methyl-pentene-1, styrene and the like. Preferably it is ethylene or styrene. Two or more of these monomers may be used. Further, specific examples of the crosslinkable polymerizable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

The average particle size of the organic polymer is preferably from 5 to 1000 μm, more preferably from 10 to 5 μm.
00 μm. The pore volume is preferably 0.1 m
1 / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² /
g, more preferably 50 to 500 m ² / g.

These organic polymers need to be dried to substantially remove water, and are preferably dried by heat treatment. The heat treatment is usually carried out at a temperature of 30 to 400 ° C., preferably 50 to 200 ° C., and more preferably 70 to 150 ° C.
Carried out in ° C. The heating time is not particularly limited, but is preferably 30 minutes to 50 hours, more preferably 1 hour to 30 hours. During further heating, for example,
Dry inert gas (eg, nitrogen or argon, etc.)
Can be circulated at a constant flow rate, or a method of reducing the pressure can be used, but the method is not limited thereto.

(B) Organometallic compound The organometallic compound (b) used in the present invention is preferably a compound represented by the following general formula (1). R ¹ _n AX ¹ _qn (1) (where A is the periodic table of elements (1993, IUPA
A metal atom belonging to Group 2, 12 or 13 of C), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon oxy group having 1 to 20 carbon atoms, and X ¹ Is a halogen atom or a hydrogen atom. n is a number satisfying 0 <n ≦ q, and q is a valence of the metal atom A. )

In the general formula (1), A is a metal atom belonging to Group 2, 12 or 13 of the Periodic Table of the Elements (1993, IUPAC), and A is preferably a boron atom or an aluminum atom. , A magnesium atom or a zinc atom. When A is a boron atom or an aluminum atom, the valence is 3 (q = 3), and when A is a magnesium atom or a zinc atom, the valence is 2 (q = 3).
2).

When A is a boron atom, R ¹ is preferably the above-mentioned hydrocarbon group, and specific examples include trimethylborane,
Trialkyl borane such as triethyl borane, tripropyl borane, tributyl borane, triphenyl borane, dimethyl chloro borane, diethyl chloro borane, dipropyl chloro borane, dibutyl chloro borane, diphenyl chloro borane, and other dialkyl halide borane, dimethyl hydride borane, diethyl Examples thereof include hydride borane, dipropyl hydrido borane, dibutyl hydrido borane, dialkyl hydrido borane such as diphenyl hydrido borane, alkyl dihalide borane such as methyl dichloro borane, ethyl dichloro borane, propyl dichloro borane, butyl dichloro borane, and phenyl dichloro borane. .

When A is an aluminum atom, R ¹ is preferably the above-mentioned hydrocarbon group. Trialkylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, dinormalbutylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halides such as dinormalhexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, Normal butyl aluminum dichlora , Aluminum alkyl dihalides such as isobutyl aluminum dichloride and normal hexyl aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, di normal butyl aluminum hydride, dialkyl aluminum hydride such as diisobutyl aluminum hydride and di normal hexyl aluminum hydride And the like. Preferred are trialkylaluminums, and more preferred are trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalbutylaluminum, and trinormalhexylaluminum. Particularly preferred are trimethylaluminum, triethylaluminum and triisobutylaluminum.

When A is a magnesium atom, R ¹ is preferably the above-mentioned hydrocarbon group, and specific examples thereof include diethylmagnesium and di-n-butylmagnesium. Illustrated. When A is a zinc atom, R ¹ is preferably the above-mentioned hydrocarbon group, such as diethyl zinc. The organometallic compound (b) is more preferably an organoaluminum compound or an organoborane compound, and most preferably an organoaluminum compound.

(C) Compound having an active hydrogen-containing functional group or a non-proton-donating Lewis basic functional group and an electron-withdrawing group Functional group having an active hydrogen contained in the compound (c) used in the present invention Alternatively, a non-proton donating Lewis basic functional group usually reacts with an organometallic compound. The functional group having active hydrogen and the non-proton donating Lewis basic functional group are the same as those described above.

The compound (c) has an electron-withdrawing group. As an index of the electron-withdrawing group, a Hammett's substituent constant σ or the like can be used.
Is a positive functional group. Specific examples of the electron-withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a phenyl group, an acetyl group, a carbonyl group, a thionyl group, a sulfone group, and a carboxyl group.

Compound (c) may have a plurality of and / or a plurality of the above-mentioned functional groups having active hydrogen or non-proton donating Lewis basic functional groups and electron-withdrawing groups. I do not care. In the compound (c), the non-proton donating Lewis basic functional group and the electron-withdrawing group may be the same. in this case,
Compound (c) may have only one such functional group.

The compound (c) is preferably a compound having a functional group having an active hydrogen and an electron-withdrawing group, and examples thereof include amines, phosphines, alcohols, and phenols having an electron-withdrawing group. Thiols, thiophenols, carboxylic acids, sulfonic acids and the like.

The compound (c) is more preferably a compound represented by the following formula (2). R ² _m ZH _zm (2) (wherein, R ² represents an electron-withdrawing group or a group containing an electron-withdrawing group, Z represents an atom of Group 15 or 16 of the periodic table, and H represents Represents a hydrogen atom, z is a valence of Z and is 2 or 3, when z is 2, m is 1, and z is
Is 3 when m is 1 or 2. )

Examples of the group containing an electron-withdrawing group for R ² in the general formula (2) include an alkyl halide group, an aryl halide group, a cyanated aryl group, a nitrated aryl group, an ester group and the like. Can be

Specific examples of the halogenated alkyl group include:
Fluoromethyl group, chloromethyl group, bromomethyl group,
Iodomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, diiodomethyl group trifluoromethyl group, trichloromethyl group, tribromomethyl group,
Triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-triiodoethyl group,
2,2,3,3,3-pentafluoropropyl group, 2,
2,3,3,3-pentachloropropyl group, 2,2
3,3,3-pentabromopropyl group, 2,2,3
3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2
A trichloro-1-trichloromethylethyl group, 2,
2,2-tribromo-1-tribromomethylethyl group,
2,2,2-triiodo-1-triiodomethylethyl group, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 1,1,1,3,3,3
A hexachloro-2-trichloromethylpropyl group,
Examples thereof include a 1,1,1,3,3,3-hexabromo-2-tribromomethylpropyl group and a 1,1,1,3,3,3-hexaiodo-2-triiodomethylpropyl group.

Specific examples of the aryl halide group include:
2-fluorophenyl group, 3-fluorophenyl group, 4
-Fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4
-Iodophenyl group, 2,6-difluorophenyl group,
3,5-difluorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2,6-dibromophenyl group, 3,5-dibromophenyl group, 2,6-
Diiodophenyl group, 3,5-diiodophenyl group,
2,4,6-trifluorophenyl group, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-triiodophenyl group, pentafluorophenyl group, pentachlorophenyl Group, pentabromophenyl group, pentaiodophenyl group, 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl)
A phenyl group, a 4- (trifluoromethyl) phenyl group,
2,6-di (trifluoromethyl) phenyl group, 3,5
-Di (trifluoromethyl) phenyl group, 2,4,6-
And a tri (trifluoromethyl) phenyl group.

Specific examples of the cyanated aryl group include 2
-Cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group and the like. Specific examples of the nitrated aryl group include a 2-nitrophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group, and the like.

Specific examples of the ester group include a methoxycarbonyl group, an ethoxycarbonyl group, a normal propyloxycarbonyl group, an isopropyloxycarbonyl group, a phenoxycarbonyl group, a trifluoromethyloxycarbonyl group and a pentafluorophenyloxycarbonyl group. Can be

R ^{2 in the} general formula (2) is preferably a halogenated alkyl group or a halogenated aryl group,
More preferably, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,2-triethyl group Fluoro-1-trifluoromethylethyl group, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 4-fluorophenyl group, 2,6-difluorophenyl group, 3.5 −
A difluorophenyl group, a 2,4,6-trifluorophenyl group or a pentafluorophenyl group, more preferably a trifluoromethyl group, a 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,
A 1,3,3,3-hexafluoro-2-trifluoromethylpropyl group or a pentafluorophenyl group.

Z in the general formula (2) is the first in the periodic table.
H represents a group 5 or 16 atom, and H represents a hydrogen atom. Specific examples of Z include a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, and the like, preferably a nitrogen atom or an oxygen atom, and more preferably an oxygen atom.

Z is the valence of Z. For example, when Z is a nitrogen atom or a phosphorus atom, z is 3, and when Z is an oxygen atom or a sulfur atom, z is 2. When z is 2, m is 1; when z is 3, m is 1 or 2.

As specific examples of the above compound (c), amines include di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, di (difluoromethyl) amine , Di (dichloromethyl) amine, di (dibromomethyl) amine, di (diiodomethyl) amine, di (trifluoromethyl) amine, di (trichloromethyl) amine, di (tribromomethyl) amine, di (triiodomethyl) Amine, di (2,2,2-trifluoroethyl) amine, di (2,2,2-trichloroethyl) amine, di (2
2,2-tribromoethyl) amine, di (2,2,2-
Triiodoethyl) amine, di (2,2,3,3,3-
Pentafluoropropyl) amine, di (2,2,3)
3,3-pentachloropropyl) amine, di (2,2,
3,3,3-pentabromopropyl) amine, di (2,
2,3,3,3-pentaiodopropyl) amine, di (2,2,2-trifluoro-1-trifluoromethylethyl) amine, di (2,2,2-trichloro-1-trichloromethylethyl) Amine, di (2,2,2-tribromo-1-tribromomethylethyl) amine, di (2,2,2-triiodo-1-triiodomethylethyl) amine, di (1,1,1,3, 3,3-hexafluoro-2-trifluoromethylpropyl) amine, di (1,1,1,3,3,3-hexachloro-2-trichloromethylpropyl) amine, di (1,1,1,3,
3,3-hexabromo-2-tribromomethylpropyl) amine, di (1,1,1,3,3,3-hexioiodo-2-triiodomethylpropyl) amine, di (2-
(Fluorophenyl) amine, di (3-fluorophenyl) amine, di (4-fluorophenyl) amine, di (2-chlorophenyl) amine, di (3-chlorophenyl) amine, di (4-chlorophenyl) amine, di (2
-Bromophenyl) amine, di (3-bromophenyl)
Amine, di (4-bromophenyl) amine, di (2-iodophenyl) amine, di (3-iodophenyl) amine, di (4-iodophenyl) amine, di (2,6-difluorophenyl) amine, di (3,5-difluorophenyl) amine, di (2,6-dichlorophenyl) amine, di (3,5-dichlorophenyl) amine, di (2
6-dibromophenyl) amine, di (3,5-dibromophenyl) amine, di (2,6-diiodophenyl) amine, di (3,5-diiodophenyl) amine, di (2,4,6- Trifluorophenyl) amine, di (2,4,6-trichlorophenyl) amine, di (2
4,6-tribromophenyl) amine, di (2,4,6
-Triiodophenyl) amine, di (pentafluorophenyl) amine, di (pentachlorophenyl) amine,
Di (pentabromophenyl) amine, di (pentaiodophenyl) amine, di (2- (trifluoromethyl) phenyl) amine, di (3- (trifluoromethyl) phenyl) amine, di (4- (trifluoromethyl) amine ) Phenyl) amine, di (2,6-di (trifluoromethyl) phenyl) amine, di (3,5-di (trifluoromethyl) phenyl) amine, di (2,4,6-tri (trifluoromethyl) ) Phenyl) amine, di (2-cyanophenyl) amine, (3-cyanophenyl) amine, di (4
-Cyanophenyl) amine, di (2-nitrophenyl)
Amines, di (3-nitrophenyl) amine, di (4-nitrophenyl) amine and the like. A phosphine compound in which a nitrogen atom is substituted by a phosphorus atom can also be exemplified. These phosphine compounds are compounds represented by rewriting the above-mentioned specific examples of amines into phosphines.

As specific examples of compound (c), alcohols such as fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodmethanol, trifluoromethanol, trichloromethanol, trichloromethanol Bromomethanol, triiodomethanol, 2,2,2-trifluoroethanol,
2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 2,2,2-triiodoethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,3,3 , 3-pentachloropropanol,
2,2,3,3,3-pentabromopropanol, 2,
2,3,3,3-pentaiodopropanol, 2,2
2-trifluoro-1-trifluoromethylethanol, 2,2,2-trichloro-1-trichloromethylethanol, 2,2,2-tribromo-1-tribromomethylethanol, 2,2,2-triiodo-1 -Triiodomethylethanol, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol,
1,1,1,3,3,3-hexachloro-2-trichloromethylpropanol, 1,1,1,3,3,3-hexabromo-2-tribromomethylpropanol, 1,
1,1,3,3,3-hexaiodo-2-triiodomethylpropanol and the like. Further, a thiol compound in which an oxygen atom is substituted by a sulfur atom can also be exemplified. These thiol compounds are compounds and the like which are represented by rewriting methanol to methanethiol, ethanol to ethanethiol, and propanol to propanethiol in the above specific examples.

Specific examples of compound (c) include phenols such as 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol,
-Bromophenol, 3-bromophenol, 4-bromophenol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol, 2,
6-dibromophenol, 3,5-dibromophenol, 2,6-diiodophenol, 3,5-diiodophenol, 2,4,6-trifluorophenol, 2,
4,6-trichlorophenol, 2,4,6-tribromophenol, 2,4,6-triiodophenol, pentafluorophenol, pentachlorophenol, pentabromophenol, pentaiodophenol, 2-
(Trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-di (trifluoromethyl) phenol, 3,5-di (trifluoromethyl) phenol,
2,4,6-tri (trifluoromethyl) phenol,
Examples thereof include 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, and 4-nitrophenol. A thiophenol compound in which an oxygen atom is substituted by a sulfur atom can also be exemplified. These thiophenol compounds are compounds represented by rewriting phenol in the specific examples described above into thiophenol.

As specific examples of compound (c), carboxylic acids include 2-fluorobenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid, 2,3-difluorobenzoic acid, 2,4-difluorobenzoic acid, 2,5-difluorobenzoic acid, 2,6-difluorobenzoic acid, 2,3,4-
Trifluorobenzoic acid, 2,3,5-trifluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4,5
-Trifluorobenzoic acid, 2,4,6-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid,
2,3,4,6-tetrafluorobenzoic acid, pentafluorobenzoic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoroethylcarboxylic acid, heptafluoropropylcarboxylic acid, 1,1,1,3,3, 3
-Hexafluoro-2-propylcarboxylic acid and the like.

As specific examples of compound (c), sulfonic acids include fluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, 1,1,1,3 , 3,3-hexafluoro-
2-propanesulfonic acid and the like.

The compound (c) is preferably amines such as di (trifluoromethyl) amine and di (2,2)
2,2-trifluoroethyl) amine, di (2,2,
3,3,3-pentafluoropropyl) amine, di (2,2,2-trifluoro-1-trifluoromethylethyl) amine, di (1,1,1,3,3,3-hexafluoro-2) -Trifluoromethylpropyl) amine,
Di (pentafluorophenyl) amine and alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro- 1-trifluoromethylethanol, 1,1,1,3,3,3-
Hexafluoro-2-trifluoromethylpropanol, as phenols, 2-fluorophenol,
3-fluorophenol, 4-fluorophenol,
2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol,
-(Trifluoromethyl) phenol, 2,6-di (trifluoromethyl) phenol, 3,5-di (trifluoromethyl) phenol, 2,4,6-tri (trifluoromethyl) phenol and carboxylic acids Examples of pentafluorobenzoic acid, trifluoroacetic acid, and sulfonic acids include trifluoromethanesulfonic acid.

More preferably, compound (c) is di (trifluoromethyl) amine, di (pentafluorophenyl) amine, trifluoromethanol, 2,2,2
-Trifluoro-1-trifluoromethylethanol,
1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol, 4-fluorophenol,
2,6-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol, 4- (trifluoromethyl) phenol, 2,6-di (trifluoromethyl) phenol, 2,4,6-tri ( Trifluoromethyl) phenol, more preferably pentafluorophenol, or 1,1,1,
3,3,3-hexafluoro-2-trifluoromethylpropanol (common name: perfluoro tertiary butanol).

(A) Modified Particles The modified particles of the present invention are prepared by bringing dried particles (a) into contact with an organometallic compound (b), and then contacting a functional group having active hydrogen or an aprotic compound. It is obtained by contacting a compound (c) having a donor Lewis basic functional group and an electron withdrawing group.

The contact treatment between (a) and (b) and the subsequent contact treatment with (c) are preferably carried out in an inert gas atmosphere. The processing temperature is usually -80 ° C to 2
00 ° C, preferably -20 ° C to 150 ° C, more preferably 0 ° C to 100 ° C. Processing time is usually 1
Minutes to 48 hours, preferably 10 minutes to 24 hours. Although it is preferable to use a solvent, the solvent used is preferably an aliphatic or aromatic hydrocarbon solvent which is inert to (a), (b) and (c). Examples of the aliphatic hydrocarbon solvent include butane, pentane, hexane, heptane, and octane, and examples of the aromatic hydrocarbon solvent include benzene, toluene, and xylene. Alternatively, a mixture of these hydrocarbon solvents arbitrarily can be used. (A)
The method of contacting with (b) and the method of contacting with (c) after the contact may be the same or different.

The contact-treated particles in each contacting step may or may not be subjected to an isolation operation, but it is preferable to isolate the treated particles after contacting in each contacting step. As an isolation method, a method of decanting the supernatant of the treatment liquid, a method of washing the treated particles with an inert solvent after filtration, a method of washing the treated particles with an inert solvent after filtration, and under a reduced pressure or an inert gas The method of drying under circulation, the solvent at the time of the contact treatment,
A method of distilling off under reduced pressure or an inert gas flow is exemplified. When the treatment operation for isolating the treated particles obtained is not performed, the particles obtained in the treatment liquid may be suspended in an inert solvent and used for the polymerization reaction.

In preparing the modified particles of the present invention,
The amount of (b) used for (a) is such that the metal atom of the organometallic compound (b) contained in the particles obtained by contacting (a) with (b) is reduced to 1 g of dry particles. The amount is preferably 0.1 mmol or more in terms of the number of moles of the contained metal atoms, and more preferably 0.5 to 20 mmol. The amount of (c) used may be a functional group having active hydrogen or a non-proton-donating Lewis basic functional group for a metal atom derived from the organometallic compound (b) contained in 1 g of particles in a dry state, and an electron. As a molar ratio (c) / (b) of the compound (c) having an attractive group,
0.01 to 100, preferably 0.05 to 5
Is more preferable, and more preferably 0.1 to 2.

(B) Transition metal compound having stereoregular polymerization ability of α-olefin The transition metal compound having stereoregular polymerization ability of α-olefin used in the present invention may be an isotactic propylene polymer or a syndiotactic polymer. There is no particular limitation as long as it is a transition metal compound that forms a single-site catalyst capable of producing a stereoregular α-olefin polymer such as a tic propylene polymer, but is not particularly limited, and is described in Periodic Table (IUPAC 1985) 4-1.
Transition metal compounds having Group 0 and lanthanoid series transition metal atoms are preferred. Such transition metal atoms include, for example, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom,
Chromium, iron, ruthenium, cobalt,
Examples include a rhodium atom, a nickel atom, a palladium atom, a samarium atom, and a ytterbium atom, and a titanium atom, a zirconium atom or a hafnium atom is preferable.

The transition metal compound (B) used in the present invention is preferably a transition metal compound represented by the following general formula (4) or a transition metal compound represented by the following general formula (5). (Wherein, M is a transition metal atom of Group 4 of the periodic table, L is an η ⁵ -indenyl group or a substituted η ⁵ -indenyl group, and two Ls may be the same or different. Y is a bridging group connecting two L, and two X ² are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, and an aryloxy group. Or a heterocyclic group.)

[0053] (Wherein, M is a transition metal atom of Group 4 of the periodic table, and Y ²
Silicon atom, a germanium atom or a tin _{^{atom, (R 2 n -C 5 H}} 4-n) and _{^{(R 2 q -C 5 H 4}} -q) each substituted eta ⁵ - be a cyclopentadienyl group , N and q are each an integer of 1 to 3. Each R ² may be the same or different from each other, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, show an aryloxy group or a heterocyclic group, a substituted eta ⁵ The position and / or type of R ^{2 in} the cyclopentadienyl group is chosen such that there is no plane of symmetry containing M. R ³ and X are each a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, an aryloxy group or a heterocyclic group, R ³ and X are all the same Or different from each other. )

In the above general formula (4) or (5),
The transition metal atom represented by M is the periodic table of the element (IU
PAC inorganic metal nomenclature, revised edition 1989). Preferably,
It is a titanium atom or a zirconium atom.

In the above formula (4), L is an η ⁵ -indenyl group or a substituted η ⁵ -indenyl group, and the two Ls may be the same or different. Specific examples of L include η ⁵ -indenyl group, η ⁵ -methylindenyl group, η ⁵ -dimethylindenyl group, η ⁵ -n-propylindenyl group, η ⁵ -isopropylindenyl group,
eta ^5-n-butyl indenyl group, eta ^5-tert-butyl indenyl group, eta ⁵ - phenyl indenyl group, eta ⁵ - methylphenyl indenyl group, eta ⁵ - naphthyl indenyl group, eta ⁵ - trimethylsilyl indenyl And a η ⁵ -tetrahydroindenyl group.

In the general formula (4), Y represents two L
Is a cross-linking group. As the bridging group, 14th of the Periodic Table of the Elements (IUPAC revised version of inorganic chemical nomenclature 1989) can be used.
Examples include a divalent crosslinking group containing a group atom, and preferably a divalent crosslinking group containing a carbon atom, a silicon atom, a germanium atom, or a tin atom. More preferably, 2
The two L-bonding atoms are a carbon atom, a silicon atom, a germanium atom and / or a tin atom, and more preferably a divalent bridging group, and more preferably the two L-bonding atoms are a carbon atom, a silicon atom, and a germanium atom. And / or a divalent bridging group having a minimum number of atoms of 3 or less between two L-bonding atoms (including the case where two L-bonding atoms are single). is there. In particular,
Methylene group, ethylene group, propylene group, dimethylmethylene group (isopropylidene group), diphenylmethylene group, tetramethylethylene group, silylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group, tetramethyldisilylene group, dimethoxysilylene group And methylene group, ethylene group, dimethylmethylene group (isopropylidene group), dimethylsilylene group, diethylsilylene group and diphenylsilylene group.

In the general formula (4), two X ² are each independently a hydrogen atom, a halogen atom, an alkyl group,
It is an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group. Examples of the halogen atom herein include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

The alkyl group may have 1 to 1 carbon atoms.
20 alkyl groups are preferable, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, isoamyl group,
n-hexyl group, n-octyl group, n-decyl group, n-
Examples thereof include a dodecyl group, an n-pentadecyl group, and an n-eicosyl group, and more preferred are a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, and an isoamyl group. Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 10 carbon atoms substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group,
Chloromethyl group, trichloromethyl group, fluoroethyl group, pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group,
Perfluorooctyl, perchloropropyl, perchlorobutyl, perbromopropyl and the like can be mentioned. All of these alkyl groups are methoxy,
It may be partially substituted with an alkoxy group such as an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

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 a (n-dodecylphenyl) methyl group, a naphthylmethyl group and an anthracenylmethyl group, and more preferably a benzyl group. All of these aralkyl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

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,
Halogen atoms such as chlorine atom, bromine atom and iodine atom,
It may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The substituted silyl group is a silyl group substituted with a hydrocarbon group. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec group. -Alkyl groups having 1 to 10 carbon atoms such as -butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group, and aryl groups such as phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group.
Disubstituted silyl group having 2 to 20 carbon atoms such as dimethylsilyl group, diethylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-
Butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, Examples thereof include a trisubstituted silyl group having 3 to 20 carbon atoms such as a triphenylsilyl group, and a trimethylsilyl group, a tert-butyldimethylsilyl group, or a triphenylsilyl group is preferable. All of these substituted silyl groups have a hydrocarbon group such as a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or a benzyloxy group. May be partially substituted with an aralkyloxy group such as a group.

The alkoxy group may have 1 to 2 carbon atoms.
An alkoxy group of 0 is preferable, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group , N-octoxy group, n-dodesoxy group, n-pentadeoxy group, n-icosoxy group and the like, and more preferably methoxy group, ethoxy group, isopropoxy group or tert-butoxy group. All of these alkoxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The aralkyloxy group is preferably an aralkyloxy group having 7 to 20 carbon atoms, for example, a benzyloxy group, a (2-methylphenyl) methoxy group,
(3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group,
(2,5-dimethylphenyl) methoxy group, (2,6-
(Dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) A) methoxy group, a (2,3,6-trimethylphenyl) methoxy group,
(2,4,5-trimethylphenyl) methoxy group,
A (2,4,6-trimethylphenyl) methoxy group,
(3,4,5-trimethylphenyl) methoxy group,
(2,3,4,5-tetramethylphenyl) methoxy, (2,3,4,6-tetramethylphenyl) methoxy, (2,3,5,6-tetramethylphenyl) methoxy, (penta (Methylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n
-Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-
Examples thereof include an octylphenyl) methoxy group, an (n-decylphenyl) methoxy group, a naphthylmethoxy group, and an anthracenylmethoxy group, and more preferably a benzyloxy group. All of these aralkyloxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The aryloxy group has 6 carbon atoms.
To 20 aryloxy groups, for example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5 -Dimethylphenoxy group, 2,6-dimethylphenoxy group,
3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group Group,
2-tert-butyl-6-methylphenoxy group, 2,
3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6
-Trimethylphenoxy group, 2-tert-butyl-
3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-te
rt-butyl-3-methylphenoxy group, 2-tert
-Butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,
4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,
4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,
4,6-trimethylphenoxy group, 2,6-di-ter
t-butyl-3,4-dimethylphenoxy group, 2,3
5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-
Di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group,
n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecyl Examples include a phenoxy group, a naphthoxy group, and an anthracenoxy group. All of these aryloxy groups are a fluorine atom, a chlorine atom,
A halogen atom such as a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group may be partially substituted.

The heterocyclic group is a group having a heterocyclic ring.
A group having an 8-membered heterocyclic ring is preferable, and a 4- to 8-membered ring is preferred.
Groups having an aromatic heterocycle are more preferred. Included in the heterocycle
Nitrogen, oxygen or sulfur atoms
Children are preferred. Specific examples of such a heterocyclic group include, for example,
Such as indolyl, furyl, thienyl, pyridyl,
Piperidyl group, quinolyl group, isoquinolyl group, etc.
More preferably, as a specific example of such a heterocyclic group
It is a furyl group. All of these heterocyclic groups are fluorine
Halogen such as atom, chlorine atom, bromine atom and iodine atom
Atom, methoxy group, ethoxy group, etc.
Aryloxy group such as nonoxy group or benzyloxy
Partially substituted with an aralkyloxy group such as
You may.

Specific examples of the transition metal compound represented by the general formula (4) include methylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl)
Zirconium dichloride, isopropylidenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, diphenylmethylenebis (indenyl) zirconium dichloride,

Methylenebis (2-methylindenyl) zirconium dichloride, methylenebis (2-n-propylindenyl) zirconium dichloride, methylenebis (2-n-butylindenyl) zirconium dichloride, methylenebis (2-n-hexylindenyl)
Zirconium dichloride, methylene bis (2-isopropylindenyl) zirconium dichloride, methylene bis (2-isobutylindenyl) zirconium dichloride, methylene bis (2-tert-butylindenyl) zirconium dichloride, methylene bis (2-
Phenylindenyl) zirconium dichloride, methylenebis (2-trimethylsilylindenyl) zirconium dichloride, methylenebis (2,4-dimethylindenyl) zirconium dichloride, methylenebis (2,4,7-trimethylindenyl) zirconium dichloride, methylenebis (2- Methyl-4-isopropylindenyl) zirconium dichloride, methylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, methylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, methylenebis (2-methyl-4,5 -Benzoindenyl) zirconium dichloride, methylenebis (4,5,6,7
-Tetrahydroindenyl) zirconium dichloride,

Ethylene bis (2-methylindenyl) zirconium dichloride, ethylene bis (2-n-propylindenyl) zirconium dichloride, ethylene bis (2-n-butylindenyl) zirconium dichloride, ethylene bis (2-n- Hexylindenyl)
Zirconium dichloride, ethylene bis (2-isopropylindenyl) zirconium dichloride, ethylene bis (2-isobutylindenyl) zirconium dichloride, ethylene bis (2-tert-butylindenyl) zirconium dichloride, ethylene bis (2-
Phenylindenyl) zirconium dichloride, ethylenebis (2-trimethylsilylindenyl) zirconium dichloride, ethylenebis (2,4-dimethylindenyl) zirconium dichloride, ethylenebis (2,4,7-trimethylindenyl) zirconium dichloride, ethylene Bis (2-methyl-4-isopropylindenyl) zirconium dichloride, ethylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, ethylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, ethylenebis ( 2-methyl-4,5-benzoindenyl) zirconium dichloride, ethylenebis (4,5,6,7
-Tetrahydroindenyl) zirconium dichloride,

Isopropylidenebis (2-methylindenyl) zirconium dichloride, isopropylidenebis (2-n-propylindenyl) zirconium dichloride, isopropylidenebis (2-n-butylindenyl) zirconium dichloride, isopropylidenebis ( 2-n-hexylindenyl) zirconium dichloride, isopropylidenebis (2-isopropylindenyl) zirconium dichloride, isopropylidenebis (2-isobutylindenyl) zirconium dichloride, isopropylidenebis (2-tert-butylindenyl) zirconium Dichloride, isopropylidenebis (2-phenylindenyl) zirconium dichloride, isopropylidenebis (2-trimethylsilylindenyl) dichloride Benzalkonium dichloride, isopropylidene-bis (2,4-dimethyl-indenyl) zirconium dichloride, isopropylidene-bis (2,4,7
Trimethylindenyl) zirconium dichloride, isopropylidenebis (2-methyl-4-isopropylindenyl) zirconium dichloride, isopropylidenebis (2-methyl-4-phenylindenyl) zirconium dichloride, isopropylidenebis (2-methyl-4) -Naphthylindenyl) zirconium dichloride, isopropylidenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, isopropylidenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-n-propylindenyl) zirconium dichloride, dimethylsilylenebis (2-n-butylindenyl) zirconium dichloride, dimethylsilylenebis ( 2-n-hexylindenyl) zirconium dichloride, dimethylsilylenebis (2-isopropylindenyl) zirconium dichloride, dimethylsilylenebis (2-isobutylindenyl) zirconium dichloride, dimethylsilylenebis (2-tert-butylindenyl) zirconium Dichloride, dimethylsilylenebis (2-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-trimethylsilylindenyl) dichloride Benzalkonium dichloride, dimethylsilylene-bis (2,4-dimethyl-indenyl) zirconium dichloride, dimethylsilylene-bis (2,4,7
Trimethylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-isopropylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4) -Naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Diphenylmethylenebis (2-methylindenyl) zirconium dichloride, diphenylmethylenebis (2-n-propylindenyl) zirconium dichloride, diphenylmethylenebis (2-n-butylindenyl) zirconium dichloride, diphenylmethylenebis ( 2-n-hexylindenyl) zirconium dichloride, diphenylmethylenebis (2-isopropylindenyl) zirconium dichloride, diphenylmethylenebis (2-isobutylindenyl) zirconium dichloride, diphenylmethylenebis (2-t
tert-butylindenyl) zirconium dichloride, diphenylmethylenebis (2-phenylindenyl) zirconium dichloride, diphenylmethylenebis (2-trimethylsilylindenyl) zirconium dichloride, diphenylmethylenebis (2,4-dimethylindenyl) zirconium dichloride, Diphenylmethylenebis (2,4,7-trimethylindenyl) zirconium dichloride, diphenylmethylenebis (2
-Methyl-4-isopropylindenyl) zirconium dichloride, diphenylmethylenebis (2-methyl-
4-phenylindenyl) zirconium dichloride,
Diphenylmethylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, diphenylmethylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, diphenylmethylenebis (4,5,6,7-tetrahydroinde Nyl) zirconium dichloride,

Diphenylsilylenebis (2-methylindenyl) zirconium dichloride, diphenylsilylenebis (2-n-propylindenyl) zirconium dichloride, diphenylsilylenebis (2-n-butylindenyl) zirconium dichloride, diphenylsilylenebis ( 2-n-hexylindenyl) zirconium dichloride, diphenylsilylenebis (2-isopropylindenyl) zirconium dichloride, diphenylsilylenebis (2-isobutylindenyl) zirconium dichloride, diphenylsilylenebis (2-t
tert-butylindenyl) zirconium dichloride, diphenylsilylenebis (2-phenylindenyl) zirconium dichloride, diphenylsilylenebis (2-trimethylsilylindenyl) zirconium dichloride, diphenylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, Diphenylsilylenebis (2,4,7-trimethylindenyl) zirconium dichloride, diphenylsilylenebis (2
-Methyl-4-isopropylindenyl) zirconium dichloride, diphenylsilylenebis (2-methyl-
4-phenylindenyl) zirconium dichloride,
Diphenylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, diphenylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, diphenylsilylenebis (4,5,6,7-tetrahydroindene) Nyl) zirconium dichloride. Further, in the above zirconium compound, a compound in which a zirconium atom is replaced with a titanium atom or a hafnium atom can also be exemplified.

Among them, dimethylsilylenebis (2-
Methylindenyl) zirconium dichloride, dimethylsilylenebis (2-n-propylindenyl) zirconium dichloride, dimethylsilylenebis (2-n-
(Butylindenyl) zirconium dichloride, dimethylsilylenebis (2-n-hexylindenyl) zirconium dichloride, dimethylsilylenebis (2-isopropylindenyl) zirconium dichloride, dimethylsilylenebis (2-isobutylindenyl) zirconium dichloride, dimethylsilylene Screw (2-te
rt-butylindenyl) zirconium dichloride,
Dimethylsilylenebis (2-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-trimethylsilylindenyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, dimethylsilylenebis (2,4,7 -Trimethylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-
Isopropylindenyl) zirconium dichloride,
Dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4,5-benzoindenyl) Zirconium dichloride, dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Diphenylsilylenebis (2-methylindenyl) zirconium dichloride, diphenylsilylenebis (2-n-propylindenyl) zirconium dichloride, diphenylsilylenebis (2-n-butylindenyl) zirconium dichloride, diphenylsilylenebis ( 2-n-hexylindenyl) zirconium dichloride, diphenylsilylenebis (2-isopropylindenyl) zirconium dichloride, diphenylsilylenebis (2-isobutylindenyl) zirconium dichloride, diphenylsilylenebis (2-t
tert-butylindenyl) zirconium dichloride, diphenylsilylenebis (2-phenylindenyl) zirconium dichloride, diphenylsilylenebis (2-trimethylsilylindenyl) zirconium dichloride, diphenylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, Diphenylsilylenebis (2,4,7-trimethylindenyl) zirconium dichloride, diphenylsilylenebis (2
-Methyl-4-isopropylindenyl) zirconium dichloride, diphenylsilylenebis (2-methyl-
4-phenylindenyl) zirconium dichloride,
Diphenylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, diphenylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, diphenylsilylenebis (4,5,6,7-tetrahydroindene) Compounds in which the bridging group Y in the general formula (4) is a disubstituted silicon atom, such as (nyl) zirconium dichloride, are preferred.

In the above general formula (5), (R ² _n -C ₅
H _4-n ) and (R ² _q -C ₅ H _4-q ) are each substituted η ⁵
-Cyclopentadienyl group, n and q are 1 to 3
Is an integer. Each R ² may be the same or different from each other, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, show an aryloxy group or a heterocyclic group, a substituted eta ⁵ The position and / or type of R ^{2 in} the cyclopentadienyl group is chosen such that there is no plane of symmetry containing M.

The halogen atom, the alkyl group, the aralkyl group, the aryl group, the substituted silyl group, the alkoxy group, the aralkyloxy group, the aryloxy group and the heterocyclic group are the same as those described in the above formula (4). It is. R ² is preferably an alkyl group or a heterocyclic group.

N and q are integers of 1 to 3, respectively. Having such R ² , the position and / or type of R ² in the substituted η ⁵ -cyclopentadienyl group is selected such that there is no plane of symmetry containing M (R ² _n -C ₅ H _{4 -n} ).
Or as the _{^{(R 2 q -C 5 H 4}} -q), such as 2-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-propyl-cyclopentadienyl group, 2
-Isopropylcyclopentadienyl group, 2-n-butylcyclopentadienyl group, 2-isobutylcyclopentadienyl group, 2-tert-butylcyclopentadienyl group, 2-n-hexylcyclopentadienyl group, 3
-Methylcyclopentadienyl group, 3-ethylcyclopentadienyl group, 3-n-propylcyclopentadienyl group, 3-isopropylcyclopentadienyl group, 3-
n-butylcyclopentadienyl group, 3-isobutylcyclopentadienyl group, 3-tert-butylcyclopentadienyl group, 3-n-hexylcyclopentadienyl group,

2,3-dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3
-Di-n-propylcyclopentadienyl group, 2,3-
Diisopropylcyclopentadienyl group, 2,3-di-
n-butylcyclopentadienyl group, 2,3-diisobutylcyclopentadienyl group, 2,3-di-tert-
Butylcyclopentadienyl group, 2,3-di-n-hexylcyclopentadienyl group, 2,4-dimethylcyclopentadienyl group, 2,4-diethylcyclopentadienyl group, 2,4-di- n-propylcyclopentadienyl group, 2,4-diisopropylcyclopentadienyl group, 2,4-di-n-butylcyclopentadienyl group,
2,4-diisobutylcyclopentadienyl group, 2,4
-Di-tert-butylcyclopentadienyl group, 2,
4-di-n-hexylcyclopentadienyl group, 3,5
-Dimethylcyclopentadienyl group, 3,5-diethylcyclopentadienyl group, 3,5-di-n-propylcyclopentadienyl group, 3,5-diisopropylcyclopentadienyl group, 3,5-di -N-butylcyclopentadienyl group, 3,5-diisobutylcyclopentadienyl group, 3,5-di-tert-butylcyclopentadienyl group, 3,5-di-n-hexylcyclopentadienyl group ,

2-ethyl-3-methylcyclopentadienyl group, 2-methyl-3-ethylcyclopentadienyl group, 2-methyl-3-n-propylcyclopentadienyl group, 2-methyl-3- Isopropylcyclopentadienyl group, 2-ethyl-3-isopropylcyclopentadienyl group, 2-methyl-3-n-butylcyclopentadienyl group, 2-methyl-3-isobutylcyclopentadienyl group, 2- Methyl-3-tert-butylcyclopentadienyl group, 2-methyl-3-n-hexylcyclopentadienyl group, 2-ethyl-4-methylcyclopentadienyl group, 2-methyl-4-ethylcyclopenta Dienyl group, 2-methyl-4-n-propylcyclopentadienyl group, 2-methyl-4-isopropylcyclopentadienyl group, 2 Ethyl-4-isopropylcyclopentadienyl group, 2-methyl-4-n-butylcyclopentadienyl group, 2-methyl-4-isobutylcyclopentadienyl group, 2-methyl-4-tert-butylcyclopenta Dienyl group, 2-methyl-4-n-hexylcyclopentadienyl group 3-ethyl-5-methylcyclopentadienyl group, 3-
Methyl-5-ethylcyclopentadienyl group, 3-methyl-5-n-propylcyclopentadienyl group, 3-methyl-5-isopropylcyclopentadienyl group, 3-
Ethyl-5-isopropylcyclopentadienyl group, 3
-Methyl-5-n-butylcyclopentadienyl group, 3
-Methyl-5-isobutylcyclopentadienyl group, 3
-Methyl-5-tert-butylcyclopentadienyl group, 3-methyl-5-n-hexylcyclopentadienyl group, 2,3,5-trimethylcyclopentadienyl group, 2,4,5-trimethylcyclo Pentadienyl group,
Examples thereof include a 2- (2-furyl) -3,5-dimethylcyclopentadienyl group and a 2- (2-furyl) -4,5-dimethylcyclopentadienyl group.

In the above general formula (5), Y ² is a carbon atom, a silicon atom, a germanium atom or a tin atom, preferably a carbon atom or a silicon atom.

In the above general formula (5), R ³ and X
Is a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group,
It is an aralkyloxy group, an aryloxy group or a heterocyclic group, and all of R ³ and X may be the same or different. The halogen atom, the alkyl group, the aralkyl group, the aryl group, the substituted silyl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the heterocyclic group are the same as those already described as R ² .

R ³ is preferably a hydrogen atom or an alkyl group. X is preferably a halogen atom, an alkyl group, an aralkyl group or an alkoxy group.

Specific examples of the transition metal compound represented by the general formula (5) include dimethylsilylene (cyclopentadienyl) (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3,5 -Trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (3-methylcyclopentadienyl)
(4-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene (3-tert-butylcyclopentadienyl) (4-tert-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) Enil)
(3,5-dimethylsilylenecyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3
5-trimethylcyclopentadienyl) (2,4,5-
Trimethylcyclopentadienyl) zirconium dichloride,

Methylene (cyclopentadienyl) (3-
Methylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3-tert
-Butylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (2,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (2,3,5-
Trimethylcyclopentadienyl) zirconium dichloride, methylene (3-methylcyclopentadienyl)
(4-methylcyclopentadienyl) zirconium dichloride, methylene (3-tert-butylcyclopentadienyl) (4-tert-butylcyclopentadienyl) zirconium dichloride, methylene (2,4
-Dimethylcyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, methylene (2,3,5-trimethylcyclopentadienyl) (2,4,5-trimethylcyclopentadienyl)
Zirconium dichloride and the like. Also,
In the above-mentioned zirconium compound, a compound in which a zirconium atom is replaced with a titanium atom or a hafnium atom can also be exemplified.

In the present invention, these transition metal compounds may be used alone or in combination of two or more.

(C) Organometallic Compound The component (C) organometallic compound is represented by the general formula (1).
And at least one compound represented by the following formula:
It is preferable to use More preferably, the following general
An organoaluminum compound represented by the formula (3). R^Three _bAlY_3-b (3)  (However, R^ThreeIs a hydrocarbon group having 1 to 8 carbon atoms, Al
Represents an aluminum atom. Y is a hydrogen atom and / or
Represents a halogen atom, and b represents a number satisfying 0 <b ≦ 3.
You. )

Specific examples of R ³ in the general formula (3) representing an organoaluminum compound include a methyl group, an ethyl group, a normal propyl group, a normal butyl group, an isobutyl group, a normal hexyl group, a 2-methylhexyl group,
Examples include a normal octyl group, and preferably an ethyl group, a normal butyl group, an isobutyl group, and a normal hexyl group. Specific examples of the case where Y is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

Specific examples of the organoaluminum compound represented by the general formula (3) include trimethylaluminum, triethylaluminum, trinormal propylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum,
Trialkylaluminum such as trinormal octyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, dinormal propyl aluminum chloride, dinormal butyl aluminum chloride, diisobutyl aluminum chloride, dialkyl aluminum chloride such as dinormal hexyl aluminum chloride, methyl aluminum dichloride, ethyl Alkyl aluminum dichloride such as aluminum dichloride, normal propyl aluminum dichloride, normal butyl aluminum dichloride, isobutyl aluminum dichloride, normal hexyl aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride,
Examples thereof include dialkyl aluminum hydride such as di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, di-iso-butyl aluminum hydride, and di-n-hexyl aluminum hydride. Of these, preferably trialkylaluminum, more preferably trimethylaluminum, triethylaluminum, trinormal butylaluminum, triisobutylaluminum, or trinormal hexylaluminum, more preferably triisobutylaluminum or trinormal hexylaluminum. is there. These organoaluminum compounds may be used alone or in combination of two or more.

The α-olefin polymerization catalyst of the present invention is obtained by contacting the modified particles (A) with the transition metal compound (B) or further with the organometallic compound (C). ) Is generally 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol, preferably 5 × 10 ⁻³ mol, per 1 g of the component (A).
× 10 ^-6 to 1 × 10 ^-4 mol. The amount of the organometallic compound used as the component (C) is 0.1 as a molar ratio (C) / (B) of the metal atom of the component (C) to the transition metal atom of the component (B). 01-1
000, preferably 0.1 to 5,000
Is more preferable, and most preferably 1 to 2,000.

In the present invention, after the component (A) is brought into contact with the α-olefin, the obtained contact product is brought into contact with the components (B) and (C) to polymerize the α-olefin. To produce an α-olefin polymer. The contact condition of the component (A) with the α-olefin is not particularly limited, but the contact temperature is preferably -5 to 90 ° C, more preferably 5 to 50 ° C. The contact is performed with an aliphatic hydrocarbon solvent such as butane, pentane, heptane, or octane, benzene,
It may be carried out in the presence of an aromatic hydrocarbon solvent such as toluene or a halogenated hydrocarbon such as methylene chloride. The α-olefin used for the contact is α-olefin to be produced.
It may be the same as or different from the monomer of the olefin polymer, and two or more α-olefins may be used.

In the present invention, as a monomer used for polymerization, an α-olefin having 3 to 20 carbon atoms can be used, and two or more kinds of monomers can be used simultaneously. Examples of such monomers are shown below, but the present invention should not be limited to these. Specific examples of such α-olefins include propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-
Examples thereof include 1, nonene-1, decene-1, 4-methyl-1-pentene, and vinylcyclohexane.

In the present invention, copolymerization of these α-olefins with a comonomer that can be copolymerized with the α-olefins is also preferably carried out. Examples of comonomers that can be copolymerized with the α-olefin include ethylene and diolefin compounds. Examples of the diolefin compound include a conjugated diene and a non-conjugated diene, and specific examples of such a compound include 1,5-
Hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene,
1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-
1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctane Diene, 5,8-endomethylenehexahydronaphthalene and the like are exemplified.
-Butadiene, isoprene, 1,3-hexadiene,
1,3-octadiene, 1,3-cyclooctadiene,
Examples thereof include 1,3-cyclohexadiene.

The method for producing an α-olefin polymer of the present invention is suitable as a method for producing an isotactic stereoregular α-olefin polymer, and particularly preferable as a method for producing an isotactic stereoregular propylene polymer. It is.

Specific examples of the isotactic stereoregular propylene polymer include a homopolymer of propylene; ethylene and / or an α-olefin having 4 to 12 carbon atoms in such an amount that the crystallinity is not lost. Or a random copolymer with a comonomer such as propylene; or a homopolymer of propylene or a copolymer of propylene and ethylene or an α-olefin having 4 to 12 carbon atoms (this is referred to as “pre-stage polymerization”) and then the number of carbon atoms Block copolymers in which 3 to 12 α-olefins and ethylene are polymerized in one or more stages (this is referred to as “post-stage polymerization”). The amount that does not lose crystallinity in the random copolymer depends on the type of comonomer. For example, in the case of ethylene, the amount of the repeating unit derived from ethylene in the copolymer is usually 10% by weight or less, In the case of other α-olefins such as butene, the amount of the repeating unit derived from the α-olefin in the copolymer is usually 30% by weight.
Or less, preferably 10% by weight or less. In the case of the first-stage polymerization in the block copolymer, for example, the polymerization amount of ethylene is usually 10% by weight or less, preferably 3% by weight or less, more preferably 0.5% by weight or less, and the polymerization amount of α-olefin is usually It is 15% by weight or less, preferably 10% by weight or less, and in the case of the second-stage polymerization, the polymerization amount of ethylene is usually 20 to 80% by weight, preferably 30 to 50% by weight.

Specific examples of the combination of monomers constituting the copolymer include propylene and ethylene, propylene and butene-1, and propylene and hexene-1. However, the present invention is not limited to these. It should not be.

An isotactic pentad fraction is used as a measure of isotactic stereoregularity.
The isotactic pentad fraction here is
A. Macromolec by Zambelli et al.
ules, 6, 925 (1973), i.e., isotactic linkage in pentad units in crystalline polypropylene molecular chains measured using ¹³ C-NMR, in other words, propylene monomer units. 5
It is the fraction of propylene monomer units at the center of a chain of meso-bonds that are consecutively formed. However, regarding the assignment of NMR absorption peaks, Macromole published afterwards
cules, 8, 687 (1975). The isotactic pentad fraction is "mm
mm% ". The theoretical upper limit of mmmm% is 1.000. In the method for producing an α-olefin polymer of the present invention, the mmmm% is 0.900 or more (more preferably 0.940 or more, even more preferably 0.95% or more).
5 or more) is preferable as a method for producing an isotactic stereoregular α-olefin polymer.

The polymerization method is not particularly limited, either.
Gas-phase polymerization in a gaseous monomer, solution polymerization using a solvent, slurry polymerization, and the like are possible. Examples of the solvent used for solution polymerization or slurry polymerization include aliphatic hydrocarbon solvents such as butane, pentane, heptane, and octane; aromatic hydrocarbon solvents such as benzene and toluene; and halogenated hydrocarbon solvents such as methylene chloride. And
Or use olefin itself as solvent (bulk polymerization)
It is also possible. The polymerization method may be either batch polymerization or continuous polymerization, and the polymerization may be performed in two or more stages under different reaction conditions. In general, the polymerization time is appropriately determined depending on the kind of the target olefin polymer and the reaction apparatus, but can range from 1 minute to 20 hours.

The present invention is particularly suitably applied to polymerization involving formation of α-olefin polymer particles (eg, slurry polymerization, gas phase polymerization, bulk polymerization, etc.). The slurry polymerization may be performed according to a known slurry polymerization method and polymerization conditions, but is not limited thereto. As a preferable polymerization method in the slurry method, a continuous reactor in which a monomer (and a comonomer), a feed, a diluent, and the like are continuously added as necessary, and a polymer product is continuously or at least periodically removed. included. Examples of the reactor include a method using a loop reactor, a plurality of stirred reactors having different reactors, and different reaction conditions in series or in parallel, or a combination thereof.

As a diluent, for example, an inert diluent (medium) such as paraffin, cycloparaffin or aromatic hydrocarbon can be used. The temperature of the polymerization reactor or reaction zone can usually range from about 0C to about 150C, preferably from 30C to 100C. The pressure can usually be varied from about 0.1 MPa to about 10 MPa, preferably from 0.5 MPa to 5 MPa. The catalyst can be kept in suspension, the medium and at least some of the monomers and comonomers can be maintained in a liquid phase, and pressure can be applied to bring the monomers and comonomers into contact. Thus, the medium, temperature, and pressure may be selected so that the α-olefin polymer is produced as solid particles and recovered in that form.

The molecular weight of the α-olefin polymer can be controlled by various known means such as adjusting the temperature of the reaction zone and introducing hydrogen. Each catalyst component, monomer (and comonomer) can be added to the reactor or reaction zone by any known method and in any order. For example,
A method of simultaneously adding each catalyst component and a monomer (and a comonomer) to the reaction zone, a method of sequentially adding the catalyst components, and the like can be used. If desired, each catalyst component can be pre-contacted in an inert atmosphere before contacting with the monomer (and comonomer).

The gas phase polymerization may be carried out according to known gas phase polymerization methods and polymerization conditions, but is not limited thereto. As the gas phase polymerization reactor, a fluidized bed type reaction vessel, preferably a fluidized bed type reaction vessel having an enlarged portion is used.
There is no problem even in a reactor in which a stirring blade is installed in the reaction tank. As a method of supplying each component to the polymerization tank, nitrogen,
Using an inert gas such as argon, hydrogen, ethylene, etc.,
A method of supplying in a state of no water, or dissolving or diluting in a solvent and supplying in a solution or slurry state can be used. Each catalyst component may be supplied individually, or any components may be contacted in any order in advance and supplied.

As the polymerization conditions, the temperature is lower than the temperature at which the polymer melts, preferably from 0 ° C to 150 ° C, particularly preferably from 30 ° C to 100 ° C. Further, hydrogen may be added as a molecular weight modifier for the purpose of adjusting the melt fluidity of the final product. In addition, at the time of polymerization, an inert gas may be allowed to coexist in the mixed gas.

In the present invention, the following prepolymerization may be performed before performing such polymerization (main polymerization).

The prepolymerization is carried out by supplying a small amount of olefin in the presence of the modified particles (A) and the transition metal compound (B), or furthermore, the organometallic compound (C). Is preferred. Examples of the solvent used for slurrying include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, when the slurry is formed, a liquid olefin can be used instead of part or all of the inert hydrocarbon solvent.

The amount of the organometallic compound used in the prepolymerization is as follows:
It can be selected from a wide range such as 0.5 to 700 mol per mol of the transition metal compound, but is preferably 0.8 to 500 mol, particularly preferably 1 to 200 mol.

The amount of the olefin to be prepolymerized is
Usually 0.01 to 1000 g per 1 g of modified particles,
Preferably 0.05 to 500 g, particularly preferably 0.1 g.
~ 200 g.

The slurry concentration for performing the prepolymerization is 1 to
500 g-modified particles / liter-solvent is preferred, especially 3-300 g-modified particles / liter-solvent. The prepolymerization temperature is preferably from -20 to 100C, particularly preferably from 0 to 80C. The partial pressure of the olefin in the gas phase during the prepolymerization is 0.001 to 2MPa.
a is preferable, and particularly preferably 0.01 to 1 MPa,
This does not apply to olefins that are liquid at the pressure and temperature of the prepolymerization. Further, the prepolymerization time is not particularly limited, but is usually preferably 2 minutes to 15 hours.

After the prepolymerization as described above or without the prepolymerization, the modified particles (A) and the transition metal compound (B), or further, the organometallic compound (C) are used. The main polymerization of α-olefin can be carried out in the presence of the α-olefin polymerization catalyst.

[0109]

The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The properties of the olefin polymer in the examples were measured by the following methods.

(1) Molecular Weight and Molecular Weight Distribution: Gel Permeation Chromatograph (1 by Waters)
50, C) under the following conditions. The molecular weight distribution (Mw / Mn) was represented by the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn). Column: Shodex AT806-M / S Measurement temperature: 145 ° C Setting Measurement concentration: 8 mg / 8 ml O-dichlorobenzene

(2) ¹³ C-NMR Measurement 200 mg of the polymer was mixed with 3 ml of a mixed solvent of ortho-dichlorobenzene / heavy-ortho-dichlorobenzene (ortho-dichlorobenzene / heavy-ortho-dichlorobenzene = 4/1 (volume ratio)). ), And measured using JEOL Ltd. JNM-EX270.

Example 1 (1) Contact treatment between particles (a) and organometallic compound (b) A 5-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer was dried under reduced pressure, and then dried under nitrogen. Replaced. The flask was heated at 300 ° C. under a stream of nitrogen and heated at 300 ° C. (Davison # 948; average particle diameter = 55.0).
μm; geometric standard deviation based on volume of particle size = 1.52; pore volume = 1.60 ml / g; specific surface area = 310 m ² / g)
366 g were collected. Thereto was added 3.3 liters of toluene to form a slurry, which was cooled to 5 ° C. using an ice bath, and 366 ml of a toluene solution of trimethylaluminum adjusted to a concentration of 2 mmol / ml was gradually added dropwise. At that time, gas generation was observed. 30 minutes at 5 ° C
After stirring at 80 ° C. for 2 hours, the supernatant was filtered, and the remaining solid component was washed four times with 80 ° C. and 3.3 liters of toluene.

(2) Compound (c) treatment After the treatment of the above (1), 3.3 liters of toluene was added thereto to form a slurry, and the slurry was cooled to 5 ° C. using an ice bath, and the concentration was adjusted to 2 mmol / ml. 400 ml of the prepared toluene solution of pentafluorophenol was slowly added. At that time, gas generation was observed. 30 minutes at 5 ° C,
After stirring at 80 ° C. for 2 hours, the supernatant was filtered, and the remaining solid component was washed four times with 80 ml of toluene at 3.3 liters, and further washed with 3.3 liters of hexane at room temperature. Times. Thereafter, the solid component was dried under reduced pressure to obtain 489 g of a fluid solid component.

(3) Propylene Polymerization After drying under reduced pressure, 1 part of toluene was placed in a 3 liter stainless steel autoclave equipped with a stirrer and purged with argon.
Then, after charging 29.7 mg of the solid component (catalyst component (A)) obtained in the above (2) and 100 g of propylene, the temperature was raised to 40 ° C. Then, in another stainless steel container, the concentration was 1 m as the catalyst component (C).
1.4 ml of a toluene solution of triisobutylaluminum adjusted to mol / ml and a toluene solution of dimethylsilylbis (2-methyl-1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml as the catalyst component (B) After contacting with 05 ml, the mixture was charged into the autoclave and polymerization was carried out at 40 ° C.
During the polymerization, propylene is continuously fed to increase the total pressure to 0.6M.
Pa was maintained. Twenty minutes later, 10 ml of isobutanol was added to terminate the polymerization, and unreacted monomers were purged. The resulting polymer was dried under reduced pressure at 60 ° C. for 5 hours,
2 g of polypropylene powder were obtained. Therefore, 1 mol of the transition metal compound and the yield of polypropylene per one hour of polymerization (hereinafter abbreviated as g-PP / mol-Zr · hr)
Is g-PP / mol-Zr · hr = 8.9 × 10 ⁷ , and the stereoregularity of the obtained propylene polymer is mmmm% =
0.964%. Table 1 shows the polymerization results.

Example 2 (1) Polymerization of Propylene The amount of the solid component (catalyst component (A)) used was 76.4 mg.
Example 1 (3) except that the polymerization time was changed to 60 minutes.
Polymerization of propylene was carried out in the same manner as described above. Table 1 shows the polymerization results.
It was shown to.

Comparative Example 1 (1) Polymerization of Propylene After drying under reduced pressure, 1 part of toluene was placed in a 3-liter stainless steel autoclave with a stirrer and purged with argon.
After charging liter and then 100 g of propylene, the temperature was raised to 40 ° C. Then, in another stainless steel container, 31.5 mg of the solid component obtained in Example 1 (2) was used as the catalyst component (A), and the concentration was 1 as the catalyst component (C).
2.1 ml of a toluene solution of triisobutylaluminum adjusted to mmol / ml, and a toluene solution of dimethylsilylbis (2-methyl-1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml as the catalyst component (B) After contacting with 05 ml, the mixture was charged into the autoclave and polymerization was carried out at 40 ° C. During the polymerization, propylene is continuously fed to reduce the total pressure to 0.1.
It was kept at 6 MPa. After 60 minutes, isobutanol 10m
After adding 1 to terminate the polymerization, unreacted monomers were purged. The produced polymer was dried under reduced pressure at 60 ° C. for 5 hours to obtain 31 g of polypropylene powder. Table 1 shows the polymerization results.

Comparative Example 2 (1) Polymerization of Propylene After drying under reduced pressure, 1 part of toluene was placed in a 3-liter stainless steel autoclave equipped with a stirrer and purged with argon.
After charging liter and then 100 g of propylene, the temperature was raised to 40 ° C. Then, a toluene solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml as a catalyst component (C) in another stainless steel container
2.1 ml, and a concentration of 2 μm as the catalyst component (B)
ol / ml of a toluene solution of dimethylsilylbis (2-methyl-1-indenyl) zirconium dichloride (1.05 ml) was brought into contact with the autoclave, and then charged into the autoclave. Solid component obtained in (2) 3
The toluene slurry to which 1.1 mg was added was charged into the autoclave, and polymerization was performed at 40 ° C. During the polymerization, propylene was continuously fed to maintain the total pressure at 0.6 MPa.
After 60 minutes, 10 ml of isobutanol was added to terminate the polymerization, and unreacted monomers were purged. The produced polymer was dried under reduced pressure at 60 ° C. for 5 hours to obtain 0.25 g of polypropylene powder. Table 1 shows the polymerization results.

[0118]

[Table 1]

[0119]

According to the present invention, a more efficient method for producing an α-olefin polymer using a single-site catalyst is 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 front page F-term (reference) 4J028 AA01A AB00A AB01A AC01A AC10A AC28A BA00A BA01B BA02B BB00A BB01B BB02B BC03B BC04B BC05B BC06B BC07B BC13B BC15B BC16B BC17B BC18B BC19C CA28C CAC CACAC CAC CAC CAC CAC CB15C CB22C CB23C CB24C CB25C CB36C CB54C CB56C CB62C CB63C CB64C CB68C CB82C CB83C CB84C CB86C CB87C CB88C CB89C EB01 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EB12 EB13 EB14 EB16 EB18 EB26 GA01 GA06 GA14 GB01 4J128 AA01 AB00 AB01 AC01 AC10 AC28 AD00 BA00A BA01B BA02B BB00A BB01B BB02B BC03B BC04B BC05B BC06B BC07B BC13B BC15B BC16B BC17B BC18B BC19B CA15C CA16C CA24C CA25C CA26C CA27C CA28C CA29C CA30C CA36C CA37C CA38C CA44C CA49C CB08C CB09C CB12C CB15C CB22C CB23C CB24C CB25C CB36C CB54C CB56C CB62C CB63C CB64C CB68C CB82C CB83C CB84C CB86C CB87C CB88C CB89C EB01 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EB12 EB13 EB14 EB16 EB18 EB26 GA01 GA06 GA14 GB01

Claims (4)

[Claims] A dried particle (a) is brought into contact with an organometallic compound (b) and has a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and an electron-withdrawing group. After bringing the modified particles (A) obtained by contacting the compound (c) into contact with an α-olefin, the obtained contact product and a transition metal compound having a stereoregular polymerization ability of the α-olefin A method for producing a stereoregular α-olefin polymer, which comprises contacting (B) and an organometallic compound (C) to polymerize an α-olefin. 2. The compound (c) having a functional group having an active hydrogen or a non-proton-donating Lewis basic functional group and an electron-withdrawing group is a compound represented by the following general formula (2). The method for producing a stereoregular α-olefin polymer according to claim 1, wherein R ² _m ZH _zm (2) (wherein, R ² represents an electron-withdrawing group or a group containing an electron-withdrawing group, Z represents an atom of Group 15 or 16 of the periodic table, and H represents Represents a hydrogen atom, z is a valence of Z and is 2 or 3, when z is 2, m is 1, and z is
Is 3 when m is 1 or 2. ) 3. The transition metal compound (B) having the stereoregular polymerization ability of an α-olefin is a transition metal compound represented by the following general formula (4) or (5). Or the method for producing a stereoregular α-olefin polymer according to 2 above. (Wherein, M is a transition metal atom of Group 4 of the periodic table, L is an η ⁵ -indenyl group or a substituted η ⁵ -indenyl group, and two Ls may be the same or different. Y is a bridging group connecting two L, and two X ² are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, and an aryloxy group. Or a heterocyclic group.) (Wherein, M is a transition metal atom of Group 4 of the periodic table, and Y ²
Silicon atom, a germanium atom or a tin _{^{atom, (R 2 n -C 5 H}} 4-n) and _{^{(R 2 q -C 5 H 4}} -q) each substituted eta ⁵ - be a cyclopentadienyl group , N and q are each an integer of 1 to 3. Each R ² may be the same or different from each other, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, show an aryloxy group or a heterocyclic group, a substituted eta ⁵ The position and / or type of R ^{2 in} the cyclopentadienyl group is chosen such that there is no plane of symmetry containing M. R ³ and X are each a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, an aryloxy group or a heterocyclic group, R ³ and X are all the same Or different from each other. ) 4. The method for producing a stereoregular α-olefin polymer according to claim 1, wherein the α-olefin is propylene.