JP2001247613A - Modified particle, support comprising the same, olefin polymerization catalyst component comprising the same, olefin polymerization catalyst comprising the same, and process for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide particles that contains a transition metal compound and can give a high-molecular-weight polymer excellent in shape and particle properties in high activity when it is applied to polymerization involving the formation of polymer particles (for example, slurry polymerization or vapor phase polymerization); a support comprising the particles; an olefin polymerization catalyst component comprising the particles; an olefin polymerization catalyst comprising the particles; and a process for producing an olefin polymer comprising using the olefin polymerization catalyst. SOLUTION: There are provided modified particles obtained by bringing (a) particles into contact with (b) a compound of an atom in the lanthanoid series and bringing the product of contact into further contact with (c) a compound having a non-proton- donating Lewis acid functional group or an electron-attracting group; a support comprising the modified particles; an olefin polymerization catalyst component comprising the modified catalyst; an olefin polymerization catalyst comprising (A) the modified particles, (B) a transition metal compound, and optionally (C) an organometallic compound; and a process for producing an olefin polymer comprising using the olefin polymerization catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to particles useful as a carrier and a catalyst component for olefin polymerization, a catalyst for olefin polymerization using the same, and a method for producing an olefin polymer using the catalyst for olefin polymerization.

[0002]

2. Description of the Related Art Olefin polymers such as polypropylene and polyethylene are widely used in various molding fields because of their excellent mechanical properties, chemical resistance, etc., and their excellent balance between properties and economy. I have. Conventionally, these olefin polymers are obtained by combining a solid catalyst component mainly obtained using a Group 4 metal compound such as titanium trichloride or titanium tetrachloride with a Group 13 metal compound represented by an organoaluminum compound. It has been produced by polymerizing olefins using a so-called Ziegler-Natta catalyst (multi-site catalyst).

In recent years, a so-called single-site catalyst in which a transition metal compound (for example, a metallocene complex or a non-metallocene compound) different from a solid catalyst component which has been used for a long time and an aluminoxane is used to polymerize an olefin is used. A method of manufacturing the united body has been proposed. For example, JP-A-58-19309 reports a method using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane.
It has also been reported to combine certain boron compounds with such transition metal compounds. For example, Table 1-5
02036 reports a method using bis (cyclopentadienyl) zirconium dimethyl and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate. Olefin polymers obtained with these single-site catalysts have a narrower molecular weight distribution than those obtained with conventional solid catalysts (multi-site catalysts), and in the case of copolymers, the comonomers are more uniformly copolymerized. Therefore, it is known that a more homogeneous olefin polymer can be obtained than when a conventional solid catalyst is used.

[0004] Usually, catalysts using these metallocene complexes or non-metallocene compounds are soluble in the reaction system, and thus are formed when used in polymerization involving formation of polymer particles (for example, slurry polymerization or gas phase polymerization). The shape of the polymer is unstable, resulting in formation of coarse polymer particles, bulk polymer, fine powder polymer, etc., decrease in bulk density of the polymer, adhesion of the polymer to the polymerization reactor wall, and the like. These factors contribute to poor electrical heating and poor heat removal in the reactor, leading to a problem that stable operation is difficult and productivity is reduced.

[0005]

As one of the solutions to this problem, Japanese Patent Laid-Open Publication No. H11-193306 is known, but further improvement in the molecular weight of the resulting polymer has been desired. In view of such circumstances, the purpose of the present invention is to:
By using with a transition metal compound, when an olefin polymerization catalyst using a transition metal compound is applied to polymerization accompanied by formation of polymer particles (for example, slurry polymerization or gas phase polymerization), it has high activity and shape, Particles having excellent particle properties and capable of giving a high molecular weight polymer, a carrier comprising the particles, an olefin polymerization catalyst component comprising the particles,
An object of the present invention is to provide an olefin polymerization catalyst using the particles and a method for producing an olefin polymer using the olefin polymerization catalyst.

[0006]

According to the present invention, there is provided a method for preparing a particle (a)
And a lanthanoid-based compound (b), followed by contact with a compound (c) having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and an electron-withdrawing group. It depends on the quality of the particles. The present invention also provides a carrier comprising the modified particles, a catalyst component for olefin polymerization comprising the modified particles, the modified particles (A) and the transition metal compound (B), or The present invention further relates to a catalyst for olefin polymerization using an organometallic compound (C) and a method for producing an olefin polymer using the catalyst for olefin polymerization. Hereinafter, the present invention will be described in more detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION (a) Particles The modified particles of the present invention are obtained by bringing particles (a) into contact with a lanthanoid-based compound (b), and then contacting a functional group having active hydrogen or a non-proton-donating compound. And a compound (c) having a Lewis basic functional group and an electron-withdrawing group.

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.

Inorganic substance that can be used 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; Allyloxy 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, 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 preferable, and magnesium chloride or butoxymagnesium is more preferable.

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

It is not necessary to remove water from these inorganic substances when they are used, but it is preferable to use those dried by heat treatment. The heat treatment is usually performed at a temperature of 100
~ 1,500 ° C, preferably 100 ~ 1,000 ° C
And more preferably at 200 to 800 ° C.
After heating, for example, a method of flowing a dried inert gas (for example, nitrogen or argon, etc.) at a constant flow rate for several hours or more, or a method of reducing the pressure for several hours, and the like are limited. It will not be done.

The average particle size of the inorganic substance is preferably
5 to 1000 μm, more preferably 10 to 500
μm, and more preferably 10 to 100 μm. The pore volume is preferably 0.1 ml / 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 10 to 1000 m ² / g.
0 to 500 m ² / g.

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 having reactivity with the lanthanoid series compound (b). Examples of such a functional group include a functional group having an active hydrogen, a non-proton donating Lewis basic functional group, and the like. As an organic polymer that can be used for the particles (a), a functional group having an active hydrogen or 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 include a primary amino group, a secondary amino group, an imino group, an amide group, a hydrazide group, an amidino group. , Hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group,
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. These groups may be substituted with 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 is a functional group having a Lewis base moiety having no active hydrogen atom. 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, nitroso, nitro, nitrooxy, furyl, carbonyl, thiocarbonyl, alkoxy, alkyloxycarbonyl,
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. These groups may be substituted with 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 a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups, or one or more other polymerizable unsaturated groups It can be obtained by copolymerizing with a monomer having a saturated group. At this time two more
It is preferable to copolymerize together a crosslinkable polymerizable monomer having at least two 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-mentioned active hydrogen-containing functional group and one or more polymerizable unsaturated groups. Examples of the monomer include a monomer having a polymerizable unsaturated group, and 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 one or more polymerizable unsaturated groups include ethylene, α-olefin, aromatic vinyl compound and the like.
Propylene, butene-1, hexene-1, 4-methyl-
Pentene-1, styrene and the like. Preferably it is ethylene or styrene. These monomers are 2
More than one species may be used. 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.

(B) Lanthanoid series compound The lanthanoid series compound (b) used in the present invention is a compound having a lanthanoid series atom in a molecule, and is preferably a compound represented by the following general formula (1). R ¹ _n AX _an (1) (where A is the periodic table of elements (1993, IUPA
C) is a lanthanoid atom, R ¹ is a hydrocarbon group or a hydrocarbon oxy group, and X is a halogen atom or a hydrogen atom. n is a number satisfying 0 ≦ n ≦ a, and a is the valence of the atom A. )

The lanthanoid atom in the general formula (1) is preferably a lanthanum atom or a samarium atom, particularly preferably a samarium atom.
Specific examples of the hydrocarbon group of R ¹ in the general formula (1) include a methyl group, an ethyl group, a propyl group, a normal butyl group, an isobutyl group, a normal hexyl group, an allyl group,
η ⁵ -cyclopentadienyl group and the like. Specific examples of the hydrocarbonoxy group include a methoxy group, an ethoxy group, a tetra-n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, and a phenoxy group. Group, a pentafluorophenoxy group, etc., more preferably a group having a cyclopentadiene-type anion skeleton, an alkoxy group or an aryloxy group, further preferably an alkoxy group or an aryloxy group, and particularly preferably an alkoxy group. And most preferably an isopropoxy group. X in the above general formula (1) is preferably a halogen atom, specifically, a fluorine atom, a chlorine atom,
Examples thereof include a bromine atom and an iodine atom. Particularly preferred is a chlorine atom. In the general formula (1), a represents an atom A
And preferably 2 to 4.

When A is a trivalent samarium atom, a specific example of the lanthanoid series compound (b) is samarium (II)
I) methoxide, samarium (III) ethoxide, samarium (III) n-propoxide, samarium (III) isopropoxide, samarium (III) n-butoxide, samarium (III) tert-butoxide, samarium (I
II) phenoxide, samarium (III) naphthate, samarium (III) oxalate, samarium (III) 2
4-pentanedionate, samarium (III) 2,2
6,6-tetramethylheptane dionate, tris (cyclopentadienyl) samarium (III), samarium (III) chloride, samarium (III) fluoride, samarium (III) oxide and the like.

When A is a divalent samarium atom, a specific example of the lanthanoid series compound (b) is samasamarium (II) iodine.

The lanthanoid-based compound (b) is preferably a samarium compound in which R ¹ is an alkoxy group or an aryloxy group in the above general formula (1), n is 3 and a is 3, and more preferably Samarium (III) methoxide, samarium (III) ethoxide, samarium (III) n-propoxide, samarium (III) isopropoxide, samarium (III) n-butoxide, samarium (III) tert-butoxide, or samarium (III) Phenoxide, most preferably samarium (III) isopropoxide.

(C) Compound having an active hydrogen-containing functional group or a non-proton-donating Lewis basic functional group and an electron-withdrawing group The functional group having an active hydrogen of the compound (c) used in the present invention Alternatively, the non-proton donating Lewis basic functional group usually reacts with the lanthanoid series compound (b). 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 electron 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.

The compound (c) may have a plurality of types 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, wherein z is the 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 represented by 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, (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 amine in the above specific examples with phosphine.

As specific examples of compound (c), alcohols include 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. A thiol compound in which an oxygen atom is substituted by a sulfur atom can also be exemplified. These thiol compounds are, for example, the compounds described above by rewriting methanol to methanethiol, ethanol to ethanethiol, and propanol to propanethiol.

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 of the above-mentioned specific examples into thiophenol.

Specific examples of compound (c) include carboxylic acids such as 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.

Specific examples of the compound (c) include sulfonic acids such as 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 particles (a) into contact with a lanthanoid compound (b), and then contacting a functional group having active hydrogen or an aprotic donor. And a compound (c) having a 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. Processing temperature is usually -80 ° C ~
The temperature is 200C, preferably -20C to 180C, more preferably 0C to 150C. The processing time is generally 1 minute to 48 hours, preferably 10 minutes to 24 hours. Preferably, a solvent is used, but 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.
As the aromatic hydrocarbon solvent, benzene, toluene,
Xylene and the like can be mentioned. Alternatively, a mixture of these hydrocarbon solvents arbitrarily can be used.
The contact method between (a) and (b) and the contact method with (c) performed 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 reduced pressure or inert gas The method of drying under circulation, the solvent during the contact treatment,
A method of distilling off under reduced pressure or under the flow of an inert gas may, for example, be mentioned. 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 in the polymerization reaction.

In preparing the modified particles of the present invention,
The amount of (b) used for (a) is such that the atoms of the lanthanoid series compound (b) contained in the particles obtained by contacting (a) and (b) are the same as those contained in 1 g of the particles. Is preferably 0.1 mmol or more, more preferably 0.5 to 20 mmol. The amount of (c) used may be a compound having a functional group having active hydrogen or an aprotic donating Lewis basic functional group and an electron-withdrawing group with respect to the atoms of the lanthanoid series compound (b) contained in 1 g of the particles. (C)
The molar ratio (c) / (b) is preferably 0.01 to 100, more preferably 0.05 to 20, and even more preferably 0.1 to 10.

The modified particles of the present invention can be used as a carrier for supporting a catalyst component for olefin polymerization such as a transition metal compound, and are suitably used for polymerization accompanied by formation of polymer particles. Further, the modified particles of the present invention can function as a catalyst component for olefin polymerization. Examples of the olefin polymerization catalyst using the modified particles of the present invention include:
One using the modified particles (A) and the transition metal compound (B), or using the modified particles (A), the transition metal compound (B), and the organometallic compound (C) Among them, the latter is more preferable because of its higher activity.

(B) Transition Metal Compound As the transition metal compound used in the present invention, any transition metal compound having an olefin polymerization activity can be used. As the transition metal, the periodic table of elements (1993,
IUPAC) Group 4 or lanthanoid series transition metals are preferred. More preferably, as the transition metal compound,
It is a metallocene transition metal compound.

The metallocene transition metal compound is, for example, a compound represented by the following general formula (3). ML _a R ³ _pa (3) (wherein M is the periodic table of elements (1993, IUPA
It is a transition metal atom of Group 4 or lanthanoid series of C). L is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and at least 1
One is a group having a cyclopentadiene-type anion skeleton. A plurality of L may be the same or different, and may be cross-linked to each other. R ³ is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. a is 0
A number that satisfies <a ≦ p, where p is the valence of the transition metal atom M. )

In the general formula (3) representing a metallocene transition metal compound, M is a periodic table of elements (1993, I
(UPAC) is a transition metal atom belonging to Group 4 or the lanthanoid series. Specific examples thereof include a titanium atom, a zirconium atom, and a hafnium atom as a transition metal atom of Group 4 of the periodic table, and a samarium atom as a lanthanoid-based transition metal atom.
Preferably, it is a titanium atom, a zirconium atom or a hafnium atom.

In the general formula (3) representing a metallocene transition metal compound, L is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and at least one is a group having a cyclopentadiene-type anion skeleton. is there. A plurality of L may be the same or different, and may be cross-linked to each other. Cyclopentadiene Examples of the group having an anionic backbone eta ⁵ - cyclopentadienyl group, eta ⁵ - substituted cyclopentadienyl group or polycyclic group having a cyclopentadiene type anion skeleton, and the like. Examples of the substituent of the η ⁵ -substituted cyclopentadienyl group include a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
Alternatively, a silyl group having 1 to 20 carbon atoms is exemplified. As the polycyclic group having a cyclopentadiene type anion skeleton eta ⁵ - indenyl group and eta ⁵ - fluorenyl group and the like. The hetero atom in the group containing a hetero atom includes a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom and the like. Examples of such a group containing a hetero atom include a hydrocarbon amino group, a hydrocarbon phosphino group, a hydrocarbon oxy group, a hydrocarbon thio group, and the like, preferably an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group. Group, dialkylamino group,
A diarylamino group, a dialkylphosphino group or a diarylphosphino group.

[0056] eta ⁵ - Specific examples of the substituted cyclopentadienyl group, eta ⁵ - methylcyclopentadienyl group, eta ⁵
- ethyl cyclopentadienyl group, eta ⁵ - normal propyl cyclopentadienyl group, eta ⁵ - isopropyl cyclopentadienyl group, eta ⁵ - n-butylcyclopentadienyl group, eta ⁵ - isobutyl cyclopentadienyl group, η ⁵ -secondary butylcyclopentadienyl group, η ^5-
Tertiary butyl cyclopentadienyl group, eta ^5-1,2-
Dimethyl cyclopentadienyl group, eta ^{5-1,3-dimethyl-cyclopentadienyl} group, eta ^{5-1,2,3-trimethyl} cyclopentadienyl group, eta ^{5-1,2,4-tri-methylcyclopentadienyl} enyl, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - trimethylsilyl cyclopentadienyl group and the like.

Specific examples of the polycyclic group having a cyclopentadiene-type anion skeleton include η ⁵ -indenyl group, η ⁵
-2-methylindenyl group, eta ^{5-4-methylindenyl} group, eta ^{5-4,5,6,7-tetrahydroindenyl} group, eta ⁵ - fluorenyl group and the like.

Specific examples of the group containing a hetero atom include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, thiomethoxy group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, and diphenylamino group. Examples include an amino group, a pyrrolyl group, and a dimethylphosphino group.

Groups having a cyclopentadiene-type anion skeleton or groups having a cyclopentadienyl skeleton and a group containing a hetero atom may be cross-linked, in which case an alkylene group such as an ethylene group or a propylene group;
Dimethylmethylene group, substituted alkylene group such as diphenylmethylene group, or silylene group, dimethylsilylene group,
A substituted silylene group such as a diphenylsilylene group or a tetramethyldisilylene group may be present.

R ³ in the general formula (3) representing a metallocene transition metal compound is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. a is a number satisfying 0 <a ≦ p, and p is the valence of the transition metal atom M. Specific examples of R ³ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom as a halogen atom, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, and a normal butyl group as a hydrocarbon group having 1 to 20 carbon atoms. Group, phenyl group, benzyl group and the like. R ³ is preferably a chlorine atom, a methyl group or a benzyl group.

Among the metallocene transition metal compounds represented by the general formula (3), specific examples of the compound in which the transition metal atom M is a zirconium atom include bis (cyclopentadienyl) zirconium dichloride and bis (cyclopentadienyl) zirconium dichloride. Methylcyclopentadienyl) zirconium dichloride, bis (normalbutylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis ( (Indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, Chirenbisu (2-methylindenyl) zirconium dichloride, ethylenebis (4,
5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (4,5,6, 7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, (cyclopentadienyl)
(Dimethylamide) zirconium dichloride, (cyclopentadienyl) (phenoxy) zirconium dichloride, dimethylsilyl (tert-butylamide)
(Tetramethylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl , Bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, bis (fluorenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, dimethylsilyl (ter
(t-butylamide) (tetramethylcyclopentadienyl) zirconium dimethyl and the like. Further, compounds in which zirconium is replaced with titanium or hafnium in the above zirconium compounds can also be exemplified. One of these metallocene transition metal compounds may be used alone, or two or more thereof may be used in combination.

(C) Organoaluminum Compound As the component (C) organoaluminum compound used in the present invention, a known organoaluminum compound can be used. Preferably, it is an organoaluminum compound represented by the following general formula (4). R ⁴ _b AlY _3-b (4) (where R ⁴ is a hydrocarbon group having 1 to 8 carbon atoms, Al
Represents an aluminum atom. Y represents a hydrogen atom and / or a halogen atom, and b represents a number satisfying 0 <b ≦ 3. )

Specific examples of R ⁴ in the general formula (4) 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 the like, 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 (4) R ⁴ _b AlY _3-b include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinorma. Trialkylaluminum such as lehexyl aluminum and 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 aluminum dichloride, normal propyl Alkyl aluminum dichloride such as aluminum dichloride, normal butyl aluminum dichloride, isobutyl aluminum dichloride, normal hexyl aluminum dichloride,
Examples thereof include dialkyl aluminum hydride such as dimethyl aluminum hydride, diethyl aluminum hydride, dinormal propyl aluminum hydride, dinormal butyl aluminum hydride, diisobutyl aluminum hydride, dinormal hexyl aluminum hydride, and the like. Of these, preferably trialkyl aluminum, more preferably trimethyl aluminum, triethyl aluminum, tri-normal butyl aluminum,
Triisobutylaluminum or trinormal hexyl aluminum, more preferably triisobutyl aluminum or trinormal hexyl aluminum. These organoaluminum compounds may be used alone or in combination of two or more.

The catalyst for olefin polymerization of the present invention comprises the modified particles (A) and the transition metal compound (B), or the organometallic compound (C). Is usually 1 × 10
⁻⁶ to 1 × 10 ⁻³ mol, preferably 5 × 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). It is preferably from 01 to 10,000, more preferably from 0.1 to 5,000, most preferably from 1 to 2,000.

In the present invention, the component (A) and the component (B), or the component (C) can be charged into the reactor in any order during the polymerization, and used. Any combination may be used after being brought into contact with a reactor in advance and used.

In the present invention, as the monomer used for the polymerization, any of olefins and diolefins having 2 to 20 carbon atoms can be used, and two or more kinds of monomers can be used at the same time. Such monomers are exemplified below, but the present invention should not be limited to the following compounds. Specific examples of such olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-
Nonene, 1-decene, 4-methyl-1-pentene, vinylcyclohexane and the like are exemplified. Examples of the diolefin compound include a conjugated diene and a non-conjugated diene. Specific examples of such a compound include, as a non-conjugated diene, 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-
Examples thereof include cyclooctadiene and 5,8-endomethylenehexahydronaphthalene. Examples of the conjugated diene include:
Examples thereof include 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, and 1,3-cyclohexadiene.

Specific examples of the monomers constituting the copolymer include ethylene and propylene, ethylene and 1-butene,
Combinations of ethylene and 1-hexene and propylene and 1-butene are exemplified, but the present invention should not be limited to the above compounds. The present invention is particularly suitable for producing a copolymer of ethylene and an α-olefin.

In the present invention, an aromatic vinyl compound can be used as a monomer. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, divinylbenzene, and the like.

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
Alternatively, the olefin itself can be used as the solvent. 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. The polymerization time is generally 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 accompanied by formation of polymer particles (for example, slurry polymerization and gas phase polymerization). The slurry polymerization may be performed according to a known slurry polymerization method and polymerization conditions, but is not limited thereto. As a preferred 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 the 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 50C to about 100C, preferably from 60C to 80C. 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 olefin polymer is produced as solid particles and recovered in that form.

The molecular weight of the olefin polymer can be controlled by various known means such as adjusting the temperature of the reaction zone and introducing hydrogen.

The catalyst components, monomers (and comonomers) can be added to the reactor or the reaction zone in any order by any known method. 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 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 for 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 and supplied in any order in advance.

As the polymerization conditions, the temperature is lower than the temperature at which the polymer melts, preferably from 20 ° C. to 100 ° C., particularly preferably from 40 ° C. to 90 ° C. Pressure is 0.1MPa ~
The range of 5MPa is preferable, more preferably 0.3MPa.
a to 4 MPa. 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 coexist in the mixed gas.

[0077]

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

(1) α-Olefin content in copolymer (short-chain branching degree): The α-olefin content (short-chain branching degree) in the obtained polymer was determined from an infrared absorption spectrum. The measurement and calculation are described in the literature (Characterization of polyethylene by infrared absorption spectrum, written by Takayama, Usami et al., Or Die Makromoleculare Chemi
e, 177, according to 461 (1976) McRae, MA, Madams, WF) The method according, alpha-olefin characteristics from absorption for example, 1375 cm ^-1 (propylene), was carried out using a 772cm ^-1. The infrared absorption spectrum was measured using an infrared spectrophotometer (FT-IR7300 manufactured by JASCO Corporation). The degree of short chain branching (SCB) was expressed as the number of short chain branches per 1000 carbons.

(2) Melting point of copolymer: Seiko SSC-
Using 5200, it was determined under the following conditions. Temperature rise: 40 ° C to 150 ° C (10 ° C / min), hold for 5 minutes Cooling: 150 ° C to 40 ° C (5 ° C / min), hold for 10 minutes Measurement: Temperature rise from 40 ° C to 160 ° C (5 ° C / minute) )

(3) Molecular Weight and Molecular Weight Distribution: Gel Permeation Chromatograph (Waters)
150, C) under the following conditions. In addition,
The molecular weight distribution (Mw / Mn) is the weight average molecular weight (Mw)
And the number average molecular weight (Mn). Column: TSK gel GMH-HT Measurement temperature: 145 ° C Setting Measurement concentration: 10 mg / 10 ml-orthodichlorobenzene

Example 1 (1) Contact treatment of particles (a) with a lanthanoid compound (b), followed by treatment with compound (c) 50 ml of a stirrer, a dropping funnel and a thermometer 4
The one-necked flask was dried under reduced pressure and replaced with nitrogen. Silica (Sylopol 948, manufactured by Devison; average particle diameter = 55 μm; pore volume = 1.66 ml / g; specific surface area) heated at 300 ° C. in a nitrogen flow to the flask.
(309 m ^{2 /} g) 1.02 g was collected. 13 ml of toluene was added thereto to form a slurry, and samarium (III)
A solution of 0.668 g (2.04 mmol) of isopropoxide in 17 ml of toluene was gradually added dropwise. After stirring at room temperature for 2 hours, the supernatant was filtered and the remaining solid compound was washed four times with 20 ml of toluene. Then, toluene 30
of pentafluorophenol (2 mol / L, toluene solution) 2.0 ml (4.0 m
mol) was added slowly. After stirring at 80 ° C. for 2 hours, the supernatant was filtered and the remaining solid compound was dissolved in toluene 2
It was washed four times with 0 ml and once with 20 ml of hexane. Thereafter, the solid compound was dried under reduced pressure to obtain a fluid solid compound. The samarium atom concentration in the solid compound is 0.7
3 mmol / g, fluorine atom concentration is 3.9 mmol / g
Met.

(2) Polymerization After drying under reduced pressure, the inside of a 400 ml-volume autoclave equipped with a stirrer, which was purged with argon, was evacuated.
0 ml and 10 ml of 1-hexene were charged and heated to 70 ° C. After that, ethylene was supplied with a partial pressure of 6 kg / cm.
² to stabilize the system and adjust the concentration to 1 mmo.
0.25 ml of a solution of triisobutylaluminum in heptane adjusted to 1 / ml was introduced. Next, adjust the concentration to 2 μmo
0.5 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride adjusted to 1 / ml was added, and then 55.1 m of the solid compound obtained in the above (1) was added.
g was charged as a solid catalyst component. The polymerization was carried out at 70 ° C. for 30 minutes while feeding ethylene so as to keep the total pressure constant. 0.87 g of an olefin polymer was obtained.
The polymerization activity per transition metal atom is 1.7 × 10 ⁶ g / m
olZr / hour, the polymerization activity per solid catalyst component was 32
g / g solid catalyst component / hour. The obtained olefin polymer had a melting point of 97.7 ° C. and a temperature of 109.6.
° C, Mw = 190000, Mw / Mn = 3.7. The polymer was particulate.

Comparative Example 1 (1) Contact treatment of particles (a) with trimethylaluminum, followed by treatment with compound (c) 200 ml four-necked flask equipped with a stirrer, dropping funnel and thermometer After drying under reduced pressure, the atmosphere was replaced with nitrogen. 382 g of silica (Syipol 948, manufactured by Devison; average particle diameter = 64 μm; pore volume = 1.62 ml / g; specific surface area = 312 m ² / g) heat-treated at 300 ° C. in a nitrogen stream was collected into the flask. Thereto was added 3.3 L of toluene to form a slurry, which was cooled to 5 ° C. To this, trimethylaluminum 75 ml of toluene 300
ml solution was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 30 minutes. Thereafter, the temperature was raised to 80 ° C., and the mixture was stirred for 2 hours. After the solvent was filtered through a glass filter, it was washed four times with toluene. After washing, 3.3 L of toluene
And cooled to 5 ° C. 420 ml of pentafluorophenol (2.0 M toluene solution) was gradually added dropwise thereto. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 30 minutes. Thereafter, the temperature was raised to 80 ° C., and the mixture was stirred for 2 hours. After filtering the solid compound by filtration, the solid compound was washed four times with toluene and once with hexane. The solid compound obtained as a result is dried under reduced pressure to obtain a solid compound 4 having fluidity.
34 g were obtained. The aluminum atom concentration in the solid compound is 1.22 mmol / g, and the fluorine atom concentration is 4.63 mm
ol / g.

(2) Polymerization After drying under reduced pressure, the inside of a 400 ml-volume autoclave equipped with a stirrer and purged with argon was evacuated, and hexane was added for 19 hours.
0 ml and 10 ml of 1-hexene were charged and heated to 70 ° C. After that, ethylene was supplied with a partial pressure of 6 kg / cm.
² to stabilize the system and adjust the concentration to 1 mmo.
0.25 ml of a solution of triisobutylaluminum in heptane adjusted to 1 / ml was introduced. Subsequently, the concentration was 2μ
0.15 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride adjusted to mol / ml was added, and then the solid compound 10.2 obtained in the above (1) was added.
mg was added as a solid catalyst component. The polymerization was carried out at 70 ° C. for 30 minutes while feeding ethylene so as to keep the total pressure constant. 20.34 g of an olefin polymer was obtained. The polymerization activity per transition metal atom is 1.4 × 10 ⁸ g
/ MolZr / hour, the polymerization activity per solid catalyst component was 4000 g / g solid catalyst component / hour. Further, the obtained olefin polymer had an SCB of 28.40, a melting point of 85.8 ° C. and 96.9 ° C., Mw = 82000, and Mw.
/Mn=2.6.

[0085]

As described in detail above, according to the present invention, by using a transition metal compound, a catalyst for olefin polymerization using a transition metal compound is subjected to polymerization accompanied by formation of polymer particles (for example, slurry polymerization or gas polymerization). When applied to phase polymerization, etc.), it is highly active, and has excellent shape and particle properties, and can provide a polymer having a high molecular weight, a carrier composed of the particles, a catalyst component for olefin polymerization composed of the particles, An olefin polymerization catalyst comprising the particles and a method for producing an olefin polymer using the olefin polymerization catalyst are provided.

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4J028 AA01A AB00A AB01A AC01A AC10A AC28A AC49A BA00A BA01B BB00A BB01B BC18B CA15C CA16C CA24C CA30C CB35C CB55C EB02 EB03 GA24

Claims (9)

[Claims] 1. A method comprising bringing a particle (a) into contact with a lanthanoid-based compound (b), and then a compound having a functional group having an active hydrogen or a non-proton-donating Lewis basic functional group and an electron-withdrawing group. c) a modified particle obtained by contacting with c). 2. The modified particles according to claim 1, wherein the lanthanoid compound (b) is a compound represented by the following general formula (1). R ¹ _n AX _an (1) (where A is the periodic table of elements (1993, IUPA
C) is a lanthanoid atom, R ¹ is a hydrocarbon group or a hydrocarbon oxy group, and X is a halogen atom or a hydrogen atom. n is a number satisfying 0 ≦ n ≦ a, and a is the valence of the atom A. ) 3. The modified particle according to claim 2, wherein A is a samarium atom. 4. A carrier comprising the modified particles according to claim 1. 5. An olefin polymerization catalyst component comprising the modified particles according to claim 1. 6. An olefin polymerization catalyst comprising the modified particles (A) according to claim 1 and a transition metal compound (B). 7. An olefin polymerization comprising the modified particles (A), the transition metal compound (B), and the organometallic compound (C) according to claim 1. Catalyst. 8. A method for producing an olefin polymer, comprising using the catalyst for olefin polymerization according to claim 6 or 7. 9. The method for producing an olefin polymer according to claim 8, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.