JP4114295B2 - Modified particle, carrier comprising the same, catalyst component for olefin polymerization comprising the same, catalyst for olefin polymerization comprising the same, and method for producing olefin polymer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to particles useful as a carrier and a catalyst component for olefin polymerization, an olefin polymerization catalyst using the same, and a method for producing an olefin polymer using the olefin polymerization catalyst.
[0002]
[Prior art]
Olefin polymers such as polypropylene and polyethylene are widely used in various molding fields due to their excellent mechanical properties, chemical resistance, etc., and their excellent balance between properties and economics. Conventionally, these olefin polymers are a combination of a solid catalyst component obtained mainly using a Group 4 metal compound such as titanium trichloride or titanium tetrachloride and a Group 13 metal compound typified by an organoaluminum compound. It has been produced by polymerizing olefins using a so-called Ziegler-Natta catalyst (multisite catalyst).
[0003]
Production of olefin polymers that polymerize olefins using so-called single-site catalysts in which transition metal compounds (for example, metallocene complexes or nonmetallocene compounds) different from solid catalyst components that have been used for a long time in recent years are combined with aluminoxane, etc. A method has been proposed. For example, JP-A-58-19309 reports a method using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane. It has also been reported that certain boron compounds are combined with such transition metal compounds. For example, JP-A-1-502036 discloses a method using bis (cyclopentadienyl) zirconium dimethyl and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate. Olefin polymers obtained using 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 comonomer is more uniformly copolymerized. Therefore, it is known that an olefin polymer more homogeneous than that obtained when a conventional solid catalyst is used can be obtained.
[0004]
Since these metallocene complexes and non-metallocene compounds are usually soluble in the reaction system, the shape of the polymer produced when used for polymerization involving the formation of polymer particles (for example, slurry polymerization or gas phase polymerization). Is unstable, leading to the formation of coarse polymer particles, bulk polymer, fine powder polymer, etc., reduction of the bulk density of the polymer, adhesion of the polymer to the polymerization reactor wall, and the like. And, due to these factors, there have been problems such as poor electric heat and poor heat removal in the reactor, resulting in a state where stable operation is difficult and productivity is lowered.
[0005]
[Problems to be solved by the invention]
Japanese Patent Application Laid-Open No. 11-193306 is known as one of the solutions to this problem, but further improvement has been desired in terms of the molecular weight of the polymer obtained.
In view of such circumstances, an object of the present invention is to apply a catalyst for olefin polymerization using a transition metal compound to polymerization (for example, slurry polymerization or gas phase polymerization) accompanied by formation of polymer particles by using the transition metal compound. Particles having high activity, excellent shape and particle properties, and capable of giving a high molecular weight polymer, a carrier comprising the particles, an olefin polymerization catalyst component comprising the particles, and an olefin comprising the particles. An object of the present invention is to provide a polymerization catalyst and a method for producing an olefin polymer using the olefin polymerization catalyst.
[0006]
[Means for Solving the Problems]
  That is, the present invention
  An olefin polymerization catalyst comprising modified particles (A), a transition metal compound (B), and an organoaluminum compound (C),,
The modified particles (A) are
Of inorganic or organic polymerParticles (a);
NextCompound represented by the following general formula (1)(B) is brought into contact with
Obtained by contacting the compound (c) represented by the following general formula (2)
Modified particles characterized by
The transition metal compound (B) is a transition metal compound represented by the following general formula (3)
Olefin polymerization catalyst,The present invention also relates to a method for producing an olefin polymer using the olefin polymerization catalyst.
      R¹ _n SnX_an          (1)
(Wherein R¹Is 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,a is the valence of Sn atom and is 4. )
      R² _m OH_zm          (2)
(WhereR ² Represents a halogenated alkyl group or a halogenated aryl group,O represents an oxygen atom, H represents a hydrogen atom.z is 2 and m is 1. )
      ML_aR^Three _pa          (3)
(Where M is the periodic table of elements (1993, IUPAC))Group 4 transition metal atomsIt is. 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. A plurality of L may be the same or different, and may be cross-linked with each other. R^ThreeIs 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. )
  Hereinafter, the present invention will be described in more detail.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
(A) Particle
The modified particles of the present invention contact the particles (a) with the Group 14 metal compound (b), and then a functional group having active hydrogen or a non-proton donating Lewis basic functional group, and an electron It is obtained by bringing the compound (c) having an attractive group into contact.
[0008]
As the particles (a), those generally used as carriers are preferably used, porous materials having a uniform particle size are preferable, and inorganic materials or organic polymers are preferably used.
[0009]
Examples of inorganic substances that can be used in the particles (a) of the present invention include inorganic oxides and magnesium compounds, and clays and clay minerals can be used as long as they do not hinder. These may be mixed and used.
Specific examples of inorganic oxides include SiO₂, Al₂O_Three, MgO, ZrO₂TiO₂, B₂O_Three, CaO, ZnO, BaO, ThO₂And mixtures thereof, such as SiO₂-MgO, SiO₂-Al₂O_Three, SiO₂-TiO₂, SiO₂-V₂O_Five, SiO₂-Cr₂O_Three, SiO₂-TiO₂-MgO etc. can be illustrated. Among these inorganic oxides, SiO₂And / or Al₂O_ThreeIs preferred. The inorganic oxide contains a small amount of Na.₂CO_Three, K₂CO_Three, CaCO_Three, MgCO_Three, Na₂SO_Four, Al₂(SO_Four)_Three, BaSO_Four, KNO_Three, Mg (NO_Three)₂, Al (NO_Three)_Three, Na₂O, K₂O, Li₂Carbonate such as O, sulfate, nitrate and oxide components may be contained.
[0010]
Magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride and octoxy magnesium chloride ; Aryloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; phenoxymagnesium, dimethylphenoxymagnesium, etc. Allyloxymagnesium; Magne Laurate Um, and the like can be exemplified carboxylates of magnesium such as magnesium stearate.
Among these, magnesium halide or alkoxymagnesium is preferable, and magnesium chloride or butoxymagnesium is more preferable.
[0011]
Examples of clay or clay mineral include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, bayophyllite, talc, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, Halloysite and the like.
Among these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite.
[0012]
These inorganic substances do not require removal of moisture before use, but those dried by heat treatment are preferably used. The heat treatment is usually performed at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C. After heating, for example, a method in which a dried inert gas (for example, nitrogen or argon) is allowed to flow for several hours or more at a constant flow rate, or a method in which the pressure is reduced for several hours can be mentioned. It will never be done.
[0013]
The average particle diameter of the inorganic substance is preferably 5 to 1000 μm, more preferably 10 to 500 μm, and still 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 100 to 500 m²/ G.
[0014]
As the organic polymer that can be used in the particles (a) of the present invention, any organic polymer may be used, and a plurality of types of organic polymers may be used as a mixture. The organic polymer is preferably an organic polymer having a functional group having reactivity with the Group 14 metal compound (b). Examples of such a functional group include a functional group having active hydrogen, a non-proton-donating Lewis basic functional group, and the like. The organic polymer that can be used in the particles (a) includes a functional group having active hydrogen or A polymer having a non-proton donating Lewis basic functional group is preferred.
[0015]
The functional group having active hydrogen is not particularly limited as long as it has active hydrogen. Specific examples include primary amino group, secondary amino group, imino group, amide group, hydrazide group, 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, piperidyl group, indazolyl group, carbazolyl group, etc. . A primary amino group, secondary amino group, imino group, amide group, imide group, hydroxy group, formyl group, carboxyl group, sulfonic acid group or thiol group is preferred. Particularly preferred are a primary amino group, a secondary amino group, an amide group or a hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
[0016]
The non-proton-donating Lewis basic functional group is not particularly limited as long as it is a functional group having a Lewis base portion that does not have an active hydrogen atom. Specific examples include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted group. 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, N, N-substituted carbamoyl group, thioalkoxy group, substituted sulfinyl group, substituted sulfonyl group, substituted sulfonic acid group and the like. 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.
[0017]
The amount of the functional group having active hydrogen or the non-proton donating Lewis basic functional group is not particularly limited, but is preferably 0.01 to 50 mmol / g as the molar amount of the functional group per unit gram of the polymer. Yes, more preferably from 0.1 to 20 mmol / g.
[0018]
The polymer having such a functional group is obtained by, for example, 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 It can be obtained by copolymerizing this and another monomer having one or more polymerizable unsaturated groups. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.
[0019]
Such a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups include the above-described functional group having active hydrogen and one or more polymerizable groups. A monomer having a saturated group, or a monomer having a functional group having a Lewis base that does not have an active hydrogen atom and one or more polymerizable unsaturated groups may be used. Examples of such polymerizable unsaturated groups include alkenyl groups such as vinyl groups and allyl groups, and alkynyl groups such as ethyne groups.
Examples of monomers having a functional group having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds, and vinyl group-containing hydroxy compounds. Can be mentioned. 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, etc. Can be mentioned.
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, and vinyl (N-substituted) indazole. Can be mentioned.
[0020]
Examples of other monomers having one or more polymerizable unsaturated groups include ethylene, α-olefin, aromatic vinyl compounds and the like. Specific examples include ethylene, propylene, butene-1, hexene-1, 4 -Methyl-pentene-1, styrene and the like. Preferred is ethylene or styrene. Two or more of these monomers may be used.
Specific examples of the crosslinkable monomer having two or more polymerizable unsaturated groups include divinylbenzene.
[0021]
The average particle diameter of the organic polymer is preferably 5 to 1000 μm, more preferably 10 to 500 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 50 to 500 m²/ G.
[0022]
(B) Group 14 metal compound
The group 14 metal compound (b) used in the present invention is a compound having a group 14 metal atom in the molecule, and is preferably a compound represented by the following general formula (1).
R¹ _nAX_an          (1)
Wherein A is a group 14 metal atom of the Periodic Table of Elements (1993, IUPAC) and R¹Is 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 and is 2 or 4. )
[0023]
As the group 14 metal atom in the general formula (1), a tin atom or a lead atom is preferable, and a tin atom is particularly preferable.
R in the general formula (1)¹Is preferably a hydrocarbonoxy group, specifically, a methoxy group, an ethoxy group, a tetra-n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, a phenoxy group, a pentafluorophenoxy group, and the like. Preferably an alkoxy group or an aryloxy group, more preferably an alkoxy group.
X in the general formula (1) is preferably a halogen atom, and specific examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Particularly preferred is a chlorine atom.
In the general formula (1), a is the valence of the atom A and is 2 or 4.
In the above general formula (1), n is a number satisfying 0 ≦ n ≦ a, and preferably n is 0 or a. Particularly preferably, a = n = 4.
[0024]
When A is a tetravalent tin atom, specific examples of the Group 14 metal compound (b) include tetraalkyltin such as tetramethyltin, tetraethyltin, tetra-n-propyltin, tetra-n-butyltin, and tetraphenyl. Tetraaryl tin such as tin, tetrakis (pentafluorophenyl) tin, trimethyltin chloride, triethyltin chloride, trialkyltin chloride such as tri-n-propyltin chloride, tri-n-butyltin chloride, dimethyltin dichloride, diethyltin Dialkyltin dichloride such as dichloride, dipropyltin dichloride, di-n-butyltin dichloride, alkyltin trichloride such as methyltin trichloride, ethyltin trichloride, n-propyltin trichloride, n-butyltin trichloride, te Tetraalkoxytin such as Lachlorotin, Tetramethoxytin, Tetraethoxytin, Tetra-n-propoxytin, Tetra-isopropoxytin, Tetra-n-butoxytin, Tetra-tert-butoxytin, etc. Tetraalkoxytin, Tetraphenoxytin, Tetrakis (penta) Tetraaryloxytin, such as (fluorophenoxy) tin.
Moreover, the compound which substituted the chloride in the said compound by fluoride, bromide, or iodo is illustrated.
[0025]
When A is a divalent tin atom, specific examples of the Group 14 metal compound (b) include tin (II) ethoxide, tin (II) methoxide, tin (II) oxalate, tin (II) 2,4- Pentandionate, tin (II) tartrate, bis (2-ethylhexanoate) tin (II), bis (neodecanoate) tin (II), tin (II) bromide, tin (II) chloride, tin (II) Fluoride, tin (II) iodine and the like.
[0026]
The group 14 metal compound (b) is preferably R in the general formula (1).¹Is an alkoxy group or an aryloxy group, and n is a tin compound, or X is a halogen atom and n is 0, more preferably tetramethoxytin, tetraethoxytin, tetra- n-propoxytin, tetra-isopropoxytin, tetra-n-butoxytin, tetra-tert-butoxytin, tetraphenoxytin, tetrakis (pentafluorophenoxy) tin, tin (II) ethoxide, tin (II) methoxide, tetrafluorotin , Tetrachlorotin, tetrabromotin, tetraiodotin, tin (II) bromide, tin (II) chloride, tin (II) fluoride or tin (II) iodine, more preferably tetramethoxytin, tetraethoxytin, Tetra-n-propoxytin, tetra-iso Ropokishisuzu is tetra -n- butoxy tin, tetra -tert- butoxy tin, tetraphenoxy cis's, tetrakis (pentafluorophenoxy) tin, tin (II) ethoxide or tin (II) methoxide.
[0027]
(C) a compound having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group, and an electron-withdrawing group
The functional group having active hydrogen or the non-proton donating Lewis basic functional group of the compound (c) used in the present invention usually reacts with the Group 14 metal compound (b).
The functional group having active hydrogen and the non-proton-donating Lewis basic functional group are the same as those already described.
[0028]
The compound (c) has an electron-withdrawing group. As an index of the electron-withdrawing group, the Hammett's substituent constant σ can be used, and the Hammett's substituent constant σ is a positive functional group. Corresponds to an electron-withdrawing 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.
[0029]
The compound (c) may have a plurality and / or a plurality of the above-mentioned functional group having active hydrogen or a non-proton-donating Lewis basic functional group and an electron-withdrawing group.
In the compound (c), the non-proton donating Lewis basic functional group and the electron withdrawing group may be the same. In this case, the compound (c) may have only one such functional group.
[0030]
The compound (c) is preferably a compound having a functional group having active hydrogen and an electron-withdrawing group. Examples thereof include amines, phosphines, alcohols, phenols, and thiols having an electron-withdrawing group. Thiophenols, carboxylic acids, sulfonic acids and the like.
[0031]
More preferred as the compound (c) is a compound represented by the following general formula (2).
R² _mZH_zm          (2)
(Wherein R²Represents 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 a hydrogen atom. z is the valence of Z and is 2 or 3. When z is 2, m is 1, and when z is 3, m is 1 or 2. )
[0032]
R in the general formula (2)²Examples of the group containing an electron-withdrawing group include a halogenated alkyl group, a halogenated aryl group, a cyanated aryl group, a nitrated aryl group, and an ester group.
[0033]
Specific examples of the halogenated alkyl group include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a diiodomethyl group, a trifluoromethyl group, a trichloromethyl group, and a tribromomethyl group. 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-trichloro-1-trichloromethyl Ethyl 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-hexachloro-2-trichloromethylpropyl group, 1,1,1,3,3,3-hexabromo-2-tribromomethylpropyl group 1,1,1,3,3,3-hexaiodo-2-triiodomethylpropyl group and the like.
[0034]
Specific examples of the halogenated aryl 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-tri Fluorophenyl group, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-triiodophenol Group, pentafluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentaiodophenyl group, 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl Group, 2,6-di (trifluoromethyl) phenyl group, 3,5-di (trifluoromethyl) phenyl group, 2,4,6-tri (trifluoromethyl) phenyl group and the like.
[0035]
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 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group and the like.
[0036]
Specific examples of the ester group include methoxycarbonyl group, ethoxycarbonyl group, normal propyloxycarbonyl group, isopropyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, pentafluorophenyloxycarbonyl group and the like.
[0037]
R in the general formula (2)²Is 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, 2,2,3,3. , 3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 4- A fluorophenyl group, a 2,6-difluorophenyl group, a 3.5-difluorophenyl group, a 2,4,6-trifluorophenyl group or a pentafluorophenyl group, more preferably a trifluoromethyl group, 2,2 , 2-trifluoro-1-trifluoromethylethyl group, 1,1,1,3,3,3-hexafluoro-2-trifluoro Methyl propyl or pentafluorophenyl group.
[0038]
Z in the general formula (2) represents an atom of Group 15 or Group 16 of the periodic table, and H represents a hydrogen atom. Specific examples of Z include a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom, preferably a nitrogen atom or an oxygen atom, and more preferably an oxygen atom.
[0039]
z is the valence of Z. For example, z is 3 when Z is a nitrogen atom or a phosphorus atom, and z is 2 when Z is an oxygen atom or a sulfur atom. When z is 2, m is 1, and when z is 3, m is 1 or 2.
[0040]
Specific examples of the compound (c) include amines such as 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-triiodo) Ethyl) amine, di (2,2,3,3,3-pentafluoropropyl) amine, di (2,2,3,3,3-pentachloropropyl) a , 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) 3,3-hexachloro-2-trichloromethylpropyl) amine, di (1,1,1,3,3,3-hexabromo-2-tribromomethylpropyl) amine, di (1,1,1,3,3) , 3-hexaiodo-2-to Iodomethylpropyl) 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-di) Iodophenyl) amine, di (3,5-diiodophenyl) amine, di (2,4,6-trifluorophenyl) amine, di (2,4,6-trichlorophenyl) amine, di (2,4,4) 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) phenyl) amine, di (2,6-di ( Trifluoromethyl) phenyl) amine, di (3,5-di (trifluoromethyl) phenyl) amine, di (2,4,6-tri (trifluoromethyl) L) phenyl) amine, di (2-cyanophenyl) amine, (3-cyanophenyl) amine, di (4-cyanophenyl) amine, di (2-nitrophenyl) amine, di (3-nitrophenyl) amine, And di (4-nitrophenyl) amine. Moreover, the phosphine compound by which the nitrogen atom was substituted by the phosphorus atom can be illustrated similarly. These phosphine compounds are compounds represented by rewriting the amine of the above-mentioned specific examples to phosphine.
[0041]
Specific examples of the compound (c) include alcohols such as fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodethanol, trifluoromethanol, trichloromethanol, tribromomethanol, 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-trifluorome Ethanol, 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. Moreover, the thiol compound by which the oxygen atom was substituted by the sulfur atom can be illustrated similarly. These thiol compounds are compounds represented by rewriting methanol in the above specific examples to methanethiol, ethanol to ethanethiol, and propanol to propanethiol.
[0042]
Specific examples of the compound (c) include phenols such as 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-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-tri Phenol, 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, 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2- Nitrophenol, 3-nitrophenol, 4-nitrophenol and the like can be mentioned. Moreover, the thiophenol compound by which the oxygen atom was substituted by the sulfur atom can be illustrated similarly. These thiophenol compounds are compounds represented by rewriting phenol of the above-mentioned specific examples with thiophenol.
[0043]
Specific examples of the 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, fluoro Acetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoroethyl carboxylic acid, heptafluoropropyl carboxylic acid, 1,1,1,3,3,3-hexafluoro-2-propyl Such as carboxylic acid, and the like.
[0044]
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, Examples include 3-hexafluoro-2-propanesulfonic acid.
[0045]
The compound (c) is preferably an amine such as di (trifluoromethyl) amine, di (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, phenols include 2-fluoro Phenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol, 2- (trifluoromethyl) phenol, 3 -(Trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-di (trifluoromethyl) phenol, 3,5-di (trifluoromethyl) phenol, 2,4,6-tri (tri Fluoromethyl) phenol and carboxylic acids include pentafluorobenzoic acid, trifluoroacetic acid, and sulfonic acids include trifluoromethanesulfonic acid.
[0046]
More preferably, the 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-trifluoro (trifluoromethyl) phenol, and more preferably pentafluorophenol, or 1,1,1,3,3 3-hexafluoro-2-trifluoromethylpropanol (common name: perfluoro A tertiary butanol).
[0047]
(A) Modified particles
The modified particles of the present invention contact the particles (a) with the Group 14 metal compound (b), and then a functional group having active hydrogen or a non-proton donating Lewis basic functional group, and an electron Obtained by contacting the compound (c) having an attractive group.
[0048]
The contact treatment between (a) and (b) and the subsequent contact treatment with (c) are preferably carried out in an inert gas atmosphere. The treatment temperature is usually -80 ° C to 200 ° C, preferably -20 ° C to 180 ° C, more preferably 0 ° C to 150 ° C. The treatment time is usually 1 minute to 48 hours, preferably 10 minutes to 24 hours. Although it is preferable to use a solvent, the solvent to be used is preferably an aliphatic or aromatic hydrocarbon solvent that 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. Or the thing in which these hydrocarbon solvents were mixed arbitrarily can also 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.
[0049]
Further, the contact-treated particles in each contact stage may or may not be isolated, but it is preferable to isolate the treated particles after contacting in each contact stage. Isolation methods include decantation of the supernatant of the treatment liquid, filtration, washing of the treated particles with an inert solvent, filtration, washing of the treated particles with an inert solvent, reduced pressure or inert gas Examples thereof include a method of drying under circulation, a method of distilling off the solvent during contact treatment under reduced pressure or inert gas. In addition, when not performing processing operation which isolates the obtained process particle | grains, you may use for the polymerization reaction in the state which suspended the particle | grains obtained in the process liquid in the inert solvent.
[0050]
In the preparation of the modified particles of the present invention, the amount of (b) used relative to (a) is the Group 14 metal compound contained in the particles obtained by contacting (a) and (b) The metal atom of (b) is preferably 0.1 mmol or more, and more preferably 0.5 to 20 mmol, in terms of the number of moles of metal atoms contained in 1 g of the particles. The amount of (c) used is such that a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and an electron-withdrawing group with respect to the metal atom of the Group 14 metal compound (b) contained in 1 g of particles. As a molar ratio (c) / (b) of the compound (c) having a ratio of 0.01 to 100, more preferably 0.05 to 20, and more preferably 0.1 to 10. Further preferred.
[0051]
The modified particle 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 is 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 those using the modified particles (A) and the transition metal compound (B), or modified particles (A ), A transition metal compound (B), and an organometallic compound (C). The latter is preferred because it is more active.
[0052]
(B) Transition metal compound
Any transition metal compound having an olefin polymerization activity can be used as the transition metal compound used in the present invention. Examples of the transition metal include group 4 or lanthanide series of the Periodic Table of Elements (1993, IUPAC). These transition metals are preferred. More preferred as the transition metal compound is a metallocene transition metal compound.
[0053]
The metallocene transition metal compound is, for example, a compound represented by the following general formula (3).
ML_aR^Three _pa          (3)
(In the formula, M is a group 4 or lanthanide series transition metal atom of the periodic table of elements (1993, IUPAC). L is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom. , At least one is a group having a cyclopentadiene type anion skeleton, and a plurality of L may be the same or different and may be cross-linked to each other.^ThreeIs 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. )
[0054]
In the general formula (3) representing the metallocene transition metal compound, M is a group 4 or lanthanide series transition metal atom of the periodic table of elements (1993, IUPAC). Specific examples thereof include titanium atoms, zirconium atoms, hafnium atoms and the like as group 4 transition metal atoms in the periodic table, and samarium atoms and the like as lanthanide series transition metal atoms. Preferred is a titanium atom, a zirconium atom or a hafnium atom.
[0055]
In the general formula (3) representing the 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. A plurality of L may be the same or different, and may be cross-linked with each other.
Examples of groups having a cyclopentadiene-type anion skeleton include η^Five-Cyclopentadienyl group, η^Five-A substituted cyclopentadienyl group or a polycyclic group having a cyclopentadiene-type anion skeleton. η^Five-As the substituent of the substituted cyclopentadienyl group, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, etc. Is mentioned. In addition, as a polycyclic group having a cyclopentadiene type anion skeleton, η^Five-Indenyl group or η^Five-A fluorenyl group etc. are mentioned.
Examples of the hetero atom in the group containing a hetero atom include a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. 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, and preferably an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group. Group, dialkylamino group, diarylamino group, dialkylphosphino group or diarylphosphino group.
[0056]
η^FiveSpecific examples of the substituted cyclopentadienyl group include η^Five-Methylcyclopentadienyl group, η^Five-Ethylcyclopentadienyl group, η^FiveA normal propylcyclopentadienyl group, η^Five-Isopropylcyclopentadienyl group, η^Five-Normal butylcyclopentadienyl group, η^Five-Isobutylcyclopentadienyl group, η^FiveA secondary butylcyclopentadienyl group, η^Five-Tertiary butylcyclopentadienyl group, η^Five-1,2-dimethylcyclopentadienyl group, η^Five-1,3-dimethylcyclopentadienyl group, η^Five-1,2,3-trimethylcyclopentadienyl group, η^Five-1,2,4-trimethylcyclopentadienyl group, η^Five-Tetramethylcyclopentadienyl group, η^Five-Pentamethylcyclopentadienyl group, η^Five-A trimethylsilylcyclopentadienyl group etc. are mentioned.
[0057]
Specific examples of the polycyclic group having a cyclopentadiene-type anion skeleton include η^FiveAn indenyl group, η^Five-2-methylindenyl group, η^Five-4-methylindenyl group, η^Five-4,5,6,7-tetrahydroindenyl group, η^Five-A fluorenyl group etc. are mentioned.
[0058]
Specific examples of the group containing a hetero atom include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a thiomethoxy group, a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diphenylamino group, A pyrrolyl group, a dimethylphosphino group, etc. are mentioned.
[0059]
Groups having a cyclopentadiene anion skeleton, or a group having a cyclopentadienyl skeleton and a group containing a hetero atom may be cross-linked. In that case, an alkylene group such as an ethylene group or a propylene group, a dimethylmethylene group Further, a substituted alkylene group such as a diphenylmethylene group or a substituted silylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group, or a tetramethyldisilylene group may be interposed.
[0060]
R in general formula (3) representing a metallocene transition metal compound^ThreeIs 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. R^ThreeSpecific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a hydrocarbon group having 1 to 20 carbon atoms as a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, A phenyl group, a benzyl group, etc. are mentioned. R^ThreeAnd preferably a chlorine atom, a methyl group or a benzyl group.
[0061]
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, bis (methylcyclopenta). Dienyl) zirconium dichloride, bis (normal butylcyclopentadienyl) 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, ethylenebis 2-methylindenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dicylide, 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 (cyclopenta) Dienyl) (fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, (cyclopentadienyl) Dimethylamido) zirconium dichloride, (cyclopentadienyl) (phenoxy) zirconium dichloride, dimethylsilyl (tert-butylamido) (tetramethylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (methylcyclo Pentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, bis (fluorenyl) zirconium dimethyl, Ethylene bis (indenyl) zirconium dimethyl, dimethylsilyl (tert-butylamide) (tetramethylcyclopentadienyl) zirconium dimethyl A chill etc. are mentioned.
Moreover, the compound which replaced the zirconium with titanium or hafnium in said zirconium compound can be illustrated similarly.
These metallocene transition metal compounds may be used alone or in combination of two or more.
[0062]
(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^Four _bAlY_3-b          (4)
(However, R^FourRepresents a hydrocarbon group having 1 to 8 carbon atoms, and Al represents an aluminum atom. Y represents a hydrogen atom and / or a halogen atom, and b represents a number satisfying 0 <b ≦ 3. )
[0063]
R in the general formula (4) representing an organoaluminum compound^FourSpecific examples thereof include methyl group, ethyl group, normal propyl group, normal butyl group, isobutyl group, normal hexyl group, 2-methylhexyl group, normal octyl group, etc., preferably ethyl group, normal butyl group, An isobutyl group and a normal hexyl group. Specific examples when Y is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.
[0064]
General formula (4) R^Four _bAlY_3-bSpecific examples of the organoaluminum compound represented by the formula: Dialkylaluminum chlorides such as chloride, diethylaluminum chloride, dinormalpropylaluminum chloride, dinormalbutylaluminum chloride, diisobutylaluminum chloride, dinormalhexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, normalpropylaluminum dichloride, normalbuty Alkyl aluminum dichloride such as aluminum dichloride, isobutyl aluminum dichloride, normal hexyl aluminum dichloride, dialkyl aluminum such as dimethyl aluminum hydride, diethyl aluminum hydride, dinormal propyl aluminum hydride, di normal butyl aluminum hydride, diisobutyl aluminum hydride, di normal hexyl aluminum hydride A hydride etc. can be illustrated. Of these, trialkylaluminum is preferable, trimethylaluminum, triethylaluminum, trinormalbutylaluminum, triisobutylaluminum, or trinormalhexylaluminum is more preferable, and triisobutylaluminum or trinormalhexylaluminum is more preferable. is there.
These organoaluminum compounds may be used alone or in combination of two or more.
[0065]
The olefin polymerization catalyst of the present invention comprises the modified particles (A) and the transition metal compound (B), or further the organometallic compound (C). The amount of the component (B) used is (A) Usually 1 × 10 for 1 g^-6~ 1x10^-3mol, preferably 5 × 10^-6~ 1x10^-Fourmol. In addition, the amount of the organometallic compound used as the component (C) is 0. As the molar ratio (C) / (B) of the metal atom of the component (C) organometallic compound to the transition metal atom of the component (B) transition metal compound. It is preferably 01 to 10,000, more preferably 0.1 to 5,000, and most preferably 1 to 2,000.
[0066]
In the present invention, the component (A), the component (B), or the component (C) can be used in the polymerization reactor in any order during polymerization, and any combination of these optional components can be used. In this case, it may be used after being brought into contact with the reactor in advance.
[0067]
In the present invention, the monomer used for the polymerization may be any of olefins and diolefins having 2 to 20 carbon atoms, and two or more types of monomers may 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. Etc. are exemplified. Examples of the diolefin compound include conjugated dienes and non-conjugated dienes. Specific examples of such compounds 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-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene Examples of conjugated dienes include 1,3-butadiene, isoprene, and 1,3-hexadiene. , 1,3-octadiene, 1,3-cyclooctadiene, it can be exemplified 1,3-cyclohexadiene and the like.
[0068]
Specific examples of the monomer constituting the copolymer include a combination of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, propylene and 1-butene, etc. It should not be limited. The present invention is particularly suitable for producing a copolymer of ethylene and an α-olefin.
[0069]
In the present invention, an aromatic vinyl compound can also be used as a monomer. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, divinylbenzene and the like.
[0070]
The polymerization method is not particularly limited, and 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. Alternatively, olefin itself can be used as a solvent. The polymerization method may be either batch polymerization or continuous polymerization, and the polymerization may be performed in two or more stages with 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 be in the range of 1 minute to 20 hours.
[0071]
The present invention is particularly preferably applied to polymerization involving the 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. A preferred polymerization method in the slurry process is a continuous reactor in which monomers (and comonomers), feeds, diluents, etc. are continuously added as required, and the 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 or different reaction conditions in series or in parallel, or a combination thereof.
[0072]
As the diluent, for example, an inert diluent (medium) such as paraffin, cycloparaffin or aromatic hydrocarbon can be used. The temperature in the polymerization reactor or reaction zone can usually range from about 50 ° C to about 100 ° C, preferably from 60 ° C to 80 ° C. The pressure can usually be changed from about 0.1 MPa to about 10 MPa, preferably 0.5 MPa to 5 MPa. A pressure can be applied to maintain the catalyst in suspension, maintain the medium and at least some of the monomer and comonomer in a liquid phase, and allow the monomer and comonomer to contact. Accordingly, the medium, temperature, and pressure may be selected such that the olefin polymer is produced as solid particles and recovered in that form.
[0073]
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.
[0074]
Each catalyst component, monomer (and comonomer) can be added to the reactor or reaction zone in any order by any known method. For example, a method of simultaneously adding each catalyst component and monomer (and comonomer) to the reaction zone, a method of adding them sequentially, and the like can be used. If desired, each catalyst component can be pre-contacted in an inert atmosphere prior to contact with the monomer (and comonomer).
[0075]
The gas phase polymerization may be performed according to a known gas phase polymerization method and polymerization conditions, but is not limited thereto. As the gas phase polymerization reaction apparatus, 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 equipped with a stirring blade in the reaction vessel.
As a method for supplying each component to the polymerization tank, an inert gas such as nitrogen or argon, hydrogen, ethylene or the like is used to supply in a moisture-free state, or dissolved or diluted in a solvent, A method such as supplying in a slurry state can be used. Each catalyst component may be supplied individually, or may be supplied by contacting arbitrary components in advance in an arbitrary order.
[0076]
As polymerization conditions, the temperature is not higher than the temperature at which the polymer melts, preferably 20 ° C. to 100 ° C., particularly preferably 40 ° C. to 90 ° C. The pressure is preferably in the range of 0.1 MPa to 5 MPa, more preferably 0.3 MPa to 4 MPa. Furthermore, hydrogen may be added as a molecular weight modifier for the purpose of adjusting the melt fluidity of the final product. In the polymerization, an inert gas may coexist in the mixed gas.
[0077]
【Example】
Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these. The properties of the olefin polymer in the examples were measured by the following methods.
[0078]
(1) α-Olefin content (short chain branching) in the copolymer: The α-olefin content (short chain branching) in the obtained polymer was determined from the infrared absorption spectrum. The measurement and calculation are based on the method described in the literature (polyethylene characterization by infrared absorption spectrum, written by Takayama, Usami et al. Or Die Makromoleculare Chemie, 177, 461 (1976) McRae, MA, Madams, WF). Characteristic absorption derived from α-olefin, for example, 1375 cm^-1(Propylene), 772 cm^-1It carried out using. 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.
[0079]
(2) Melting point of copolymer: It was determined under the following conditions using Seiko SSC-5200.
Temperature rise: 40 ° C to 150 ° C (10 ° C / min), held for 5 minutes
Cooling: 150 ° C to 40 ° C (5 ° C / min), hold for 10 minutes
Measurement: 40 ° C to 160 ° C (heated at 5 ° C / min)
[0080]
(3) Molecular weight and molecular weight distribution: The molecular weight and molecular weight distribution were determined under the following conditions using a gel permeation chromatograph (150, C manufactured by Waters). In addition, molecular weight distribution (Mw / Mn) was represented by ratio of a weight average molecular weight (Mw) and a number average molecular weight (Mn).
Column: TSK gel GMH-HT
Measurement temperature: 145 ° C setting
Measurement concentration: 10 mg / 10 ml-orthodichlorobenzene
[0081]
[Example 1]
(1) Contact treatment between particles (a) and Group 14 metal compound (b), followed by treatment with compound (c)
A 50 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was dried under reduced pressure and purged with nitrogen. Silica heat-treated at 300 ° C. under nitrogen flow (Sypolol 948, manufactured by Devison; average particle size = 55 μm; pore volume = 1.66 ml / g; specific surface area = 309 m)²/ G) 0.94 g was collected. Thereto was added 13 ml of toluene to prepare a slurry, and a solution of 0.77 g (1.88 mmol) of tetra-tert-butoxytin in 17 ml of toluene was gradually added dropwise. After stirring at 80 ° C. for 2 hours, the supernatant was filtered, and the remaining solid compound was washed 4 times with 20 ml of toluene. Thereafter, 30 ml of toluene was added to form a slurry, and 5.6 ml (5.6 mmol) of pentafluorophenol (1 mol / L, toluene solution) was slowly added. After stirring at 80 ° C. for 2 hours, the supernatant was filtered, and the remaining solid compound was washed 4 times with 20 ml of toluene and once with 20 ml of hexane. Thereafter, the solid compound was dried under reduced pressure to obtain a fluid solid compound. The tin atom concentration in the solid compound was 1.0 mmol / g, and the fluorine atom concentration was 3.5 mmol / g.
[0082]
(2) Polymerization
After drying under reduced pressure, the inside of an autoclave with a stirrer having an internal volume of 400 ml replaced with argon was evacuated, 190 ml of hexane and 10 ml of 1-hexene were charged, and the temperature was raised to 70 ° C. After that, ethylene, the partial pressure is 6kg / cm²Then, 0.25 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.5 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added, and then 92.9 mg of the solid compound obtained in (1) above was added as a solid catalyst component. Polymerization was carried out at 70 ° C. for 30 minutes while feeding ethylene so as to keep the total pressure constant. 7.70 g of olefin polymer was obtained. Polymerization activity per transition metal atom is 1.5 × 10⁷At g / mol Zr / hour, the polymerization activity per solid catalyst component was 170 g / g solid catalyst component / hour. Moreover, the obtained olefin polymer was SCB = 16.89, melting | fusing point 97.6, and 107.7 degreeC, Mw = 220,000, and Mw / Mn = 4.2. The polymer was particulate.
[0083]
[Comparative Example 1]
(1) Contact treatment between particles (a) and trimethylaluminum, followed by treatment with compound (c)
A 200 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was dried under reduced pressure, and then purged with nitrogen. Silica heat-treated at 300 ° C. under nitrogen flow (Sypolol 948 manufactured by Devison; average particle size = 64 μm; pore volume = 1.62 ml / g; specific surface area = 312 m)²/ G) 382 g was collected. Thereto was added 3.3 L of toluene to form a slurry, which was cooled to 5 ° C. A solution of trimethylaluminum 75 ml in toluene 300 ml was gradually added dropwise thereto. After completion of dropping, the mixture was stirred at 5 ° C. for 30 minutes. Then, it heated up to 80 degreeC and stirred for 2 hours. The solvent was filtered through a glass filter and then washed four times with toluene. After washing, 3.3 L of toluene was added and cooled to 5 ° C. To this, 420 ml of pentafluorophenol (2.0 M toluene solution) was gradually added dropwise. After completion of dropping, the mixture was stirred at 5 ° C. for 30 minutes. Then, it heated up to 80 degreeC and stirred for 2 hours. After filtering the solid compound by filtration, it was washed four times with toluene and once with hexane. The solid compound obtained as a result was dried under reduced pressure to obtain 434 g of a fluid solid compound. The aluminum atom concentration in the solid compound was 1.22 mmol / g, and the fluorine atom concentration was 4.63 mmol / g.
[0084]
(2) Polymerization
After drying under reduced pressure, the inside of an autoclave with a stirrer having an internal volume of 400 ml replaced with argon was evacuated, 190 ml of hexane and 10 ml of 1-hexene were charged, and the temperature was raised to 70 ° C. After that, ethylene, the partial pressure is 6kg / cm²Then, 0.25 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Subsequently, 0.15 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added, and then 10.2 mg of the solid compound obtained in (1) above was added as a solid catalyst component. . 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 × 10⁸At g / mol Zr / hour, the polymerization activity per solid catalyst component was 4000 g / g solid catalyst component / hour. Moreover, the obtained olefin polymer was SCB = 28.40, melting | fusing point 85.8 degreeC and 96.9 degreeC, Mw = 82000, Mw / Mn = 2.6.
[0085]
【The invention's effect】
As described above in detail, according to the present invention, by using a transition metal compound, an olefin polymerization catalyst using the transition metal compound is used for polymerization involving formation of polymer particles (for example, slurry polymerization or gas phase polymerization). When applied, particles having high activity, excellent shape and particle properties, and capable of giving a high molecular weight polymer, a carrier made of the particles, an olefin polymerization catalyst component made of the particles, and using the particles And a method for producing an olefin polymer using the olefin polymerization catalyst. According to the present invention, it is possible to obtain an olefin polymer having a wider molecular weight distribution, which is more excellent in processability, and the industrial value is extremely great.

Claims (3)

An olefin polymerization catalyst comprising the modified particles (A), the transition metal compound (B), and the organoaluminum compound (C) ,
The modified particles (A) are
Inorganic or organic polymer particles (a);
Subsequently, the compound (b) represented by the following general formula (1) is contacted,
A modified particle obtained by contacting a compound (c) represented by the following general formula (2):
The transition metal compound (B) is a transition metal compound represented by the following general formula (3)
Olefin polymerization catalyst.
^{_{R 1 n Sn X an (1}} )
(In the formula, R ¹ is a hydrocarbon group or a hydrocarbon oxy group, X is a halogen atom or a hydrogen atom, n is a number satisfying 0 ≦ n ≦ a, and a is the valence of Sn atom. There is 4 )
R ² _m O H _zm (2)
(In the formula, R ² represents a halogenated alkyl group or a halogenated aryl group , O represents an oxygen atom , H represents a hydrogen atom, z is 2, and m is 1. )
ML _a R ³ _pa (3)
(In the formula, M is a transition metal atom of Group 4 of the Periodic Table of Elements (1993, IUPAC) . L is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and at least 1 And a group having a cyclopentadiene type anion skeleton, wherein a plurality of L may be the same or different, and may be bridged with each other, R ³ may be a halogen atom or 1 to 20 carbon atoms; A is a number satisfying 0 <a ≦ p, and p is a valence of the transition metal atom M.) A method for producing an olefin polymer, comprising using the olefin polymerization catalyst according to claim 1 . The method for producing an olefin polymer according to claim 2, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.