JP2005194454A - Anti-static agent, seed powder, method for polymerizing olefin and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an olefin polymer in a good efficiency by suppressing sheeting in a gas phase fluidized bed type polymerization, a method for polymerizing an olefin in a good efficiency, and a material for them. <P>SOLUTION: The subject anti-static agent consists of a silicon compound expressed by the formula (I): R<SB>r</SB>Si(OR')<SB>4-r</SB>[wherein, R, R' are each independently a 1-20C hydrocarbon; (r) is 2 or 3; in the case that a plurality of the Rs present, they may be the same or different; and also in the case that a plurality of the R's present, they may be the same or different]. The method for producing the olefin polymer comprises filling seed powder attached with the silicon compound in a gas phase fluidized bed type polymerization reaction vessel, then initiating the polymerization to polymerize the olefins, and also the method for producing the olefin polymer comprise using the gas phase fluidized bed type polymerization reaction vessel coated with the silicon compound expressed by the formula (I) on its inside wall surface, to polymerize the olefin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antistatic agent, seed powder charged in a gas phase fluidized bed polymerization reactor, an olefin polymerization method using the gas phase fluidized bed polymerization reactor, and an olefin polymer production method.

  In recent years, as a polymerization method of olefins, a gas phase polymerization method generally performed in a gas phase polymerization state with less investment and less energy cost compared to other polymer production processes such as suspension polymerization and solution polymerization. Is often used. As a gas phase polymerization reaction apparatus, a fluidized bed reactor using a fluidized bed is usually used. The gas phase fluidized bed polymerization reactor is a suspension of powder particles filled in the reactor by a gas introduced from a plate having a large number of pores at the bottom of the apparatus (this is called a gas dispersion plate). The reaction is performed in a bed in a state (this is called a fluidized bed or a fluidized bed).

  Such a gas-phase fluidized bed polymerization reactor usually has a cylindrical fluidized bed portion and a dilute layer portion (the two are collectively referred to as a straight body portion) and a conical entrained separation portion (this is referred to as an enlarged portion). Called). When starting the polymerization, the seed powder is supplied to the reactor under an inert gas atmosphere such as nitrogen, and the polymerization pressure is increased by the monomer as a raw material, hydrogen used for molecular weight adjustment, nitrogen as an inert gas, etc. After increasing the pressure and adjusting the gas composition, the catalyst is introduced to start the polymerization.

  In such gas phase polymerization, powder particles (seed powder or catalyst-containing polymer powder grown by polymerization) are formed by the static electricity generated by friction between particles in the fluidized bed or friction between the particles and the inner wall of the reactor. ) May adhere to the inner wall surface of the reactor, and a sheet-like agglomerate may be formed due to poor heat removal. The formation of this sheet-like agglomerate is called sheeting. When the sheet-like agglomerated material accumulates and becomes heavy, it is peeled off from the wall surface, blocking the outlet of the product, clogging the pores of the gas dispersion plate, etc. It can be difficult.

  As a method for preventing such sheeting, Patent Document 1 discloses an example in which tetraethoxysilane is fed during a polymerization reaction using a gas phase fluidized bed polymerization reactor.

US Pat. No. 5,731,392

  However, the method of Patent Document 1 sometimes causes a decrease in polymerization activity. An object of the present invention is to provide a method for efficiently producing an olefin polymer, a method for efficiently polymerizing olefins, and materials therefor, by suppressing sheeting in gas phase fluidized bed polymerization.

The present invention relates to an antistatic agent comprising a silicon compound represented by the formula (I). The present invention also relates to a seed powder to be filled in a gas phase fluidized bed polymerization reactor, which is applied to the seed powder to which the silicon compound represented by the formula (I) is attached. Method of starting olefins after filling the seed powder into the gas phase fluidized bed polymerization reactor, and filling the seed powder with the silicon compound attached into the gas phase fluidized bed polymerization reactor Then, the polymerization is started and the method for producing an olefin polymer for polymerizing olefins is applied. Furthermore, the present invention relates to a method for producing an olefin polymer in which olefins are polymerized using a gas phase fluidized bed polymerization reactor in which a silicon compound represented by the formula (I) is coated on the inner wall surface.
R _r Si (OR ′) _4-r (I)
(In the formula, R and R ′ are each independently a hydrocarbon group having 1 to 20 carbon atoms, r is 2 or 3, and when there are plural Rs, they may be the same or different from each other). Well, when there are a plurality of R ′, they may be the same or different.)

  According to the present invention, there are provided a method for efficiently producing an olefin polymer, a method for efficiently polymerizing olefins, and materials therefor, while suppressing sheeting in gas phase fluidized bed polymerization.

The present invention is described in detail below.
In the present invention, the term “polymerization” includes not only homopolymerization but also copolymerization, and the term “polymer” includes not only homopolymers but also copolymers.

The compound used as an antistatic agent in the present invention is a silicon compound represented by the formula (I).
R _r Si (OR ′) _4-r (I)
(In the formula, R and R ′ are each independently a hydrocarbon group having 1 to 20 carbon atoms, r is 2 or 3, and when there are plural Rs, they may be the same or different from each other). Well, when there are a plurality of R ′, they may be the same or different.)

  Examples of the hydrocarbon group having 1 to 20 carbon atoms in R and R ′ include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group, and preferably an alkyl group having 1 to 20 carbon atoms and the number of carbon atoms. A 7-20 aralkyl group, an aryl group having 6-20 carbon atoms, or an alkenyl group having 3-20 carbon atoms is preferred.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, Neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, etc. are mentioned, more preferably methyl group, ethyl group, isopropyl Group, tert-butyl group, isobutyl group or amyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethylphenyl). ) Methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3 , 5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3 , 4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4) 6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, ( Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc. More preferred is a benzyl group.

  Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, and 2,5-xylyl group. Group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethyl Phenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2 , 3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butyl group Nyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group More preferred is a phenyl group.

  Examples of the alkenyl group having 3 to 20 carbon atoms include an allyl group, a methallyl group, a crotyl group, a 1,3-diphenyl-2-propenyl group, and more preferably an allyl group or a methallyl group.

R is more preferably an alkyl group, an aralkyl group or an aryl group, and still more preferably an alkyl group.
R ′ is more preferably an alkyl group, an aralkyl group or an aryl group, and still more preferably an alkyl group.

R in the above formula (I) is 2 or 3, and is preferably 2.
When r is 2, both R and R ′ exist, but they may be the same or different. When r is 3, there are three Rs, which may be the same or different.

  The antistatic agent comprising the silicon compound represented by the above formula (I) of the present invention is suitably used as an antistatic agent for gas phase polymerization of olefins. As an aspect when the antistatic agent of the present invention is used as an antistatic agent for gas phase polymerization of olefins, (A) the antistatic agent is added to the seed powder previously supplied to the reactor when the polymerization is started. Examples thereof include a method of adhering and (B) a method of applying the power failure preventing agent to the inner wall surface of the gas phase fluidized bed polymerization reactor.

  In the case of the embodiment (A), as the seed powder, a seed powder to which the silicon compound represented by the above formula (I) is attached is prepared.

The means for attaching the silicon compound to the seed powder is not particularly limited as long as the silicon compound can be attached to the seed powder. For example, the silicon compound and seed powder are mixed with a V-type mixer such as a V-blender, a ribbon-type mixer such as a ribbon blender, a tumbler-type mixer such as a tumbler blender, or a stirring type mixer with a shaker such as a Henschel mixer. There is a method of mixing with a machine. There is also a method of spraying the silicon compound in a nitrogen atmosphere from above the seed powder in a seed powder stock drum. In that case, the silicon compound may be diluted with a suitable solvent such as a hydrocarbon solvent. Also, a stirrer may be installed on the stock drum.
Alternatively, the silicon compound may be adhered to a part of the seed powder at a high concentration, and mixed with a seed powder to which the silicon compound is not adhered may be diluted.

  If the adhesion amount of the silicon compound is too small, the antistatic action may not be exhibited. However, if the amount is too large, the effect may not be seen for the amount. The adhesion amount is preferably 0.01 to 1000 wtppm, more preferably 0.1 to 400 wtppm, further preferably 1 to 300 wtppm, and particularly preferably 5 to 200 wtppm.

  In the case of the embodiment (B), the silicon compound represented by the above formula (I) is applied in advance to the inner wall surface of the gas phase fluidized bed polymerization reactor.

The coating range is preferably 5% or more of the entire region where the reactor such as the gas dispersion plate and the wall surface of the straight body part and the flowing powder particles are in contact with each other, and 25% of the entire region. % Is more preferable, and the entire region is most preferable.
As the amount of coating, it is preferable to applying the silicon compound in an amount of 0.01 to 10 g / ^{m 2} with respect to the unit wall, further preferably applied in an amount of 0.05 to 2 g / ^{m 2} . If the coating amount is too small, the antistatic effect may not be exhibited, and even if the coating amount is too large, the effect may not be improved so much.

At the start of gas phase polymerization, seed powder is supplied to the reactor, and the fluidized bed polymerization reactor is charged electrostatically at the start-up stage where the pressure is increased to the polymerization pressure with raw material monomers, hydrogen, etc. Even if an attempt is made to apply a charge removal treatment to the surface, the treatment may not be effective.
Charging at the stage of start-up can be achieved by using a seed polymer to which the above compound is attached (Aspect A) or by applying the above compound to the inner wall surface in advance before the start of polymerization (Aspect B). This is especially effective when prevention is a major problem.

  In the present invention, as a catalyst used when producing an olefin polymer, when producing an olefin polymer having a wide molecular weight distribution using a homogeneous catalyst, charging at the start-up stage is a major problem. However, since charging after the start of polymerization is relatively unproblematic, the present invention is particularly preferably applied to the production of an olefin polymer having a wide molecular weight distribution using a homogeneous catalyst.

  In general, in a gas phase polymerization method, a prepolymerized catalyst obtained by subjecting a catalyst containing a solid component to a prepolymerization treatment is used as a catalyst. In the present invention, a homogeneous solid catalyst is usually used as the homogeneous catalyst.

  As such a homogeneous solid catalyst, a transition metal compound and an aluminoxane such as methylaluminoxane are immobilized and supported on an inorganic metal oxide carrier such as silica (for example, JP-A-60-35006, JP-A-60). -35007, JP-A-60-35008); homogeneous solid catalyst obtained from transition metal compound, boron compound and carrier, or homogeneous obtained from transition metal compound, boron compound, organoaluminum compound and carrier And a modified clay obtained by treating a clay mineral with a compound capable of introducing a cation between its layers, as an alternative to an aluminoxane or boron compound, and a solid catalyst (Japanese Patent Application Laid-Open No. 5-502906 and JP-A-6-336502); , Solid metal catalyst comprising transition metal compound and organoaluminum compound -224106 JP) and the like.

Among them, a catalyst for olefin polymerization obtained by contacting a transition metal compound (A), an organoaluminum compound (B), and modified particles (C), wherein the modified particles (C) A solid catalyst for olefin polymerization, which is a modified particle obtained by bringing the organometallic compound (a), the compound (b) having active hydrogen and an electron-withdrawing group into contact with the particle (d), is preferable.
Hereinafter, this preferred solid catalyst for olefin polymerization will be described in detail.

(A) Transition metal compound As the transition metal compound (A), a transition metal compound that forms a single site catalyst is used, and the modified particles (C) and the organoaluminum compound (B) are activated as cocatalyst components. There is no particular limitation as long as it is a Group 3-11 or lanthanoid series transition metal compound exhibiting addition polymerization activity. The single-site catalyst referred to here is not only a narrowly-defined single-site catalyst that has a narrow molecular weight distribution and, in the case of copolymerization, a narrow composition distribution, but is similar to such a narrowly-defined single-site catalyst. If the catalyst is obtained by the above-described adjustment method, an addition polymer having a broad molecular weight distribution and a catalyst capable of obtaining an addition polymer having a wide composition distribution in the case of copolymerization are also included.

The transition metal compound (A) is preferably a transition metal compound represented by the following general formula [1] or a μ-oxo type transition metal compound dimer thereof.
L _a MX ¹ _b [1]
(In the formula, M is a transition metal atom of Groups 3 to 11 of the periodic table or a lanthanoid series. L is a group having a cyclopentadiene type anion skeleton or a group containing a hetero atom, and a plurality of L are directly Or may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, X ¹ is a halogen atom, a hydrocarbon group (provided that And a hydrocarbon oxy group, a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8.)

  In the general formula [1], M is a transition metal atom of Group 3 to 11 or lanthanoid series of the periodic table (IUPAC 1989). Specific examples thereof include scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom. , Samarium atoms, ytterbium atoms, and the like. M in the general formula [1] is preferably a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a chromium atom, an iron atom, a cobalt atom or a nickel atom, and particularly preferably a titanium atom, a zirconium atom or a hafnium atom. Most preferably, it is a zirconium atom.

  In the general formula [1], L is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L may be the same or different. A plurality of L may be directly connected to each other, or may be connected via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Examples of the group having a cyclopentadiene-type anion skeleton in L include η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl group, η ^5- (substituted) fluorenyl group and the like. Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -ethylcyclopentadienyl group, η ⁵ -n-butylcyclopentadienyl group, η ⁵ -Tert-butylcyclopentadienyl group, η ⁵ -1,2-dimethylcyclopentadienyl group, η ⁵ -1,3-dimethylcyclopentadienyl group, η ⁵ -1-methyl-2-ethylcyclopenta Dienyl group, η ⁵ -1-methyl-3-ethylcyclopentadienyl group, η ⁵ -1-tert-butyl-2-methylcyclopentadienyl group, η ⁵ -1-tert-butyl-3-methyl Cyclopentadienyl group, η ⁵ -1-methyl-2-isopropylcyclopentadienyl group, η ⁵ -1-methyl-3-isopropylcyclopentadienyl group, η ⁵ -1-methyl-2-n-butyl Cyclopentadienyl group, η ⁵ -1-methyl-3-n-butylcyclopentadienyl group, η ⁵ -1,2,3-trimethylcyclopentadienyl group, η ⁵ -1,2,4-trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - indenyl group, eta ^{5-4,5,6,7-tetrahydroindenyl} group, η ⁵ -2-methylindenyl group, η ⁵ -3-methylindenyl group, η ⁵ -4-methylindenyl group, η ⁵ -5-methylindenyl group, η ⁵ -6-methylindenyl group, eta ^{5-7-methylindenyl} group, η ⁵ -2-tert- butyl indenyl group, η ⁵ -3-tert- butyl indenyl group, η ⁵ -4-tert- butylindenyl group, eta ⁵ -5 -Tert-butylindenyl group, η ^5-6 -tert-butylindenyl group, η ⁵ -7-tert-butylindenyl group, η ⁵ -2,3-dimethylindenyl group, η ⁵ -4,7-dimethylindenyl group, η ^5- 2,4,7-trimethylindenyl group, η ⁵ -2-methyl-4-isopropylindenyl group, η ⁵ -4,5-benzindenyl group, η ⁵ -2-methyl-4,5-benzindenyl group, η ^5-4-phenyl indenyl group, eta ^{5-2-methyl-5-phenyl} indenyl group, eta ^{5-2-methyl-4-phenyl} indenyl group, eta ^{5-2-methyl-4-naphthyl} indenyl group , Η ⁵ -fluorenyl group, η ⁵ -2,7-dimethylfluorenyl group, η ⁵ -2,7-di-tert-butylfluorenyl group, and substituted products thereof.
In the present specification, “η ⁵ −” may be omitted for the names of transition metal compounds.

  Examples of the hetero atom in the group containing a hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Examples of such a group include an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, and an alkyl group. Amino group, arylamino group, alkylphosphino group, arylphosphino group, chelating ligand, or aromatic or aliphatic heterocyclic group having an oxygen atom, sulfur atom, nitrogen atom and / or phosphorus atom in the ring Is preferred.

  Specific examples of groups containing heteroatoms include methoxy, ethoxy, propoxy, butoxy, phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethyl. Phenoxy group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6-diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group, 2,6 -Di-sec-butylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2,6-di-tert-butylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethoxyphenoxy group, 3,5 -Dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy group, 4-nitrophene Xy group, 2-aminophenoxy group, 3-aminophenoxy group, 4-aminothiophenoxy group, 2,3,6-trichlorophenoxy group, 2,4,6-trifluorophenoxy group, thiomethoxy group, dimethylamino group, Diethylamino group, dipropylamino group, diphenylamino group, isopropylamino group, tert-butylamino group, pyrrolyl group, dimethylphosphino group, 2- (2-oxy-1-propyl) phenoxy group, catechol, resorcinol, 4- Isopropylcatechol, 3-methoxycatechol, 1,8-dihydroxynaphthyl group, 1,2-dihydroxynaphthyl group, 2,2′-biphenyldiol group, 1,1′-bi-2-naphthol group, 2,2 ′ -Dihydroxy-6,6'-dimethylbiphenyl group, 4,4 ', 6,6'-te La -tert- butyl 2,2 'methylenedianiline phenoxy group, 4,4', 6,6'-tetramethyl-2,2'-isobutenyl dust Denji phenoxy group and the like.

Moreover, as group containing the said hetero atom, group represented by following General formula [2] can also be illustrated.
R ¹ ₃ P = N− [2]
(Wherein R ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group in each case, and they may be the same or different from each other, and two or more of them may be bonded to each other; A ring may be formed.)

Specific examples of R ¹ in the general formula [2] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples thereof include, but are not limited to, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclohexyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a benzyl group.

（式中、Ｒ² はそれぞれの場合に水素原子、ハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭化水素オキシ基、シリル基またはアミノ基を表し、それらは互いに同じであっても異なっていても良く、それら２つ以上が互いに結合していても良く、環を形成していても良い。） Further, examples of the group containing a hetero atom include a group represented by the following general formula [3].

(Wherein R ² represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon oxy group, a silyl group or an amino group in each case, and they may be the same or different from each other. Or two or more of them may be bonded to each other and may form a ring.)

Specific examples of R ² in the general formula [3] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, phenyl group, 1-naphthyl group, 2-naphthyl group, tert-butyl group, 2 , 6-dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl group, methyl Group, triethylsilyl group, diphenylmethylsilyl group, 1-methyl-1-phenylethyl group, 1,1-dimethylpropyl group, 2-chlorophenyl group, pentafluorophenyl group, etc., but are not limited thereto is not.

  The chelating ligand refers to a ligand having a plurality of coordination sites. Specifically, acetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, triethylenetetramine, Porphyrin, crown ether, cryptate and the like can be mentioned.

  Specific examples of the heterocyclic group include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, preferably a pyridyl group.

  A group having a cyclopentadiene type anion skeleton, a group having a cyclopentadiene type anion skeleton and a group containing a hetero atom, or a group containing a hetero atom may be directly connected to each other, such as a carbon atom, silicon It may be linked via a residue containing an atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Such a residue is preferably a divalent residue in which two atoms bonded to L are a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and more preferably two A divalent residue wherein the atom bonded to L is a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and the minimum number of atoms between the two L bonded atoms is 3 or less ( This includes the case where there is a single atom bonded to two L). Specifically, an alkylene group such as an ethylene group or a propylene group, a substituted alkylene group such as a dimethylmethylene group or a diphenylmethylene group, or a substituted silylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group, or a tetramethyldisylylene group. Or a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, particularly preferably a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a dimethylsilylene group, a diethylsilylene group or a diphenylsilylene. It is a group.

X ¹ in the general formula [1] is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton), or a hydrocarbon oxy group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The hydrocarbon group here does not include a group having a cyclopentadiene type anion skeleton. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Preferably, the alkyl group has 1 to 20 carbon atoms, the aralkyl group has 7 to 20 carbon atoms, and the number of carbon atoms. An aryl group having 6 to 20 carbon atoms or an alkenyl group having 3 to 20 carbon atoms is preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, Neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, etc. are mentioned, more preferably methyl group, ethyl group, isopropyl Group, tert-butyl group, isobutyl group or amyl group.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 10 carbon atoms substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, Examples thereof include a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group.
Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethylphenyl). ) Methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3 , 5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3 , 4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4) 6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, ( Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc. More preferred is a benzyl group.
These aralkyl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, and 2,5-xylyl group. Group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethyl Phenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2 , 3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butyl group Nyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group More preferred is a phenyl group.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group Etc. may be partially substituted.

  Examples of the alkenyl group having 3 to 20 carbon atoms include an allyl group, a methallyl group, a crotyl group, a 1,3-diphenyl-2-propenyl group, and more preferably an allyl group or a methallyl group.

  The hydrocarbon oxy group herein includes an alkoxy group, an aralkyloxy group, an aryloxy group, and the like, and preferably an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or carbon. An aryloxy group having 6 to 20 atoms is preferred.

Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, and a neopentoxy group. , N-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group, etc., more preferably methoxy group, ethoxy group, isopropoxy group, or tert-butoxy group. .
These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3- (Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl) Phenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) Methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy Group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like. More preferably, it is a benzyloxy group.
These aralkyloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, and 2,4-dimethylphenoxy group. 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl -4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethyl Phenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di -Tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3 , 4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, Isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, Anthracenoxy group etc. are mentioned.
These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

X ¹ is more preferably chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, trifluoro Methoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4- A pentafluorophenylphenoxy group or a benzyl group.

  In the general formula [1], a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valence of M. When M is a titanium atom, a zirconium atom or a hafnium atom, a is preferably 2, and b is also preferably 2.

  Only one type of transition metal compound may be used, or two or more types may be used in combination.

  The transition metal compound (A) is preferably a transition metal compound represented by the above general formula [1]. Among them, a transition metal compound in which M in the general formula [1] is a Group 4 atom is preferable, and a transition metal compound having at least one group having a cyclopentadiene-type anion skeleton is particularly preferable as L in the general formula [1]. .

(B) Organoaluminum compound As the organoaluminum compound (B), a known organoaluminum compound is used. Preferably, it is an organoaluminum compound represented by the following general formula [4].
R ³ _c AlY _3-c [4]
(Wherein R ³ represents a hydrocarbon group, and all R ³ may be the same or different. Y represents a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group or an aryloxy group; All Y may be the same or different, and c represents a number satisfying 0 <c ≦ 3.)

R ³ in the general formula [4] representing the organoaluminum compound is preferably a hydrocarbon group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, n-octyl group and the like, preferably ethyl group, n -A butyl group, an isobutyl group, an n-hexyl group, or an n-octyl 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.
The alkoxy group in Y is preferably an alkoxy group having 1 to 24 carbon atoms. Specific examples thereof include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, t -Butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadexoxy group, n-icosoxy group, etc., preferably methoxy group, ethoxy group or t -Butoxy group.

  The aryloxy group in Y is preferably an aryloxy group having 6 to 24 carbon atoms. Specific examples thereof include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3 -Dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4 -Trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5 -Trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group N-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like.

  The aralkyloxy group in Y is preferably an aralkyloxy group having 7 to 24 carbon atoms. Specific examples include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4 -Methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, 2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6- Limethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy Group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group , (Tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group , Anthracenylmethoxy group and the like, preferably a benzyloxy group That.

  Specific examples of the organoaluminum compound represented by the general formula [4] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri -Trialkylaluminum such as n-octylaluminum; Dialkylaluminum such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride Chloride: methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminum Alkyl aluminum dichlorides such as mudichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n- Dialkylaluminum hydrides such as hexylaluminum hydride; trialkoxyaluminums such as trimethoxyaluminum, triethoxyaluminum, tri (t-butoxy) aluminum; methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-t-butoxy) Alkyl (dialkoxy) aluminum such as aluminum; dimethyl (Methoxy) aluminum, dimethyl (ethoxy) aluminum, dialkyl (alkoxy) aluminum such as dimethyl (t-butoxy) aluminum; triphenoxyaluminum, tris (2,6-diisopropylphenoxy) aluminum, tris (2,6-diphenylphenoxy) Triaryloxyaluminum such as aluminum; methyl (diphenoxy) aluminum, alkyl (diaryloxy) aluminum such as methylbis (2,6-diisopropylphenoxy) aluminum, methylbis (2,6-diphenylphenoxy) aluminum; dimethyl (phenoxy) aluminum, Dialkyl such as dimethyl (2,6-diisopropylphenoxy) aluminum, dimethyl (2,6-diphenylphenoxy) aluminum ( Aryloxy) aluminum and the like can be exemplified.

Of these, trialkylaluminum is preferable, and trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, or tri-n-octylaluminum is particularly preferable. Triisobutylaluminum or tri-n-octylaluminum is preferred.
These organoaluminum compounds may be used alone or in combination of two or more.

(C) Modified Particles Modified particles (C) are obtained by contacting an organometallic compound (a), a compound (b) having active hydrogen and an electron-withdrawing group, and particles (d). . As the modified particles (C), those obtained by bringing water (c) into contact with these particles (a), (b) and (d) are more preferable.

(A) Organometallic compound The organometallic compound (a) is a compound having a bond between a carbon atom and a metal atom, and is preferably a compound represented by the following general formula [5].
R ⁴ _n AX ² _qn [5]
Wherein A is a metal atom of Group 2, 12 or 13 of the Periodic Table of Elements (1993, IUPAC), and R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms or A hydrocarbon oxy group having 1 to 20 carbon atoms, X ² is a halogen atom or a hydrogen atom, n is a number satisfying 0 <n ≦ q, and q is a valence of a metal atom A Number.)

  In the above general formula [5], A is a metal atom of Group 2, 12 or 13 of the Periodic Table of Elements (1993, IUPAC), and A is preferably a boron atom, an aluminum atom or a magnesium atom. Or it is a zinc atom. When A is a boron atom or an aluminum atom, the valence is 3 (q = 3), and when A is a magnesium atom or a zinc atom, the valence is 2 (q = 2).

When A is a boron atom, R ⁴ is preferably the above hydrocarbon group. Specific examples include trialkylborane such as trimethylborane, triethylborane, tripropylborane, tributylborane, triphenylborane, dimethylchloroborane, diethylchloro Dialkyl halide boranes such as borane, dipropylchloroborane, dibutylchloroborane, diphenylchloroborane, dimethylhydridoborane, diethylhydridoborane, dipropylhydridoborane, dibutylhydridoborane, diphenylhydridoborane, etc., methyldichloroborane, Examples thereof include alkyl dihalide boranes such as ethyldichloroborane, propyldichloroborane, butyldichloroborane and phenyldichloroborane.

When A is an aluminum atom, R ⁴ is preferably the above hydrocarbon group. Specific examples thereof include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, trinormalbutylaluminum, triisobutylaluminum, and trinormalhexylaluminum. Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, dinormal butylaluminum chloride, diisobutylaluminum chloride, dinormalhexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, normal butylaluminum Dichloride, isobu Alkyl aluminum dihalides such as rualuminum dichloride and normal hexyl aluminum dichloride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, dinormalbutylaluminum hydride, diisobutylaluminum hydride, dialkylaluminum hydride such as dinormalhexylaluminum hydride, etc. Can be mentioned.
Trialkylaluminum is preferable, and trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalbutylaluminum, and trinormalhexylaluminum are more preferable. Particularly preferred are trimethylaluminum, triethylaluminum, and triisobutylaluminum.

When A is a magnesium atom, R ⁴ is preferably the above hydrocarbon group, and specific examples include diethyl magnesium, dinormal butyl magnesium and the like, and dinormal butoxy magnesium where R ⁴ is the above hydrocarbon oxy group, etc. Illustrated.

When A is a zinc atom, R ⁴ is preferably the above hydrocarbon group, and specific examples include dialkyl zinc such as dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-n-hexyl zinc and the like. Diaryl zinc such as diphenyl zinc, dinaphthyl zinc and bis (pentafluorophenyl) zinc; dialkenyl zinc such as diallyl zinc; bis (cyclopentadienyl) zinc; methyl zinc chloride, ethyl zinc chloride, propyl zinc chloride, -n -Butyl zinc, isobutyl zinc chloride, -n-hexyl chloride, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, -n-butyl zinc bromide, isobutyl zinc bromide, -n-hexyl zinc bromide , Methyl zinc iodide, ethyl zinc iodide, propyl zinc iodide, n-butyl zinc iodide, isobutyl iodide Le zinc, halogenated alkyl zinc such as iodide -n- hexyl zinc; zinc fluoride, zinc chloride, zinc bromide, and halogenated zinc such as zinc iodide.

  The organometallic compound (a) is more preferably an organoaluminum compound or an organozinc compound, and most preferably an organozinc compound.

(B) Compound having active hydrogen and electron withdrawing group Examples of the compound (b) having active hydrogen and an electron withdrawing group include phenol compounds and alcohol compounds having an electron withdrawing group. The compound represented by these is preferable.
R ⁵ _t-1 TH [6]
(In the formula, R ⁵ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and when a plurality of R ⁵ are present, they may be the same or different from each other. T is a periodic table. Represents a group 15 or group 16 atom, and t represents a number corresponding to the valence of T.)

T in the general formula [6] represents an atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples of the Group 15 atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 atom include an oxygen atom and a sulfur atom. T is preferably a nitrogen atom or an oxygen atom, and particularly preferably T is an oxygen atom.
In the general formula [6], t represents a number corresponding to the valence of T. When T is a Group 15 atom, t is 3, and when T is a Group 16 atom, t is 2.

R ⁵ in the above general formula [6] represents an electron-withdrawing group or a group containing an electron-withdrawing group, and when a plurality of R ⁵ are present, they may be the same as or different from each other. As an index of electron withdrawing property, Hammett's rule substituent constant σ and the like are known, and functional groups having positive Hammett's rule constant σ are listed as electron withdrawing groups.

  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 carbonyl group, a sulfone group, and a phenyl group. Examples of the group containing an electron-withdrawing group include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl) aryl group, a cyanated aryl group, a nitrated aryl group, an ester group (an alkoxycarbonyl group, an aralkyloxycarbonyl group, Aryloxycarbonyl group), acyl group and the like.

  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-bis (trifluoromethyl) -2,2, 2-trifluoroethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 1,1-bis (tribromomethyl) -2,2,2-tribromoethyl group, 1 , 1-bis (triiodomethyl) -2,2,2-triiodoethyl group and the like.

  Specific examples of the halogenated aryl group include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl. Group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2 -Naphthyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 2,6 Dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 3,4,5-trichlorophenyl group, 2,3,5,6-tetrachlorophenyl group, penta Chlorophenyl group, 2,3,5,6-tetrachloro-4-trichloromethylphenyl group, 2,3,5,6-tetrachloro-4-pentachlorophenylphenyl group, perchloro-1-naphthyl group, perchloro-2- Naphtyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,4-dibromophenyl group, 2,6-dibromophenyl group, 3,4-dibromophenyl group, 3,5-dibromo Phenyl group, 2,4,6-tribromophenyl group, 3,4,5-tribromophenyl group, 2,3,5,6-tetrabromide Phenyl group, pentabromophenyl group, 2,3,5,6-tetrabromo-4-tribromomethylphenyl group, 2,3,5,6-tetrabromo-4-pentabromophenylphenyl group, perbromo-1-naphthyl group Perbromo-2-naphthyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,4-diiodophenyl group, 2,6-diiodophenyl group, 3,4-diiodo Phenyl group, 3,5-diiodophenyl group, 2,4,6-triiodophenyl group, 3,4,5-triiodophenyl group, 2,3,5,6-tetraiodophenyl group, pentaiodophenyl Group, 2,3,5,6-tetraiodo-4-triiodomethylphenyl group, 2,3,5,6-tetraiodo-4-pentaiodophenylphenyl group, A do-1-naphthyl group, a periodo-2-naphthyl group, etc. are mentioned.

  Specific examples of the (halogenated alkyl) aryl group include 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6-bis (tri Fluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 3,4,5-tris (trifluoromethyl) phenyl group, etc. Can be mentioned.

  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.

  Specific examples of the ester group include methoxycarbonyl group, ethoxycarbonyl group, normal propoxycarbonyl group, isopropoxycarbonyl group, phenoxycarbonyl group, trifluoromethoxycarbonyl group, pentafluorophenoxycarbonyl group and the like.

  Specific examples of the acyl group include formyl group, ethanoyl group, propanoyl group, butanoyl group, trifluoroethanoyl group, benzoyl group, pentafluorobenzoyl group and the like.

R ⁵ is preferably a halogenated hydrocarbon group, more preferably a halogenated alkyl group or a halogenated aryl group. More preferably, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trimethyl Fluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-tri Fluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoro Tilphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2-naphthyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, 2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,2-trichloro-1-trichloromethylethyl group, 1,1-bis (trichloromethyl)- 2,2,2-trichloroethyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3.5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 3,4,5-trichlorophenyl group, or A pentachlorophenyl group, particularly preferably a fluoroalkyl group or a fluoroaryl group, and most preferably a trichlorophenyl group. Fluoromethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 3,5-difluorophenyl group, A 3,4,5-trifluorophenyl group or a pentafluorophenyl group.

(D) Particles As the particles (d), those generally used as carriers are preferably used, porous materials having a uniform particle size are preferred, inorganic materials or organic polymers are suitably used, and inorganic materials are preferably used. More preferably used.
The particle (d) is preferably 2.5 or less, more preferably 2.0 or less, more preferably 2.0 or less as a volume-based geometric standard deviation of the particle size of the particle (d) from the viewpoint of the particle size distribution of the obtained polymer. Is 1.7 or less.

Examples of inorganic substances that can be used as the particles (d) include inorganic oxides, and clays and clay minerals can also be used. These may be mixed and used.
Specific examples of the inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, and mixtures thereof such as SiO ₂ — Examples thereof include MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , and SiO ₂ —TiO ₂ —MgO. Among these inorganic oxides, SiO ₂ and / or Al ₂ O ₃ are preferable, and SiO ₂ (that is, silica) is particularly preferable. The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O
Such carbonates, sulfates, nitrates, and oxide components may be contained.

Clay or clay minerals 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.

Of these inorganic substances, inorganic oxides are preferably used.
These inorganic substances are preferably dried to substantially remove moisture, and those dried by heat treatment are preferred. The heat treatment is usually carried out at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C. for an inorganic substance whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Further, during heating, for example, a method of circulating a dry inert gas (for example, nitrogen or argon) at a constant flow rate or a method of reducing the pressure can be used, but the method is not limited thereto.

  In addition, a hydroxyl group is usually formed on the surface of an inorganic oxide, but a modified inorganic oxide in which active hydrogen of the surface hydroxyl group is substituted with various substituents may be used as the inorganic oxide. good. In this case, the substituent is preferably a silyl group. Specific examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilanes such as triphenylchlorosilane, dialkyldichlorosilanes such as dimethyldichlorosilane, and diaryldisilanes such as diphenyldichlorosilane. Dialkyldialkoxy such as chlorosilane, alkyltrichlorosilane such as methyltrichlorosilane, aryltrichlorosilane such as phenyltrichlorosilane, trialkylalkoxysilane such as trimethylmethoxysilane, triarylalkoxysilane such as triphenylmethoxysilane, and dimethyldimethoxysilane Diaryl dialkoxysilanes such as silane, diphenyldimethoxysilane, and alkyltria such as methyltrimethoxysilane Contact treatment with aryltrialkoxysilane such as coxisilane, phenyltrimethoxysilane, tetraalkoxysilane such as tetramethoxysilane, alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane, tetrachlorosilane, etc. Inorganic oxides.

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 1
It is 00-500 m < ² > / g.

  As the organic polymer that can be used as the particles (d), any organic polymer may be used, and a plurality of types of organic polymers may be used as a mixture. As the organic polymer, a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group is preferable.

  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.

  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.

  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.

  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 a polymerizable unsaturated group. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.

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 having no 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.

Examples of other monomers having a polymerizable unsaturated group include ethylene, α-olefin, aromatic vinyl compounds and the like. Specific examples include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1 -Pentene, 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.

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 m ² / g.

  These organic polymers are preferably dried to substantially remove moisture, and those dried by heat treatment are preferred. The heat treatment is usually carried out at a temperature of 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Further, during heating, for example, a method of circulating a dry inert gas (for example, nitrogen or argon) at a constant flow rate or a method of reducing the pressure can be used, but the method is not limited thereto.

The amount of each compound (a), (b), (c) used is not particularly limited, but the molar ratio of the amount of each compound used is (a) :( b) :( c) = 1: y: z It is preferable that y and z substantially satisfy the following formula (1).
| M−y−2z | ≦ 1 (1)
(In the above formula (1), m represents a number corresponding to the valence of the metal atom in (a) (for example, A in the general formula [5]).)
In the above formula (1), y is preferably a number of 0.01 to 1.99, more preferably a number of 0.10 to 1.80, and still more preferably a number of 0.20 to 1.50. Yes, most preferably a number from 0.30 to 1.00, and the same preferred range of z in the above formula (1) is determined by m, y and the above formula (1).

  In the actual contact treatment of each compound, even if the use of each compound is intended to completely satisfy the above formula (1), the amount used may fluctuate slightly and remain unreacted. In consideration of the amount of the compound to be used, etc., it is usual to slightly increase or decrease the amount used as appropriate. Here, “substantially satisfying the formula (1)” is obtained by bringing each compound into contact with each other at a molar ratio satisfying the above formula (1) without completely satisfying the above formula (1). It is meant to be included when attempting to obtain such objects.

  In the preparation of the modified particles, the amount of (d) used for (a) is the metal derived from (a) contained in the particles obtained by contacting (a) and (d). It is preferable that the amount of atoms is 0.1 mmol or more, more preferably 0.5 to 20 mmol, in terms of the number of moles of metal atoms contained in 1 g of the obtained particles. What is necessary is just to decide suitably so that it may become.

  The prepolymerization catalyst used in the present invention is obtained by subjecting a catalyst containing such a solid component to a prepolymerization treatment.

  The prepolymerization treatment is preferably carried out in a slurry state by supplying a small amount of olefins in the presence of the catalyst containing the solid component. Examples of the solvent used for the slurry include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. In addition, liquid olefins can be used in place of some or all of the inert hydrocarbon solvent during slurrying.

  The amount of olefins to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the solid component in the catalyst.

  The slurry concentration at the time of prepolymerization is preferably 0.1 to 50 g-solid component / liter-solvent in the catalyst, and more preferably 0.5 to 20 g-solid component / liter-solvent in the catalyst. The prepolymerization temperature is preferably -20 ° C to 100 ° C, particularly preferably 0 ° C to 80 ° C. Further, the partial pressure of olefins in the gas phase part during prepolymerization is preferably 0.001 MPa to 2 MPa, and particularly preferably 0.01 MPa to 1 MPa. For olefins that are liquid at prepolymerization pressure and temperature, This is not the case. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is preferable.

When carrying out the prepolymerization, as a method of supplying the catalyst, if the catalyst is composed of a plurality of catalyst components, all or a part of the catalyst components are contacted in advance and then supplied to the prepolymerization reactor. Alternatively, all catalyst components may be fed separately to the prepolymerization reactor and contacted therein to form the catalyst. Further, as a method for supplying olefins, either a method of sequentially supplying olefins while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of supplying all of a predetermined amount of olefins first is used. It may be used.
It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the resulting polymer.

  The resulting prepolymerization catalyst usually removes the remaining olefins and is fed to the gas phase fluidized bed polymerization reactor together with the solvent, or removes the used solvent and the remaining olefins and is inert under reduced pressure or normal pressure. After being sufficiently dried in a gas atmosphere, it is supplied to a gas phase fluidized bed polymerization reactor using a carrier gas such as a polymerization monomer or an inert gas.

The gas phase polymerization may be performed according to a known gas phase polymerization method and polymerization conditions, but is not limited thereto.
In general, the polymerization process involves the polymerization reaction of one or more olefins with a catalytically effective amount of catalyst in the absence of a catalyst poison such as moisture, oxygen, carbon dioxide in a gas phase fluidized bed polymerization reactor. This is done by contacting at a temperature and pressure sufficient to initiate. These polymerization methods are described in, for example, US Pat. Nos. 4,482,687, 4,558,790, 4,994,534 and the like. The pressure of the gas phase polymerization may be within a range in which olefins can exist as a gas phase in the reactor, and is usually 0.1 to 5.0 MPa, preferably 1.5 to 3.0 MPa. The reaction temperature is appropriately selected depending on the catalyst to be used, the pressure in the reactor, the type of olefin to be polymerized, etc., but generally 30 to 110 ° C. is used. The gas flow rate in the reactor during the gas phase polymerization is usually in the range of 10 to 100 cm / s, preferably 20 to 70 cm / s.
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. 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.

Examples of the olefins used in the present invention include olefins having 2 to 20 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, polar monomers and the like, and two or more monomers can be used at the same time. it can.
Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1-octene and 1-nonene. Olefins such as 1-decene; 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-endomethylenehexahydronaphth Diolefins such as len, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene; norbornene, 5-methylnorbornene, 5- Ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8 -Ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbo Cyclic olefins such as nene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; styrene, 2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene Alkenylbenzene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3 , 4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butyl styrene, alkyl styrene such as p-secondary butyl styrene, bisalkenyl benzene such as divinylbenzene, Alkene such as alkenylnaphthalene such as 1-vinylnaphthalene Nyl aromatic hydrocarbons; α, β such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid -Unsaturated carboxylic acids and their metal salts such as sodium, potassium, lithium, zinc, magnesium, calcium, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, t-butyl acrylate, acrylic acid Such as 2-ethylhexyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, α, β-unsaturated carboxylic acid esters, maleic acid, itaconic acid, etc. Unsaturated dicarboxylic acid, vinyl acetate, vinyl propionate, capro Polar monomers such as vinyl esters such as vinyl acid, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. Is mentioned.

  The present invention is applied to homopolymerization or copolymerization of these monomers. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, ethylene and 1-octene, propylene and 1-butene. And ethylene, 1-butene and 1-hexene, ethylene, 1-butene and 4-methyl-1-pentene.

  The olefin polymer produced in the present invention is particularly preferably a copolymer of ethylene and an α-olefin, and particularly preferably a copolymer of ethylene and an α-olefin having a polyethylene crystal structure. The α-olefin herein is preferably an α-olefin having 3 to 8 carbon atoms, and specifically includes 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. .

  Moreover, since it is difficult to be charged after the catalyst is charged, the molecular weight distribution of the produced olefin polymer is preferably 3 to 30, and a homogeneous solid catalyst for producing an olefin polymer having a wide molecular weight distribution is preferably used.

  Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these. The measured value of each item in an Example was measured with the following method.

(1) Electrostatic charge amount The electrostatic charge amount in the reactor was measured by installing an electrostatic voltmeter S-21 manufactured by Ditec Co., Ltd. at positions 258 mm above and 958 mm above the gas dispersion plate.

(2) Density The density was measured according to JIS K-6760.

(3) Melt flow rate = MFR: Measured at 190 ° C. under a load of 21.18 N (2.16 kg) according to the method defined in JIS K7210-1995 (unit: g / 10 minutes).

(4) Swell ratio = SR: A value obtained by dividing the strand diameter obtained at the time of MFR measurement by 2.095 mm which is the inner diameter of the die.

(5) Melt flow rate ratio = MFRR: A melt flow rate value measured at 190 ° C. and a load of 211.82 N (21.60 kg) in accordance with the method defined in JIS K7210-1995 is calculated as a load of 21.18 N (2. It is a value divided by the melt flow rate value (MFR) measured at 16 kg).
For all the melt flow rate measurements, a polymer containing 1000 ppm of an antioxidant in advance was used.

(6) Bulk density It measured according to JIS K-6721.

(7) Intrinsic viscosity [η]
Using an Ubbelohde viscometer, the polymer was melted in a tetralin solution at 135 ° C. and measured (unit: dl / g).

(8) Molecular weight and molecular weight distribution It measured by the gel permeation chromatography (GPC) on the following conditions. A calibration curve was prepared using standard polystyrene. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Model: Model 150C manufactured by Millipore Waters Inc .: TSK-GEL GMH-HT 7.5 × 600 × 2 Measurement temperature: 140 ° C.
Solvent: orthodichlorobenzene,
Measurement concentration: 5 mg / 5 ml

(9) Elemental analysis Zn: The sample was poured into a sulfuric acid aqueous solution (1M), and then ultrasonic waves were applied to extract metal components. The obtained liquid portion was quantified by ICP emission spectrometry.
F: Combustion gas generated by burning a sample in a flask filled with oxygen was absorbed in an aqueous sodium hydroxide solution (10%), and the obtained aqueous solution was quantified using an ion electrode method.
[Example 1]
(1) Synthesis of solid catalyst component (1) The solid catalyst component (1) was prepared in the same manner as component (A) in Example 10 (1) and (2) of JP-A No. 2003-171415. Zn = 2.5 mmol / g, F = 5.1 mmol / g.

(2) Prepolymerization Into an autoclave with a stirrer having an internal volume of 210 liters, which had been purged with nitrogen in advance, 80 liters of butane, 4 liters of hydrogen at normal temperature and pressure, and 8 g of butene were charged, and then the autoclave was heated to 40 ° C. After 0.1 kg of ethylene was charged and the system was stabilized, 210 mmol of triisobutylaluminum, 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide, and subsequently 690 g of the solid catalyst component (1) of Example 1 (1) To start polymerization. After the start of the polymerization, the polymerization temperature in the tank was raised from 40 ° C. to 50 ° C. over 1 hour, and the first 0.5 hour was 0.5 kg / hour of ethylene and 4.3 at room temperature and normal pressure as hydrogen. From 0.5 hour after the start of polymerization, 1.8 kg / hour of ethylene and 13.8 liter / hour of hydrogen at room temperature and normal pressure were fed for a total of 6 hours. Polymerization was performed. After completion of the polymerization, ethylene and hydrogen gas are purged, transferred to a drying drum, and nitrogen circulation drying is performed, and 11.8 g of ethylene-butene copolymer is preliminarily polymerized per 1 g of the solid catalyst component (1). A polymerized olefin polymerization catalyst was obtained.

(3) Adhesion of antistatic agent to seed powder A powder of ethylene / 1-hexene copolymer polymerized by a gas phase method and trimethylmethoxysilane were mixed to prepare MB powder with 5000 ppm of trimethylmethoxysilane adhered. . The MB powder to which trimethylmethoxysilane is adhered is added to a separately prepared seed powder of ethylene / 1-hexene copolymer so that the ratio is 1.36 wt%, and 80 kg of seed powder to which trimethylmethoxysilane is adhered is 68 wtppm. Prepared.
After 80 kg of the seed powder was supplied to the stock drum, the inside of the stock drum was decompressed with a vacuum pump for 95 hours. Then, the inside of the stock drum was made into nitrogen atmosphere.

(4) Gas phase polymerization After replacing the inside of the gas phase fluidized bed reactor with a nitrogen atmosphere, nitrogen gas was circulated at a linear velocity of 28 cm / s in the reactor under the conditions of a tank pressure of 0.23 MPaG and a temperature of 80 ° C. did. Thereafter, the pressure in the tank of the seed powder stock drum was increased to 1.0 MPaG with nitrogen gas, and 80 kg of seed powder was transferred to the gas phase fluidized bed reactor. Thereafter, 250 mmol of triisobutylaluminum was added, and the pressure was increased with the raw material monomer, comonomer, H _{2 and the} like, and the pressure was increased to a polymerization pressure of 2.0 MPaG. During this time, the electrostatic charge amount was between -0.4 KV and +0.1 KV, and almost no static electricity was generated.
After completion of pressurization, using the prepolymerized olefin polymerization catalyst obtained in Example 1 (2) above, in a continuous fluidized bed gas phase polymerization apparatus, the total pressure was 2.0 MPa, the polymerization temperature was 75 ° C., the pressure was 2.0 MPaG, The holdup was adjusted to 80 kg and copolymerization of ethylene and 1-hexene was carried out. The gas composition during operation was 91 mol% ethylene, 1.05 mol% hydrogen, 0.51 mol% 1-hexene, 7.4 mol% nitrogen, and the prepolymerized olefin polymerization catalyst obtained in Example 1 (2) above. About 68 g / h was supplied, and triisobutylaluminum was supplied at 21 mmol / h to obtain about 21 kg / h of ethylene / 1-hexene copolymer. During this time, the electrostatic charge amount indicated by the electrostatic voltmeter was -0.5 to +0.5 KV and was stable. In such a state, stable operation with almost no generation of agglomerates could be carried out for about 3 days.
The density of the gas phase polymer produced at this time was 0.9239 g / cm ³ , the MFR was 4.1 g / 10 min, the SR was 1.55, the MFRR was 73.2, and the molecular weight distribution was 11.4. .

[Example 2]
(1) Prepolymerization Into an autoclave with a stirrer having an internal volume of 210 liters, which had been purged with nitrogen in advance, 80 liters of butane, 12 liters of hydrogen at room temperature and normal pressure, and 8 g of butene were charged, and the autoclave was heated to 40 ° C. After 0.3 kg of ethylene was charged and the system was stabilized, 210 mmol of triisobutylaluminum, 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide, and subsequently 690 g of the solid catalyst component (1) of Example 1 (1) To start polymerization. After the start of polymerization, the polymerization temperature in the tank was raised from 40 ° C. to 50 ° C. over 1 hour, and the first 0.5 hour was 0.6 kg / hour of ethylene and 5.2 at room temperature and normal pressure as hydrogen. From 0.5 hour after the start of polymerization, 1.8 kg / hour of ethylene and 14.0 liter / hour of hydrogen at room temperature and normal pressure are fed for a total of 6 hours. Polymerization was performed. After completion of the polymerization, ethylene and hydrogen gas are purged, transferred to a drying drum, and nitrogen circulation drying is performed, so that 13.0 g of ethylene-butene copolymer is preliminarily polymerized per 1 g of the solid catalyst component (1). A polymerized olefin polymerization catalyst was obtained.

(2) Adhesion of antistatic agent to seed powder MB in which powder of ethylene / 1-hexene copolymer polymerized by gas phase method and trimethyl tertiary butoxysilane were mixed and 5000 ppm of trimethyl tertiary butoxysilane adhered Prepared to powder. The MB powder to which trimethylmethoxysilane is adhered is added to a separately prepared seed powder of ethylene / 1-hexene copolymer so as to have a ratio of 1.26 wt%, and the seed powder to which 63 wtppm of trimethyl tertiary butoxysilane is adhered. 80 kg was prepared.
80 kg of the seed powder was supplied to the stock drum. Then, the inside of the stock drum was made into nitrogen atmosphere.

(3) Gas phase polymerization After replacing the inside of the gas phase fluidized bed reactor with a nitrogen atmosphere, nitrogen gas was circulated at a linear velocity of 28 cm / s in the reactor under the conditions of 0.23 MPaG in the tank and a temperature of 80 ° C. did. Thereafter, the pressure in the tank of the seed powder stock drum was increased to 1.0 MPaG with nitrogen gas, and 80 kg of seed powder was transferred to the gas phase fluidized bed reactor. Thereafter, 250 mmol of triisobutylaluminum was added, and the pressure was increased with the raw material monomer, comonomer, H _{2 and the} like, and the pressure was increased to a polymerization pressure of 2.0 MPaG. During this time, the electrostatic charge amount was between -2.9 KV and +0.3 KV, and almost no static electricity was generated.
After completion of pressurization, using the prepolymerized olefin polymerization catalyst obtained in Example 2 (1) above, in a continuous fluidized bed gas phase polymerization apparatus, the total pressure was 2.0 MPa, the polymerization temperature was 75 ° C., the pressure was 2.0 MPaG, The hold-up was adjusted to 80 kg and terpolymerization of ethylene, 1-butene and 1-hexene was carried out. The gas composition during operation was ethylene 90.4 mol%, hydrogen 0.74 mol%, 1-hexene 0.2 mol%, 1-butene 3.2 mol%, nitrogen 5.5 mol%, and in Example 2 (1) above. The obtained prepolymerized olefin polymerization catalyst was fed at about 42 g / h, and triisobutylaluminum was fed at 21 mmol / h to obtain about 20.2 kg / h of ethylene / 1-hexene / 1-butene copolymer. It was. During this time, the electrostatic charge amount indicated by the electrostatic voltmeter was +0.1 to +0.7 KV and was stable. In this state, stable operation with almost no generation of agglomerates could be performed for about 4 days. In the open inspection after the operation was completed, no sheeting lump was seen.
The density of the gas phase polymer produced at this time was 0.9184 g / cm ³ , the MFR was 0.47 g / 10 min, the SR was 1.27, the MFRR was 140.4, and the molecular weight distribution was 11.8. .

[Example 3]
(1) Preliminary polymerization Into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, 80 liters of butane, 4 liters of hydrogen at room temperature and normal pressure, and 8 g of butene were charged, and then the autoclave was heated to 40 ° C. After charging 0.3 kg of ethylene and stabilizing the system, 225 mmol of triisobutylaluminum, 75 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide, and then 730 g of the solid catalyst component (1) of Example 1 (1) To start polymerization. After the start of polymerization, the polymerization temperature in the tank was raised from 40 ° C. to 50 ° C. over 1 hour, and the first 0.5 hour was 3.9 as 0.5 kg / hour of ethylene and hydrogen at normal temperature and pressure. From 0.5 hour after the start of polymerization, 1.8 kg / hour of ethylene and 19.6 liter / hour of hydrogen at room temperature and normal pressure were fed for a total of 6 hours of reserve. Polymerization was performed. After completion of the polymerization, ethylene and hydrogen gas were purged, transferred to a drying drum, and nitrogen circulation drying was carried out, so that 12.0 g of ethylene-butene copolymer per 1 g of the solid catalyst component (1) was prepolymerized. A polymerized olefin polymerization catalyst was obtained.

(2) Adhesion of antistatic agent to seed powder Ethylene / 1-hexene copolymer powder polymerized by gas phase method and normal propylmethyldimethoxysilane are mixed for 2 minutes with a Henschel mixer, and then normalpropylmethyldimethoxysilane is mixed. Was prepared to MB powder with 5000 ppm adhered. The MB powder to which the normal propylmethyldimethoxysilane was attached was added to a separately prepared ethylene / 1-hexene copolymer seed powder so that the ratio was 1.12 wt%, and 56 wtppm of normalpropylmethyldimethoxysilane was attached. 80 kg of seed powder was adjusted.
80 kg of the seed powder was supplied to the stock drum. Then, the inside of the stock drum was made into nitrogen atmosphere.

(3) Gas phase polymerization After replacing the inside of the gas phase fluidized bed reactor with a nitrogen atmosphere, nitrogen gas was circulated at a linear velocity of 28 cm / s in the reactor under the conditions of 0.23 MPaG in the tank and a temperature of 80 ° C. did. Thereafter, the pressure in the tank of the seed powder stock drum was increased to 1.0 MPaG with nitrogen gas, and 80 kg of seed powder was transferred to the gas phase fluidized bed reactor. Thereafter, 250 mmol of triisobutylaluminum was added, and the pressure was increased with the raw material monomer, comonomer, H _{2 and the} like, and the pressure was increased to a polymerization pressure of 2.0 MPaG. During this time, the electrostatic charge amount was between -2.5 KV and +0 KV, and almost no static electricity was generated.
After completion of pressurization, using the prepolymerized olefin polymerization catalyst obtained in Example 3 (1) above, in a continuous fluidized bed gas phase polymerization apparatus, the total pressure was 2.0 MPa, the polymerization temperature was 75 ° C., the pressure was 2.0 MPaG, The holdup was adjusted to 80 kg, and ethylene and 1-butene were copolymerized. The gas composition during operation was 87.7 mol% ethylene, 0.31 mol% hydrogen, 6.6 mol% 1-butene, 5.4 mol% nitrogen, and used for prepolymerized olefin polymerization obtained in Example 3 (1) above. The catalyst was supplied at about 45 g / h, and triisobutylaluminum was supplied at 21 mmol / h to obtain about 19.3 kg / h of ethylene / 1-butene copolymer. On the way, the linear velocity of the reactor was increased to 37 cm / s. During this time, the electrostatic charge amount indicated by the electrostatic voltmeter was -0.1 to 0 KV and was stable. In this state, stable operation with almost no generation of agglomerates could be carried out for about 3.5 days. In the open inspection after the operation was completed, no sheeting lump was seen.
The density of the gas phase polymer produced at this time was 0.903 g / cm ³ , the MFR was 0.03 g / 10 min, the MFRR was 264.7, and the molecular weight distribution was 9.2.

[Example 4]
(1) Preliminary polymerization Into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, 80 liters of butane, 4 liters of hydrogen at room temperature and normal pressure, and 8 g of butene were charged, and then the autoclave was heated to 40 ° C. After charging 0.3 kg of ethylene and stabilizing the system, 225 mmol of triisobutylaluminum, 75 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide, followed by 720 g of the solid catalyst component (1) of Example 1 (1) To start polymerization. After the start of polymerization, the polymerization temperature in the tank was raised from 40 ° C. to 50 ° C. over 1 hour, and the first 0.5 hour was 0.6 kg / hour of ethylene and 3.8 as hydrogen at normal temperature and pressure. From 0.5 hour after the start of polymerization, 1.8 kg / hour of ethylene and 14.4 liter / hour of hydrogen at room temperature and normal pressure were fed for a total of 6 hours of reserve. Polymerization was performed. After completion of the polymerization, ethylene and hydrogen gas are purged, transferred to a drying drum, and nitrogen circulation drying is performed, so that 13.0 g of ethylene-butene copolymer is preliminarily polymerized per 1 g of the solid catalyst component (1). A polymerized olefin polymerization catalyst was obtained.

(2) Adhesion of the antistatic agent to the seed powder The powder of ethylene / 1-hexene copolymer polymerized by the gas phase method and tertiary butyl normal propyl dimethoxysilane are mixed for 2 minutes with a Henschel mixer. An MB powder having 5000 ppm of normal propyl dimethoxysilane was prepared. The MB powder to which tertiary butyl normal propyl dimethoxysilane is adhered is added to a separately prepared ethylene / 1-hexene copolymer seed powder so that the ratio becomes 0.98 wt%, and tertiary butyl normal propyl dimethoxy silane is added. 80 kg of seed powder with 49 wtppm attached was prepared.
80 kg of the seed powder was supplied to the stock drum. Then, the inside of the stock drum was made into nitrogen atmosphere.

(3) Gas phase polymerization After replacing the inside of the gas phase fluidized bed reactor with a nitrogen atmosphere, nitrogen gas was circulated at a linear velocity of 25 cm / s in the reactor under the conditions of a tank pressure of 0.23 MPaG and a temperature of 80 ° C. did. Thereafter, the pressure in the tank of the seed powder stock drum was increased to 1.0 MPaG with nitrogen gas, and 80 kg of seed powder was transferred to the gas phase fluidized bed reactor. Thereafter, 250 mmol of triisobutylaluminum was added, and the pressure was increased with the raw material monomer, comonomer, H _{2 and the} like, and the pressure was increased to a polymerization pressure of 2.0 MPaG. During this time, the electrostatic charge amount was between -1.0 KV and +0.2 KV, and almost no static electricity was generated.
After completion of pressurization, using the prepolymerized olefin polymerization catalyst obtained in Example 4 (1) above, in a continuous fluidized bed gas phase polymerization apparatus, the total pressure was 2.0 MPa, the polymerization temperature was 70 ° C., the pressure was 2.0 MPaG, The holdup was adjusted to 80 kg and ethylene and 1-hexene were copolymerized. The gas composition during operation was 93.1 mol% ethylene, 0.22 mol% hydrogen, 0.61 mol% 1-hexene, 6.0 mol% nitrogen, and used for the prepolymerized olefin polymerization obtained in Example 4 (1) above. The catalyst was fed at about 33 g / h and triisobutylaluminum was fed at 17 mmol / h to obtain about 20.8 kg / h ethylene / 1-butene copolymer. During this time, the electrostatic charge amount indicated by the electrostatic voltmeter was -0.2 to +0.2 KV and was stable. In this state, stable operation with almost no generation of agglomerates could be carried out for about 3.5 days. In the open inspection after the operation was completed, no sheeting lump was seen.
The density of the gas phase polymer produced at this time was 0.9294 g / cm ³ , the MFR was 0.56 g / 10 min, the SR was 1.27, the MFRR was 128.3, and the molecular weight distribution was 8.8. .

[Comparative Example 1]
(1) Synthesis of contact product (e) To a 5-liter four-necked flask purged with nitrogen, 1.50 liters of tetrahydrofuran, hexane solution of diethylzinc (2.0 mol / liter) and 1.343 liters (2.68 mol) were added. And cooled to 5 ° C. A solution prepared by dissolving 199.2 g (1.08 mol) of pentafluorophenol in 340 ml of tetrahydrofuran was added dropwise thereto over 60 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 60 minutes, the temperature was raised to 45 ° C. over 30 minutes, and stirring was performed for 60 minutes. Thereafter, the temperature was lowered to 19.6 ° C. in an ice bath, and 43.6 g (2.42 mol) of H ₂ O was added dropwise over 90 minutes. Then, it stirred at 20 degreeC for 60 minutes, heated up to 45 degreeC over 25 minutes, and stirred for 60 minutes. Thereafter, the solvent was distilled off under reduced pressure for 2.5 hours while raising the temperature to 50 ° C., and then dried under reduced pressure at 120 ° C. for 8 hours. As a result, 414 g of a solid product was obtained.

(2) Synthesis of Component (B) 414 g of the solid product synthesized in Comparative Example 1 (1) and 3 liters of tetrahydrofuran were placed in a 5-liter four-necked flask purged with nitrogen and stirred. This was charged with 311.1 g of silica (Sypolol 948 manufactured by Devison; average particle size = 59 μm; pore volume = 1.61 ml / g; specific surface area = 306 m ² / g) heated at 300 ° C. under a nitrogen flow. After heating to 40 ° C. and stirring for 2 hours, the mixture was allowed to stand, the solid component was allowed to settle, and when the interface between the precipitated solid component layer and the upper slurry portion was seen, the upper slurry portion was removed. . As a washing operation, 3 liters of tetrahydrofuran was added thereto, and after stirring, the mixture was allowed to stand to allow the solid component to settle. Similarly, when the interface was seen, the upper slurry portion was removed. The above washing operation was repeated 5 times in total. Thereafter, drying was performed at 120 ° C. under reduced pressure for 8 hours to obtain 509.6 g of a solid catalyst component (1).

(3) Prepolymerization After charging 100 liters of butane containing triisobutylaluminum at a concentration of 2.5 mmol / liter in an autoclave with a stirrer with an internal volume of 210 liters previously substituted with nitrogen, and 12 liters as hydrogen at normal temperature and pressure, The autoclave was heated to 45 ° C. After ethylene was charged by 0.3 MPaA as the gas phase pressure in the autoclave and the system was stabilized, 250 mmol of triisobutylaluminum, 37.5 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide, and then Comparative Example 1 252 g of the solid catalyst component (1) obtained in (2) was added to initiate polymerization. Immediately after charging the catalyst, 4.0 kg / hour of ethylene and 10 liter / hour of hydrogen at ordinary temperature and pressure were supplied. After the start of polymerization, the polymerization temperature in the tank was raised from 40 ° C. to 50 ° C. over 1 hour, and then polymerization was carried out at 50 ° C. to carry out preliminary polymerization for a total of 2.5 hours. After completion of the polymerization, purging ethylene, butane and hydrogen gas and filtering the solvent, the resulting solid was vacuum-dried at room temperature, and 37.1 g of ethylene homopolymer per 1 g of the solid catalyst component (1). A prepolymerized olefin polymerization catalyst in which the polymer was prepolymerized was obtained. The preliminary polymer obtained had an intrinsic viscosity [η] of 0.91 dl / g.

(4) Gas phase polymerization After replacing the inside of the gas phase fluidized bed reactor with a nitrogen atmosphere, nitrogen gas was circulated at a linear velocity of 24 cm / s in the reactor under the conditions of a tank pressure of 0.23 MPaG and a temperature of 80 ° C. did. Thereafter, the pressure of the seed powder stock drum is increased to 1.0 MPaG with nitrogen gas, and 80 kg of seed powder, which is a gas phase polymerization powder of ethylene / 1-hexene copolymer, is transferred to the gas phase fluidized bed reactor. did. The electrostatic voltmeter installed at 258 mm showed a value of −13 KV when the seed powder was transferred, the pressure was increased with the raw material monomer, comonomer, H _{2 and the} like, and the pressure was increased to the polymerization pressure of 2.0 MPaA. Thereafter, when the electrostatic charge amount was reduced to about −7 KV, the prepolymerized olefin polymerization catalyst obtained in Comparative Example 1 (3) was used, and the total pressure was 2.0 MPa, the polymerization temperature was 85 ° C., the circulation gas line Copolymerization of ethylene and 1-hexene was carried out at a speed of 25 cm / s and a hold-up of 80 kg. The gas composition during operation was ethylene 92.7 mol%, hydrogen 0.07 mol%, 1-hexene 0.92 mol%, nitrogen 4.1 mol%, and used for prepolymerized olefin polymerization obtained in Comparative Example 1 (3). Catalyst was fed and triisobutylaluminum was fed at 79 mmol / h. At that time, the activity exhibited smoothly, but showed a value of −20 KV after 2 hours from the start of the catalyst charging. Therefore, the supply of the catalyst was once stopped, and the catalyst was re-feeded after waiting for the electrostatic charge amount to be -6 KV. Thereafter, the amount of powder produced was increased to 6.7 kg / h. However, after 13 hours from the start of catalyst addition, defective extraction of the produced powder occurred and polymerization was stopped. The powder produced during that time was 50 kg. When the inside of the reactor was opened after the operation was stopped, it was confirmed that about 24 kg of sheet-like agglomerates were formed inside the reactor.
At this time, the density of the powder remaining in the reactor was 0.9287 g / cm ³ , MFR was 1.8 g / 10 min, SR was 1.63, MFRR was 47.5, and molecular weight distribution was 4.0. It was.

Claims (8)

An antistatic agent comprising a silicon compound represented by the formula (I).
R _r Si (OR ′) _4-r (I)
(In the formula, R and R ′ are each independently a hydrocarbon group having 1 to 20 carbon atoms, r is 2 or 3, and when there are plural Rs, they may be the same or different from each other). Well, when there are a plurality of R ′, they may be the same or different.) A seed powder filled in a gas phase fluidized bed polymerization reactor, to which a silicon compound represented by the formula (I) is adhered.
R _r Si (OR ′) _4-r (I)
(In the formula, R and R ′ are each independently a hydrocarbon group having 1 to 20 carbon atoms, r is 2 or 3, and when there are plural Rs, they may be the same or different from each other). Well, when there are a plurality of R ′, they may be the same or different.)   The seed powder according to claim 2, wherein the adhesion amount is 0.01 to 1000 wtppm. A method for polymerizing olefins, in which polymerization is started after a seed powder having a silicon compound represented by formula (I) attached thereto is charged in a gas phase fluidized bed polymerization reactor.
R _r Si (OR ′) _4-r (I)
(In the formula, R and R ′ are each independently a hydrocarbon group having 1 to 20 carbon atoms, r is 2 or 3, and when there are plural Rs, they may be the same or different from each other). Well, when there are a plurality of R ′, they may be the same or different.) A method for producing an olefin polymer, in which a seed powder having a silicon compound represented by formula (I) is charged into a gas phase fluidized bed polymerization reactor and then polymerization is started to polymerize olefins.
R _r Si (OR ′) _4-r (I)
(In the formula, R and R ′ are each independently a hydrocarbon group having 1 to 20 carbon atoms, r is 2 or 3, and when there are plural Rs, they may be the same or different from each other). Well, when there are a plurality of R ′, they may be the same or different.)   A method for producing an olefin polymer, wherein an olefin is polymerized using a gas phase fluidized bed polymerization reactor in which a silicon compound represented by the formula (I) is coated on an inner wall surface.   The method for producing an olefin polymer according to claim 5 or 6, wherein the olefin polymer is an olefin polymer having a molecular weight distribution of 3 to 30. The method for producing an olefin polymer according to claim 7, wherein olefins are polymerized in the presence of a homogeneous solid catalyst.