JP2007039603A - Catalyst composition for olefin polymerization - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for olefin polymerization having high activity, having good bulk density and particle properties of catalyst powder, suppressing adhesion to polymerization reactor wall, etc., in a catalyst feed step and a polymerization step and capable of continuing stable polymerization operation. <P>SOLUTION: The catalyst composition for olefin polymerization is obtained by mixing a solid catalyst component [A] for olefin polymerization containing a transition metal compound (component [a]) of group III to X of the periodic table and a cocatalyst support (component [b]) with inorganic oxide fine particles (component [B]) having ≥35% hydrophobization degree in a weight ratio of 0.0001-0.1. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a catalyst composition for olefin polymerization, and more particularly to a catalyst composition for olefin polymerization that is highly active and excellent in powder properties such as fluidity and adhesion.

  In producing an olefin polymer by polymerizing an olefin in the presence of a catalyst, a method using a catalyst comprising a metallocene compound and an aluminoxane is already known (for example, see Patent Documents 1 and 2). It is known that the polymerization method using these catalysts provides a polymer having a high polymerization activity per transition metal and a narrow molecular weight distribution and composition distribution compared with the conventional method using a Ziegler-Natta catalyst. It has been.

However, these catalyst systems are often soluble in the reaction system, and olefin polymers obtained by slurry polymerization or gas phase polymerization usually have very poor particle properties. Is a major problem in the manufacturing process. In order to solve these problems, a catalyst in which one or both of a transition metal compound and an aluminoxane are supported on an inorganic oxide or organic substance such as silica or alumina and solidified or powdered has also been proposed (for example, (See Patent Documents 3 and 4).
However, in general, when an olefin polymerization catalyst is dried and handled as powder, there are various problems such as so-called catalyst powder properties such as poor adhesion, fluidity, angle of repose, and bulk density. For the purpose of improving the properties of such catalyst powder, a solid catalyst obtained by adding a fine metal oxide to a prepolymerized metallocene catalyst component has been proposed (for example, see Patent Document 5). However, when the fine metal oxide described in Patent Document 5 is added to a catalyst component that has not been pre-polymerized, the catalyst powder properties are deteriorated or the polymerization activity is reduced. There has been a demand for an invention of an improved technique for powder properties of catalyst components.

In addition, since the catalyst component for olefin polymerization that is solidified and handled in this way is likely to cause adhesion in the manufacturing apparatus, in actual processes, such as adhesion and blockage in the catalyst supply process. As a result, there is a problem that the catalyst supply is difficult to stabilize, and that the stable polymerization operation cannot be continued due to the adhesion to the polymerization reactor wall.
Japanese Examined Patent Publication No. 4-12283 Japanese Unexamined Patent Publication No. 60-35007 JP-A-61-108610 Japanese Patent Laid-Open No. 61-276805 JP-A-9-324008

  In view of the above problems, the object of the present invention is to improve the catalyst powder properties of a catalyst component for olefin polymerization that is solidified and handled in powder, is highly active, and has a bulk density and particles of the catalyst powder. An object of the present invention is to provide a catalyst composition for olefin polymerization which has good properties, suppresses adhesion to a polymerization reactor wall or the like in a catalyst supply step or a polymerization step, and can continue a stable polymerization operation.

  In order to solve the above-mentioned problems, the present inventors have intensively studied to find a method in which the catalyst powder has good bulk density, adhesion, fluidity and other properties and does not impair the performance such as polymerization activity. By mixing inorganic oxide fine particles having a specific degree of hydrophobicity with a solid catalyst for olefin polymerization containing a transition metal compound and a co-catalyst support, the bulk density and particle size of the catalyst powder are high. The inventors have found that an olefin polymerization catalyst composition having very good properties and in which problems such as adhesion in the catalyst supply step and the polymerization step are eliminated can be obtained.

  That is, according to 1st invention of this invention, the solid catalyst for olefin polymerization containing the transition metal compound (component [a]) of the 3rd-10th groups of a periodic table, and a promoter support (component [b]) ( It is characterized by mixing inorganic oxide fine particles (component [B]) having a hydrophobization degree of 35% or more with respect to component [A]) in a weight ratio of 0.0001 to 0.1. An olefin polymerization catalyst composition is provided.

  According to the second invention of the present invention, in the first invention, the component [a] is a transition metal compound belonging to Groups 4 to 6 of the periodic table. Is provided.

According to the third invention of the present invention, in the first or second invention, the component [b] contains one or more selected from the following [b-1] to [b-5]. Provided is a catalyst composition for olefin polymerization, which is a catalyst carrier.
[B-1] A carrier carrying an aluminum oxy compound [b-2] A carrier carrying an ionic compound or Lewis acid capable of reacting with component [a] to convert component [a] into a cation [B-3] Solid acid [b-4] An organometallic compound, a compound having a functional group having active hydrogen or an aprotic Lewis basic functional group and an electron-withdrawing group, and a compound R _t-2 TH ₂ (R represents a hydrocarbon group or a halogenated hydrocarbon group, T represents a group 15 or group 16 nonmetal atom of the periodic table, and t represents the valence of T of the compound.) Modified particle support [b-5] layered silicate obtained by contacting with

  According to a fourth aspect of the present invention, there is provided the catalyst composition for olefin polymerization according to any one of the first to third aspects, wherein the average particle size of the component [B] is 30 μm or less. Provided.

  According to the fifth aspect of the present invention, in any one of the first to fourth aspects, the ratio of the average particle diameter of the component [B] to the average particle diameter of the component [A] is 0.0001-0. The catalyst composition for olefin polymerization is provided.

  According to the sixth invention of the present invention, in any one of the first to fifth inventions, the component [B] is an oxide or composite oxide of Mg, Ca, Ti, Zr, Al or Si. An olefin polymerization catalyst composition is provided, wherein the catalyst composition is selected from among products.

  According to a seventh aspect of the present invention, there is provided the catalyst composition for olefin polymerization according to any one of the first to sixth aspects, further comprising an organoaluminum compound (component [C]). Provided.

  According to an eighth aspect of the present invention, there is provided an olefin polymerization catalyst composition characterized in that, in any one of the first to seventh aspects, the catalyst is a gas phase polymerization catalyst.

  According to a ninth aspect of the present invention, the catalyst composition for olefin polymerization according to any one of the first to eighth aspects, wherein adhesion to a metal container is 0.1 g / 10 cc or less. Is provided.

  The catalyst composition for olefin polymerization of the present invention has a high activity, and the catalyst powder has a very good bulk density and particle properties, which eliminates problems such as adhesion in the catalyst supply process and polymerization process. It is a thing. Such a catalyst composition does not substantially cause problems such as adhesion to the catalyst supply line and clogging due thereto, and adhesion to the polymerization reactor wall, and enables continuous and stable catalyst supply. Olefin polymerization can be performed stably.

  The catalyst composition for olefin polymerization of the present invention is a solid catalyst for olefin polymerization (component [component [b]) containing a transition metal compound (component [a]) of groups 3 to 10 of the periodic table and a promoter catalyst (component [b]). A]) is a catalyst composition in which inorganic oxide fine particles (component [B]) having a degree of hydrophobicity of 35% or more are mixed. Hereinafter, constituent components, olefin polymerization, and the like will be described in detail.

1. Olefin Polymerization Catalyst Composition Component (1) Component [A]
The solid catalyst for olefin polymerization (component [A]) used in the catalyst composition for olefin polymerization of the present invention contains a transition metal compound (component [a]) and a promoter support (component [b]), and further required. Accordingly, an organoaluminum compound (component [c]) is contained.
Moreover, the average particle diameter of component [A] becomes like this. Preferably it is 5-500 micrometers, More preferably, it is 10-100 micrometers. When the average particle size of component [A] is less than 5 μm, stable production operation cannot be continued due to adhesion to the catalyst supply line, clogging or adhesion to the polymerization reactor wall, and formation of finely divided polymer. Even if it exceeds 500 μm, stable production operation cannot be continued due to deterioration of fluidity or generation of a large particle size polymer.

(I) Component [a]
Component [a] used in the present invention is a transition metal compound component having olefin polymerization ability. Examples of the transition metal compound component include all transition metal compounds of Groups 3 to 10 of the periodic table. Preferably, a metallocene compound of a Group 3-6 metal, a bisamide of a Group 4 metal, a biimino compound of a Group 8-10 metal, or a salicylaldiminato compound of a Group 4-10 metal is used.

  In the case where these transition metal compounds are not dialkyl compounds, an organic metal compound such as Li, Na, K, Mg, Ca, Ag, Hg, Zn, Al, Ga or the like that can convert them into a dialkyl compound is polymerized in advance, or It is necessary to exist at the same time.

  Examples of the transition metal compounds of Group 3 to 6 of the periodic table having at least one conjugated 5-membered ring ligand, that is, metallocene compounds include those represented by the following general formulas (1) to (4). be able to.

^{_{(C 5 H 5-a R}} 1 a) (C 5 H 5-b R 2 b) MXY ... (1)
^{_{Q (C 5 H 4-c}} R 1 c) (C 5 H 4-d R 2 d) MXY ... (2)
^{_{Q (C 5 H 4-e}} R 3 e) ZMXY ... (3)
^{_{(C 5 H 5-f R}} 4 f) MXYW ... (4)

  Here, in the general formulas (1) to (4), Q is added adjacent to two conjugated 5-membered ring ligands, a conjugated 5-membered ring ligand and a Z group, or two conjugated 5-membered rings. It is a bonding group that bridges rings formed by bonding alkyl groups, and is a hydrocarbon group having 1 to 20 carbon atoms, or a silicon, germanium, oxygen, nitrogen, or phosphorus-containing hydrocarbon having 1 to 40 carbon atoms A group, M is a group 3-6 transition metal in the periodic table, X, Y, and W are each independently a hydrogen atom, a halogen, a C1-C20 hydrocarbon group, or a C1-C20 group, O represents an oxygen, nitrogen, silicon or phosphorus-containing hydrocarbon group, and Z represents oxygen, sulfur or a silicon, oxygen, nitrogen or phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms. M is particularly preferably Ti, Zr, or Hf.

R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrocarbon group having 1 to 20 carbon atoms, or a halogen, oxygen, silicon, phosphorus, nitrogen or boron-containing hydrocarbon having 1 to 20 carbon atoms. Show. Examples of the oxygen-containing hydrocarbon group include an alkoxy group, an alkoxyalkyl group, an aryloxy group, and an alkoxyaryl group.

Two adjacent R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a 4-membered ring to a 10-membered ring. a, b, c, d, e, and f are integers that satisfy 0 ≦ a, b, f ≦ 5, 0 ≦ c, d, and e ≦ 4, respectively.

Among the above-mentioned ^{_{ligands, (C 5 H 5-a}} R 1 a), (C 5 H 5-b R 2 b), (C 5 H 4-c R 1 c), (C 5 H 4 _-d R ² _d), are added ^{_{(C 5 H 4-e R}} 3 e), (C 5 H 5-f R 4 f) is a cyclopentadienyl group, an indenyl group, a fluorenyl group, an azulenyl group or a partially hydrogenated Indenyl, fluorenyl and azulenyl groups are preferred.

  Examples of the crosslinkable group Q include an alkylene group, an alkylidene group, a silylene group, and a germylene group. Specifically, a methylene group, an ethylene group, a dimethylsilylene group, a diphenylsilylene group, a dimethylgermylene group, and the like are preferable.

  Examples of specific zirconium complexes represented by the above general formulas (1) to (4) are exemplified below, but compounds in which zirconium is replaced with hafnium or titanium can also be used.

  Examples of the zirconium complex represented by the general formula (1) include biscyclopentadienylzirconium dimethyl, bis (2-methylcyclopentadienyl) zirconium dimethyl, and bis (2-methyl-4,5-benzoindenyl) zirconium dimethyl. Bisfluorenylzirconium dimethyl, biscyclopentadienylzirconium dichloride, bis (2-methyl-4-phenylazurenyl) zirconium dichloride, (indenyl) (1,3-dimethylcyclopentadienyl) zirconium dimethyl, etc. It is done.

  Examples of the zirconium complex represented by the general formula (2) include dimethylsilylene bis (1,1′-cyclopentadienyl) zirconium dimethyl, dimethylsilylene bis (1,1′-2-methylindenyl) zirconium dimethyl, and dimethylsilylene. Bis (1,1'-2-methyl-4,5-benzoindenyl) zirconium dimethyl, dimethylsilylene bis (1,1'-cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (1,1'-2- Methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilylene bis (1,1′-2-methyl-4-phenylazurenyl) zirconium dichloride, dimethylgermylene bis (1,1′-2-methyl-4) -Phenylazurenyl) zirconium dichloride, dimethylsilylene The [7,7 '- {1-isopropyl-3- (4-chlorophenyl) indenyl)} zirconium dichloride, and the like.

  Examples of the zirconium complex represented by the general formula (3) include dimethylsilylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dimethyl, (t-butylamide) (tetramethylcyclopentadienyl) -1,2-ethane. Diylzirconium dimethyl, (t-butylamide) (tetramethylcyclopentadienyl) silanediylzirconium dimethyl, (phenylphosphide) dimethyl (tetradimethylcyclopentadienyl) silanediylzirconium dimethyl, (t-butylamide) (tetramethylcyclo Pentadienyl) -1,2-ethanediylzirconium dichloride, (t-butylamide) (tetramethylcyclopentadienyl) silanediylzirconium dichloride, and the like.

  As the zirconium complex represented by the general formula (4), (cyclopentadienyl) (phenoxy) zirconium dimethyl, (2,3-dimethylcyclopentadienyl) (phenoxy) zirconium dimethyl, (pentamethylcyclopentadienyl) (Phenoxy) zirconium dimethyl, (cyclopentadienyl) (phenoxy) zirconium dichloride, (2,3-dimethylcyclopentadienyl) (phenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (phenoxy) zirconium dichloride, Pentamethylcyclopentadienyl) (2,6-di-i-propylphenoxy) zirconium dichloride, (cyclopentadienyl) zirconium chlorodimethyl, (pentamethylcyclopentadienyl) zirconium Chlorodimethyl, (pentamethylcyclopentadienyl) zirconium isopropoxydimethyl, (cyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (cyclopentadienyl) zirconium triisopropoxide, (Pentamethylcyclopentadienyl) zirconium triisopropoxide and the like.

As the metallocene compound, reaction products obtained by bringing the following components (I) to (III) into contact with each other can also be used.
Component (I): Compound represented by the following general formula (5) Me ¹ R ¹ _p (OR ² ) _q X ¹ _4-pq (5)
(Wherein R ¹ and R ² are each independently a hydrocarbon group having 1 to 24 carbon atoms, X ¹ is a hydrogen atom or a halogen atom, Me ¹ is Ti, Zr or Hf, and p and q are 0 ≦ p, respectively. ≦ 4, 0 ≦ q ≦ 4, 0 ≦ p + q ≦ 4)
Component (II): Compound represented by the following general formula (6) Me ² R ³ _m (OR ⁴ ) _n X ² _zm-n (6)
(Wherein R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 24 carbon atoms, X ² is a hydrogen atom or a halogen atom, Me ² is a Group 1-13 element of the periodic table, and z is a valence of Me ² . And m and n are 0 ≦ m ≦ z, 0 ≦ n ≦ z, and 0 <m + n ≦ z, respectively.)
Component (III): an organic cyclic compound having two or more conjugated double bonds

  The compounds represented by the general formulas (5) and (6) of the above components (I) and (II) and the compound of the component (III) are specifically exemplified, but the compounds in which zirconium is replaced with hafnium and titanium are similarly exemplified. Can be used.

  Examples of the compound represented by the general formula (5) include tetramethoxy zirconium, tetraethoxy zirconium, tetrapropoxy zirconium, tetra-iso-propoxy zirconium, tetra-iso-butoxy zirconium, tetramethyl zirconium, tetraethyl zirconium, tetrapropyl zirconium, tetra -N-butyl zirconium, tetrachloro zirconium, trimethyl monochloro zirconium, triethyl monochloro zirconium, trimethoxy monochloro zirconium and the like.

  Examples of the compound represented by the general formula (6) include methyl lithium, ethyl lithium, n-butyl lithium, tert-butyl lithium, phenyl lithium, methyl ethyl magnesium, dimethyl zinc, diethyl zinc, trimethyl aluminum, triethyl aluminum, tri-iso. -Butylaluminum, tri-n-hexylaluminum, diethylaluminum hydride, diethylaluminum chloride and the like.

  Examples of the component (III) compound include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, iso-propylcyclopentadiene, n-butylcyclopentadiene, sec-butylcyclopentadiene, tert-butylcyclopentadiene, trimethylsilylcyclohexane. Pentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1-methyl-3-propylcyclopentadiene, pentamethylcyclopentadiene, indene, 2-methylindene, 4-methylindene, 4,7-dimethyl Examples include indene, 4,5,6,7-tetrahydroindene, 4,5-benzoindene, and azulene.

  Furthermore, as a special example of a metallocene compound, a ligand containing one or more elements other than carbon in a 5-membered ring or a 6-membered ring disclosed in JP-A-7-188335 and JACS, 1996, 118, p2291 Transition metal compounds having can also be used.

  Next, as a nonmetallocene compound whose central metal is a group 4 or group 8-10 element, N atoms or O atoms as shown in the following general structural formulas (7) to (12) are directly formed on the central metal. Examples thereof include a bridged transition metal compound that is coordinated and has a bulky substituent on a nitrogen atom or an oxygen atom.

  Examples of the group 4 metal compound of the periodic table include bisamide compounds having an NN type ligand as shown in the following general formula (7).

In general formula (7), R ⁵ represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen, oxygen or silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and U represents a bonding group that bridges two N atoms. A hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 40 carbon atoms, silicon, nitrogen, oxygen or sulfur, M ′ is a group 4 transition metal in the periodic table, and X and Y are A hydrogen atom, a halogen, a C1-C20 hydrocarbon group, or a C1-C20 oxygen, nitrogen, silicon, or phosphorus containing hydrocarbon group is shown.

Specifically, it is preferable that R ⁵ = tert-butyl, trimethylsilyl, 2,6-diisopropylphenyl, or 2,4,6-trimethylphenyl group.

U is preferably U = propenyl, 2-phenylpropenyl, 2,2-diphenylpropenyl. M ′ is any one of Ti, Zr, and Hf, and X and Y are preferably any one of Cl, methyl, benzyl, and dimethylamide.
More specifically, (R ⁵ , U, M ′, X, Y) = (tert-butyl, propenyl, Ti, Cl, Cl), (trimethylsilyl, propenyl, Ti, Cl, Cl), (2, 6 Combinations that are -diisopropenylphenyl, propenyl, Ti, Cl, Cl) or (trimethylsilyl, 2-phenylpropenyl, Ti, Cl, Cl) are preferred.
Examples of these compounds are disclosed in Macromolecules, 1996, p5241; JACS, 1997, 119, p3830; JACS, 1999, 121, p5798.

  Moreover, the bisamidinato compound which has a NN type ligand as shown in following General formula (8) can be mentioned.

In the general formula (8), R ⁶ and R ⁷ are a hydrocarbon group having 1 to 20 carbon atoms, a halogen, oxygen or silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and M ′ is group 4 of the periodic table. In the transition metal, X and Y represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen, nitrogen, silicon or phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms.

Specifically, it is preferable that R ⁶ = tert-butyl, cyclohexyl, trimethylsilyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, and R ⁷ = methyl, isopropyl, phenyl, paratolyl. It is preferable that it is either. M ′ is preferably any one of Ti, Zr, and Hf, and X and Y are preferably any one of Cl, methyl, benzyl, and dimethylamide.

More specifically, (R ⁶ , R ⁷ , M ′, X, Y) = (tert-butyl, phenyl, Zr, Cl, Cl), (trimethylsilyl, phenyl, Zr, Cl, Cl), (2, 6-diisopropenylphenyl, propenyl, Ti, Cl, Cl) or (trimethylsilyl, tolyl, Zr, Cl, Cl) is preferred. Examples of these compounds are disclosed in Organometallics, 1998, p3155.

  Furthermore, a salicylaldiminato compound having an N—O type ligand as shown in the following general formula (9) can be mentioned.

In the general formula (9), R ⁸ and R ⁹ are hydrocarbon groups having 1 to 20 carbon atoms, or halogen-containing oxygen, nitrogen, silicon or sulfur-containing hydrocarbons having 1 to 20 carbon atoms, and R ¹⁰ is a hydrogen atom. , A hydrocarbon group having 1 to 20 carbon atoms, or a halogen, oxygen, nitrogen or silicon-containing hydrocarbon having 1 to 20 carbon atoms, M ′ is a Group 4 transition metal in the periodic table, X and Y are hydrogen atoms, A halogen, a C1-C20 hydrocarbon group, or a C1-C20 oxygen, nitrogen, silicon, or phosphorus containing hydrocarbon group is shown.

Specifically, the case where R ⁸ = hexyl, cyclohexyl, phenyl, tolyl, pentafluorophenyl, paramethoxyphenyl, or 2,4-dimethylpyrrolyl is preferable, and R ⁹ = t-butyl or an adamantyl group And R ¹⁰ is preferably a hydrogen atom, methyl, ethyl, or methoxy group. M is preferably any one of Ti, Zr, and Hf, and X and Y are preferably any one of Cl, methyl, benzyl, and dimethylamide.

More specifically, (R ⁸ , R ⁹ , R ¹⁰ , M ′, X, Y) = (cyclohexyl, tert-butyl, hydrogen atom, Zr, Cl, Cl), (phenyl, t-butyl, hydrogen atom) , Zr, Cl, Cl), (tolyl, t-butyl, hydrogen atom, Zr, Cl, Cl), (pentafluorophenyl, t-butyl, hydrogen atom, Zr, Cl, Cl), (pentafluorophenyl, t -Butyl, hydrogen atom, Ti, Cl, Cl), (2,5-dimethylpyrrolyl, tert-butyl, hydrogen atom, Zr, Cl, Cl) are preferred. Examples of these compounds are disclosed in JP-A-11-315109.

  Examples of the group 8-10 metal compounds of the periodic table include biimino compounds having an NN type ligand as shown in the following general formulas (10) to (11).

In the general formulas (10) and (11), M is Fe or Co, R ¹¹ and R ¹³ are hydrocarbon groups having 1 to 20 carbon atoms, or halogen, oxygen, nitrogen, silicon or 1 to 20 carbon atoms R ¹² and R ¹⁴ represent a sulfur-containing hydrocarbon, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen, oxygen, nitrogen or silicon-containing hydrocarbon having 1 to 20 carbon atoms, and R ¹⁴ represents each other. May be combined. M ′ represents Ni or Pd, and X and Y represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen, nitrogen, silicon or phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms.

Specifically, R ¹¹ = paratolyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, or 2,4,6-trimethylphenyl, and R ¹² = hydrogen atom, methyl, ethyl, or propyl , R ¹³ = 2,6-dimethylphenyl, 2-t-butylphenyl, or 2,6-diisopropylphenyl. R ¹⁴ is a hydrogen atom, methyl, and examples of those bonded to each other are 1,8-naphthyl, —SCH ₂ CH ₂ S—, or —OCH ₂ CH ₂ O—. M ′ = Ni or Pd, and X, Y = Cl, Br, methyl, or benzyl group.

More ^{specifically, (R 11, R 12,} X, Y) = (2,6- dimethylphenyl, hydrogen atom, Cl, Cl), (2,4,6-trimethylphenyl, a hydrogen atom, Cl, Cl ), (2,6-diisopropylphenyl, hydrogen atom, Cl, Cl), (p-tolyl, methyl, Cl, Cl), (2,6-dimethylphenyl, methyl, Cl, Cl), or (2,6 A combination which is -dimethylpyrrolyl, hydrogen atom, Cl, Cl) is preferred.

Alternatively, (R ¹³ , R ¹⁴ , M ′, X, Y) = (2,6-dimethylphenyl, hydrogen atom, Ni, Br, Br), (2-t-butylphenyl, hydrogen atom, Ni, Br, Br), (2,6-diisopropylphenyl, hydrogen atom, Ni, Br, Br), (2,6-diisopropylphenyl, 1,8-naphthyl, Ni, Br, Br), (2,5-dimethylpyrrolyl) , Hydrogen atom, Ni, Br, Br) or (2,6-diisopropylphenyl, hydrogen atom, Pd, Br, Br).

  These compounds are disclosed in JACS, 1995, 117, p6414, WO 96/23010, Chemical Communication, 1998, p849, JACS, 1998, 120, p4049, WO 98/27124.

  Moreover, the salicylaldiminato compound which has a NO type ligand as shown in the following general formula (12) can be mentioned.

In the general formula (12), R ⁸ and R ⁹ are hydrocarbon groups having 1 to 20 carbon atoms, or hydrocarbons having 1 to 20 carbon atoms, such as halogen, oxygen, nitrogen, silicon or sulfur, and R ¹⁰ is a hydrogen atom. , A hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing oxygen, nitrogen or silicon-containing hydrocarbon having 1 to 20 carbon atoms, M ′ is Ni or Pd, X and Y are hydrogen atoms, halogens, carbon number 1 -20 hydrocarbon group or a C1-C20 oxygen, nitrogen, silicon, or phosphorus containing hydrocarbon group is shown.

Specifically, R ⁸ = hexyl, cyclohexyl, phenyl, tolyl, pentafluorophenyl, paramethoxyphenyl, or pyrrole group, R ⁹ = t-butyl or adamantyl group, R ¹⁰ = hydrogen atom, methyl, Preferred is an ethyl or methoxy group, M ′ = Ni, X, Y = Cl, methyl, benzyl or dimethylamide.

More specifically, (R ⁸ , R ⁹ , R ¹⁰ , M ′, X, Y) = (phenyl, t-butyl, hydrogen atom, Ni, Br, Br), (p-tolyl, t-butyl, (Hydrogen atom, Ni, Br, Br), (phenyl, t-butyl, hydrogen atom, Ni, Br, Br) or (2,5-dimethylpyrrolyl, t-butyl, hydrogen atom, Ni, Br, Br) A combination is preferred. Examples of these compounds are disclosed in JP-A-11-315109.

  Further, a mixture of these compounds may be used, and those in which tetrahydrofuran or the like is complexed with each exemplified complex can also be used.

(Ii) Component [b]
Component [b] of the promoter support used in the olefin polymerization catalyst of the present invention is a promoter support containing at least one selected from the following [b-1] to [b-5].

[B-1] A carrier carrying an aluminum oxy compound [b-2] A carrier carrying an ionic compound or Lewis acid capable of reacting with component [a] to convert component [a] into a cation [B-3] Solid acid [b-4] An organometallic compound, a compound having a functional group having active hydrogen or an aprotic Lewis basic functional group and an electron-withdrawing group, and a compound R _t-2 TH ₂ (R represents a hydrocarbon group or a halogenated hydrocarbon group, T represents each independently a group 15 or group 16 nonmetallic atom of the periodic table, and t represents the valence of T of the compound.) Modified particle support [b-5] layered silicate obtained by contacting with

  In the above [b-1], the aluminum oxy compound, in [b-4] the reaction product of the organic Zn compound, fluorinated phenol and water, and in [b-2] the component [a] An ionic compound or a Lewis acid that can be converted to a cation corresponds to a promoter. [B-3] and [b-5] show the case where the cocatalyst and the support are composed of the same substance. [B-1] to [b-5] will be described in detail below.

[B-1] A carrier on which an aluminum oxy compound is supported:
First, the aluminum oxy compound will be described, and the carrier will be described later. Specific examples of the aluminum oxy compound include compounds represented by the following general formula (13), (14) or (15).

In the general formulas (13) to (15), R ⁴ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. The plurality of R ⁴ may be the same or different. P represents an integer of 0 to 40, preferably 2 to 30.

  The compounds represented by the general formulas (13) and (14) are also called alumoxanes, and among these, methylalumoxane or methylisobutylalumoxane is preferable. The above-mentioned alumoxane can be used in combination within a group and between groups. And said alumoxane can be prepared on well-known various conditions.

The compound represented by the general formula (15) is 10: 1 to 1: 1 of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the following general formula (16). It can be obtained by a (molar ratio) reaction. In General Formula (16), R ⁵ represents a hydrocarbon residue or halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
R ⁵ B (OH) ₂ (16)

[B-2] A carrier carrying an ionic compound or Lewis acid capable of reacting with component [a] to convert component [a] into a cation:
Examples of ionic compounds that can react with the component [a] to convert the component [a] into a cation include cations such as a carbonium cation and an ammonium cation, tetraphenylboron, and tetrakis (3,5-difluoro And a complex with an anion of an organic boron compound such as phenyl) boron and tetrakis (pentafluorophenyl) boron.

  Examples of the Lewis acid that can convert the component [a] into a cation include various organic boron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halogen compounds such as aluminum chloride and magnesium chloride are exemplified. In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with component [a] and can convert component [a] into a cation. Therefore, the compounds belonging to both the Lewis acid and the ionic compound belong to either one. The carrier will be described later.

[B-3] Solid acid Examples of the solid acid include solid acids such as alumina, silica / alumina, and vanadium oxide.

[B-4] an organometallic compound, a functional group having active hydrogen or a compound having an aprotic Lewis basic functional group and an electron-withdrawing group, and a compound R _t-2 TH ₂ (where R is a hydrocarbon group or Represents a halogenated hydrocarbon group, T represents each independently a nonmetallic atom of Group 15 and Group 16 of the Periodic Table, and t represents a valence of T of the compound). Modified particle carrier:
As the organometallic compound in [b-4], a metal compound belonging to Group 12 of the periodic table can be exemplified. Specific examples of the compound include dimethyl zinc, diethyl zinc, dipropyl zinc, and di-n-hexyl zinc. And diaryl zinc such as dialkyl zinc, diphenyl zinc, dinaphthyl zinc and bis (pentafluorophenyl) zinc.
Examples of the compound having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and an electron-withdrawing group include amines such as bis (trifluoromethyl) amine and bis (pentafluorophenyl) amine, Alcohols such as trifluoromethanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 2-fluorophenol, Examples thereof include phenols such as 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, and pentafluorophenol.
Further, the compound R _t-2 TH ₂ (R represents a hydrocarbon group or a halogenated hydrocarbon group, T represents each independently a non-metal atom of Group 15 or Group 16 of the Periodic Table, and t represents a compound. As the valence of T.), amines such as water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline, 4- Fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4 -(Trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (tri Anilines such as fluoromethyl) aniline and 2,4,6-tris (trifluoromethyl) aniline.

  Next, the carriers in [b-1], [b-2] and [b-4] described above will be described. The carrier of the present invention is not particularly limited with respect to its elemental composition and compound composition. For example, the support | carrier consisting of an inorganic or organic compound can be illustrated. Examples of the inorganic carrier include silica, alumina, silica / alumina, magnesium chloride, activated carbon, inorganic silicate, and the like. Alternatively, a mixture thereof may be used.

Examples of the organic carrier include polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturated hydrocarbons such as styrene and divinylbenzene. Examples thereof include a porous polymer fine particle carrier made of a polymer or the like. Alternatively, a mixture thereof may be used.
These carriers usually have an average particle size of 1 μm to 5 mm, preferably 5 μm to 1 mm, more preferably 10 to 200 μm.

[B-5] Layered silicate:
As the layered silicate used in the present invention, an ion-exchangeable layered silicic acid having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other and binding ions can be exchanged. Salt (hereinafter, simply abbreviated as silicate). Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. But you can. Various known silicates can be used. Specific examples include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
Montmorillonite, Sauconite, Beidellite, Nontronite, Saponite, Hectorite, Stevensite, etc. , Pyrophyllite, talc, chlorite group.

  The silicate used in the present invention may be a layered silicate in which the above mixed layer is formed. The main component silicate is preferably a silicate having a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. Silicates obtained as natural products or industrial raw materials can be used as they are without any particular treatment, but are preferably subjected to chemical treatment. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned. These processes may be used in combination with each other. In the present invention, these treatment conditions are not particularly limited, and known conditions can be used.

Moreover, since these ion-exchange layered silicates usually contain adsorbed water and interlayer water, it is preferable to use them after removing moisture by heat dehydration under an inert gas flow.
Moreover, in order to improve the powder property of the polymer particle obtained by superposition | polymerization, it is preferable to make the said silicate spherical. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation or the like may be used. However, in general, commercially available silicates are indefinite, and thus operations such as granulation, sizing and fractionation are often performed.
The concentration of the silicate in the raw slurry liquid for spray granulation for obtaining spherical particles is 0.1 to 70%, preferably 1 to 50%, particularly preferably 2 to 30%. The temperature at the inlet of the hot air for spray granulation varies depending on the dispersion medium, but is 80 to 260 ° C, preferably 100 to 220 ° C when water is taken as an example.
In the present invention, shape control may be performed by pulverization, granulation, or the like before chemical treatment, during treatment, or after treatment. Various known methods can be employed for granulation, and preferably, stirring granulation method and spray granulation method are exemplified.

  Among the above-mentioned component [b], the one having a particularly large effect is a support on which [b-1] aluminum oxy compound is supported.

In addition, in the component [A] in the olefin polymerization catalyst of the present invention, [b-1] a carrier carrying an aluminum oxy compound, [b-2] reacting with the component [a] to convert the component [a] into a cation. An ionic compound that can be converted or a carrier carrying a Lewis acid, [b-3] a solid acid, [b-4] an organometallic compound, a functional group having active hydrogen or an aprotic Lewis basicity A compound having a functional group and an electron-withdrawing group; and a compound R _t-2 TH ₂ (wherein R represents a hydrocarbon group or a halogenated hydrocarbon group, and T independently represents groups 15 and 16 of the periodic table). And a modified particle carrier obtained by contacting the compound with a non-metallic atom, or [b-5] an ion-exchange layered silicate, respectively. Used as ingredient [b] In addition to being used, these four components can be used in appropriate combination.

(Iii) Component [c]
In the solid catalyst for olefin polymerization [A] of the present invention, the component [c] used as necessary is an organoaluminum compound.
As the organoaluminum compound that can be used as the component [c], AlR ⁶ _j X _3-j (wherein R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms, X is hydrogen, halogen, alkoxy group, j is It is preferable that 0 <j ≦ 3. In particular, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, or halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride or diethylaluminum methoxide is preferable. In addition, aluminoxane such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferable. These can be used alone or in admixture of two or more.

(Iv) Production of Component [A] Component [A] in the olefin polymerization catalyst of the present invention may be produced by contacting component [a], component [b] and, if necessary, component [c]. it can. Although the contact method is not specifically limited, it can contact in the following contact sequences. Further, this contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin.
(A) Component [a] and component [b] are contacted.
(A) Component [c] is added after contacting component [a] and component [b].
(C) Component [b] is added after contacting component [a] and component [c].
(D) Component [a] is added after contacting component [b] and component [c].
(E) Contact the three components simultaneously.

  When contacting each component of the catalyst, or after the contact, a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may coexist or contact.

  The contact may be carried out in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene. The contact temperature is between −20 ° C. and the boiling point of the solvent, particularly preferably between room temperature and the boiling point of the solvent.

  The amount of each catalyst component used is 0.0001 to 10 mmol, preferably 0.001 to 5 mmol for component [a] per 1 g of component [b], and 0.01 to 10,000 mmol, preferably 0.001 for component [c]. 1 to 100 mmol. Moreover, the atomic ratio of the transition metal in component [a] and the aluminum in component [c] is 1: 0.01-1 million, Preferably it is 0.1-100,000.

  The component [A] obtained in this way was subjected to ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1 in advance of polymerization (main polymerization). -It can be subjected to a preliminary polymerization treatment comprising contacting an olefin such as butene, vinylcycloalkane, styrene or the like and polymerizing it in a small amount. The prepolymerized catalyst can be further subjected to a washing treatment as necessary.

  This preliminary polymerization is preferably carried out in an inert solvent under mild conditions as compared with the main polymerization, and 0.01 to 1000 g, preferably 0.1 to 100 g, of polymer per 1 g of the solid catalyst is obtained. It is desirable to do so.

(2) Component [B]
Component [B] used in the olefin polymerization catalyst composition of the present invention is an inorganic oxide hydrophobized by surface treatment and a mixture thereof. The component [B] used in the present invention can be used in the form of primary particles, but the primary particles are aggregated into secondary particles or tertiary particles, or a mixture of these. But it can be used. Any component [B] can be used as long as the effect of the present invention is recognized. For example, the component [B] can be obtained by hydrophobizing the following compounds. TiO ₂ , SiO ₂ , Al (OH) ₃ , Al ₂ O ₃ , CaCO ₃ , MgCO ₃ , Al ₂ O ₃ · 4SiO ₂ · H ₂ O, Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O, Al ₂ O _{3 · 2SiO 2, 3MgO · 4SiO} 2 · H 2 O, 3CaO · Al 2 O 3 · 3CaSO 4 · 31H 2 O, SiO 2 · nH 2 O, BaSO 4, Al 2 SiO 5, 3CaO · SiO 2, Ba 2 _{SiO 4, Al 2 O 3 ·} Na 2 O · 6SiO 2, Al 2 O 3 · CaO · 2SiO 2, Cd 2 SiO 4, BaTiO 3, ZrO 2, there are zeolite, preferably _zeolite, Al _{2 O} 3, TiO ₂ , SiO _2, ZrO _{2 and the} like, more preferably TiO ₂ , Al ₂ O ₃ and SiO ₂ , particularly preferably SiO ₂ .

In addition, the manufacturing method of the inorganic oxide before the hydrophobization process generally includes the following method described in the fine particle engineering large volume I basic technology 637-764.
Chemical flame method, electric furnace heating method, thermal plasma method, laser heating method, laser excitation reaction method, resistance heating method, electron beam heating method, thermal plasma heating method, coprecipitation method, uniform precipitation method, compound precipitation method, metal alkoxide Method, hydrothermal synthesis method, sol-gel method, spray method, freeze-drying method, emulsion method, nitrate decomposition method, solution combustion method, crystallization method, thermal decomposition method, mechanical grinding, and the like.

  These inorganic oxides usually have adsorbed water and surface hydroxyl groups, but the surface hydroxyl groups are substituted with alkoxy groups, organic silyl groups, alkoxysilyl groups, organic silyloxy groups, organic siloxy groups, etc., and have a degree of hydrophobicity. It has become expensive.

The component [B] is at least one inorganic oxide fine particle selected from inorganic oxides hydrophobized by one or more surface treatments selected from the following [B-1] to [B-6]. is there.
[B-1] Dehydration condensation reaction with alcohol [B-2] Dealkane condensation reaction with alkyl metal compound [B-3] Dehydrohalogenation condensation reaction with organic silyl halide [B-4] Dealcoholization with alkoxysilyl compound Condensation reaction [B-5] Desilanol condensation reaction with siloxane compound [B-6] Deammonia condensation reaction with silazane compound

  For the surface hydrophobization treatment of the above [B-1] to [B-6], at least any one hydrophobization treatment agent represented by the following general formulas (17) to (22) is used.

R ¹ OH (17)
In General Formula (17), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms. Specific compounds represented by the general formula (17) include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, iso-butanol, pentanol, and neo-pen. Examples include tanol, hexanol, and cyclohexanol.

R ² _k M (OR ³ ) _1−k (18)
In general formula (18), R ² and R ³ are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and M is Li, Na, K, Mg, Ca, Zn, B, Al, Sn. Where k is a positive number less than or equal to the valence of M, and l is the valence of M. Specific compounds represented by the general formula (18) include methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, phenyl lithium, sodium hydride, potassium hydride, calcium hydride, n -Butylethylmagnesium, dimethylzinc, diethylzinc, trimethylaluminum, triethylaluminum, tri-iso-butylaluminum, diethylaluminum ethoxide and the like.

R ⁴ _a SiX _4-a (19)
In general formula (19), R ⁴ is the same or different hydrocarbon group having 1 to 20 carbon atoms, X is halogen, and a is 1, 2 or 3. Specific compounds represented by the general formula (19) include trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane, triphenylchlorosilane, dimethylpropylchlorosilane, dimethylphenylchlorosilane, dimethylvinylchlorosilane, diphenylmethylchlorosilane, dimethylchlorosilane, diethyl Examples include dichlorosilane, diphenyldichlorosilane, phenylvinyldichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, octyltrichlorosilane, and the like.

R ⁵ _b Si (OR ⁶ ) _4-b (20)
In General Formula (20), R ⁵ and R ⁶ are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and b is 1, 2 or 3. Specific compounds represented by the general formula (20) include methoxytrimethylsilane, ethoxytrimethylsilane, methoxytripropylsilane, ethoxytriphenylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, diethoxydimethylsilane, diethoxydiethyl. Examples include silane, diethoxydiphenylsilane, diethoxymethylvinylsilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

R ⁷ [—Si (R ⁸ ) ₂ O—] _c R ⁹ (21)
In General Formula (21), R ⁷ , R ⁸ , and R ⁹ are the same or different hydrocarbon groups having 1 to 10 carbon atoms, and c is an integer of 2 to 50. Specific examples of the compound represented by the general formula (21) include hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, hexaphenyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and the like.

(R ¹⁰ ₃ Si) _d NH _3-d (22)
In general formula (22), R ¹⁰ is the same or different hydrocarbon group having 1 to 20 carbon atoms, and d is an integer of 1 to 3. Specific compounds represented by the general formula (22) include trimethylsilylamine, 1,1,3,3-tetramethyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane, tris (Trimethylsilyl) amine and the like.

The degree of hydrophobicity of the inorganic oxide hydrophobized by the surface treatment can be measured by the following method.
Place 50 milliliters of water in a 200 milliliter beaker and add 0.2 grams of inorganic oxide. While gently stirring with a magnetic stirrer, methanol is dropped from a burette whose tip is immersed in water, and the amount of methanol added when the floating inorganic oxide completely sinks can be obtained by the following formula.
Hydrophobicity (%) = {methanol drop volume ml / (50 + methanol drop volume ml)} × 100
The higher the degree of hydrophobicity, the higher the hydrophobicity of the inorganic oxide.
In the present invention, the degree of hydrophobicity of component [B] is 35% or more, preferably 40% or more, more preferably 45% or more. If the degree of hydrophobicity is less than 35%, the catalyst powder properties such as catalyst adhesion, fluidity, angle of repose, and bulk density are deteriorated, and polymerization activity is reduced.

The particle property of the component [B] can be arbitrary as long as the effect of the present invention is recognized, but the following are generally preferable. As the shape, either spherical or irregular shapes can be used.
The average particle size of component [B] needs to be smaller than the average particle size of component [A] used in the present invention. Therefore, it is preferably 30 μm or less, more preferably 4 μm or less, and still more preferably 1 μm or less. When the average particle size exceeds 30 μm, when the polymer obtained is processed into a film or the like, a poor appearance due to fish eyes or the like occurs.
Here, the average particle size refers to the size of the secondary particles or tertiary particles as the primary particles aggregate to produce secondary particles or tertiary particles. Moreover, in the case of a primary particle diameter, a small thing is preferable and the average particle diameter of a primary particle has a preferable thing of 1 micrometer or less, More preferably, it is 0.1 micrometer or less. In addition, generally a primary particle diameter is measured by the method of a coloring material, 61 [11] 614-6211.188.

  Furthermore, the ratio of the average particle size of component [B] to the average particle size of component [A] is preferably in the range of 0.0001 to 0.5, more preferably 0.0005 to 0.1. The reason is not clear so far, but the present inventors presume that it is important that the component [B] is adsorbed on the particle surface of the component [A].

The inorganic oxide fine particles hydrophobized by these surface treatments usually contain adsorbed water.
Here, the adsorbed water is water adsorbed on the surface or crystal fracture surface of the surface-treated inorganic oxide.

  If the amount of adsorbed water is excessively large, the catalyst performance may be deteriorated, and the above-mentioned compounds such as inorganic oxides usually contain excessively adsorbed water. Usually, the component [B] is obtained by removing water.

The removal method of adsorbed water can be any suitable method, but in the present invention, it is desirable to use a method from which these adsorbed water has been removed by heat drying treatment, vacuum drying treatment, gas circulation drying treatment, etc. . The heat treatment method of the adsorbed water is not particularly limited, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used.
The temperature at the time of heating is preferably 100 ° C. or higher, and more preferably 200 ° C. or higher so that adsorbed water does not remain. The upper limit is about 800 ° C.
The heating time is 0.05 hours or longer, preferably 0.5 hours or longer, more preferably 1 hour or longer.

At that time, the water content of the component [B] after removal is 3% by weight or less when the water content is 0% by weight when dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 760 mmHg, preferably It is preferable that it is 1 weight% or less, More preferably, it is 0.5 weight% or less, and a minimum is 0 weight%.
In the present invention, the component [B], which has been dehydrated and adjusted to have a water content of 3% by weight or less, is preferably handled so as to maintain the same water content when contacting the component [A]. .

2. Production and Polymerization Reaction of Olefin Polymerization Catalyst Composition The olefin polymerization catalyst composition of the present invention contains a component [A] and a component [B], and such a catalyst is prepared by preparing a component [ In the presence or absence of the olefin to be polymerized, the component [A], the component [B], and the third component (optional component) outside the polymerization tank or in the polymerization tank. Can be obtained by mixing with.
At this time, the usage-amount of component [B] exists in the range of 0.0001-0.1 by weight ratio with respect to component [A], Preferably, it exists in the range of 0.001-0.1. . The mixing method of the component [A] and the component [B] (and these and the third component) can be arbitrary as long as the effect of the present invention is recognized, but an inert gas (fully purified one is preferable). For example, there are a method of mixing in a nitrogen gas atmosphere and a method of mixing in the presence of an inert solvent, for example, a hydrocarbon solvent such as hexane or heptane. By mixing the component [A] and the component [B] prepared in advance, it is presumed that the component [B] mainly exists in a state of adhering to the surface of the component [A]. The mixing is performed by a method of stirring, a method of mixing with a mill such as a vibration mill or a rotating ball mill, a method of using a shaker, or the like. The mixing time is 1 minute to 100 hours, preferably about 5 minutes to 10 hours.

  In addition, the olefin polymerization catalyst composition thus obtained is used for the polymerization reaction, and if necessary, a new organoaluminum compound (component [C]) can also be used in combination. Specific examples of the organoaluminum compound used in this case can include those described above as the component [c]. The amount of the organoaluminum compound is selected so that the atomic ratio of aluminum in the organoaluminum compound component to the transition metal in component [a] is preferably 1: 0 to 10,000.

  The thus obtained olefin polymerization catalyst composition of the present invention preferably has a metal container adhesion derived from the amount of adhesion when a metal container having an internal volume of 300 cc is filled with 10 cc of the catalyst component and vibrated. Is 0.1 g / 10 cc or less. If the adhesion to the metal container is 0.1 g / 10 cc or less, there will be no problems such as adhesion to the catalyst supply line, clogging due to it, and adhesion to the polymerization reactor wall, and a continuous and stable catalyst. Supply is possible, and there is an advantage that olefin polymerization can be performed stably.

  Olefin can be stably polymerized using the olefin polymerization catalyst composition of the present invention. Examples of the olefin used for the polymerization include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcycloalkane, styrene, These derivatives are available. In addition to homopolymerization, the polymerization can be suitably applied to generally known random copolymerization and block copolymerization.

The polymerization reaction is performed in the presence or absence of an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene, cyclohexane, or a solvent such as a liquefied α-olefin. The temperature is −50 ° C. to 250 ° C., and the pressure is not particularly limited, but is preferably in the range of normal pressure to about 2000 kgf / cm ² . Also, hydrogen can be present as a molecular weight regulator in the polymerization system.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples. The evaluation methods used in the examples are as follows, and the following catalyst synthesis step and polymerization step are all carried out in a purified nitrogen atmosphere, and the solvent used was dehydrated and purified with molecular sieve-4A. It was.

(1) Amount of catalyst composition for polymerization: 10 cc of the catalyst composition was filled into a 300 cc stainless steel container under nitrogen, shaken for 2 minutes with a shaker, and the contents were discarded by inclining to leave the catalyst. The weight of the adhesion amount was measured.
(2) Flowability of polymerization catalyst composition: Stainless steel funnel with a conical angle of 30 ° having various outflow hole diameters of 3.0 mmφ, 5.0 mmφ, 5.8 mmφ, 6.5 mmφ, 8.0 mmφ, and 12 mmφ, Measurement was carried out by introducing 14 cc of the catalyst composition powder. The numbers are shown as the minimum pore size from which all the catalyst flows out within 15 seconds.
(3) Bulk density of the catalyst composition for polymerization: The weight when the catalyst composition was poured into a 10 cc container from a stainless steel funnel having a 5.0 mmφ outflow hole diameter was measured and displayed as the weight per cc.
(4) MFR of polymer: Measured in accordance with JIS K6760 under conditions of 190 ° C. and 2.16 kg load.
(5) Bulk density of polymer: The apparent density of the polymer was measured according to JIS K7365.
(6) Average particle diameter of components [A] and [B]: measured using a particle size distribution measuring apparatus (HORIBA: LA-920). The dispersion was measured with ethanol at an ultrasonic time of 1 minute, and the obtained median diameter was defined as the average particle diameter.

Example 1
(1) Preparation of solid catalyst for olefin polymerization Under nitrogen, 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, and then 3.3 g of tetrapropoxyzirconium (Zr (On-Pr) ₄ ) and indene 9. 3 grams was added and stirred at room temperature for 30 minutes, and the system was maintained at 0 ° C., and 11.1 grams of triethylaluminum (AlEt ₃ ) was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction system was brought to room temperature for 5 hours. Stir. This solution is designated as solution A. The Zr concentration of the solution A was 0.057 mmol / ml as Zr. Next, 200 ml of purified toluene was added to another 3 L three-necked flask equipped with a stirrer under nitrogen, and 96 ml of the solution A, followed by 548 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) were reacted. This is designated as solution B.
Next, 400 ml of purified toluene was added to a 3 L three-necked flask equipped with a stirrer under nitrogen, and then 100 g of silica (made by Fuji Devison, grade # 952, surface area 300 m ² / g) previously calcined at 600 ° C. for 5 hours was added. After the addition, the whole amount of the solution B was added and stirred at room temperature for 2 hours. Subsequently, the solvent was removed by nitrogen blowing to obtain a powdery solid catalyst for olefin polymerization (component [A]) having good fluidity. The average particle size of component [A] was 40.9 μm.
(2) Mixing of solid catalyst for olefin polymerization (component [A]) and component [B] 20 grams of solid catalyst powder obtained in (1) above and component [ B], 0.1 g (0.5%) of silica R972 (primary particle average diameter 16 nm, dimethylsilylated product, degree of hydrophobicity 48.4%) manufactured by Nippon Aerosil Co., Ltd., which was previously vacuum-dried at 200 ° C. for 2 hours. % By weight) and mixed with a shaker for 1 hour. When properties of the obtained catalyst composition were examined, the amount of the catalyst adhered was 0.0668 g / 10 cc, the bulk density was 0.420 g / cc, and the fluidity was 3.0 mmφ.
(3) Vapor phase copolymerization of ethylene and 1-hexene 80 g of triethylaluminum in a 1 liter stainless steel autoclave having a stirring and temperature control device and having a sufficiently dehydrated and deoxygenated particle diameter of 850 μm to 2000 μm Was heated to 90 ° C. with stirring. Ethylene containing 10% by weight of 1-hexene was introduced until the partial pressure reached 2.0 MPa, and then 50 mg of the catalyst composition obtained in the above (2) was injected with argon gas for polymerization for 55 minutes. . As a result, 31.2 grams of polyethylene was produced.
Table 1 shows the properties of the component [B], and Table 2 shows the properties of the catalyst composition and the polymerization results.

(Example 2)
In Example 1 (2), 0.2 g (1.0%) of Component [B] Silica R972 manufactured by Nippon Aerosil Co., Ltd. (average primary particle diameter: 16 nm, dimethylsilylated product, hydrophobicity: 48.4%) The catalyst composition was produced in the same manner as in Example 1 (2) except that (wt%) was added. The catalyst adhesion amount of the catalyst composition was 0.1089 g / 10 cc, the bulk density was 0.406 g / cc, and the fluidity was 3.0 mmφ. Furthermore, when this catalyst composition was used for vapor phase copolymerization in the same manner as in Example 1 (3), 29.2 grams of polyethylene was produced in a polymerization time of 60 minutes.
Table 1 shows the properties of the component [B], and Table 2 shows the properties of the catalyst composition and the polymerization results.

(Comparative Example 1)
When the properties of the solid catalyst (component [A]) powder obtained in Example 1 (1) were examined, the adhesion amount was 0.1526 g / 10 cc, the bulk density was 0.436 g / cc, and the fluidity was 3. It was 0 mmφ. Furthermore, when this solid catalyst powder was used for vapor phase copolymerization in the same manner as in Example 1 (3), 29.6 grams of polyethylene was produced in a polymerization time of 52 minutes.
Table 2 shows the properties of the solid catalyst powder and the polymerization results.

(Comparative Example 2)
In Example 1 (2), RA200H manufactured by Nippon Aerosil Co., Ltd. (average primary particle size 12 nm, trimethylsilylated and methylaminosilylated product, degree of hydrophobicity 32.9 as component [B] instead of R972 manufactured by Nippon Aerosil Co., Ltd. %) Was used in the same manner to produce a catalyst composition. The catalyst adhesion amount was 0.2115 g / 10 cc, the bulk density was 0.390 g / cc, and the fluidity was 3.0 mmφ. Furthermore, when this catalyst composition was used for vapor phase copolymerization in the same manner as in Example 1 (3), 19.8 grams of polyethylene was produced in a polymerization time of 60 minutes.
Table 1 shows the properties of the component [B], and Table 2 shows the properties of the catalyst composition and the polymerization results.

(Comparative Example 3)
In Example 2, instead of R972 manufactured by Nippon Aerosil Co., Ltd., RA200H (primary particle average diameter 12 nm, trimethylsilylated and methylaminosilylated product, degree of hydrophobicity 32.9%) was used as component [B] instead of R972 manufactured by Nippon Aerosil Co., Ltd. A catalyst composition was produced in the same manner except that it was used. The adhesion amount of the catalyst was 0.2468 g / 10 cc, the bulk density was 0.341 g / cc, and the fluidity was 8.0 mmφ. Further, when this catalyst composition was used for vapor phase copolymerization in the same manner as in Example 1 (3), 9.0 grams of polyethylene was produced in a polymerization time of 60 minutes.
Table 1 shows the properties of the component [B], and Table 2 shows the properties of the catalyst composition and the polymerization results.

(Example 3)
In Example 1 (2), instead of R972 manufactured by Nippon Aerosil Co., Ltd. as component [B], T805 manufactured by Nippon Aerosil Co., Ltd. (average primary particle diameter of 21 nm, normal octyl diethoxysilylation treatment, degree of hydrophobicity of 88.9%) A catalyst composition was produced in the same manner except that was used. The adhesion amount of the catalyst was 0.1055 g / 10 cc, the bulk density was 0.445 g / cc, and the fluidity was 3.0 mmφ. Furthermore, when this catalyst composition was used for vapor phase copolymerization in the same manner as in Example 1 (3), 33.0 grams of polyethylene was produced in a polymerization time of 60 minutes.
Table 1 shows the properties of the component [B], and Table 2 shows the properties of the catalyst composition and the polymerization results.

(Comparative Example 4)
In Example 3, P25 (average primary particle diameter 21 nm, no surface treatment, hydrophobization degree 0%) manufactured by Nippon Aerosil Co., Ltd. was used instead of T805 manufactured by Nippon Aerosil Co., Ltd. as component [B]. A catalyst composition was produced. The adhesion amount of the catalyst was 0.1742 g / 10 cc, the bulk density was 0.440 g / cc, and the fluidity was 3.0 mmφ. Furthermore, when this catalyst composition was used for vapor phase copolymerization in the same manner as in Example 1 (3), 14.5 grams of polyethylene was produced in a polymerization time of 60 minutes.
Table 1 shows the properties of the component [B], and Table 2 shows the properties of the catalyst composition and the polymerization results.

Example 4
In Example 1 (2), instead of R972 manufactured by Nippon Aerosil Co., Ltd., R812 manufactured by Nippon Aerosil Co., Ltd. (average primary particle size: 7 nm, trimethylsilylated product, hydrophobization degree: 55.3%) was used as the component [B]. Except for this, the catalyst composition was produced in the same manner. The adhesion amount of the catalyst was 0.0672 g / 10 cc, the bulk density was 0.415 g / cc, and the fluidity was 3.0 mmφ. Further, when this catalyst composition was used for vapor phase copolymerization in the same manner as in Example 1 (3), 34.0 grams of polyethylene was produced in a polymerization time of 60 minutes.
Table 1 shows the properties of the component [B], and Table 2 shows the properties of the catalyst composition and the polymerization results.

(Comparative Example 5)
In Example 1 (2), instead of R972 manufactured by Nippon Aerosil Co., Ltd., 300CF manufactured by Nippon Aerosil Co., Ltd. (average primary particle diameter: 7 nm, untreated surface, hydrophobization degree 0%) was used as the component [B]. Similarly, the catalyst composition was produced. The adhesion amount of the catalyst was 0.2952 g / 10 cc, the bulk density was 0.322 g / cc, and the fluidity was 8.0 mmφ. Furthermore, when this catalyst composition was used for polymerization in the same manner as in Example 1 (3), 10.5 grams of polyethylene was produced in a polymerization time of 60 minutes.
Table 1 shows the properties of the component [B], and Table 2 shows the properties of the catalyst composition and the polymerization results.

(Example 5)
(1) Production of Solid Catalyst Component Commercially available porous silica (Silopol 948 manufactured by Grace Japan Co., Ltd.) was measured according to ASTM D1921 (1996) and TEST METHOD A No. The fine particles were passed through a 230 (mesh 63 μm) mesh sieve, and silica (SiO ₂ -1) on the fine particle side that passed through was used. The average particle size of the SiO ₂ -1 was measured using a laser diffraction / scattering particle size distribution measuring device LA-920 manufactured by Horiba, Ltd., and the dispersion solvent was distilled water, the refractive index was 1.0, and the shape factor was 1.0. As a result, the average particle diameter in terms of the arithmetic average diameter was 45 μm, and the particle size of 100 μm or more was 0%.
Into a 3 liter glass flask, 400 grams of the classified silica SiO ₂ -1 obtained above was introduced, and then 4 grams of CrO ₃ was dissolved in 2 liters of distilled water and stirred for 15 minutes. Next, after removing the supernatant, nitrogen gas was introduced while heating, and when the powder became granular, the temperature was raised to 150 ° C., and further dried for 4 hours, and chromium-supporting silica (Cr—SiO ₂ -1) was removed. Obtained. As a result, this supported silica contained 0.2% by weight of chromium.
Next, 400 grams of this dry carrier was introduced into a 3 liter flask, 1 liter of isopentane and 100 grams of isopropyl titanate were introduced, and the mixture was stirred at 50 ° C. for 2 hours, after which isopentane was distilled off. Furthermore, 1 gram of (NH ₄ ) ₂ SiF ₆ was added and dried at 150 ° C. for 1 hour under a nitrogen gas flow. After returning to room temperature, it was transferred to a firing tube under nitrogen, and further dried at 150 ° C. under nitrogen in a firing furnace for 1 hour, then the gas was switched from nitrogen to dry air, 350 ° C. for 2 hours, and further at 750 ° C. for 4 hours. Baked for hours. After the calcination, the gas was switched to nitrogen gas, and then slowly returned to room temperature to obtain a solid catalyst carrying chromium and titanium. This catalyst contained 3.5% by weight of titanium.
(2) Mixing of solid catalyst for olefin polymerization and component [B] 20 grams of the solid catalyst powder obtained in Example 5 (1) and component [B] in a stainless steel cylinder with an internal volume of 200 ml sufficiently purged with nitrogen, 0.1 g (0.5 wt%) of silica R972 (primary particle average diameter 16 nm, dimethylsilylated product, degree of hydrophobicity 48.4%) manufactured by Nippon Aerosil Co., Ltd., which was previously vacuum-dried at 200 ° C. for 2 hours, was added. And mixed for 1 hour with a shaker. When the properties of the obtained catalyst composition were examined, the catalyst adhesion amount was 0.0303 g / 10 cc, the bulk density was 0.409 g / cc, and the fluidity was 3.0 mmφ.
(3) Copolymerization of ethylene and 1-butene Using the catalyst composition of (2) above, a mixed gas of ethylene and 1-butene (1-butene / (ethylene + 1-butene) = 7.5 mol%) fluid While maintaining a concentration of 0.10 ppm in oxygen, gas phase copolymerization was performed at a temperature of 90 ° C., a total pressure of 2.0 MPa, a residence time of 3.5 hours, MFR 0.77 g / 10 minutes, ash content 0.021%, A powdery linear low-density polyethylene (ethylene-1-butene copolymer) having a bulk density of 0.436 g / cc was obtained.
Table 1 shows the properties of the component [B], and Table 2 shows the properties of the catalyst composition and the polymerization results.

(Example 6)
(1) Production of solid catalyst component 1 kg of synthetic ummo (ME-100 manufactured by Co-op Chemical Co.) is dispersed in 3.2 kg of demineralized water in which 0.2 kg of zinc sulfate heptahydrate is dissolved, and then at room temperature for 1 hour. Stir and filter. After washing with demineralized water, the solid content concentration was adjusted to 25%, and the slurry was introduced into a spray dryer to obtain spherical granulated particles. The particles were further dried under reduced pressure at 200 ° C. for 2 hours.
30 g of the spherical particles were slurried with 500 ml of n-heptane, and 5.6 g of triisobutylaluminum (28 mmol, 34 ml of heptane solution) was added thereto with stirring at room temperature. After stirring for 10 minutes, 1.26 g (24.1 mmol, 200 ml of toluene solution) of an iron complex having the following structural formula was added, and the mixture was further stirred for 10 minutes. The solvent was distilled off under reduced pressure at room temperature to obtain a solid catalyst for olefin polymerization.

(2) Mixing of solid catalyst for olefin polymerization and component [B] 200 g of the solid catalyst powder obtained in the above (1) and 200 parts of component [B] were placed in advance in a 200 ml stainless steel cylinder sufficiently purged with nitrogen. 0.1 g (0.5 wt%) of silica R972 (primary particle average diameter 16 nm, dimethylsilylated product, hydrophobization degree 48.4%) manufactured by Nippon Aerosil Co., Ltd., vacuum-dried at 2 ° C. for 2 hours, Mix for 1 hour with a shaker. When the properties of the obtained catalyst composition were examined, the catalyst adhesion amount was 0.0349 g / 10 cc, the bulk density was 0.440 g / cc, and the flowability was 3.0 mmφ.
(3) Ethylene-1-hexene copolymerization Slurry polymerization was performed using the catalyst obtained in (2). That is, 1.5 L of n-heptane, 2.5 mmol of triisobutylaluminum, 180 ml of 1-hexene and a small amount of hydrogen (0.0285 NL) were added to a 3 L autoclave, the temperature was raised to 80 ° C., ethylene gas was introduced, and the total pressure was increased. The pressure was increased to 1.96 MPa (20 Kg / cm ² G). Next, 100 mg of the catalyst composition obtained in the above (2) was introduced together with ethylene mixed with a trace amount of hydrogen (hydrogen / ethylene ratio = 0.42 mol%), and the total pressure was 2.16 MPa (22 Kg / cm ² G The polymerization was carried out at 80 ° C. The hydrogen / ethylene ratios 5 minutes after the start of polymerization and immediately before the termination of the polymerization were 0.13 mol% and 0.42 mol%, respectively. After 25 minutes, ethanol was added to stop the polymerization. The obtained polymer was separated by filtration and dried under hot air. The obtained polymer was in the form of particles, and no adhesion to the polymerization tank was observed. The resulting polymer was 190 grams.
Table 1 shows the properties of the component [B], and Table 2 shows the properties of the catalyst composition and the polymerization results.

  The catalyst composition of the present invention is a highly active catalyst composition for olefin polymerization in which the bulk density and particle properties of the catalyst powder are extremely good, and problems such as adhesion in the catalyst supply process and polymerization process are eliminated. Such a catalyst composition is substantially free from problems such as adhesion to the catalyst supply line and clogging and adhesion to the polymerization reactor wall, thereby providing a continuous and stable catalyst supply. The olefin can be stably polymerized, and the industrial value is extremely high.

Claims (9)

  Hydrophobic degree of the solid catalyst for olefin polymerization (component [A]) containing a transition metal compound of group 3 to 10 of the periodic table (component [a]) and a promoter support (component [b]) A catalyst composition for olefin polymerization, comprising 35% or more of inorganic oxide fine particles (component [B]) mixed in a weight ratio of 0.0001 to 0.1.   The olefin polymerization catalyst composition according to claim 1, wherein the component [a] is a transition metal compound of Groups 4 to 6 of the periodic table. The catalyst for olefin polymerization according to claim 1 or 2, wherein the component [b] is a promoter support containing one or more selected from the following [b-1] to [b-5]. Composition.
[B-1] A carrier carrying an aluminum oxy compound [b-2] A carrier carrying an ionic compound or Lewis acid capable of reacting with component [a] to convert component [a] into a cation [B-3] Solid acid [b-4] An organometallic compound, a compound having a functional group having active hydrogen or an aprotic Lewis basic functional group and an electron-withdrawing group, and a compound R _t-2 TH ₂ (R represents a hydrocarbon group or a halogenated hydrocarbon group, T represents each independently a group 15 or group 16 nonmetallic atom of the periodic table, and t represents the valence of T of the compound.) Modified particle support [b-5] layered silicate obtained by contacting with   The average particle diameter of component [B] is 30 micrometers or less, The catalyst composition for olefin polymerization of any one of Claims 1-3 characterized by the above-mentioned.   The ratio of the average particle diameter of the component [B] to the average particle diameter of the component [A] is 0.0001 to 0.5, for olefin polymerization according to any one of claims 1 to 4 Catalyst composition.   The component [B] is selected from oxides or composite oxides of any one of Mg, Ca, Ti, Zr, Al, and Si. A catalyst composition for olefin polymerization.   Furthermore, the organoaluminum compound (component [C]) is contained, The catalyst composition for olefin polymerization of any one of Claims 1-6 characterized by the above-mentioned.   The catalyst composition for olefin polymerization according to any one of claims 1 to 7, which is a catalyst for gas phase polymerization.   Adhesivity to a metal container is 0.1 g / 10cc or less, The catalyst composition for olefin polymerization of any one of Claims 1-8 characterized by the above-mentioned.