JP2006316160A - Method for preservation of olefin polymerization catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for the preservation of an olefin polymerization catalyst, dispensing with a melt-kneading process consuming a large amount of energy, having excellent preservability of the olefin polymerization catalyst for the production of an olefin resin containing an effectively incorporated small amount of antioxidant, and giving an olefin polymer having high bulk density, large particle diameter and excellent particle form without forming fine powder and bulky material even by using a catalyst preserved for a long period. <P>SOLUTION: The method for the preservation of an olefin polymerization catalyst comprises the preservation of an olefin polymerization catalyst containing (I) an olefin polymerization solid catalyst component having an average particle diameter of 40-200μm and (II) an antioxidant for a resin in the presence of an organic aluminum compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for storing an olefin polymerization catalyst, and more particularly, to a method for storing an olefin polymerization catalyst with little deterioration with time of the catalyst and little decrease in activity.

  Polyolefin resin obtained with a highly active olefin polymerization catalyst is an energy-saving production method because it eliminates the need for a catalyst removal step. However, since it contains a small amount of catalyst residue, it is more stable than the polyolefin resin from which the catalyst was removed. Therefore, it is necessary to use a large amount of an antioxidant because the product life is shortened. Therefore, stabilizers typified by various antioxidants are blended into the polymer obtained as a fine powder polymer, and it is uniformly dispersed by heating and melting with a granulator, etc., to form granules that are easy to handle. Long-term stability has been achieved by molding.

However, it is inefficient to melt and knead various stabilizers after polymerization because it consumes a lot of energy, and more stabilizers must be added to cope with poor dispersion of the stabilizers. There was a case. In a polymerization method in which a granular polymer is directly obtained, it has been reported that a stabilizer can be uniformly dispersed during the polymerization, and the granulation kneading step can be omitted during the polymerization. .
For example, as a method of blending a stabilizer immediately after polymerization, a method in which a phosphorus-based antioxidant, a phenol-based antioxidant, a thioether, and a light stabilizer are attached to a polymerization powder with paraffin wax and coated (see, for example, Patent Document 1). ), A method of adding a stabilizer in a liquid monomer in a step after polymerization, but in a step before flushing the liquid monomer (see, for example, Patent Document 2), A method is disclosed in which a polyolefin resin is contact-treated with water vapor and then sprayed with an antioxidant (for example, see Patent Document 3).
However, these methods of adding a stabilizer after polymerization are difficult to uniformly disperse in the polymer, and require a separate step for addition.

In addition, as a method for allowing a stabilizer or the like to be present in the polymerization system, for example, in polymerization using a Ziegler-Natta catalyst system, a method of polymerizing α-olefin in the presence of a phosphorus-based antioxidant is shown, which is added later. It has been shown that it exhibits better stability than can and eliminates an extruder for mixing with antioxidants (see, for example, Patent Document 4). In addition, by using a catalyst using a specific ether compound, an excellent stabilization effect can be obtained when a phenolic antioxidant is used during polymerization, and there are no problems such as a decrease in polymerization activity or coloring of the resin. (For example, refer to Patent Document 5). Furthermore, a method for producing an olefin polymer in which at least one of a phosphorus compound, a sterically hindered amine, a sterically hindered phenol or an acid scavenger is added and polymerized on a transition metallocene catalyst has been proposed (for example, see Patent Document 6). ).
However, in the method of adding a stabilizer to these polymerization systems, although there is an advantage that the blending step of the stabilizer by processing after the polymerization can be omitted, there is a possibility that the stabilizer is entrained in the unreacted monomer, It may also cause problems such as contamination, adhesion, and blockage of the monomer recycling line. There is also a problem that the stabilizer is not used effectively.

On the other hand, the olefin polymerization catalyst is difficult to store, the polymerization activity decreases with time with storage, the amount of fine powder in the resulting polymer particles increases, or the polymer particles are combined to form coarse particles. There was a problem that it occurred and the bulk density decreased. In particular, if the granulation process is omitted to achieve energy saving, it is required that the particle size is relatively large and easy to handle, but the decrease in the bulk density of the polymer particles deteriorates the handling of the polymer particles themselves. Let In the case of polymerized particles that omit the granulation step, it is necessary to add a stabilizer in a powder state. Cheap. Therefore, there is a need for a method of dispersing the stabilizer uniformly with respect to the large particles and effectively stabilizing the particles.
The particle properties of the polymer particles largely depend on the particle properties of the olefin polymerization catalyst. The deterioration of the particle properties of the polymer particles obtained by storing the catalyst is caused by the particle properties of the catalyst particles during storage of the olefin polymerization catalyst. This is thought to be due to the deterioration. Therefore, in order to enable long-term storage of the olefin polymerization catalyst and to produce polymer particles having excellent particle properties even during long-term storage, a storage method that does not impair the particle properties of the olefin polymerization catalyst is important. There has been proposed a method for storing an olefin polymerization catalyst having excellent storage properties and particle properties by storing in the presence of organoaluminum (see, for example, Patent Document 7). However, the catalyst system of this method does not contain a stabilizer in the olefin polymerization catalyst, the stability of the obtained polyolefin resin is low, the particle size of the polymer itself is small, and a stabilizer is added. A granulation kneading step is required.
JP-A-3-220248 JP-A-6-179713 JP 2003-231711 A JP-A-63-92613 JP-A-5-271335 Japanese Patent Laid-Open No. 9-12621 JP 2002-60411 A

  The object of the present invention is that it does not require a melt-kneading process using a great deal of energy, and is excellent in storability of an olefin polymerization catalyst for producing a polyolefin resin to which a small amount of an antioxidant is effectively added. A method for storing an olefin polymerization catalyst that can produce an olefin polymer having a high bulk density, a large particle size, and an excellent particle property without producing fine powders or lumps even if the catalyst stored in 1 is used. It is to provide.

  As a result of intensive studies to solve such problems, the inventor of the present invention can obtain a polymer powder having excellent storability and good particle properties by storing the olefin polymerization catalyst in the presence of organoaluminum. The present invention has been found to be able to preserve a catalyst for olefin polymerization that can effectively impart stability to polyolefin with a small amount of stabilizer, and does not necessarily require addition by melt-kneading using a great amount of energy. Reached.

That is, according to the first invention of the present invention, the olefin polymerization catalyst containing the following component [I] and component [II] is stored in the presence of an organoaluminum compound. A method for preservation of the catalyst is provided.
Component [I]: Solid catalyst component for olefin polymerization having an average particle size of 40 to 200 μm Component [II]: Antioxidant for resin

  According to the second invention of the present invention, the catalyst for olefin polymerization according to the first invention, wherein the component [II] is composed of a phenolic antioxidant and / or a phosphorus antioxidant. A storage method is provided.

According to the third invention of the present invention, in the first or second invention, the component [I] is obtained by bringing the following component [A] into contact with the component [B]. A method for preserving a catalyst for olefin polymerization is provided.
Component [A]: Periodic Table 4-6 Group transition metal compound component [B]: Component (b-1) containing at least one selected from the following (b-1) to (b-4) (b-1) Organic Particulate carrier (b-3) carrying an ionic compound or Lewis acid capable of reacting with aluminum or organoaluminum oxy compound (b-2) component [A] to convert component [A] into a cation Solid acid particles (b-4) Ion exchange layered silicate particles

According to the fourth invention of the present invention, in the first or second invention, the component [I] is obtained by contacting the following component [A], component [B] and component [C]. A method for storing an olefin polymerization catalyst is provided.
Component [A]: Group 4-6 transition metal compound component [B]: Solid component (b-1) containing one or more selected from the following (b-1) to (b-4) Particulate carrier (b-3) carrying an ionic compound or Lewis acid capable of reacting with organoaluminum or organoaluminum oxy compound (b-2) component [A] to convert component [A] into a cation ) Solid acid particle (b-4) Ion exchange layered silicate particle component [C]: Organoaluminum compound (However, when (b-1) is used, the same organoaluminum compound as (b-1) is excluded)

  According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the component [I] is a prepolymerized prepolymerized catalyst in which an olefin is previously contacted. A method for storing an olefin polymerization catalyst is provided.

According to a sixth invention of the present invention, in any one of the first to fifth inventions, the olefin polymerization solution catalyst containing the following component [I] and component [II] is present in the presence of an organoaluminum compound. A method for preserving an olefin polymerization catalyst characterized by being dried is provided.
Component [I]: Solid catalyst component for olefin polymerization having an average particle size of 40 to 200 μm Component [II]: Antioxidant for resin

  By using the method for preserving an olefin polymerization catalyst of the present invention, a polyolefin resin that is excellent in long-term storability of an olefin polymerization catalyst, has a large particle size, good powder properties, and is highly stabilized can be stably produced. be able to. Furthermore, the conventional method for polymerizing polyolefins in which an antioxidant is melt kneaded after polymerization for stabilization is inefficient because it consumes a great deal of energy, and it also supports poor dispersion of antioxidants. In view of the drawbacks of the state of the art that an excessive amount of stabilizers must be added in order to achieve this, a melt-kneading step using a great amount of energy or a separate addition step is not required, and a small amount of antioxidant Can be stably produced.

  The present invention relates to a component [I] a solid catalyst component for olefin polymerization having an average particle size of 40 to 200 μm, preferably a component [A] group 4-6 transition metal compound, component [B] (b-1). Solid component containing one or more selected from (b-4), [C] a solid catalyst component for olefin polymerization having an average particle size of 40 to 200 μm obtained by further contacting with an organoaluminum compound as necessary, and This is a method for storing an olefin polymerization catalyst, wherein the olefin polymerization catalyst containing component [II] an antioxidant for resin is stored in the presence of an organoaluminum compound. Hereinafter, each component, the catalyst for olefin polymerization, a storage method, etc. are demonstrated in detail.

1. Component constituting the catalyst for olefin polymerization (1) Solid catalyst component for olefin polymerization [I] having an average particle size of 40 to 200 μm
Examples of the olefin polymerization catalyst-fixed catalyst component [I] used in the olefin polymerization catalyst of the present invention include titanium-based ZN catalysts using a known magnesium compound or silicon compound as a carrier and metallocene catalysts composed of transition metals. In the present invention, it is necessary to prepare so that the average particle diameter of the solid catalyst component is 40 to 200 μm, preferably 40 to 150 μm, and more preferably 50 to 150 μm. If the average particle size is less than 40 μm, the polymerized polymer produced is small, and it is difficult to obtain a large particle size polymer that is easy to handle. This may cause generation of a lump or blockage due to poor flow.

  Examples of a method for preparing a titanium-based ZN catalyst using the magnesium compound as a carrier include activated magnesium chloride and a titanium compound described in JP-A-53-45688 and JP-A-55-90510. And, if necessary, a method in which an electron donating compound is contacted simultaneously or stepwise in a co-grinding or liquid state, Japanese Patent Laid-Open No. 54-40293, Japanese Patent Laid-Open No. 56-811, Japanese Patent Laid-Open No. Precipitation obtained by allowing a halogenating agent, a reducing agent, etc. to act on a magnesium compound in a uniform state described in JP-A-58-183708 and JP-A-58-183709 in the presence of an electron donor compound A method of contacting a product with a titanium compound and, if necessary, an electron donor compound, JP-A-52-14672, There is a method in which a halogenating agent, a reducing agent or the like is allowed to act on an organomagnesium compound such as a Grignard reagent described in Japanese Utility Model Publication No. 53-100706 and the like, and then an electron donor compound and a titanium compound are brought into contact therewith. Can be mentioned.

As a manufacturing method of a magnesium compound, it can obtain by spray granulating the suspension of the magnesium oxygen containing compound with an average particle diameter of 0.01-20 micrometers.
A magnesium compound having an average particle diameter of 0.01 to 20 μm may be used by pulverizing a commercially available solid magnesium oxygen-containing compound having a large particle diameter. This is suspended in water or an organic solvent and sprayed in hot air to produce spherical particles of 40 to 200 μm. A preferable method for this production is a disk-shaped suspension in which a magnesium compound suspension having a concentration of 1 to 60 wt%, preferably 5 to 40 wt% is used, using a known technique and apparatus, using a spray nozzle or rotating at high speed. By selecting the number of revolutions using a disk, it is sprayed into hot air to produce spherical particles. The hot air temperature, pressure, suspension temperature, and supply amount are selected so that the residual amount of solvent present in the magnesium oxygen-containing compound is 10 wt% or less. As the solvent to be used, hydrocarbon water such as hexane, heptane and toluene, and alcohols such as methanol and ethanol are used. In general, it is preferable to select a solvent having a low boiling point in order to dry quickly.
It can also be obtained by a method in which an emulsion obtained by mixing a magnesium oxygen-containing compound and an alcohol in an inert hydrocarbon liquid, raising the melting temperature, and stirring vigorously is cooled in a very short time. After the particles are dried, they are partially dealcoholized by heating to a temperature of 50 to 130 ° C. The partially dealcoholized particles are spherical particles having an average particle size of 40 to 200 μm, a surface area of 10 to 50 m ² / g, and a porosity of 0.6 to ² cm ³ / g (mercury). Measured by press-fitting method). In the dealcoholization, the alcohol content is 2 mol or less, preferably 0.15 to 1.5 mol, per 1 mol of the magnesium oxygen-containing compound.

  The magnesium oxygen-containing compound thus obtained is used for catalyst preparation after a drying operation to reduce the amount of residual solvent as required. In addition to direct reaction with the titanium compound, the catalyst preparation method is a method in which a magnesium oxygen-containing compound is pretreated with an electron donor, a halogenating agent or an organometallic compound and then reacted with the titanium compound. A method of reacting an electron donor with a halogenating agent, or a titanium compound, and then reacting one or more of an electron donor, a halogenating agent or an organometallic compound in an arbitrary order, with titanium as required A method of allowing a compound to act at an arbitrary stage can be employed. In particular, after reacting the titanium compound, about 0.1 to 6 moles, preferably about 1 to 4 moles of an electron donor is reacted per 1 atom of titanium fixed on the carrier, and then the organometallic compound is donated. A catalyst component with higher activity can be obtained by a method of reacting about 0.5 to 5 mol per mol of the body, washing it as necessary, and reacting the titanium compound again.

In the case of a titanium-based ZN catalyst, the transition metal compounds of Group 4 to 6 of the periodic table of the component [A] have a general formula of Ti (OR) _n X _a-n (a = 3 or 4, n = 0 to a, R is a hydrocarbon component having 1 to 10 carbon atoms, and X is a halogen atom), specifically, TiCl ₃ , TiCl ₄ , Ti (OBu) ₄ , Ti (OBu) _{2 Cl 2, Ti (OBu)} Cl 3, TiBr 4, TiI 4, TiBr 3, TiI 3, bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, etc. are exemplified. In addition, as the component [B] containing one or more selected from (b-1) to (b-4) in the case of a titanium-based ZN catalyst, the organic aluminum or organic component (b-1) is mainly used. Aluminum oxy compounds are used. An electron donating compound or an organosilicon compound can be coexisted with the component [A] and the component [B]. After the component [A] is brought into contact with the magnesium compound, the component [B] and the electron donating compound An organosilicon compound can also be contacted.

Examples of the metallocene catalyst composed of the transition metal include an olefin polymerization catalyst containing a transition metal compound belonging to Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand. A] transition metal compounds of Groups 4 to 6 of the periodic table, and component [B] (b-1) particulate solid carrying organoaluminum or organoaluminum oxy compound, (b-2) component [A] and Particulate carrier carrying an ionic compound or Lewis acid capable of reacting to convert component [A] into a cation, (b-3) solid acid particles, (b-4) ion-exchange layered silicate What was obtained by making it contact with the solid component containing 1 or more types chosen from particle | grains is used.
Further, in the present invention, as a metallocene catalyst composed of the above transition metal, in addition to the component [A] and the component [B], as an optional component, a component [C] an organoaluminum compound is combined, can do.

In the description of the present invention, “including”, “consisting of”, and “combined” mean that a compound other than the component is combined with the listed compound as long as the effects of the present invention are not impaired. It can be used.
Furthermore, the detail of each component is demonstrated below.

[A] Component: Transition Metal Compounds of Groups 4-6 of the Periodic Table The transition metal compounds of Groups 4-6 of the Periodic Table used in the present invention include the following general formulas (1), (2) , (3) and (4).

  In the above general formulas (1), (2), (3) and (4), A and A ′ may be a conjugated five-membered ring ligand which may have a substituent (in the same compound, A and A ′ are Q may be the same or different, and Q represents a bonding group that bridges two conjugated five-membered ring ligands at any position, and Z represents a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom. Q ′ represents a binding group that bridges Z with an arbitrary position of the conjugated five-membered ring ligand, M represents a metal atom selected from Groups 4 to 6 in the periodic table, X and Y are a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group (in the same compound, X and X ′ may be the same or different) Show.

Examples of A and A ′ include a cyclopentadienyl group. The cyclopentadienyl group may be one having five hydrogen atoms [C ₅ H _5- ], or a derivative thereof, that is, one in which some of the hydrogen atoms are substituted with substituents. May be.
Examples of this substituent are hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms. Even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, and when there are a plurality of these, two of them are bonded at the other end (ω-end) to form a cyclopenta A ring may be formed together with a part of dienyl. Examples of the latter include those in which two substituents are each bonded at the ω-end to share two adjacent carbon atoms in the cyclopentadienyl group to form a condensed six-membered ring, That is, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and those forming a condensed seven-membered ring, that is, an azulenyl group and a tetrahydroazurenyl group can be mentioned.

Preferable specific examples of the conjugated five-membered ring ligand represented by A and A ′ include a substituted or unsubstituted cyclopentadienyl group, indenyl group, fluorenyl group, or azulenyl group. Of these, a substituted or unsubstituted indenyl group or an azulenyl group is particularly preferable.
As the substituent on the cyclopentadienyl group, in addition to the hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, halogen atom groups such as fluorine, chlorine and bromine, and alkoxy having 1 to 12 carbon atoms. A group, for example, a silicon-containing hydrocarbon group represented by -Si (R ¹ ) (R ² ) (R ³ ), a phosphorus-containing hydrocarbon group represented by -P (R ¹ ) (R ² ), or -B (R ¹ ) a boron-containing hydrocarbon group represented by (R ² ). When there are a plurality of these substituents, each substituent may be the same or different. R ¹ , R ² and R ³ described above may be the same or different and each represents an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms.

Q is a bonding group that bridges between two conjugated five-membered ring ligands at an arbitrary position, and Q ′ is a bond that bridges an arbitrary position of the conjugated five-membered ring ligand with a group represented by Z. Represents a sex group.
Specific examples of Q and Q ′ include the following groups.
(I) Methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, cyclohexylene group and other alkylene groups (b) dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, Silylene groups such as methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisylylene group (c) hydrocarbon groups containing germanium, phosphorus, nitrogen, boron or aluminum Specifically, (CH ₃ ) ₂ Ge, (C ₆ H ₅ ) ₂ Ge, (CH ₃ ) P, (C ₆ H ₅ ) P, (C ₄ H ₉ ) N, (C ₆ H ₅ ) _N, is a _{(C 4 H 9) B,} (C 6 H 5) B, (C 6 H 5) Al (C 6 H 5 O) groups represented by Al or the like Preference is given to alkylene groups and silylene groups.

  M is a metal atom transition metal selected from Groups 4 to 6 of the Periodic Table, preferably a Group 4 metal atom of the Periodic Table, specifically titanium, zirconium, hafnium and the like. In particular, zirconium and hafnium are preferable.

  Z represents a ligand, a hydrogen atom, a halogen atom or a hydrocarbon group containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom. Preferable specific examples include an oxygen atom, a sulfur atom, a thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, and 1 to 1 carbon atoms. 40, preferably a nitrogen-containing hydrocarbon group having 1 to 18 carbon atoms, 1 to 40 carbon atoms, preferably a phosphorus-containing hydrocarbon group having 1 to 18 carbon atoms, a hydrogen atom, chlorine, bromine, or a hydrocarbon group having 1 to 20 carbon atoms. .

  X and Y are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, a diphenylphosphino group, etc. A phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms such as a trimethylsilyl group or a bis (trimethylsilyl) methyl group. . X and Y may be the same or different. Of these, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an amino group having 1 to 12 carbon atoms are particularly preferable.

As the compound represented by the general formula (1), for example,
(1) bis (methylcyclopentadienyl) zirconium dichloride,
(2) bis (n-butylcyclopentadienyl) zirconium dichloride,
(3) bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
(4) bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride,
(5) bis (1-methyl-3-trifluoromethylcyclopentadienyl) zirconium dichloride,
(6) bis (1-methyl-3-trimethylsilylcyclopentadienyl) zirconium dichloride,
(7) bis (1-methyl-3-phenylcyclopentadienyl) zirconium dichloride,
(8) bis (indenyl) zirconium dichloride,
(9) bis (tetrahydroindenyl) zirconium dichloride,
(10) Bis (2-methyl-tetrahydroindenyl) zirconium dichloride and the like can be mentioned.

Examples of the compound represented by the general formula (2) include:
(1) Dimethylsilylenebis {1- (2-methyl-4-isopropyl-4H-azurenyl)} zirconium dichloride,
(2) Dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(3) Dimethylsilylenebis [1- {2-methyl-4- (4-fluorophenyl) -4H-azulenyl}] zirconium dichloride,
(4) Dimethylsilylenebis [1- {2-methyl-4- (2,6-dimethylphenyl) -4H-azulenyl}] zirconium dichloride,
(5) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropyl-4H-azurenyl)} zirconium dichloride,
(6) Diphenylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(7) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(8) ethylenebis {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,

(9) Dimethylsilylenebis {1- [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(10) Dimethylsilylenebis {1- [2-methyl-4- (2 ′, 6′-dimethyl-4-biphenylyl) -4H-azulenyl]} zirconium dichloride,
(11) Dimethylsilylene {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} {1- [2-methyl-4- (4-biphenylyl) indenyl]} zirconium dichloride,
(12) Dimethylsilylene {1- (2-ethyl-4-phenyl-4H-azulenyl)} {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(13) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-7-fluoro-4H-azulenyl)} zirconium dichloride,
(14) Dimethylsilylenebis {1- (2-ethyl-4-indolyl-4H-azurenyl)} zirconium dichloride,
(15) Dimethylsilylenebis [1- {2-ethyl-4- (3,5-bistrifluoromethylphenyl) -4H-azurenyl}] zirconium dichloride,
(16) Dimethylsilylene bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium bis (trifluoromethanesulfonic acid),
(17) Dimethylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(18) Dimethylsilylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(19) Dimethylsilylenebis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(20) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropylindenyl)} zirconium dichloride,

(21) Dimethylsilylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(22) ethylene-1,2-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(23) ethylene-1,2-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(24) isopropylidenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(25) ethylene-1,2-bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(26) isopropylidenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(27) Dimethylgermylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(28) Dimethylgermylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(29) phenylphosphinobis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,

(30) Dimethylsilylenebis [3- (2-furyl) -2,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(31) Dimethylsilylenebis [2- (2-furyl) -3,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(32) Dimethylsilylenebis [2- (2-furyl) -indenyl] zirconium dichloride,
(33) Dimethylsilylenebis [2- (2- (5-methyl) furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(34) Dimethylsilylenebis [2- (2- (2- (5-trimethylsilyl) furyl) -4,5-dimethyl-cyclopentadienyl) zirconium dichloride,
(35) Dimethylsilylenebis [2- (2-thienyl) -indenyl] zirconium dichloride,
(36) Dimethylsilylene [2- (2- (5-methyl) furyl) -4-phenylindenyl] [2-methyl-4-phenylindenyl] zirconium dichloride,
(37) Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
(38) Dimethylsilylenebis (2,3-dimethyl-5-ethylcyclopentadienyl) zirconium dichloride,
(39) Dimethylsilylene bis (2,5-dimethyl-3-phenylcyclopentadienyl) zirconium dichloride and the like.

Examples of the compound represented by the general formula (3) include:
(1) (tetramethylcyclopentadienyl) titanium (bis t-butylamide) dichloride,
(2) (tetramethylcyclopentadienyl) titanium (bisisopropylamide) dichloride,
(3) (tetramethylcyclopentadienyl) titanium (biscyclododecylamide) dichloride,
(4) (Tetramethylcyclopentadienyl) titanium {bis (trimethylsilyl) amide)} dichloride,
(5) (2-Methyl-4-phenyl-4H-azurenyl) titanium {bis (trimethylsilyl) amide} dichloride,
(6) (2-methylindenyl) titanium (bis t-butylamide) dichloride,
(7) (fluorenyl) titanium (bis t-butylamide) dichloride,
(8) (3,6-diisopropylfluorenyl) titanium (bis t-butylamide) dichloride,
(9) (Tetramethylcyclopentadienyl) titanium (phenoxide) dichloride,
(10) (tetramethylcyclopentadienyl) titanium (2,6-diisopropylphenoxide) dichloride and the like.

Examples of the compound represented by the general formula (4) include:
(1) Dimethylsilanediyl (tetramethylcyclopentadienyl) (t-butylamido) titanium dichloride,
(2) Dimethylsilanediyl (tetramethylcyclopentadienyl) (cyclododecylamide) titanium dichloride,
(3) Dimethylsilanediyl (2-methylindenyl) (t-butylamido) titanium dichloride,
(4) Dimethylsilanediyl (fluorenyl) (t-butylamido) titanium dichloride and the like.

  The partial component A represented by the general formulas (1) to (4) can be used as a mixture of two or more compounds represented by the same general formula and / or compounds represented by different general formulas. Examples of the dichloride of these exemplified compounds include compounds in which dibromide, difluoride, dimethyl, diphenyl, dibenzyl, bisdimethylamide, bisdiethylamide and the like are substituted. Furthermore, compounds in which zirconium and titanium in the exemplified compounds are replaced with hafnium, titanium and zirconium, respectively, are also exemplified.

Component [B]: Component (b-1) containing one or more selected from the following (b-1) to (b-4): Organic aluminum or organic aluminum oxy compound (b-1) Examples of the organoaluminum compound ()) include the organoaluminum compounds shown in the later-described component [C]. The organic aluminum oxyoxy compound (b-1) may be a conventionally known aluminoxane, or a benzene insoluble organic aluminum oxy compound as exemplified in JP-A-2-78687. There may be.
The conventionally known aluminoxane can be produced, for example, by the following method and is usually obtained as a solution in a hydrocarbon solvent.
(I) A compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and cerium chloride hydrate. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the above suspension of the hydrocarbon medium.
(Ii) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(Iii) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor solvent for aluminoxane.
Specifically, as the organoaluminum compound used in preparing the aluminoxane, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. The above organoaluminum compounds are used singly or in combination of two or more.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organic organoaluminum or organoaluminum oxy compound is one in which the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms. That is, those which are insoluble or hardly soluble in benzene are preferred.

  Examples of the organoaluminum oxy compound used in the present invention include an organoorgano aluminum or organoaluminum oxy compound containing boron represented by the general formula (5).

In General Formula (5), R ⁷ represents a hydrocarbon group having 1 to 10 carbon atoms. R ⁸ may be the same as or different from each other, and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.
The organic organoaluminum or organoaluminum oxy compound containing boron represented by the general formula (5) is an inert compound in which an alkyl boronic acid represented by the general formula (6) and the organoaluminum compound are inert in an inert gas atmosphere. It can manufacture by making it react at the temperature of -80 degreeC-room temperature for 1 minute-24 hours in a solvent.
R ⁷ -B (OH) ₂ (6)
(Wherein R ⁷ represents the same group as described above.)

  Specific examples of the alkyl boronic acid represented by the general formula (6) include methyl boronic acid, ethyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, cyclohexyl boronic acid, phenyl boronic acid, and 3,5-difluorophenyl boron. Examples include acid, pentafluorophenylboronic acid, and 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.

Specifically, trialkylaluminum and tricycloalkylaluminum are preferable as the organoaluminum compound to be reacted with such an alkylboronic acid, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.
The above (b-1) organoaluminum or organoaluminum oxy compound is used singly or in combination of two or more, and is supported on a particulate carrier.

(B-2) Component As (b-2) used in the present invention, particles carrying an ionic compound or Lewis acid capable of reacting with component [A] to convert component [A] into a cation A carrier. Examples of the ionic compound capable of reacting with the component [A] to convert the component [A] into a cation include cations such as a carbonium cation and an ammonium cation, triphenylboron, and tris (3,5-difluoro And a complex of a cation of an organic boron compound such as phenyl) boron and tris (pentafluoro) boron.
Examples of the Lewis acid that can convert the component [A] into a cation include various organic boron compounds such as tris (pentafluoro) boron. Alternatively, metal halogen compounds such as aluminum chloride and magnesium chloride are exemplified. In addition, a certain thing of the said Lewis's acid can also be grasped | ascertained as an ionic compound which can react with component [A] and can convert into component [A] and a cation. Therefore, the compounds belonging to both the Lewis acid and the ionic compound belong to either one.

(B-3) Solid acid particles Examples of the (b-3) solid acid particles used in the present invention include solid acids such as silica / alumina and zeolite.

Here, the particles in (b-1), (b-2) and (b-3) will be described.
The particulate carrier used in the present invention is not particularly limited with respect to its elemental composition and compound composition. For example, a particulate carrier made of an inorganic or organic compound can be exemplified. 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 particle carrier made of a polymer or the like. Alternatively, a mixture thereof may be used.
These particulate carriers preferably have an average particle size of 40 μm to 200 μm, preferably 40 to 150 μm, and more preferably 50 to 150 μm. If the average particle size is less than 40 μm, the polymerized polymer produced is small, and it is difficult to obtain a large particle size polymer that is easy to handle. This may cause generation of a lump or blockage due to poor flow.

(B-4) Ion-exchangeable layered silicate (b-4) The ion-exchangeable layered silicate used in the present invention has a crystal structure in which surfaces constituted by ionic bonds and the like are stacked in parallel with each other by a binding force. And the silicate compound in which the contained ion is exchangeable is said. Most silicates are naturally produced mainly as the main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. But you can. Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other smectites, vermiculite and other vermiculites, mica, illite, sericite and sea chlorite and other mica, attapulgite, sepiolite and palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.
The silicate used as a raw material in the present invention is preferably a silicate in which the main component silicate has a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.

  The silicate used in the present invention can be used as it is without any particular treatment, but it is preferable to perform a chemical treatment. Here, the chemical treatment may be any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the structure of the clay. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like described below can be mentioned.

(I) Acid treatment In addition to removing impurities on the surface, the acid treatment can elute some or all of cations such as Al, Fe, Mg, etc. having a crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid. Two or more salts and acids may be used in the treatment. The treatment conditions with salts and acids are not particularly limited, but usually the salt and acid concentrations are selected from 0.1 to 50% by weight, the treatment temperature is from room temperature to boiling point, and the treatment time is from 5 minutes to 24 hours. Then, it is preferable to carry out under the condition that at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchanged layered silicate is eluted. In addition, salts and acids are generally used in an aqueous solution.

(Ii) Salt treatment In the present invention, 40% or more, preferably 60% or more of the exchangeable group 1 metal cation contained in the ion-exchangeable layered silicate before being treated with salts is described below. It is preferable to exchange ions with cations dissociated from the salts shown.
The salt used in the salt treatment for the purpose of ion exchange is a group consisting of a cation containing at least one atom selected from the group consisting of group 1 to 14 atoms, a halogen atom, an inorganic acid, and an organic acid. A compound comprising at least one anion selected from the group consisting of at least one anion selected from the group consisting of 2 to 14 atoms, and Cl, Br, I, F, PO. ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), At least one anion selected from the group consisting of OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₅ H ₅ O ₇ Is a compound consisting of
_{Specifically, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O 4, LiClO 4, Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg (PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , MgC ₄ H ₄ O _{4 and the} like.
Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr ( NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF ( CO ₃ ) ₂ , HF (NO ₃ ) ₄ , HF (SO ₄ ) ₂ , HFOCl ₂ , HFF ₄ , HFCl ₄ , V (CH ₃ COCHCOCH ₃ ) ₃ , VOSO ₄ , VOCl ₃ , VCl ₃ , VCl ₄ , BCl _{4 3rd} .
Cr (CH ₃ COCHCOCH ₃ ) ₃ , Cr (OOCCH ₃ ) ₂ OH, Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI ₃ , Mn (OOCCH ₃ ) ₂ , Mn (CH ₃ COCHCOCH ₃ ) ₂ , MnCO ₃ , Mn (NO ₃ ) ₂ , MnO, Mn (ClO ₄ ) ₂ , MnF ₂ , MnCl ₂ , Fe (OOCCH ₃ ) ₂ , Fe (CH ₃ COCHCOCH ₃ ) ₃ , FeCO ₃ , Fe (NO ₃ ) ₃ , Fe (ClO ₄ ) ₃ , FePO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , FeF ₃ , FeCl ₃ , FeC ₆ H ₅ O ₇ etc.
Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _{2 and the} like.
Zn (OOCCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.

(Iii) Alkali treatment Examples of the treating agent used in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) ₂ .

(Iv) Organic matter treatment Examples of the organic matter used for the organic matter treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Examples of the anion that constitutes the organic treatment agent include hexafluorophosphate, tetrafluoroborate, tetraphenylborate, and the like in addition to the anions exemplified as the anion that constitutes the salt treatment agent. It is not limited.

These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as the component (b-4).
The heat treatment method of the adsorbed layered silicate adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the water content of the component (b-4) 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 1 mmHg. , Preferably 1% by weight or less.
As described above, in the present invention, the component (b-4) is particularly preferably an ion-exchangeable layered material having a water content of 3% by weight or less obtained by performing a salt treatment and / or an acid treatment. Silicate.

The component (b-4) is preferably a spherical particle having an average particle size of 40 μm or more. More preferably, the average particle diameter is 40 μm or more and 200 μm or less from the viewpoint of improving the fluidity and bulk density of the catalyst and polymer particles and preventing the generation of fine powder and coarse powder which hinder the polymerization operation.
Here, the measurement of the particles refers to a value measured using a particle size distribution measuring apparatus by a laser diffraction method. The measurement uses ethanol as a dispersion medium, and calculates the particle size distribution and average particle size with a refractive index of 1.33 and a shape factor of 1.0.
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.
Examples of the granulation method used here include agitation granulation method and spray granulation method, but commercially available products can also be used.

  Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization process. In the case of an ethylene polymerization catalyst, further strength is required, and it is 4.0 MPa or more, more preferably 10 MPa or more. The upper limit is about 40 MPa. The crushing strength is obtained by measuring the compressive strength of any 10 or more particles using a micro compression tester and calculating the average value as the crushing strength. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited especially when prepolymerization is performed.

  In the olefin polymerization catalyst of the present invention, (b-1) an organoaluminum or an organoaluminum oxy compound, a particulate carrier carrying an organoaluminum or an organoaluminum oxy compound, (b-2) reacting with component [A]. A particulate carrier carrying an ionic compound or Lewis acid capable of converting component [A] into a cation, (b-3) solid acid particles, or (b-4) an ion-exchange layered silicate. The particles can be used alone as component [B], or any combination of these four components.

[C] Component: Organoaluminum Compound In the solid catalyst component for olefin polymerization of the present invention, component [C] an organoaluminum compound can be used as necessary. The organoaluminum compound used as component [C] is preferably a compound represented by general formula (7).
AlR ⁷ pX _3-p (7)
In this invention, it cannot be overemphasized that the compound represented by General formula (7) can be used individually, in mixture of multiple types or in combination. In the general formula (7), R ⁷ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen, hydrogen, an alkoxy group, or an amino group. p is a number greater than 0 and up to 3, and q is less than 3. R ⁷ is preferably an alkyl group, and X is chlorine when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and 1 to 8 carbon atoms when it is an amino group. The amino group of is preferable.

Specific examples of preferred compounds include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum sesquioxide. Such as chloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum phenoxide, diethylaluminum pentafluorenoxide, diisobutylaluminum phenoxide, methylaluminum diphenoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride It is below. Of these, trialkylaluminum and dialkylaluminum hydride having p = 3 and q = 1 are preferable. More preferably, R ⁷ is a trialkylaluminum having 1 to 8 carbon atoms.
In the case of using organoaluminum as (b-1) in component [B], redundant use of the same compound as (b-1) is excluded.

(2) Component [II]: Antioxidant for Resin Component [II] Antioxidant for resin used in the catalyst for olefin polymerization of the present invention is used or molded from among stabilizers in which ordinary polyolefin resin is used. Depending on the choice, there are no particular restrictions such as phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, UV absorbers, hindered amine compounds, nucleating agents, flame retardants, hydrotalcites, etc. Phenol antioxidants or phosphorus antioxidants selected from organic phosphite compounds or organic phosphonite compounds are preferred, and phenol and phosphorus antioxidants may be mixed and used.

Examples of preferred phenolic antioxidants are:
2,6-ditert-butyl-4-methylphenol, 2-ditert-butyl-4,6-dimethylphenol, 2,6-ditert-butyl-4-ethylphenol, 2,6-ditert-butyl -4-n-butylphenol, 2,6-ditert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2 , 6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-ditert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,6 Di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl hydroquinone, 2,5-di-tert-butyl amyl hydroquinone, 2,6-diphenyl-4-o Tadecyloxyphenol, 2,2′-thiobis (6-tert-butyl-4-methylphenol), 2,2′-thiobis (4-octylphenol), 4,4′-thiobis (6-tert-butyl-3) -Methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis ( 6-tert-butyl-4-ethylphenol), 2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol) 2,2′-methylenebis (6-nonyl-4-methylphenol), 2,2′-methylenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4,6 Ditertiarybutylphenol), 2,2′-ethylidenebis (6-tertiarybutyl-4-isobutylphenol), 2,2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2 '-Methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-ditert-butylphenol), 4,4'-methylenebis (6-tert-butyl- 2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl) Phenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3′-tert-butyl-4′-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5) -Methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,3,5 -Tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, bis (3,5-ditert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5- Di-tert-butyl-4-hydroxybenzyl mercaptoacetate, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) ) Isocyanurate, dioctadecyl 3,5-ditert-butyl-4-hydroxybenzylphosphonate, and calcium salt of monoethyl 3,5-ditert-butyl-4-hydroxybenzylphosphonate

  Among the above-mentioned phenolic antioxidants, particularly preferred phenolic antioxidants are 2,6-ditertiarybutyl-4-methylphenol, stearyl (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,1,3-tris (5-tert-butyl-4-hydroxy-) 2-methylphenyl) butane and tocopherols (vitamin E). These may be used alone or in a mixture.

  The amount of the phenolic antioxidant added is 0.001 to 10% by weight based on the polymer obtained by polymerization. Preferably, it is 0.002-1 wt%. More preferably, it is 0.002 to 0.5% by weight. The addition by this method exhibits the effect of stabilizing the polymer in a smaller amount than the method of adding at the time of granulation kneading later.

Phosphorous antioxidants are likewise known stabilizers for the thermal oxidative aging of plastics, especially polyolefins. These are described as organic phosphite compounds and organic phosphonite compounds.
Examples of preferred organic phosphite compounds are trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite or tristearyl sorbitol triphosphite. Aromatic phosphites are preferred. An aromatic phosphite is a phosphite having an aromatic hydrocarbon group, such as a phenyl group. Examples thereof are triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite. In particular, tris (nonylphenyl) phosphite, tris (2,4-ditertiarybutylphenyl) phosphite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphosphite and 2,2'-ethylidenebis ( 2,4-ditertiarybutylphenyl) fluorophosphite is preferred.
Preferable specific examples of the organic phosphonite compound include tetrakis (2,4-ditert-butylphenyl) -4,4′-biphenylenediphosphonite [Irgafos PEPQ], tetrakis (2-tert-butyl-4- Methylphenyl) biphenylenediphosphonite, tetrakis (2,4-ditertiaryaluminphenyl) biphenylenediphosphonite, tetrakis (2,4-ditertiarybutyl-5-methylphenyl) biphenylenediphosphonite, tetrakis (2- Tert-butyl-4,6-dimethylphenyl) biphenylenediphosphonite. These may be used alone or in a mixture.

  The amount of the phosphorus antioxidant added is 0.001 to 10% by weight with respect to the polymer obtained by polymerization. Preferably, it is 0.002-1 wt%. More preferably, it is 0.002 to 0.5% by weight. The addition by this method exhibits the effect of stabilizing the polymer in a smaller amount than the method of adding at the time of granulation kneading later.

2. Synthesis of Olefin Polymerization Catalyst (1) Contact of Each Component The olefin polymerization catalyst of the present invention is obtained by contacting each of the above components in a polymerization tank simultaneously or continuously, or once or multiple times. Can be formed. The contact of each component is usually carried out in an inert gas such as nitrogen, or in an inert aliphatic hydrocarbon or aromatic hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC and 150 degreeC. Any desired combination of contact orders is possible.

For example, taking a metallocene catalyst as an example, particularly preferable ones are shown as follows. When component [C] is used, before contacting component [A] with component [B], component [A], or component [B], or both component [A] and component [B] The component [C] or the component [A] and the component [B] are contacted simultaneously with the component [C], or the component [A] and the component [B] are contacted with each other. It is possible to contact the component [C] after, but preferably, either the method without using the component [C] or the component [C] before contacting the component [A] with the component [B] It is the method of making it contact.
Moreover, after contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of components [A], [B] and [C] used in the present invention is arbitrary. For example, the amount of the component [A] used relative to the component [B] is preferably in the range of 0.1 to 1000 μmol, particularly preferably 0.5 to 500 μmol, relative to 1 g of the component [B]. The amount of component [C] used relative to component [B] is preferably such that the amount of transition metal is 0.001 to 100 μmol, particularly preferably 0.005 to 50 μmol, relative to 1 g of component [B]. Therefore, the amount of the component [C] relative to the component [A] is preferably in the range of 10 ⁻⁵ to 50, particularly preferably 10 ^{−4 to} 5 in terms of the molar ratio of the transition metal.

  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 catalyst for olefin polymerization of the present invention contains at least one component [II] antioxidant for resin. Taking a metallocene catalyst as an example, the addition of component [II] is a method of adding component [B] in advance, a method of adding component [II] to the contact product of component [A] and component [B], and component There is a method of adding the component [II] to the contact product of the component [A], the component [B], and the component [C], and any method is possible.
Component [II] is used in an amount of 0.001% to 0.5% by weight based on the polymer obtained by polymerization. Preferably, it is 0.002 to 0.1% by weight.
The polymer powder obtained from the catalyst thus obtained can effectively stabilize the polyolefin with the addition of a small amount of stabilizer, and does not necessarily require addition by melt kneading using a great deal of energy.

(2) Prepolymerization In the synthesis of the olefin polymerization catalyst of the present invention, the olefin polymerization catalyst prepared by the above-described method can be further subjected to treatment. As one of the treatments, a method of preliminarily contacting the olefin and prepolymerizing can be employed.
The olefin used in the prepolymerization treatment is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcyclohexane. Examples include alkanes and styrene. The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 to 100 ° C. and 5 minutes to 24 hours, respectively. Moreover, the amount of prepolymerization is preferably 0.01 to 500, more preferably 0.1 to 100 with respect to the solid catalyst component before the prepolymerization.

The component [C] can be added or added during the preliminary polymerization.
That is, a method of bringing the organoaluminum compound and / or component [II] into contact after all the catalyst components are brought into contact or after prepolymerization is also possible. The method of adding component [II] at the time of prepolymerization is preferable because it does not cause a decrease in catalyst activity, and can produce an olefin polymerization catalyst having good powder properties without generation of fine powder.
A method of contacting the organoaluminum compound and / or component [II] after the prepolymerization is also possible. The method of adding component [II] at the time of prepolymerization is preferable because it does not cause a decrease in catalyst activity, and can produce an olefin polymerization catalyst having good powder properties without generation of fine powder. Polymerized powder obtained from the prepolymerized catalyst has excellent powder properties, no particle crushing, fine powder generation, and high bulk density, so it adheres to the catalyst supply line, is clogged, and the polymerization reactor inner wall and piping, heat There is no adhesion or blockage in an exchange or the like, and olefin polymerization can be performed stably.

3. Preservation of Olefin Polymerization Catalyst The preservation of the olefin polymerization catalyst of the present invention is carried out in the presence of an organoaluminum compound. The olefin polymerization catalyst may be stored either in a slurry state containing a solvent, in a semi-dry state containing a small amount of solvent, or in a completely dry state after completely removing the solvent. Here, the solvent means a single or mixture of inert hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, toluene, xylene, and liquid paraffin. The slurry concentration is 0.0001 g to 10 g, preferably 0.01 g to 0.5 g, per mL of solvent.
The storage temperature of the catalyst for olefin polymerization may be 90 ° C. or lower, preferably 50 ° C. or lower. The lower the temperature, the higher the effect.

  The organoaluminum compound to be present during storage of the olefin polymerization catalyst can be used without particular limitation as long as it can achieve the object of the present invention, such as an aluminoxane, a trialkylaluminum compound, etc. When (b-1) an organoaluminum or organoaluminum oxy compound is used as the component and an organoaluminum compound is used as the component [C], or an organoaluminum compound is added in the prepolymerization, and these remain, Can be saved in state. In the present invention, the organoaluminum or organoaluminum oxy compound is treated as belonging to the organoaluminum compound.

The amount of organoaluminum used for storage of the olefin polymerization catalyst can be arbitrarily selected. However, if the addition amount is too large, the particle properties of the catalyst will be deteriorated, while if it is too small, the storage stability will be impaired.
Specifically, taking a metallocene catalyst as an example, the amount of organoaluminum added is such that the molar ratio of organoaluminum / component [A] is 0.1 to 1000, preferably 1 to 100. Moreover, the quantity of the organoaluminum per 1g of component [B] is 0.001-10 mmol, Preferably it is 0.01-5 mmol.

The catalyst for olefin polymerization of the present invention is stored in the presence of the organoaluminum compound, and further, the storage effect can be maintained by drying and storing.
As a method for drying the olefin polymerization catalyst containing a solvent, methods such as heat removal, removal under gas flow, and pressure reduction removal are used. Either method is performed in an inert gas atmosphere such as nitrogen or argon so that the catalyst does not come into contact with air or moisture.
The drying temperature is 80 ° C. or lower or the boiling point of the solvent or lower, preferably 0 ° C. to 50 ° C. An inert gas such as nitrogen or argon is used as a gas used for drying under a gas flow. When removing the solvent by drying, the solid component in the catalyst slurry may be settled and the supernatant liquid may be removed beforehand by decantation or the like. The initial concentration of the catalyst slurry for starting the drying is not particularly limited, but the component [B] per mL of the solvent may be 0.0001 g to 10 g, preferably 0.01 g to 0.5 g.
The aluminum concentration in the solvent-containing catalyst when drying in the presence of organoaluminum is 0.1 to 1000, preferably 1 to 100, in terms of the molar ratio of organoaluminum / component [A]. Moreover, the quantity of the organoaluminum per 1g of component [B] is 0.001-10 mmol, Preferably it is 0.01-5 mmol.

4). Olefin polymerization In the polymerization of olefins using the olefin polymerization catalyst of the present invention, the polymerizable olefin is preferably an α-olefin having about 2 to 20 carbon atoms, specifically, ethylene, propylene, 1-butene, 1 -Hexene, 1-octene and the like. More preferred are propylene and ethylene. In addition to homopolymerization, copolymerization may be performed, and the type of comonomer is preferably about 2 to 20 carbon atoms (excluding those used as monomers), specifically ethylene, propylene, 1-butene, Linear olefins such as 1-hexene and 1-octene, linear diolefins such as 1,5-pentadiene, 1,5-hexadiene, 2-methyl-1,6-heptadiene, and cyclics such as cyclopentadiene and norbornene Examples thereof include olefins and aromatic olefins such as styrene and divinylbenzene. In the case of copolymerization, the type of comonomer used can be selected from olefins other than the main component among those mentioned as the olefin. Preferred olefins are ethylene and propylene, ethylene or a homopolymer of propylene, a copolymer with other α-olefins mainly using ethylene, binary, ternary or higher with ethylene or higher olefins mainly using propylene. It is possible to use it for the production of random copolymers and block copolymers.

As the polymerization mode of the olefin, any mode can be adopted as long as the catalyst component and each monomer come into contact efficiently. Specifically, a slurry method using an inert solvent, a slurry method using propylene as a solvent substantially without an inert solvent, a solution polymerization method, or a gas that keeps each monomer in a gaseous state without using a liquid solvent substantially. Phase method can be adopted. Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent. The polymerization temperature is 0 to 200 ° C., and hydrogen can be used as an auxiliary molecular weight regulator. The polymerization pressure can be carried out in the range of 0 to 2000 kg / cm ² G.

  A polyolefin obtained by polymerizing the olefin polymerization catalyst of the present invention as an olefin polymerization catalyst is a highly stabilized polyolefin because the stabilizer is highly dispersed in the polymer.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited by these examples without departing from the gist thereof. In Examples and Comparative Examples, physical properties are evaluated as follows.
(1) MFR: Melt index value measured with a load of 2.16 kg at 230 ° C. according to JIS-K-6758.
(2) Polymer BD: The bulk density of the polymer measured according to ASTM D1895-69.

Example 1
(1) Synthesis of catalyst 1,700 g of pure water was put into a 5 L separable flask equipped with a stirring blade and a reflux device, and 500 g of 98% sulfuric acid was added dropwise. Thereto, 300 g of granulated montmorillonite having an average particle diameter of 45 μm (manufactured by Mizusawa Chemical Industry Co., Ltd., using Benclay SL) was added and stirred. Thereafter, the mixture was reacted at 90 ° C. for 2 hours. This slurry was filtered and washed. To the recovered cake, 1230 g of 27% lithium sulfate aqueous solution was added and reacted at 90 ° C. for 2 hours. This slurry was filtered and further washed until the pH of the filtrate reached 4 or higher. The recovered cake was pre-dried at 100 ° C. and then dried at 200 ° C. for 2 hours. As a result, 275 g of chemically treated montmorillonite was obtained. The average particle size was 43 μm, the shape was spherical, and the number of particles having an M / L value of 0.8 to 1.0 was 93%.
To the 1 L flask, 10 g of chemically treated montmorillonite was added, 65 ml of heptane and 35.4 ml (25 mmol) of a heptane solution of triisobutylaluminum were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the residue was washed with heptane to a residual liquid ratio of 1/100, and finally the amount of slurry was adjusted to 100 ml. Furthermore, 2.1 ml (1.5 mmol) of a heptane solution of triisobutylaluminum was added and stirred at room temperature for 10 minutes.
(R) -Dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl}] hafnium (300 μmol) in toluene (60 ml) in a 200 ml flask Was added to the 1 L flask and stirred for 60 minutes at room temperature.
(2) Prepolymerization In a 50 ml flask, 10 ml of a 30% by weight heptane solution of stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate as a phenol stabilizer and Tris (2, After mixing with 10 ml of a 30 wt% heptane solution of 4-ditert-butylphenyl) phosphite, the mixture was added to the 1 L flask and stirred for 30 minutes.
The entire amount of the slurry was introduced into a stirring autoclave having an internal volume of 1.0 L that had been sufficiently replaced with nitrogen. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 2 hours, the supply of proprene was stopped and maintained for an additional hour. After completion of the prepolymerization, the remaining monomer was purged, the stirring was stopped, and the slurry was extracted into a 1 L flask that had been sufficiently purged with nitrogen. Subsequently, 8.5 ml (6.0 mmol) of a heptane solution of triisobutylaluminum was added and stirred at room temperature for 10 minutes, and then this slurry was dried under reduced pressure at 40 ° C. to recover 36.4 g of a prepolymerized catalyst. The average particle size of the prepolymerized catalyst was 61 μm.
(3) Polymerization After the inside of the autoclave with an induction stirrer with an internal volume of 3 L was sufficiently substituted with propylene, 2.9 ml of a heptane solution of triisobutylaluminum (140 mg / ml) was added, and 200 ml of hydrogen and then 750 g of liquid propylene were introduced. The temperature was raised to 65 ° C. The prepolymerized catalyst obtained in the above (1) was made into a heptane slurry, and 144 mg was injected as a prepolymerized catalyst to initiate polymerization. The bath temperature was maintained at 65 ° C. One hour after the catalyst was added, the remaining monomer was purged, and the inside of the tank was replaced with argon five times to stop the polymerization. The recovered polymer was dried for 1 hour in a vacuum dryer at 40 ° C. The obtained polymer was 210 g. The polymer BD was 0.48 g / cm ³ and the powder properties were good. The phenol-based stabilizer content and the phosphorus-based stabilizer content in the polymer were 45 ppm each. The results are shown in Table 1.
(4) Stability evaluation of polymer The stability of the obtained polymer was evaluated by measuring MFR three times with a melt indexer. It was 18.4 g / 10min when MFR was measured without adding an additional stabilizer for the obtained polymer. The obtained strand was again introduced into the melt indexer, MFR was measured, and this was repeated twice. The third MFR was 21.7 g / 10 min and was stable. The results are shown in Table 2.
(5) Storage The dried catalyst obtained in (2) above was transferred to a Pyrex (registered trademark) pressure-resistant bottle under a nitrogen atmosphere, sealed, and stored for 3 months in a storage container sealed with nitrogen at room temperature.
(6) Polymerization using storage catalyst Polymerization was carried out in the same manner as in (3) using the catalyst stored in (4) above. As a result, the obtained polymer was 205 g, and the polymer BD was 0.48 g / cm ³ . The results are shown in Table 1.
(7) Stability evaluation of polymer Stability evaluation was carried out in the same manner as (3) above. The results are shown in Table 2. The MFR was stable.

(Example 2)
(1) Prepolymerization After the catalyst was prepared in the same manner as in Example 1 (1), tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-) was used as a phenol-based stabilizer in a 50 ml flask. 4′-hydroxyphenyl) propionate] After mixing 5 ml of a 30 wt% heptane solution of methane with 5 ml of a 30 wt% heptane solution of tris (2,4-ditert-butylphenyl) phosphite as a phosphorus stabilizer. The mixture was added to the 1 L flask and stirred for 30 minutes.
The entire amount of the slurry was introduced into a stirring autoclave having an internal volume of 1.0 L that had been sufficiently replaced with nitrogen. When the temperature was stabilized at 50 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 2 hours, the supply of proprene was stopped and maintained for an additional hour. After completion of the prepolymerization, the remaining monomer was purged, the stirring was stopped, and the slurry was extracted into a 1 L flask that had been sufficiently purged with nitrogen. Subsequently, 12.5 ml (8.8 mmol) of a heptane solution of triisobutylaluminum was added and stirred at room temperature for 10 minutes, and then this slurry was dried under reduced pressure at 40 ° C. to recover 33.4 g of a prepolymerized catalyst. The average particle size of the prepolymerized catalyst was 58 μm.
(2) Polymerization After the inside of an autoclave with an induction stirrer with an internal volume of 3 L was sufficiently substituted with propylene, 2.9 ml of a heptane solution of triisobutylaluminum (140 mg / ml) was added, and 200 ml of hydrogen and then 750 g of liquid propylene were introduced. The temperature was raised to 65 ° C. The prepolymerized catalyst obtained in the above (1) was made into a heptane slurry, and 116 mg was injected as a prepolymerized catalyst to initiate polymerization. The bath temperature was maintained at 65 ° C. One hour after the catalyst was added, the remaining monomer was purged, and the inside of the tank was replaced with argon five times to stop the polymerization. The recovered polymer was dried for 1 hour in a vacuum dryer at 40 ° C. The obtained polymer was 230 g. The polymer BD was 0.47 g / cm ³ and the powder properties were good. The MFR was 12.8 g / 10 min. The phenol-based stabilizer content and the phosphorus-based stabilizer content in the polymer were each 26 ppm. The results are shown in Table 1.
(3) Storage The dried catalyst obtained in (1) above was transferred to a Pyrex (registered trademark) pressure-resistant bottle under a nitrogen atmosphere, sealed, and stored for 3 months in a storage container sealed with nitrogen at room temperature.
(4) Polymerization using storage catalyst Polymerization was carried out in the same manner as in (2) using the catalyst stored in (3) above. As a result, the obtained polymer was 240 g, the polymer BD was 0.48 g / cm ³ , and the MFR was 16.5 g / 10 min. The results are shown in Table 1.

(Example 3)
(1) Storage The dried catalyst obtained in Example 2 (1) was transferred to a Pyrex (registered trademark) pressure bottle in a nitrogen atmosphere, sealed, and stored at room temperature for 6 months in a storage container sealed with nitrogen. .
(2) Polymerization using storage catalyst Polymerization was carried out in the same manner as in Example 2 (2) using the catalyst stored in (1) above. As a result, the obtained polymer was 220 g, the polymer BD was 0.48 g / cm ³ , and the MFR was 11.3 g / 10 min. The results are shown in Table 1.

Example 4
(1) Synthesis of catalyst 150 g of commercially available montmorillonite (Mizusawa Chemical Co., Ltd. Benclay SL) was gradually added to 2850 g of distilled water, and the mixture was stirred for several hours. .1 μm particles were obtained. To a glass flask equipped with a 1.0 L stirring blade, 510 g of distilled water and 150 g of concentrated sulfuric acid (96%) were slowly added to disperse 80 g of the granulated particles, followed by heat treatment at 90 ° C. for 2 hours. After cooling, the slurry was filtered under reduced pressure to recover the cake. It was washed several times with distilled water and dried at 110 ° C. to obtain 67.5 g of acid-treated particles. 50 g of acid-treated particles were gradually added to 150 g of distilled water and stirred. This slurry was spray granulated again to recover 45 g of spherical catalyst support particles having an average particle size of 69.3 μm. When the shape was measured, the number of particles having an M / L of 0.8 or more and 1.0 or less was 92%. The particles were dried under reduced pressure at 200 ° C. for 2 hours.
To the 1 L flask, 10 g of the catalyst carrier particles prepared as described above were added, 65 ml of heptane and 35.4 ml (25 mmol) of a heptane solution of triisobutylaluminum were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the residue was washed with heptane to a residual liquid ratio of 1/100, and finally the amount of slurry was adjusted to 100 ml. Furthermore, 2.1 ml (1.5 mmol) of a heptane solution of triisobutylaluminum was added and stirred at room temperature for 10 minutes.
(R) -Dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl}] hafnium (300 μmol) in toluene (60 ml) in a 200 ml flask Was added to the 1 L flask and stirred for 60 minutes at room temperature.
(2) Prepolymerization In a 50 ml flask, 10 ml of a 30% by weight heptane solution of stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate as a phenol stabilizer and Tris (2, After mixing with 10 ml of a 30 wt% heptane solution of 4-ditert-butylphenyl) phosphite, the mixture was added to the 1 L flask and stirred for 30 minutes.
The entire amount of the slurry was introduced into a stirring autoclave having an internal volume of 1.0 L that had been sufficiently replaced with nitrogen. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 2 hours, the supply of proprene was stopped and maintained for an additional hour. After completion of the prepolymerization, the remaining monomer was purged, the stirring was stopped, and the slurry was extracted into a 1 L flask that had been sufficiently purged with nitrogen. Subsequently, 8.5 ml (6.0 mmol) of a heptane solution of triisobutylaluminum was added and stirred at room temperature for 10 minutes, and then this slurry was dried under reduced pressure to recover 37.7 g of a prepolymerized catalyst. At this time, the ratio of polypropylene to the catalyst was 2.1 g / g. The average particle size of the prepolymerized catalyst was 98.3 μm.
(3) Polymerization Polymerization was carried out in the same manner as in Example 1 (3). 75 mg was introduced as a prepolymerization catalyst. The recovered polymer was dried for 1 hour in a vacuum dryer at 40 ° C. The obtained polymer was 259 g. The polymer BD was 0.41 g / cm ³ and the powder properties were good. The phenol-based stabilizer content and the phosphorus-based stabilizer content in the polymer were each 23 ppm.
(4) Stability evaluation of polymer The stability of the obtained polymer was evaluated by measuring MFR three times with a melt indexer. It was 15.3 g / 10min when MFR was measured for the obtained polymer without adding an additional stabilizer. The obtained strand was again introduced into the melt indexer, MFR was measured, and this was repeated twice. The third MFR was 19.1 g / 10 min and was stable. The results are shown in Table 1.
(5) Storage The dried catalyst obtained in (2) above was transferred to a Pyrex (registered trademark) pressure-resistant bottle under a nitrogen atmosphere, sealed, and stored for 3 months in a storage container sealed with nitrogen at room temperature.
(6) Polymerization using storage catalyst Polymerization was carried out in the same manner as in (3) using the catalyst stored in (4) above. As a result, the obtained polymer was 270 g, and the polymer BD was 0.41 g / cm ³ . The results are shown in Table 1.
(7) Stability evaluation of polymer Stability evaluation was carried out in the same manner as (3) above. The results are shown in Table 2. The MFR was stable.

(Example 5)
(1) Catalyst synthesis A high-speed agitator with an internal volume of 2 L was sufficiently replaced with nitrogen, and 700 g of purified kerosene, 10 g of commercially available MgCl ₂ , 24.2 g of ethanol, and 3 g of Emazole 320 (Kao Atlas, sorbitan distearate) were added. The mixture was heated with stirring and stirred at 3000 rpm for 30 minutes at 120 ° C. Under high-speed stirring, it was transferred to a 2 L glass flask in which 1 l of refined kerosene previously cooled to −10 ° C. was put in using a Teflon (registered trademark) tube having an inner diameter of 5 mm. The produced solid was collected by filtration and washed with hexane to obtain a carrier. The particle size was 40 μm to 100 μm.
10 g of the above carrier (containing 30.7 mmol of MgCl ₂ ) and 100 ml of purified kerosene were placed in a 300 ml glass flask, and 21.1 ml of triethylaluminum was added dropwise at 5 ° C. with stirring, followed by stirring at 25 ° C. for 1 hour, and further 80 Stir at 0 ° C. for 3 hours. The solid part was filtered, washed with hexane and dried. The resulting solid was suspended in 100 ml of purified kerosene, and dry air was blown with stirring at room temperature for 2 hours. The solid part was filtered and washed with hexane. After suspending the produced solid in 100 ml of purified kerosene, 1.9 ml of ethyl benzoate was added, and the mixture was stirred at 25 ° C. for 1 hour, and further stirred at 80 ° C. for 2 hours. The solid part was collected by filtration, washed thoroughly with hexane and dried. 100 ml of TiCl ₄ was added to the solid transferred to a 200 ml glass flask, and the mixture was stirred at 90 ° C. for 2 hours. The supernatant was removed by decantation, and 100 ml of TiCl ₄ was further added and stirred at 90 ° C. for 2 hours. The solid part collected by hot filtration was sufficiently washed with hot kerosene and hexane, and the solid part was dried under reduced pressure to obtain a titanium-containing catalyst containing 2.4 wt% in terms of Ti atoms. The average particle size was 52 μm.
(2) Prepolymerization In a 20 ml flask, 5 ml of a 30 wt% heptane solution of stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate as a phenol stabilizer and Tris (2, 4-Di-tert-butylphenyl) phosphite was mixed with 5 ml of a 30 wt% heptane solution and stirred.
After adding 500 g of hexane, 1 mmol of triethylaluminum, the above-mentioned stabilizer slurry and 2 g of the titanium-containing catalyst (1.0 mmol in terms of titanium atom) to a stirred autoclave having an internal volume of 1.0 L sufficiently substituted with nitrogen, 20 ° C. Then, 10.5 g of propylene was supplied for 120 minutes for prepolymerization. After completion of the reaction, unreacted propylene was purged, stirring was stopped, and the slurry was extracted into a 1 L flask that had been sufficiently purged with nitrogen. Subsequently, 1.7 ml (1.2 mmol) of a heptane solution of triisobutylaluminum was added and stirred at room temperature for 10 minutes, and then this slurry was dried under reduced pressure at 40 ° C. to recover 6.3 g of a prepolymerized catalyst. At this time, the ratio of polypropylene to the catalyst was 2.1 g / g. The average particle size of the prepolymerized catalyst was 67.3 μm.
(3) Polymerization After the inside volume of the autoclave with an induction stirrer with a volume of 3 L was sufficiently substituted with propylene, 0.5 mmol of triethylaluminum, 0.1 mmol of diisopropyldimethoxysilane, 500 g of hydrogen and liquid propylene were introduced, and the temperature was raised to 65 ° C. . Polymerization was initiated by injecting 21 mg of a prepolymerized catalyst. The bath temperature was maintained at 65 ° C. One hour after the catalyst was added, the remaining monomer was purged, and the inside of the tank was replaced with argon five times to stop the polymerization. The recovered polymer was dried for 1 hour in a vacuum dryer at 40 ° C. The obtained polymer was 150 g. The polymer BD was 0.48 g / cm ³ and the powder properties were good. The phenol-based stabilizer content and the phosphorus-based stabilizer content in the polymer were each 18 ppm.
(4) Stability evaluation of polymer The stability of the obtained polymer was evaluated by measuring MFR three times with a melt indexer. It was 23.5 g / 10min when MFR was measured for the obtained polymer without adding an additional stabilizer. The obtained strand was again introduced into the melt indexer, MFR was measured, and this was repeated twice. The third MFR was 30.3 g / 10 min and was stable. The results are shown in Table 1.
(5) Storage The dried catalyst obtained in (2) above was transferred to a Pyrex (registered trademark) pressure-resistant bottle under a nitrogen atmosphere, sealed, and stored for 3 months in a storage container sealed with nitrogen at room temperature.
(6) Polymerization using storage catalyst Polymerization was carried out in the same manner as in (3) using the catalyst stored in (4) above. As a result, the obtained polymer was 140 g, and the polymer BD was 0.48 g / cm ³ . The results are shown in Table 1.
(7) Stability evaluation of polymer Stability evaluation was carried out in the same manner as (3) above. The results are shown in Table 2. The MFR was stable.

(Comparative Example 1)
(1) Prepolymerization As in Example 1 (2), except that synthesis of the catalyst was carried out in the same manner as in Example 1 (1) and triisobutylaluminum was not added when the catalyst was dried, Prepolymerization was performed.
In a 50 ml flask, 10 ml of a 30% by weight heptane solution of stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate as a phenolic stabilizer and tris (2,4-ditertiary as a phosphorus stabilizer. (Butylphenyl) phosphite was mixed with 10 ml of a 30 wt% heptane solution, added to the 1 L flask and stirred for 30 minutes.
The entire amount of the slurry was introduced into a stirring autoclave having an internal volume of 1.0 L that had been sufficiently replaced with nitrogen. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 2 hours, the supply of proprene was stopped and maintained for an additional hour. After completion of the prepolymerization, the remaining monomer was purged, the stirring was stopped, and the slurry was extracted into a 1 L flask that had been sufficiently purged with nitrogen. This slurry was dried under reduced pressure at 40 ° C. to recover 36.1 g of a prepolymerized catalyst. The average particle size of the prepolymerized catalyst was 56 μm.
(2) Polymerization After the inside of an autoclave with an induction stirrer with an internal volume of 3 L was sufficiently substituted with propylene, 2.9 ml of a heptane solution of triisobutylaluminum (140 mg / ml) was added, and 200 ml of hydrogen and then 750 g of liquid propylene were introduced. The temperature was raised to 65 ° C. The prepolymerized catalyst obtained in the above (1) was made into a heptane slurry, and 145 mg was injected as a prepolymerized catalyst to initiate polymerization. The bath temperature was maintained at 65 ° C. One hour after the catalyst was added, the remaining monomer was purged, and the inside of the tank was replaced with argon five times to stop the polymerization. The recovered polymer was dried for 1 hour in a vacuum dryer at 40 ° C. The obtained polymer was 200 g. The polymer BD was 0.42 g / cm ³ and generation of fine powder was observed. The phenol-based stabilizer content and the phosphorus-based stabilizer content in the polymer were each 39 ppm. The results are shown in Table 1.
(3) Stability evaluation of polymer The stability of the obtained polymer was evaluated by measuring MFR three times with a melt indexer. When the MFR of the obtained polymer was measured without adding an additional stabilizer, it was 10.6 g / 10 min. The obtained strand was again introduced into the melt indexer, MFR was measured, and this was repeated twice. The third MFR was 12.2 g / 10 min and was stable. The results are shown in Table 2.
(4) Storage The dried catalyst obtained in (1) above was transferred to a Pyrex (registered trademark) pressure-resistant bottle under a nitrogen atmosphere, sealed, and stored for 1 month in a storage container sealed with nitrogen at room temperature.
(5) Polymerization using storage catalyst Polymerization was performed in the same manner as (2) using the catalyst stored in (4) above. As a result, the obtained polymer was 68 g, and the polymer BD was 0.30 g / cm ³ . The results are shown in Table 1.
(6) Stability evaluation of polymer Stability evaluation was carried out in the same manner as (3) above. As a result, the first MFR was 35.2 g / 10 min, and the MFR measured the third time was 50.9 g / 10 min. Moreover, the MFR strand was colored yellow. The results are shown in Table 2.

  By using the method for preserving an olefin polymerization catalyst of the present invention, a polyolefin resin that is excellent in long-term storability of an olefin polymerization catalyst, has a large particle size, good powder properties, and is highly stabilized can be stably produced. be able to. Furthermore, the conventional method for polymerizing polyolefins in which an antioxidant is melt kneaded after polymerization for stabilization is inefficient because it consumes a great deal of energy, and it also supports poor dispersion of antioxidants. In view of the drawbacks of the state of the art that an excessive amount of stabilizers must be added in order to achieve this, a melt-kneading step using a great amount of energy or a separate addition step is not required, and a small amount of antioxidant Can be produced stably, and its industrial value is extremely large.

Claims (6)

A method for storing an olefin polymerization catalyst comprising storing an olefin polymerization catalyst containing the following component [I] and component [II] in the presence of an organoaluminum compound.
Component [I]: Solid catalyst component for olefin polymerization having an average particle size of 40 to 200 μm Component [II]: Antioxidant for resin   Component [II] consists of a phenolic antioxidant and / or phosphorus antioxidant, The preservation method of the catalyst for olefin polymerization according to claim 1 characterized by things. The method for storing an olefin polymerization catalyst according to claim 1 or 2, wherein the component [I] is obtained by bringing the following component [A] into contact with the component [B].
Component [A]: Periodic Table 4-6 Group transition metal compound component [B]: Component (b-1) containing at least one selected from the following (b-1) to (b-4) (b-1) Organic Particulate carrier (b-3) carrying an ionic compound or Lewis acid capable of reacting with aluminum or organoaluminum oxy compound (b-2) component [A] to convert component [A] into a cation Solid acid particles (b-4) Ion exchange layered silicate particles The preservation of the olefin polymerization catalyst according to claim 1 or 2, wherein the component [I] is obtained by contacting the following component [A], component [B] and component [C]. Method.
Component [A]: Group 4-6 transition metal compound component [B]: Solid component (b-1) containing one or more selected from the following (b-1) to (b-4) Particulate carrier (b-3) carrying an ionic compound or Lewis acid capable of reacting with organoaluminum or organoaluminum oxy compound (b-2) component [A] to convert component [A] into a cation ) Solid acid particle (b-4) Ion exchange layered silicate particle component [C]: Organoaluminum compound (However, when (b-1) is used, the same organoaluminum compound as (b-1) is excluded)   The method for preserving an olefin polymerization catalyst according to any one of claims 1 to 4, wherein the component [I] is a prepolymerized prepolymerized catalyst in which an olefin has been contacted in advance. The olefin polymerization catalyst containing the following component [I] and component [II] is dried in the presence of an organoaluminum compound, according to any one of claims 1 to 5. A method for storing a catalyst for olefin polymerization.
Component [I]: Solid catalyst component for olefin polymerization having an average particle size of 40 to 200 μm Component [II]: Antioxidant for resin