JP4866624B2 - Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing polyolefin using the same - Google Patents

Description

  The present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing a polyolefin using the same, and more specifically, a solid catalyst component for olefin polymerization containing an antioxidant, a catalyst for olefin polymerization, and a polyolefin. It relates to the manufacturing method.

The polyolefin obtained using the conventional solid catalyst component for olefin polymerization is treated with an alcohol or a chelating agent because the catalyst metal or halogen compound remains in the produced polymer and greatly deteriorates the stability of the polymer. Furthermore, catalyst residues have been removed by adding steps such as water washing treatment. However, in recent years, the catalyst-derived compound remaining in the polymer has been reduced due to the high activation of the polymerization catalyst, and thus the catalyst residue removal step has been omitted to reduce the production cost. In addition, there is an increasing demand for a method for producing a polyolefin resin that is highly energy-saving and can be obtained with high stability by blending a small amount of an antioxidant or the like for environmental measures such as global warming.
Polyolefin resin obtained with a highly active catalyst is an energy-saving production method because a catalyst removal step is not required, but it contains a small amount of catalyst residue, so it is more stable than polyolefin resin after catalyst removal. It is necessary to use a large amount of antioxidant because it is low and the product life obtained 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 stabilizer. 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 by adding a stabilizer after polymerization during the polymerization, and the granulation kneading step can be omitted. .

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 not always difficult to uniformly disperse in the polymer, and require a new process 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 (see, for example, 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 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, a catalyst for olefin polymerization obtained by contacting a transition metal compound of group 4 to 6 of the periodic table having a conjugated 5-membered ring ligand, a layered silicate, a phenol compound, and an organoaluminum compound as required is disclosed. (For example, refer to Patent Document 7). However, the phenol compound used here is for providing an olefin polymerization catalyst capable of obtaining an olefin polymer with higher activity, and a known stabilizer for the thermal oxidative aging of polyolefin. Are different and cause the same problems as described above, and this method cannot be expected to have an effective effect of stabilizing the powder.
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 2003-113210 A

  The object of the present invention is that 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. In view of the drawbacks of the state of the art that an excessive amount of stabilizer must be added in order to cope with poor dispersion, it does not require a melt-kneading step using a great amount of energy or another addition step in place of it, and a small amount. An object of the present invention is to provide a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing polyolefin using the same for producing a polyolefin resin to which an antioxidant is effectively added.

  As a result of intensive studies to solve such problems, the present inventor has produced a small amount of a polyolefin resin using a solid catalyst component for olefin polymerization containing a specific metallocene compound-based solid catalyst component and an antioxidant. The present inventors have found that an antioxidant can effectively impart stability to polyolefin and that addition by melt kneading using a great amount of energy is not necessarily required.

That is, according to the first invention of the present invention, (a) a metallocene compound of a group 4 transition metal in the periodic table,
(B) a solid support,
(C) at least one compound selected from the group consisting of the following (c-1), (c-2) and (c-3),
(C-1) an organometallic compound (c-2) an organoaluminum oxy compound (c-3) a compound that reacts with a metallocene compound of a group 4 transition metal of the periodic table and (d) a phenolic antioxidant A solid catalyst component for olefin polymerization is provided, which contains an agent and / or a phosphorus-based antioxidant.

  According to the second invention of the present invention, in the first invention, the component (d) is at least one of a phenolic antioxidant, an organic phosphite compound or an organic phosphonite compound, alone or in combination with each other. A solid catalyst component for olefin polymerization is provided.

According to the third invention of the present invention, in the first or second invention, the phenol-based antioxidant of component (d) is 2,6-ditertiarybutyl-4-methylphenol, stearyl (3 , 5-Ditert-butyl-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, or tocopherols (vitamin E), a solid catalyst component for olefin polymerization is provided.

  According to a fourth aspect of the present invention, in any one of the first to third aspects, the component (b) is spherical and has an average particle size of 10 to 200 μm. A solid catalyst component is provided.

  According to a fifth invention of the present invention, in any one of the first to fourth inventions, the component (b) is clay, clay mineral or ion-exchange layered compound, for olefin polymerization A solid catalyst component is provided.

  According to a sixth aspect of the present invention, in any one of the first to fourth aspects, the component (b) is a porous oxide or an inorganic chloride, and the solid catalyst for olefin polymerization Ingredients are provided.

  According to a seventh aspect of the present invention, there is provided an olefin polymerization catalyst comprising the solid catalyst component for olefin polymerization according to any one of the first to sixth aspects.

  According to an eighth aspect of the present invention, there is provided a method for producing a polyolefin, characterized in that polymerization or copolymerization is carried out by bringing the olefin polymerization catalyst of the seventh aspect into contact with an olefin.

  The solid catalyst component for olefin polymerization of the present invention contains a stabilizer in the solid catalyst component, and the polyolefin obtained using this as a catalyst for olefin polymerization becomes a highly stabilized polyolefin resin. In addition, by containing a stabilizer in the solid catalyst component, the stabilizer is highly dispersed inside the polymer after polymerization, reducing the amount of various antioxidants and weathering improvers used during molding processing. Can be expected. Furthermore, since the polymerized polymer contains a stabilizer, a granulation step for introducing the stabilizer can be omitted, and energy for stabilization can be reduced.

  Hereinafter, the solid catalyst component for olefin polymerization of the present invention, the production of a solid catalyst component for olefin polymerization, the catalyst for olefin polymerization containing the same, and the method for producing polyolefin using the same will be described in detail.

1. Solid catalyst component for olefin polymerization The solid catalyst component for olefin polymerization of the present invention comprises (a) a metallocene compound of a transition metal of Groups 4-6 of the periodic table, (b) a solid support, (c) (c-1) an organometallic. At least one selected from the group consisting of a compound, (c-2) an organoaluminum oxide compound, and (c-3) a compound that reacts with a metallocene compound of a transition metal of Group 4-6 of the periodic table to form an ion pair A solid catalyst component for olefin polymerization containing a compound, (d) an antioxidant. Hereinafter, each component will be specifically described.

(A) Metallocene compound of group 4-6 transition metal of periodic table (a) Group 4-6 transition metal metallocene compound used in the solid catalyst component for olefin polymerization of the present invention is a conjugated five-membered ring ligand. Is a transition metal compound of Groups 4 to 6 of the periodic table. Preferred as such a transition metal compound are compounds represented by the following general formulas (1), (2), (3) and (4).

  In general formulas (1), (2), (3), and (4), A and A ′ are conjugated five-membered ring ligands that may have a substituent (in the same compound, A and A ′ are the same) Q represents a bonding group that bridges two conjugated five-membered ring ligands at an arbitrary 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, and X And Y represents 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) .

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, etc. (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 (1,3-dimethylcyclopentadienyl) zirconium dimethyl,
(6) bis (1,3-dimethylcyclopentadienyl) zirconium methyl chloride,
(7) bis (1,3-dimethylcyclopentadienyl) zirconium diethyl,
(8) bis (1,3-dimethylcyclopentadienyl) zirconium diisobutyl,
(9) Bis (1,3-dimethylcyclopentadienyl) zirconium chloride monohydride,
(10) Bis (1-n-butyl-3-methyl-cyclopentadienyl) zirconium dihydride,
(11) bis (1,3-dimethylcyclopentadienyl) zirconium dimethoxide,
(12) bis (1,3-dimethylcyclopentadienyl) zirconium bis (dimethylamide),
(13) Bis (1-n-butyl-3-methyl-cyclopentadienyl) zirconium diethylamide monochloride,
(14) bis (1-methyl-3-trifluoromethylcyclopentadienyl) zirconium dichloride,
(15) bis (1-methyl-3-trimethylsilylcyclopentadienyl) zirconium dichloride,
(16) bis (1-methyl-3-phenylcyclopentadienyl) zirconium dichloride,
(17) Bis (indenyl) zirconium dichloride,
(18) Bis (tetrahydroindenyl) zirconium dichloride,
(19) 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-chlorophenyl) -4H-azulenyl}] zirconium dichloride,
(4) Dimethylsilylenebis [1- {2-methyl-4- (4-fluorophenyl) -4H-azulenyl}] zirconium dichloride,
(5) Dimethylsilylenebis [1- {2-methyl-4- (3-chlorophenyl) -4H-azulenyl}] zirconium dichloride,
(6) Dimethylsilylenebis [1- {2-methyl-4- (2,6-dimethylphenyl) -4H-azulenyl}] zirconium dichloride,
(7) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropyl-4H-azurenyl)} zirconium dichloride,
(8) Diphenylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(9) methylphenylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(10) Dimethylphenylsilylenebis [1- {2-methyl-4- (1-naphthyl) -4H-azurenyl}] zirconium dichloride,
(11) methylphenylsilylenebis [1- {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride,
(12) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(13) Dimethylsilylenebis [1- {2-ethyl-4- (1-naphthyl) -4H-azurenyl}] zirconium dichloride,
(14) Dimethylsilylenebis [1- {2-ethyl-4- (1-anthracenyl) -4H-azulenyl}] zirconium dichloride,
(15) Dimethylsilylenebis [1- {2-ethyl-4- (2-anthracenyl) -4H-azurenyl}] zirconium dichloride,
(16) Dimethylsilylenebis [1- {2-ethyl-4- (9-anthracenyl) -4H-azulenyl}] zirconium dichloride,
(17) Dimethylsilylenebis [1- {2-ethyl-4- (1-phenanthryl) -4H-azulenyl}] zirconium dichloride,
(18) Dimethylmethylenebis {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(19) Dimethylgermylenebis {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(20) ethylenebis {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(21) Dimethylsilylenebis {1- [2-i-propyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(22) Dimethylsilylenebis {1- [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(23) Dimethylsilylenebis {1- [2-methyl-4- (2 ′, 6′-dimethyl-4-biphenylyl) -4H-azulenyl]} zirconium dichloride,
(24) Dimethylsilylene {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} {1- [2-methyl-4- (4-biphenylyl) indenyl]} zirconium dichloride,
(25) Dimethylsilylenebis {1- [2-ethyl-4- (4-biphenylyl) -4H-5,6,7,8-tetrahydroazulenyl]} zirconium dichloride,
(26) Dimethylsilylene {1- (2-ethyl-4-phenyl-4H-azurenyl)} {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(27) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-6-isopropyl-4H-azurenyl)} zirconium dichloride,
(28) Dimethylsilylenebis {1- (2-ethyl-4,6-diphenyl-4H-azurenyl)} zirconium dichloride,
(29) Dimethylsilylenebis [1- {2-methyl-4- (pentafluorophenyl) -4H-azulenyl}] zirconium dichloride,
(30) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-7-fluoro-4H-azulenyl)} zirconium dichloride,
(31) Dimethylsilylenebis {1- (2-ethyl-4-indolyl-4H-azurenyl)} zirconium dichloride,
(32) Dimethylsilylenebis {1- (2-dimethylborano-4-indolyl-4H-azulenyl)} zirconium dichloride,
(33) Dimethylsilylenebis [1- {2-ethyl-4- (3,5-bistrifluoromethylphenyl) -4H-azurenyl}] zirconium dichloride,
(34) Dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dimethyl,
(35) Dimethylsilylene bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium bis (trifluoromethanesulfonic acid),
(36) Dimethylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(37) Dimethylsilylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(38) Dimethylsilylenebis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(39) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropylindenyl)} zirconium dichloride,
(40) Dimethylsilylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(41) Dimethylsilylenebis [1- {2-ethyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(42) Dimethylsilylenebis [1- {2-ethyl-4- (9-anthryl) indenyl}] zirconium dichloride,
(43) Dimethylsilylenebis [1- {2-ethyl-4- (9-phenanthryl) indenyl}] zirconium dichloride,
(44) Dimethylsilylene {1- (2-ethyl-4-phenylindenyl)} {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(45) Dimethylsilylenebis [1- {2-methyl-4- (pentafluorophenyl) indenyl}] zirconium dichloride,
(46) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-7-fluoroindenyl)} zirconium dichloride,
(47) ethylene-1,2-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(48) ethylene-1,2-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(49) ethylene-1,2-bis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(50) isopropylidenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(51) ethylene-1,2-bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(52) ethylene-1,2-bis {1- (2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(53) ethylene-1,2-bis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(54) ethylene-1,2-bis [1- {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride,
(55) isopropylidenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(56) ethylene-1,2-bis {1- (2-ethyl-4-indolyl-4H-azurenyl)} zirconium dichloride,
(57) Dimethylgermylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(58) Dimethylgermylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(59) methylaluminum bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(60) phenylphosphinobis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(61) phenylaminobis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(62) Dimethylsilylenebis [3- (2-furyl) -2,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(63) Dimethylsilylenebis [2- (2-furyl) -3,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(64) Dimethylsilylenebis [3- (2-furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(65) Dimethylsilylenebis [2- (2-thienyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(66) Dimethylsilylenebis [2- (2-furyl) -indenyl] zirconium dichloride,
(67) Dimethylsilylenebis [2- (2- (5-methyl) furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(68) Dimethylsilylenebis [2- (2- (5-t-butyl) furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(69) Dimethylsilylenebis [2- (2- (2- (5-trimethylsilyl) furyl) -4,5-dimethyl-cyclopentadienyl) zirconium dichloride,
(70) Dimethylsilylenebis [2- (2-thienyl) -indenyl] zirconium dichloride,
(71) Dimethylsilylenebis [2- (2- (5-methyl) furyl) -indenyl] zirconium dichloride,
(72) Dimethylsilylenebis [2- (2- (5-methyl) furyl) -4-phenylindenyl] zirconium dichloride,
(73) Dimethylsilylene [2- (2- (5-methyl) furyl) -4-phenylindenyl] [2-methyl-4-phenylindenyl] zirconium dichloride,
(74) Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
(75) Dimethylsilylenebis (2,3-dimethyl-5-ethylcyclopentadienyl) zirconium dichloride,
(76) Dimethylsilylenebis (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 portion [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. Further, compounds in which zirconium and titanium in the exemplified compounds are replaced with hafnium are also exemplified.

(B) Solid carrier (b) The solid carrier used in the solid catalyst component for olefin polymerization of the present invention is an inorganic or organic compound, and the solid form is a fine solid. Among these, as the inorganic compound, porous oxides, inorganic chlorides, clays, clay minerals, or ion-exchangeable layered compounds are preferable.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or a composite or mixture containing these. using, for example, natural or synthetic _{zeolites, SiO 2 -MgO, SiO 2 -Al} 2 O 3, SiO 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO Etc. can be used. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred. The inorganic oxide includes a small amount of NaCO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained. Such porous oxides, Characterization is different depending on the type and production method, the carrier preferably used in the present invention has a specific surface area of 50~1200m ² / g, preferably in the range of 100~1000m ² / g The pore volume is desirably in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic chloride, MgCl ₂ , MgBr ₂ , MnCl ₂ or the like is used. The inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material obtained by melting an inorganic chloride in a solvent such as alcohol and then precipitating it into fine particles with a precipitating agent.

Clay is usually composed mainly of clay minerals. In addition, the ion-exchangeable layered compound is a compound having a crystal structure in which planes constituted by ionic bonds and the like are stacked in parallel with a weak binding force, and the ions contained therein can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used. Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.
Such clays, clay minerals or ion-exchangeable layered compound is preferably not less than 0.1 cm ³ / g radius 20Å or more pore volume measured by mercury porosimetry, 0.1~5.0cm ³ / Particularly preferred is g. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 ⁴に よ り by mercury porosimetry using a mercury porosimeter.

  The clay, clay mineral or ion-exchange layered compound used in the present invention is preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing surface impurities, acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure, forming ionic complexes, molecular complexes, organic derivatives, etc. And the interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . Such a bulky ion may play a role of a column supporting the layered structure, and in such a case, a pillar is usually called. Introducing another substance between layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , and [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Can be mentioned. These compounds are used alone or in combination of two or more. Moreover, when intercalating these compounds, obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.) Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.
Specific examples of preferable ones are montmorillonite, vermiculite, hectorite, teniolite, and synthetic mica.
These may be used alone or in combination of two or more. Further, it may be used in combination with a porous oxide or inorganic chloride.

  As the inorganic compound used in the present invention, the above-mentioned various compounds may be used as they are, or may be used after performing treatments such as ball milling, sieving and granulation. Examples of the granulation method include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation method, emulsion granulation method, submerged granulation method Method, compression molding granulation method and the like, but are not particularly limited. Preferred examples of the granulation method include agitation granulation method, spray granulation method, rolling granulation method, and fluidized granulation method, and particularly preferred examples include agitation granulation method and spray granulation method. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. The heat dehydration temperature is 100 to 1000 ° C, preferably 150 to 700 ° C.

  Examples of the organic compound of component (b) used in the present invention include a granular or fine particle solid made of a polymer of an organic compound having a particle size in the range of 10 to 200 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by using as a main component, and modified products thereof.

  The solid support (b) preferably used in the present invention has a particle size of 1 to 300 μm, preferably 10 to 200 μm, more preferably 25 to 150 μm. The shape is preferably spherical. Specifically, the number of particles having an M / L value of 0.8 or more and 1.0 or less is 50% or more and 100% or less of all particles (where L is the maximum number of particles in the projected view) It is a shape that satisfies the diameter value, and M is the diameter value orthogonal to L.) Preferably, the number of particles having an M / L value of 0.8 or more and 1.0 or less is 85% or more and 100% or less of all particles. M / L is obtained by observing 100 or more of arbitrary particles with an optical microscope and image-processing them.

(C) Component The component (c) used in the solid catalyst component for olefin polymerization of the present invention includes (c-1) an organometallic compound, (c-2) an organoaluminum oxy compound, and (c-3) described below. It is at least one compound selected from compounds that react with metallocene compounds of Group 4-6 transition metals in the periodic table to form ion pairs.

(C-1) Organometallic compound As the (c-1) organometallic compound used in the present invention, specifically, (c-1a) of the first, second, and thirteenth and thirteenth groups of the periodic table shown below ), (C-1b), and (c-1c) organometallic compounds.

(C-1a): Organoaluminum compound represented by general formula (5) R ^a _m Al (OR ^b ) _n H _p X _q (5)
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3.)

(C-1b): Complex alkylated product of Group 1 metal of the periodic table represented by the general formula (6) and aluminum M ² AlR ^a ₄ (6)
(In the formula, M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)

(C-1c): Dialkyl compound of group 2 or group 12 metal of the periodic table represented by formula (7) R ^a R ^b M ³ (7)
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. .)

Examples of the organoaluminum compound belonging to (c-1a) include organoaluminum compounds represented by general formulas (8) to (11).
R ^a _m Al (OR ^b ) _3-m (8)
(In Formula (8), R ^a and R ^b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 1.5. ≦ m ≦ 3.)
R ^a _m AlX _3-m (9)
(In Formula (9), R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3.)
R ^a _m AlH _3-m (10)
(In the formula (10), Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3.)
R ^a _m Al (OR ^b ) _n X _q (11)
(In the formula (11), R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is a number such that 0 <m ≦ 3, n is 0 ≦ n <3, q is 0 ≦ q <3, and m + n + q = 3.)

More specifically, examples of the organoaluminum compound belonging to (c-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum. Tri (n-alkyl) aluminum; triisopropylaluminum, triisobutylaluminum, tri (sec-butyl) aluminum, tri (tert-butyl) aluminum, tri (2-methylbutyl) aluminum, tri (2-methylpentyl) aluminum, tri Tri-branched alkylaluminums such as (2-methylhexyl) aluminum and tri (2-ethylhexyl) aluminum; tricyclohexylaluminum, Tricycloalkyl aluminum such as cyclooctyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum _hydride; triphenyl aluminum, triaryl aluminum such as tri tolyl aluminum _{(i-C 4 H 9)} x Al y (C 5 H 10) z (Wherein x, y and z are positive numbers and z ≧ 2x) and the like. Trialkenylaluminum such as triisoprenylaluminum; isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum Alkyl aluminum alkoxides such as isopropoxide; Dialkylaluminums such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide Mualkoxide; alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially alkoxylated alkyl having an average composition represented by R ^a _2.5 Al (OR ^b ) _0.5 Aluminum; diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2, Dialkylaluminum aryloxides such as 6-di-t-butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum Dialkylaluminum halides such as muchloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides such as dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride and others Partially hydrogenated alkyl aluminum, ethyl aluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride, etc. partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide and the like.

In addition, as the organoaluminum compound (c-1a), compounds similar to the above can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to (c-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .
Other organometallic compounds include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, butyl magnesium bromide, Butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.
Furthermore, a compound that can form the organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium may be used.

  (C-1) Among organometallic compounds, organoaluminum compounds are preferred. The above (c-1) organometallic compounds are used singly or in combination of two or more.

(C-2) Organoaluminum Oxy Compound The (a-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. A benzene-insoluble organoaluminum oxy compound may also be used.
A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.

(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
(2) 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.
(3) 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 aluminoxane solvent.
Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (c-1a).
Of these, 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 organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, those that are insoluble or hardly soluble in benzene are preferred.

  Examples of the organoaluminum oxy compound used in the present invention include an organoaluminum oxy compound containing boron represented by the general formula (12).

In General Formula (12), 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 organoaluminum oxy compound containing boron represented by the general formula (12) is an alkylboronic acid represented by the general formula (13) and the organoaluminum compound in an inert solvent under an inert gas atmosphere. It can manufacture by making it react for 1 minute-24 hours at the temperature of -80 degreeC-room temperature.
R ⁷ -B (OH) ₂ (13)
(Wherein R ⁷ represents the same group as described above.)

Specific examples of the alkyl boronic acid represented by the general formula (13) 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.
Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (c-1a).
Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.
The above (c-2) organoaluminum oxy compounds are used singly or in combination of two or more.

(C-3) Compound which reacts with metallocene compound of transition metal of group 4-6 of periodic table to form ion pair Metallocene of group 4-6 transition metal of periodic table used in solid catalyst component for olefin polymerization of the present invention As the compound (c-3) (hereinafter referred to as “ionized ionic compound”) which forms an ion pair by reacting with a compound transition metal compound, JP-A-1-501950, JP-A-1-503636, Lewis acids, ionic compounds, and borane compounds described in JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. And carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, methyl group, trifluoromethyl group, or fluorine) is exemplified. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (P-Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like can be mentioned.

  As an ionic compound, the compound represented by General formula (14) is mentioned, for example.

In the general formula (14), ^examples of R ⁹⁺ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.
R ^{10 to} R ¹³ may be the same as or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.
Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.
Specific examples of the ammonium cation include trialkylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation; N, N-diethylanilinium cation, N, N-dialkylanilinium cation such as N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as di (isopropyl) ammonium cation and dicyclohexylammonium cation Etc.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ⁹ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.
Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenol) Le) boron, tri (n- butyl) ammonium tetra (o-tolyl) and boron and the like.

  Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6. -Pentamethylanilinium tetra (phenyl) boron and the like.

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, ferroceniumtetra (pentafluorophenyl) borate, triphenylcarbeniumpenta Mention may also be made of phenylcyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the general formula (15) or (16), and the like.

（式中、Ｅｔはエチル基を示す。）

(In the formula, Et represents an ethyl group.)

  Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] un. Salts of anions such as decaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate Metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) And the like.

  Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecarborane (14), dodecahydride-1-phenyl-1, 3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,7-dicarboundecarborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundecarborane , Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbadecaborate, (N-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) Ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-dicarbaound decaborate (12), tri (n-butyl) ammonium 2,9-dicarbaound decaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicar Bound Decaborate, Tri (n-butyl) ammonium Undecahigh Ride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride 8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4, Salts of anions such as 6-dibromo-7-carbaundecaborate; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaoundecabo Rate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride) -7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n- (Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundeca) Borate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-di) Til-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbundecaborate) cobaltate (III), tris [ Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate ) Manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis ( Metal carbonates such as undecahydride-7-carbaundecaborate) nickelate (IV) Such as the salt of borane anion, and the like.

The heteropoly compound is composed of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, lintongost vanadic acid, germanotangostovanadic acid, phosphomolybdotangostobanamic acid, germanomolybdo tungstovanadate, phosphomolybdo Tungstic acid, phosphomolybniobic acid, and salts of these acids, such as metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium ,barium Salts with organic salts of triphenyl ethyl salts, and the like can be used but not limited thereto.
The above (c-3) ionized ionic compounds are used singly or in combination of two or more.

(D) Antioxidant The (d) antioxidant used in the solid catalyst component for olefin polymerization of the present invention is not particularly limited, but is selected from a phenolic antioxidant, an organic phosphite compound, or an organic phosphonite compound. Phosphorous antioxidants are preferred, and phenolic and phosphorus antioxidants may be mixed and used.

  Phenolic antioxidants are likewise known stabilizers for the thermal oxidative aging of plastics, especially polyolefins. The phenol-based antioxidant includes, for example, at least one group represented by the general formula (17).

（式中、Ｒ’は水素原子、メチル基又は第三ブチル基を表わし、Ｒ”は置換又は非置換アルキル基、或いは置換又は非置換アルキルチオアルキル基を表わす。）

(In the formula, R ′ represents a hydrogen atom, a methyl group or a tertiary butyl group, and R ″ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkylthioalkyl group.)

  Particularly suitable phenolic antioxidants are those of the general formula (18)

（式中、Ａは水素原子、炭素原子数１ないし２４のアルキル基、炭素原子数５ないし１２のシクロアルキル基、フェニル−炭素原子数１ないし４のアルキル基、フェニル基又は−ＣＨ_２−Ｓ−Ｒ^２５基又は一般式（１９）

Wherein A is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl-alkyl group having 1 to 4 carbon atoms, a phenyl group, or —CH ₂ —S. -R ²⁵ group or general formula (19)

D represents an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl-alkyl group having 1 to 4 carbon atoms, a phenyl group, or —CH ₂ —S. represents -R ²⁵ group, X is a hydrogen atom, C 1 -C 18 alkyl group or the group of the ^{_{following: -C a H 2a -S q -R}} 26, -C b H 2b -CO-O-R 27 ^{_{, -C b H 2b -CO-N}} (R 29) (R 30), - CH 2 N (R 34) (R 35), the general formula (20) or (21)

R represents a hydrogen atom or a group represented by —CO—CH═CH ₂ , G ^* represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ²⁵ Represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a group represented by — (CH ₂ ) _c —CO—OR ²⁸ or —CH ₂ CH ₂ OR ³³ , R ²⁶ represents a hydrogen atom, or one carbon atom Thru | or 18 alkyl group, a phenyl group, a benzyl group, or General formula (22)

Or a — (CH ₂ ) c —CO—OR ²⁸ group or —CH ₂ —CH ₂ —OR ³³ group, wherein R ²⁷ is an alkyl group having 1 to 30 carbon atoms or —CHR ^31. —CH ₂ —S—R ³² , general formula (23) or (24)

(Wherein Q represents an alkylene group having 2 to 8 carbon atoms, a thiaalkylene group having 4 to 6 carbon atoms, or a —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _d — group). R ²⁸ represents an alkyl group having 1 to 24 carbon atoms, R ²⁹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a cyclohexyl group, and R ³⁰ represents one to 1 carbon atom. 18 alkyl groups, cyclohexyl groups, phenyl groups, alkyl-substituted phenyl groups having 1 to 18 carbon atoms, or general formulas (25) to (27)

R ²⁹ and R ³⁰ together represent an alkylene group having 4 to 8 carbon atoms which may be interrupted by an —O— group or an —NH— group. , R ³¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, R ³² represents an alkyl group having 1 to 18 carbon atoms, and R ³³ represents a hydrogen atom, having 1 to 24 carbon atoms. Represents an alkyl group, a phenyl group, an alkanoyl group having 2 to 18 carbon atoms or a benzyl group, and R ³⁴ represents an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group, a phenyl group, or an alkyl group having 1 to 18 carbon atoms. Substituted phenyl group or general formula (28)

R ³⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group, or a general formula (29)

Or R ³⁴ and R ³⁵ together represent an alkylene group having 4 to 8 carbon atoms which may be interrupted by an —O— group or an —NH— group, and a is 0, 1 represents 1, 2 or 3; b represents 0, 1, 2 or 3; c represents 1 or 2; d represents 1 to 5; f represents 2 to 8; , 3 or 4).

In the formula, A is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, a phenyl group, or a —CH ₂ —S—alkyl group having 1 to 18 carbon atoms, or the general formula (30)

D represents an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, a phenyl group, or a —CH ₂ —S—alkyl group having 1 to 18 carbon atoms, and X represents a hydrogen atom or a carbon atom. An alkyl group of 1 to 8 or the following group: -C _a H _2a -S _q -R ²⁶ , -C _b H _2b -CO-O-R ²⁷ , -CH ₂ N (R ³⁴ ) (R ³⁵ ), Formula (31) or (32)

R ²⁶ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a — (CH ₂ ) _c —CO—OR ²⁸ group, and R ²⁷ represents 1 to 12 carbon atoms. 18 alkyl groups or general formula (33) or (34)

In the formula, Q represents an alkylene group having 2 to 8 carbon atoms, a —CH ₂ —CH ₂ —S—CH ₂ —CH ₂ — group or a —CH ₂ CH ₂ (OCH ₂ CH ₂ ) _d — group, and R ²⁸ represents an alkyl group having 1 to 18 carbon atoms, R ³⁴ and R ³⁵ independently of each other represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, or R ³⁴ and R ³⁵ together. Represents an alkylene group having 4 to 8 carbon atoms which may be interrupted by an —O— group or an —NH— group, a represents 1 or 2, b represents 1 or 2, and c represents 1 or 2 And a compound represented by the general formula (18) in which d represents 1, 2 or 3 is preferred.

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

Particularly preferred phenolic antioxidants are 2,6-ditert-butyl-4-methylphenol, stearyl (3,5-ditert-butyl-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 tocopherol (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.
The organic phosphite compound is, for example, a compound represented by general formulas (35) to (39).

In general formulas (35) to (39), R ₁ ′, R ₂ ′ and R ₃ ′ are each independently an alkyl group having 1 to 18 carbon atoms; a halogen atom, a —COOR ₄ ′ group, a —CN group or -CONR _{4 'R 4'} alkyl group having 1 to carbon atoms are substituted with group 18; -S- group, -O- group, or -NR ₄ '- 2 -C interrupted by groups 18 of Alkyl group; cycloalkyl group having 5 to 8 carbon atoms; phenyl group or naphthyl group; substituted by halogen atom or by 1 to 3 alkyl group or alkoxy group having 1 to 18 carbon atoms in total Phenyl or naphthyl group; 2,2,6,6-tetramethylpiperid-4-yl group; N-allyl- or N-benzyl- or N having 1 to 4 carbon atoms in the alkyl moiety -Archi -2,2,6,6-tetramethylpiperid-4-yl group; or N-alkanoyl-2,2,6,6-tetramethylpiperido- having 1 to 4 carbon atoms in the alkyl moiety A 4-yl group; or an N-alkylene-2,2,6,6-tetramethylpiperidyl group having 1 to 3 carbon atoms in the alkylene moiety and 1 to 18 carbon atoms in the alkoxy moiety Or an N-alkylene-4-alkoxy-2,2,6,6-tetramethylpiperidyl group, wherein the groups R ₄ ′ and R ₄ ′ are independently of each other a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Represents a cycloalkyl group having 5 to 12 carbon atoms or a phenylalkyl group having 1 to 4 carbon atoms in the alkyl moiety, n ′ represents 2, 3 or 4, and A ′ represents n ′ or q But When representing the an alkylene group of C 2 -C 12; -S- group, -O- group, or -NR 4 _'- group (wherein, R _4' represents the same meaning as defined above Or an alkylene group having 2 to 12 carbon atoms interrupted by the above formula; or the general formula (40) or (41)

A ′ represents a group represented by C _r H _2r-1 — or N (CH ₂ CH ₂ —) ₃ when n ′ or q represents ₃ , and r is 5 Or A ′ represents a group represented by C (CH ₂ —) ₄ when n ′ represents ₄ , and R ₅ ′ and R ₆ ′ are each independently a hydrogen atom or carbon C 1 atom to an alkyl group of _{8, a "-CH 2 -,} - CHR 4 '-, - CR 1' R 4 '-, - represents a group or a direct bond represented by S-, wherein, R ₁ ′ and R ₄ ′ represent the same meaning as defined above, p represents 1 or 2, D ′ represents a methyl group when p represents 1, and p represents 2. when representing the _-CH 2 OCH ₂ - represents a group, _{R 9} 'represents a methyl group, and _{R 10'} relative to the _{R 1} ' Represents the same meaning as defined above, q represents 2 or 3, y represents 1, 2 or 3, and Q represents an alkyl group having 1 to 18 carbon atoms when y represents 1, —OR ₁₆ ′, —NR ₁₇ ′ represents a group represented by —R ₁₈ ′ or a fluorine atom, and Q represents an —O—A ″ ′ — O— group or a formula (42) when y represents 2.

In represents a group represented by, Q is, if y represents _{3, R 4 'C (CH 2} O-) 3, N (C 2 H 4 O-) 3 or _{N (C 3} H 6 O- ) ₃ (where R ₄ 'represents the same meaning as defined above), R ₁₆ ' represents the same meaning as defined for R ₁ ', and R ₁₇ 'And R ₁₈ ' are independently of each other an alkyl group having 1 to 18 carbon atoms, a benzyl group, a cyclohexyl group, or 2,2,6,6-tetra- or 1,2,2,6,6-penta. Represents a methylpiperid-4-yl group, or R ₁₇ ′ and R ₁₈ ′ together represent a butylene group, a pentylene group, a hexylene group or a —CH ₂ CH ₂ —O—CH ₂ CH ₂ — group. , A ″ ′ was defined for A ′ where n ′ represents 2 Represent the same meaning as taste, R _{19 'represents} a hydrogen atom or a methyl group, the substituents R _14' independently of one another, represent a hydrogen atom, an alkyl group or a cycloalkyl group of C 1 -C 9, R ₁₅ 'represents a hydrogen atom or a methyl group, and Z is a direct bond, -CH ₂ - _{group, -C (R 14' -)} 2 - represents a group or -S- group, where the substituents _{R 14} ' Are the same or different and represent the same meaning as defined above.

Particularly suitable phosphites of general formula (35) are those in which R ₁ ′, R ₂ ′ and R ₃ ′ are independently of each other an alkyl group having 1 to 18 carbon atoms; a phenyl group; Phenyl group substituted by 1 to 3 alkyl groups having from 1 to 18 carbon atoms; or 2,2,6,6-tetramethylpiperid-4-yl group; and, in particular, independently of each other A phosphite representing a phenyl group substituted by 1 to 3 alkyl groups having a total of 1 to 12 carbon atoms.

A particularly suitable phosphite represented by the general formula (36) is preferably an alkylene group of 2 to 12 carbon atoms, —CH ₂ CH ₂ , wherein A ′ is preferably, and when n ′ is 2, —O—CH ₂ CH ₂ — group, —CH ₂ CH ₂ —O—CH ₂ CH ₂ —O—CH ₂ CH ₂ — group or —CH ₂ CH ₂ —NR ₄ ′ —CH ₂ CH ₂ — group [formula R ₄ ′ represents an alkyl group having 1 to 4 carbon atoms], or when A ′ represents n ′ of 3, a group represented by N (CH ₂ CH ₂ —) ₃ It is a phosphite that represents.

Furthermore, particularly suitable phosphites of the general formula (37) are those in which p represents 1, D ′ represents a methyl group, R ₉ ′ represents a methyl group, and R ₁₀ ′ represents a total of 1 A phosphite representing a phenyl group substituted by 1 to 3 alkyl groups having from 18 to 18 carbon atoms.

Furthermore, a particularly suitable phosphite represented by the general formula (39) is a group in which, when Q is 1, y represents 1, an —OR ₁₆ ′ group, an —NR ₁₇ ′ R ₁₈ ′ group, Or when Q is 2 and y is 2, the group is —O—CH ₂ CH ₂ —NR ₄ ′ —CH ₂ CH ₂ —O—, or when Q is 3 Represents an N (CH ₂ CH ₂ O—) ₃ group, wherein R ₁₆ ′ represents an alkyl group having 1 to 18 carbon atoms, and R ₁₇ ′ and R ₁₈ ′ independently represent carbon atoms. Represents an alkyl group having 1 to 18 atoms, a cyclohexyl group or a benzyl group, or R ₁₇ ′ and R ₁₈ ′ together represent a piperidyl group, a morpholinyl group or a hexamethyleneimino group, and R ₄ ′ represents the above-mentioned Means the same as defined in Z represents a direct bond, a —CH ₂ — group or a —CH (CH ₃ ) — group, and the two substituents R ₁₄ ′ independently of one another represent an alkyl group having 1 to 4 carbon atoms. And in particular when Q represents 1 when y represents 1, it represents a 2-ethylhexyloxy group or a fluorine atom, R ₁₄ 'represents a tertiary butyl group, R ₁₅ ' represents a hydrogen atom, and Z represents A —CH ₂ — group or a —CH (CH ₃ ) — group, or when Q represents y, —O—CH ₂ CH ₂ —NCH ₃ —CH ₂ CH ₂ —O— It is a phosphite that represents.

  Examples of preferred phosphites are trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite or tristearyl sorbitol triphosphite.

  Furthermore, 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 and, among others, tris (nonylphenyl) phosphite, tris (2,4-ditert-butylphenyl) phosphite, bis (2, 4-ditertiarybutylphenyl) pentaerythritol diphosphite and 2,2'-ethylidenebis (2,4-ditertiarybutylphenyl) fluorophosphite.

  A particularly important phosphite is a phosphite containing the group P—O—Ar as a structural element, where Ar represents an aromatic group, preferably an alkyl-substituted phenyl group. Suitable alkyl substituents are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 5 to 7 carbon atoms; preferred are alkyl groups having 1 to 4 carbon atoms, and especially tert-butyl groups. (Group described as follows in the structural formula).

  Examples of the phosphite containing the group P—O—Ar include phosphites represented by the following structural formulas.

  Among these, it is particularly preferable to use tris (2,4-ditert-butylphenyl) phosphite or a compound having the following structural formula.

  Examples of the phosphonite that can be used in the present invention are compounds represented by the general formula (43).

（式中、Ｒ^＊は１個ないし５個の炭素原子数１ないし８のアルキル基を表わし、Ｘ’は一般式（４４）で表わされる基を表わし、

(Wherein R ^* represents an alkyl group having 1 to 5 carbon atoms having 1 to 8 carbon atoms, X ′ represents a group represented by the general formula (44),

（ただし、Ｘは、直接結合、−（Ｏ）Ｓ（Ｏ）−基、−Ｃ（Ｏ）−基、−Ｓ−基、−Ｏ−基又はアリーレン基を表わす。アリーレン基は、例えばナフチレン基、ｍ−フェニレン基又はｐ−フェニレン基である。）

(However, X represents a direct bond, — (O) S (O) — group, —C (O) — group, —S— group, —O— group or arylene group. The arylene group is, for example, a naphthylene group. M-phenylene group or p-phenylene group.)

In particular, R ^* represents 1 to 3 tert-butyl groups or methyl groups. X ′ particularly represents a 4,4′-biphenyldiyl group.

  Particularly preferred phosphonites include tetrakis (2,4-ditert-butylphenyl) -4,4′-biphenylenediphosphonite [Irgafos PEPQ], tetrakis (2-tert-butyl-4-methylphenyl) biphenyl. Rangephosphonite, tetrakis (2,4-ditertiaryaluminumphenyl) biphenylenediphosphonite, tetrakis (2,4-ditertiarybutyl-5-methylphenyl) biphenylenediphosphonite, tetrakis (2-tertiarybutyl- 4,6-dimethylphenyl) biphenylene diphosphonite. 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.

In the present invention, the combination of (b) the solid carrier and (d) the antioxidant can be used by appropriately combining the above (b) and (d). The combination of is preferable.
When clays are used as the solid carrier, a phosphorus antioxidant or a mixture of a phenolic antioxidant and a phosphorus antioxidant is preferred, and a porous oxide or inorganic chloride is used as the solid carrier. Is preferably a phenolic antioxidant or a mixture of a phenolic antioxidant and a phosphorus antioxidant.

2. Production of Solid Catalyst Component for Olefin Polymerization The solid catalyst component for olefin polymerization of the present invention comprises the above components (a), (b), (c) and (d) at the same time or outside of the polymerization tank or in the polymerization tank. It can be formed by contacting them continuously or once or several times. The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC and 150 degreeC. As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.

Usually, the component (a) and the component (b) are first contacted. Component (c) can be added to component (b) before, simultaneously with, or after component (a). Component (d) is added in advance by adding component (b), method of adding component (d) to the contact product of component (a) and component (b), component (a), component (b) There is a method of adding the component (d) to the contact product of the component (c), and any method is possible.
A preferable contact order for improving the catalytic activity and polymer particle properties is a method of adding the component (c) to the component (b), subsequently contacting the component (a), and then adding the component (d). . At this time, it is possible to use the same or different component (c) as that previously used for the component (b) for the component (a).
The amount of components (a), (b) and (c) used in the present invention is arbitrary. For example, the amount of component (a) used relative to component (b) is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of 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) 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.
Component (d) 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 solid catalyst component for olefin polymerization of the present invention can be preliminarily polymerized by bringing a polymerizable monomer into contact therewith and polymerizing the monomer in a small amount, and is preferable. The stage of performing the prepolymerization is optional, and a method of contacting the component (c) and / or the component (d) after contacting all the catalyst components of the present invention or after performing the prepolymerization is also possible. It is. The polymerization conditions at that time are usually milder than those of the main polymerization. As the prepolymerized monomer, α-olefin can be used, and ethylene or propylene is preferable. The amount of prepolymerization is usually 0.01-100 g-PP / g-catalyst, preferably 0.1-50 g-PP / g-catalyst. Moreover, when superposing | polymerizing using a prepolymerization catalyst, an additional component (d) may be used and it is preferable.
At the time of or after the contact of each of the above components, a polymer such as polyethylene and polypropylene, and a solid of an inorganic oxide such as silica and titania may coexist or may be brought into contact.

3. Olefin Polymerization Catalyst and Polyolefin Production Method The olefin polymerization solid catalyst component of the present invention can be supplemented with a co-catalyst or the like as necessary to form an olefin polymerization catalyst, and an α-olefin can be polymerized or copolymerized. Preferred α-olefins that can be polymerized are those having about 2 to 20 carbon atoms, and specific examples include ethylene, propylene, 1-butene, 1-hexene, 1-octene and the like. In the case of copolymerization, the type of comonomer used can be selected from α-olefins other than the main component among those listed as the α-olefin.
The amount of comonomer can be carried out under any conditions in order to produce a polymer having desired physical properties (melting point, molecular weight, rigidity, etc.), but the catalyst of the present invention is usually difficult to produce due to deterioration of particle properties, for example. Suitable for the production of random polymers and the like, particularly suitable for the production of low melting point propylene random copolymers and so-called ethylene / propylene block copolymers having a high rubber content.

  By using the olefin polymerization catalyst using the solid catalyst component for olefin polymerization of the present invention, a polymer having a uniform shape and a relatively large particle diameter can be produced. The obtained polymer has a particle size of 500 μm to 5 mm. Also, a polymer having a large pore volume and relatively large pores can be obtained. There is an effect of remarkably improving adhesion between polymers and fouling to the polymerization reaction layer.

  As the polymerization mode, 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 solution polymerization method, a bulk method using propylene as a solvent that does not substantially use an inert solvent, or gasifying each monomer substantially without using a liquid solvent. A gas phase method can be used. Further, it is applied to continuous polymerization and batch polymerization. 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 ° C. to 200 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure can be carried out in the range of 0 to 200 MPa.

  The polyolefin obtained by polymerizing the solid catalyst component for olefin polymerization 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, but the present invention is not limited thereto. In addition, the MFR value in an Example is a melt index value measured by 230 degreeC and the 2.16kg load based on JIS-K-6758.

Example 1
(1) Synthesis of solid catalyst component 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 commercially available granulated montmorillonite (Mizusawa Chemical Industries, 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 24 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 slurry amount 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.
In a 200 ml flask, (r) -dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl}] hafnium (300 μmol) in toluene (60 ml) Was added to the 1 L flask and stirred for 60 minutes at room temperature.
In a 50 ml flask, 10 ml of a 30 wt% 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. This slurry was dried under reduced pressure to recover 16.4 g of a solid catalyst component.

(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 solid catalyst component obtained in the above (1) was made into a heptane slurry, and 48 mg was injected as a solid catalyst to initiate polymerization. The tank temperature was maintained at 65 ° C. One hour after the catalyst was charged, 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 234 g. The phenol-based stabilizer content and the phosphorus-based stabilizer content in the polymer were each 38 ppm.

(3) Stability evaluation The stability of the obtained polymer was evaluated by repeated measurement of MFR by a melt indexer three times. It was 13.4 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 15.8 g / 10 min and was stable. The results are shown in Table 1.

(Example 2)
A polymer was obtained in the same manner as in Example 1 except that the polymerization time was 15 minutes. The obtained polymer was 73 g. Stabilization evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1. The MFR was stable.

(Comparative Example 1)
A solid catalyst component was prepared in the same manner as in Example 1 except that the phenol-based stabilizer and the phosphorus-based stabilizer were not added, and a polymer was obtained by polymerization using the solid catalyst component. The obtained polymer was 350 g. Stabilization evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1. An increase in MFR was observed with each measurement, and the polymer deteriorated.

(Comparative Example 2)
Stearyl (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate and tris (2,4-ditertiarybutylphenyl) phosphite were each 0 per 100 parts by weight of the polymer obtained in Comparative Example 1. Stabilization evaluation was performed in the same manner as in Example 1 by adding the powder in an amount of .015 parts by weight. The results are shown in Table 1. It can be seen that a large amount of antioxidant is required to obtain the same MFR change rate as in the Examples.

(Example 3)
(1) Synthesis of solid catalyst component 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 commercially available montmorillonite (Mizusawa Chemical Industries, Benclay SL) was added and stirred. Thereafter, the mixture was reacted at 90 ° C. for 2 hours. This slurry was filtered and further washed until the pH of the filtrate reached 4 or higher. To this, 150 g of stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate and 150 g of tris (2,4-ditert-butylphenyl) phosphite were added to form a 30 wt% slurry. After processing with a homogenizer for 10 minutes to obtain a uniform slurry, spray granulation was performed using a spray granulator manufactured by Okawara Kako. As a result, granulated particles having an average particle size of 30 μm were obtained. The shape was spherical, and the number of particles having an M / L value of 0.8 or more and 1.0 or less was 95%. This powder was dried at 200 ° C. for 2 hours to obtain a solid carrier containing an antioxidant.
To the 1 L flask, 10 g of the solid carrier 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 slurry amount 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.
In a 200 ml flask, (r) -dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl}] hafnium (300 μmol) in toluene (60 ml) Was added to the 1 L flask and stirred for 60 minutes at room temperature. After removing the supernatant, it was dried under reduced pressure to recover 10.4 g of a solid catalyst component.
Polymerization of propylene was carried out in the same manner as in Example 1 using the solid catalyst component. As a result, the obtained polymer was 170 g. The phenol-based stabilizer content and the phosphorus-based stabilizer content in the polymer were each 70 ppm.
The obtained polymer was evaluated for stabilization in the same manner as in Example 1. The results are shown in Table 1. The MFR was stable.

(Comparative Example 3)
Examples were prepared except that stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate and tris (2,4-ditert-butylphenyl) phosphite were not added when producing the solid support. A solid catalyst component was produced in the same manner as in No. 3, and polymerization and stabilization evaluation were performed. The results are shown in Table 1. An increase in MFR was observed and deterioration was progressing.

Example 4
(1) Preparation of catalyst 46.5 ml of a 30% solution of toluene in methylaluminoxane was charged into a 1 L flask purged with dry nitrogen. Then 35 ml of toluene and (r) -dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl}] hafnium (200 μmol) were added and 20 ml at room temperature. After stirring for 10 minutes, 10 g of SiO ₂ (Grace 951) was gradually added. The mixture was heated to 50 ° C. and stirred for 30 minutes.
In a 50 ml flask, 10 ml of a 30 wt% 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. This slurry was dried under reduced pressure to recover 16.8 g of a solid catalyst component.
(2) Evaluation of polymerization and stability Polymerization was carried out in the same manner as in Example 1 to obtain 120 g of a polymer. The contents of the phenol-based stabilizer and phosphorus-based stabilizer in the polymer were 74 ppm, respectively. When the obtained polymer was repeatedly evaluated for extrusion using a melt indexer, the first MFR value was 9.8 g / 10 min, and the third time was 11.8 g / 10 min, which was stable. The results are shown in Table 1.

(Examples 5 to 9)
In Example 1, catalyst components were prepared using the antioxidants listed in Table 2, and polymerization was performed. Table 2 shows the antioxidant content in the obtained polymer and the stability evaluation results. In both cases, the MFR was stable.

(Example 10)
(1) Preparation of catalyst 46.5 ml of a 30% solution of toluene in methylaluminoxane was charged into a 1 L flask purged with dry nitrogen. Then 35 ml of toluene and (r) -dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl}] hafnium (200 μmol) were added and 20 ml at room temperature. After stirring for 10 minutes, 10 g of SiO ₂ (Grace 951) was gradually added. The mixture was heated to 50 ° C. and stirred for 30 minutes.
In a 50 ml flask, 10 ml of a 30 wt% heptane solution of tetrakis (2,4-ditert-butylphenyl) -4,4′-biphenylenediphosphonite is prepared as a phosphorus stabilizer and added to the 1 L flask. Stir for 30 minutes. This slurry was dried under reduced pressure to recover 13.2 g of a solid catalyst component.
(2) Evaluation of polymerization and stability Polymerization was carried out in the same manner as in Example 1 to obtain 160 g of a polymer. The content of the phosphorus stabilizer in the polymer was 56 ppm. When the obtained polymer was repeatedly evaluated for extrusion using a melt indexer, the first MFR value was 10.4 g / 10 min, and the third time was 13.2 g / 10 min, which was stable. The results are shown in Table 2.

  According to the present invention, a solid catalyst component capable of providing a highly stabilized polyolefin resin can be provided. In addition, since a stabilizer is contained in the catalyst, it is highly dispersed inside the polymer, so it can be expected to reduce the amount of various antioxidants and weather resistance improvers incorporated during molding processing. Since it contains a stabilizer, the granulating step for introducing the stabilizer can be omitted, energy for stabilization can be reduced, and its industrial value is extremely large.

Claims (8)

(A) a metallocene compound of a transition metal of Group 4 of the periodic table,
(B) a solid carrier,
(C) at least one compound selected from the group consisting of the following (c-1), (c-2) and (c-3),
(C-1) Organometallic compound (c-2) Organoaluminum oxy compound (c-3) Compound that reacts with metallocene compound of group 4 transition metal of periodic table and (d) Phenol-based antioxidant A solid catalyst component for olefin polymerization, comprising an agent and / or a phosphorus-based antioxidant.   2. The solid catalyst component for olefin polymerization according to claim 1, wherein component (d) uses at least one of a phenolic antioxidant, an organic phosphite compound or an organic phosphonite compound, either alone or in combination with each other. . The phenolic antioxidant of component (d) is 2,6-ditert-butyl-4-methylphenol, stearyl (3,5-ditert-butyl-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 Or a solid catalyst component for olefin polymerization according to claim 1 or 2, which is a tocopherol (vitamin E).   The solid catalyst component for olefin polymerization according to any one of claims 1 to 3, wherein the component (b) is spherical and has an average particle size of 10 to 200 µm.   The solid catalyst component for olefin polymerization according to any one of claims 1 to 4, wherein the component (b) is clay, clay mineral or ion-exchangeable layered compound.   The solid catalyst component for olefin polymerization according to any one of claims 1 to 4, wherein the component (b) is a porous oxide or an inorganic chloride.   An olefin polymerization catalyst comprising the solid catalyst component for olefin polymerization according to any one of claims 1 to 6.   A method for producing a polyolefin, wherein polymerization or copolymerization is carried out by bringing the olefin polymerization catalyst according to claim 7 into contact with an olefin.