JP2009079182A - Manufacturing method for olefinic polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for an olefinic polymer capable of reducing a scattering ratio of a fine particle accompanied with an unreacted monomer. <P>SOLUTION: In the manufacturing method for the olefinic polymer, at least ethylene and 1-octene are copolymerized using a vapor phase polymerization reaction apparatus. In the manufacturing method for the olefinic polymer (provided that the whole amount of gas contained in the vapor phase polymerization reactor is made to 100 mol%), a concentration of 1-octene in the gas contained in the vapor phase polymerization reactor is in a range of 0.01 mol% to 1.1 mol%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an olefin polymer. More specifically, the present invention relates to a method for producing an olefin polymer that can reduce the scattering rate of fine particles entrained by unreacted monomers.

Conventionally, in the gas phase polymerization method of olefins, it has been known that the unreacted gas stream containing fine powder polymer discharged from the gas phase polymerization zone of olefins is led to a cyclone to collect the fine powder polymer. It has been.
For example, Japanese Patent Application Laid-Open No. 57-128706 (Patent Document 1) describes a problem of adhesion and clogging due to a finely divided polymer contained in an unreacted gas stream discharged from a gas phase polymerization zone of olefins. As a method for overcoming this, a fine powdery polymer-containing unreacted gas stream discharged from the gas phase polymerization zone of olefins is guided to a cyclone to collect the fine powdery polymer, and a suction force is applied from the lower part of the cyclone. A method of vapor phase polymerization of olefins is described in which the collected fine powder polymer is sucked and removed from the cyclone, and the removed fine powder polymer is circulated through the gas phase polymerization zone. It is described that ethylene, 1-butene, 1-hexene and 1-octene can be copolymerized by a gas phase polymerization method of olefins.

JP-A-57-128706

  However, in the above method, when ethylene and 1-butene are copolymerized, when ethylene and 1-hexene are copolymerized, or when ethylene and 1-octene are copolymerized, they are accompanied by unreacted monomers. Fine particles may scatter and the scattering rate may be high, which is not always a satisfactory polymerization method.

  Under such circumstances, the problem to be solved by the present invention, that is, the object of the present invention is to provide a method for producing an olefin polymer capable of reducing the scattering rate of fine particles entrained by unreacted monomers. It is in.

That is, the present invention
A method for producing an olefin polymer in which at least ethylene and 1-octene are copolymerized using a gas phase polymerization reactor, wherein the concentration of 1-octene in a gas contained in the gas phase polymerization reactor is 0.01 mol. % To 1.1 mol% of the olefin polymer production method (however, the total amount of gas contained in the gas phase polymerization reactor is 100 mol%).

  According to the production method of the present invention, an olefin polymer can be produced by reducing the scattering rate of fine particles entrained by unreacted monomers.

  In the present invention, the term “polymerization” includes not only homopolymerization but also copolymerization, and the term “polymer” includes not only homopolymers but also copolymers.

  As the fluidized bed reactor used in the present invention, a known gas phase fluidized bed reactor can be used. For example, the gas phase flow described in JP-A-58-201802, JP-A-59-126406, JP-A-2-233708, JP-A-4-234409, JP-A-7-62009, etc. A floor reactor can be mentioned.

  A collecting device may be installed in the circulation line of the unreacted monomer of the fluidized bed reactor, and the collecting device may be a cyclone type. The fine powder polymer collected by the collection device may be discharged to the outside or returned to the fluidized bed using an ejector or the like.

  In the present invention, olefin is continuously supplied to a fluidized bed reactor, an olefin polymerization catalyst is supplied into the fluidized bed, a fluidized bed of solid particles containing the olefin polymerization catalyst is formed, and the olefin is polymerized. .

  In the polymerization of olefins using the fluidized bed reactor of the present invention, the flow rate of the olefin gas that has passed through the fluidized bed is usually reduced in the deceleration region provided in the upper part of the fluidized bed type reaction vessel. Then, it is discharged out of the fluidized bed type reaction vessel through a gas outlet provided in the upper part of the fluidized bed type reaction vessel. Then, the gas discharged from the fluidized bed type reaction vessel is blown again into a position below the gas dispersion plate of the fluidized bed type reaction vessel by the compressor through the circulation gas line. At this time, it does not matter whether or not a collection device is installed between the gas outlet provided in the upper part of the reactor and the compressor. Also, since the olefin gas usually needs to remove the heat of polymerization reaction of the gas before it is blown again below the gas dispersion plate of the fluidized bed reactor, heat exchange is performed on the circulating gas line. An oven is provided and the gas is cooled by this heat exchanger. The circulating gas line is provided with an olefin introduction pipe and a hydrogen introduction pipe, and olefin and hydrogen are supplied from the olefin introduction pipe and the hydrogen introduction pipe.

In the present invention, olefin polymerization is carried out under known polymerization conditions. The internal pressure of the reactor may be within a range in which the entire olefin or at least a part thereof can exist as a gas phase, and is usually 0.1 to 5.0 MPa, preferably 1.5 to 3.0 MPa. The temperature in the reactor is appropriately selected depending on the catalyst used, the pressure in the reactor, the type of olefin to be polymerized, and the like, but is generally 30 to 110 ° C. The circulating gas flow rate in the reactor is usually 10 to 100 cm / second, preferably 20 to 70 cm / second. In general, hydrogen may coexist with the circulating gas, or an inert gas may coexist.
However, the faster the circulating gas flow rate, the greater the amount of fine powder polymer scattered in the collection device. In producing a polymer having the same physical properties, the lower the polymerization temperature, the greater the amount of fine powder polymer scattered.

  In the present invention, the 1-octene concentration in the circulating gas is preferably controlled and controlled in the range of 0.01 mol% to 1.1 mol%. More preferably, the concentration of 1-octene is 0.1 to 0.6 mol%.

  As the olefin used in the method for producing an olefin polymer of the present invention, ethylene and 1-octene are essential, and in addition, propylene, 1-butene, 1-hexene, an α-olefin having 9 to 20 carbon atoms, and a diolefin. And cyclic olefins, alkenyl aromatic hydrocarbons, and the like.

  Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1-nonene and 1-decene. Α-olefins such as 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4- Hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, Norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1 Diolefins such as 3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene; norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5 -Butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclo Dodecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene, 8- Cyclic olefins such as methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; styrene, alkenylbenzene (2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene, etc.) ), Alkylstyrene (p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3 , 4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butyl styrene, p-secondary butyl styrene, etc.), bisalkenylbenzene (divinylbenzene, etc.), alkenyl Alkenyl such as naphthalene (1-vinylnaphthalene, etc.) Aromatic hydrocarbon; α, β- such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid Unsaturated carboxylic acid compound; metal salt of α, β-unsaturated carboxylic acid compound and sodium, potassium, lithium, zinc, magnesium, calcium, etc .; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate Α, β-unsaturated carboxylic acids such as t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Ester compounds; unsaturated dicarboxylic acid compounds such as maleic acid and itaconic acid; vinegar Vinyl ester compounds such as vinyl, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; unsaturated carboxylic acids such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate And acid glycidyl ester compounds.

  Specific examples of the copolymer of the present invention include an ethylene-1-octene copolymer, an ethylene-1-octene-propylene copolymer, an ethylene-1-octene-1-butene copolymer, and an ethylene-1-octene. Examples include a -1-hexene copolymer and an ethylene-1-octene-4-methyl-1-pentene copolymer.

  As the olefin polymerization catalyst used in the production of the olefin polymer of the present invention, a known olefin polymerization catalyst such as a Ziegler type catalyst or a Philips type catalyst is used, but a metallocene catalyst using a metallocene compound is used. Is preferred.

  Examples of the metallocene catalyst include a solid catalyst component obtained by supporting a promoter component such as an organoaluminum compound, an organoaluminum oxy compound, and a boron compound and a metallocene compound on a particulate carrier (for example, JP-A-61-108610). A solid catalyst component described in JP-A-61-296008, JP-A-63-89505, JP-A-3-234709, JP-A-6-336502, etc. Accordingly, particles obtained by polymerizing a small amount of olefin (hereinafter referred to as prepolymerization) in combination with a promoter component such as an organoaluminum compound and a boron compound can be mentioned.

  In addition, as the metallocene catalyst, a solid catalyst component obtained by supporting a promoter component such as an organoaluminum compound, an organoaluminum oxy compound, a boron compound, and an organozinc compound on a particulate carrier (for example, JP-A-2003-171212). And particles obtained by prepolymerizing a small amount of olefins in combination with a catalyst component such as a metallocene compound or an organoaluminum compound.

As the metallocene compound, a transition metal compound represented by the following general formula [1] or a μ-oxo type transition metal compound dimer thereof is preferable.
L ¹ _a M ¹ X ¹ _b [1]
(Wherein, a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8. M ¹ represents a transition metal atom of Group 3 to 11 of the periodic table or a lanthanoid series) there .L ¹ is a group having a cyclopentadiene type anion skeleton, if L ¹ there are a plurality or multiple of L ¹ are connected directly to one another, or a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur X ¹ is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton), or a hydrocarbon oxy group, which may be linked via a residue containing an atom or a phosphorus atom. .)

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

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

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

The groups having a cyclopentadiene type anion skeleton, or the group having a cyclopentadiene type anion skeleton and X ¹ may be directly connected to each other, and may be a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, They may be linked via a bridging group containing a sulfur atom or a phosphorus atom. Examples of such cross-linking groups include: alkylene groups such as ethylene groups and propylene groups; substituted alkylene groups such as dimethylmethylene groups and diphenylmethylene groups; or substituted silylenes such as silylene groups, dimethylsilylene groups, diphenylsilylene groups, and tetramethyldisilylene groups. Group; hetero atoms such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom;

X ¹ in the general formula [1] is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton), or a hydrocarbon oxy group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The hydrocarbon group here does not include a group having a cyclopentadiene type anion skeleton. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Examples of the hydrocarbon oxy group include an alkoxy group, an aralkyloxy group, and an aryloxy group.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, amyl group, n -Hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, and these alkyl groups are all fluorine atom, chlorine atom, bromine atom, It may be substituted with a halogen atom such as an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorobutyl group. Examples thereof include a fluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group. Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group.

  Examples of the aralkyl group include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2, 4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl Group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) ) Methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) Nyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl Group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexyl) Phenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc., and these aralkyl groups Are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group An alkoxy group such as ethoxy group; a portion at an aralkyl group such as aryloxy or benzyloxy group, such as phenoxy group may be substituted.

  Examples of the aryl group include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, and 2,6-xylyl group. Group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,4 6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6- Tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentyl Phenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, etc. All of the aryl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; and aralkyloxy groups such as benzyloxy group May be partially substituted.

  Examples of the alkenyl group include an allyl group, a methallyl group, a crotyl group, and a 1,3-diphenyl-2-propenyl group.

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n -Octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group and the like, and these alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methoxy group, An alkoxy group such as an ethoxy group; an aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group may be partially substituted.

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n -Octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group and the like, and these alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methoxy group, An alkoxy group such as an ethoxy group; an aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group may be partially substituted.

  Examples of the aralkyloxy group include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, ( 2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) ) Methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5- Trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy , (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, Pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert -Butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group, and the like. All of the aralkyloxy groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom. Emissions atoms; an alkoxy group such as methoxy group and ethoxy group; a portion at an aralkyl group such as aryloxy or benzyloxy group, such as phenoxy group may be substituted.

  Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, and 2,5-dimethylphenoxy group. Group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6- Trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2- tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert-butyl- 3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3, 4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,4,6- Trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-tert-butyl group -3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n -Butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group, etc. These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; and benzyloxy groups. Partially placed with an aralkyloxy group It may be replaced.

  Specific examples of metallocene compounds include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl). ) Titanium dichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, bis (1,2-dimethylcyclopentadienyl) titanium dichloride, bis (1,3-dimethylcyclopentadienyl) titanium dichloride, bis (1 -Methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-n-butylcyclopentadienyl) titanium dichloride, Screw (1- Til-3-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-isopropylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-isopropylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-2-methylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-3-methylcyclopentadienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) ) Titanium dichloride, bis (1,2,4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride Id, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenyl indenyl) titanium dichloride,

Bis [2- (bis-3,5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4-trifluoromethylphenyl) Indenyl] titanium dichloride, bis [2- (4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) indenyl] titanium dichloride , Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride , Pentamethylcyclopentadienyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindene) Nil) titanium dichloride,

Dimethylsilylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-n- Butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4 -Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene bis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,5-ethylmethylcyclo) Pentadienyl) titanium dichloride, dimethylsilylene bis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2, 3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride,

Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylindenyl) titanium Dichloride, dimethylsilylene bis (2,4,7-trimethylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylene bis (4,5-benzindenyl) titanium dichloride, dimethyl Silylene bis (2-methyl-4,5-benzindenyl) titanium dichloride, dimethylsilylene bis (2-phenylindenyl) titanium dichloride, dimethylsilylene bis (4-phenyl) Indenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-5-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-naphthyl) Indenyl) titanium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetra Methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilyl (Indenyl) (fluorenyl) titanium dichloride, dimethylsilylenebis (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (fluorenyl) ) Titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadienyl (dimethylamido) titanium dichloride, cyclopentadienyl (phenoxy) titanium dichloride, cyclopentadienyl (2,6-dimethylphenyl) ) Titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, cyclopentadienyl (2,6-di-tert-butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethyl) Phenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-tert-butylphenyl) thi Njikuroraido, indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl (2,6-diisopropylphenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl -2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2) -Phenoxy Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-) 2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride Id, dimethylsilylene (cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) 5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopenta Dienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl Down (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (n- Tilcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) ( 3,5-diamil- -Phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium Dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5) -Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (tert-butylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene ( tert-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethyl Len (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadieni) ) (3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (1- Naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy) -2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (trimethylsilylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadi) Enyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl) Rudimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-diamil-2-phenoxy) titanium dichloride Dimethylsilylene (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) ( -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl -5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diamil-2-phenoxy) ) Titanium dichloride, dimethylsilylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (1-naphthoxy-2-yl) titanium dichloride,

(Tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyltitanium dichloride, (tert-butylamide) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (phenylphosphide) tetramethylcyclopentadi Enyldimethylsilane titanium dichloride, (tert-butylamido) indenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) tetrahydroyl Denyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) indenyldimethylsilane titanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilane titanium Dichloride, (tert-butylamido) fluorenyldimethylsilane titanium dichloride,

(Dimethylaminomethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyl titanium (III) dichloride (N-pyrrolidinylethyl) tetramethylcyclopentadienyl titanium dichloride, (B-dimethylaminoborabenzene) cyclopentadienyl titanium dichloride, cyclopentadienyl (9-mesitylboraanthracenyl) titanium dichloride, etc. Or a compound obtained by changing titanium of these compounds to zirconium or hafnium, (2-phenoxy) to (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert Compound changed to butyldimethylsilyl-2-phenoxy), Compound changed from dimethylsilylene to methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethylsilylene, diphenylsilylene, or dimethoxysilylene, dichloride to difluoride, dibromide , Diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di (n-propoxide), di (isopropoxide), diphenoxide, or di (pentafluorophenoxide), trichloride Trifluoride, tribromide, triiodide, trimethyl, triethyl, triisopropyl, triphenyl, tribenzyl, trimethoxide, triethoxide De, tri (n- propoxide), tri (isopropoxide), tri phenoxide or a compound was changed to tri (pentafluorophenyl phenoxide), etc., can be exemplified.

  Specific examples of the transition metal compound of the transition metal compound represented by the general formula [1] include μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], Μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2 -Phenoxy) titanium chloride], μ-oxobis [ Sopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], [Mu] -oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2 -Phenoxy) chita Chloride], .mu. Okisobisu [such as dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride] and the like. Examples include compounds in which the chloride of these compounds is changed to fluoride, bromide, iodide, methyl, ethyl, isopropyl, phenyl, benzyl, methoxide, ethoxide, n-propoxide, isopropoxide, phenoxide, or pentafluorophenoxide. can do.

The particulate carrier is preferably a porous material, and inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ ; Clay and clay minerals such as smectite, montmorillonite, hectorite, laponite and saponite; organic polymers such as polyethylene, polypropylene and styrene-divinylbenzene copolymer are used.

  The weight average particle diameter of the solid catalyst component is usually 10 to 100 μm, preferably 20 to 80 μm, and more preferably 40 to 60 μm. The content of the olefin polymer in the particles preliminarily polymerized with a small amount of olefin is usually 0.01 to 1000 g, preferably 0.05 to 500 g, more preferably 0, per 1 g of the solid catalyst component. .1 to 200 g. In addition, as a prepolymerization method, a well-known method is used and it is normally performed by a slurry polymerization method.

  In the main polymerization using the particles obtained by the above prepolymerization, a promoter such as an organoaluminum compound, an organoaluminum oxy compound, a boron compound, or an organozinc compound may be used as necessary.

As the metallocene catalyst, a solid catalyst component obtained by contacting the following component (a), the following component (b), the following component (c) and the following component (d), an organoaluminum compound, and a metallocene compound: The particles used are prepolymerized olefins.
(A): Compound represented by the following general formula [2] M ² L ² _m [2]
(B): Compound represented by the following general formula [3] R ¹ _t-1 TH [3]
(C): Compound represented by the following general formula [4] R ² _t-2 TH ₂ [4]
(D): particulate carrier In the above general formulas [2] to [4], M ² represents a metal atom of Group 1, ² , 12, 14 or 15 of the periodic table, and m represents the valence of M ² . The number corresponding to. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when a plurality of L ² are present, they may be the same as or different from each other. R ¹ represents a group containing an electron-withdrawing group or an electron-withdrawing group, and when a plurality of R ¹ are present, they may be the same as or different from each other. R ² represents a hydrocarbon group or a halogenated hydrocarbon group. Each T independently represents a non-metal atom of Group 15 or Group 16 of the periodic table, and t represents a number corresponding to the valence of T of each compound. Specific examples include diethyl zinc as component (a), fluorinated phenol as component (b), water as component (c), and silica as component (d).

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The measured value of each item in an Example was measured with the following method.
(1) Density (Unit: Kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The sample was annealed according to JIS K6760-1995.

(2) Melt flow rate (MFR, unit: g / 10 minutes)
According to the method defined in JIS K7210-1995, the measurement was performed under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(3) Molecular weight distribution (Mw / Mn)
It measured on the following conditions by the gel permeation chromatography (GPC). A calibration curve was prepared using standard polystyrene. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Model: Millipo Waters 150C type Column: TSK-GEL GMH-HT 7.5 × 600 2 Measurement temperature: 140 ° C.
Solvent: Orthodichlorobenzene Solvent flow rate: 1.0 mL / min Measurement concentration: 5 mg / 5 ml
Detector: Differential refraction

(4) Amount of cold xylene soluble part (CXS, unit: wt%)
It was measured according to the method specified in §1755.120 of Code of federal regulations, Food Drugs Administration, USA.

(5) Scattering rate (unit: ppm by weight)
Divide the amount of fine particles obtained per hour by the amount of olefin copolymer obtained per hour in a collecting device for collecting scattered fine particles installed in the circulation line of unreacted monomers. Value.

Example 1
(1) Silica treatment In a reactor equipped with a nitrogen-replaced stirrer, 24 kg of toluene as a solvent and silica heat-treated at 300 ° C. under a nitrogen stream as a fine particle carrier (a) (Sypolol 948 manufactured by Devison; average particle diameter = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 2.81 kg was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.91, 1 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.43 kg of toluene was maintained in 32 minutes while maintaining the reactor temperature at 5 ° C. It was dripped. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 95 ° C. for 3.3 hours. Thereafter, the obtained solid product was washed 6 times with 21 kg of toluene. Thereafter, 7.1 kg of toluene was added and allowed to stand overnight.

(2) Preparation of solid catalyst component (A) To the toluene slurry obtained in Example 1 (1) above, 1.75 kg of 50 wt% diethylzinc hexane solution as compound (b) and 1.0 kg of hexane as solvent were added. Charged and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.78 kg of trifluorophenol as the compound (c) and 1.41 kg of toluene as the solvent was added dropwise over 61 minutes while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, the temperature was lowered to 22 ° C., and 0.11 kg of water was added dropwise as compound (d) over 1.5 hours while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 22 ° C for 1.5 hours, at 40 ° C for 2 hours, and further at 80 ° C for 2 hours. Stirring was stopped and the supernatant liquid was withdrawn until the remaining amount reached 16 liters, and 11.6 kg of toluene was added and stirred. The temperature was raised to 95 ° C. and stirred for 4 hours. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Then, the solid catalyst component (A) was obtained by drying. As a result of elemental analysis, Zn = 11 wt%, Si = 30 wt%, F = 5.9 wt%, and N = 2.3 wt%.
From this, the proportion of the fine particle carrier (a) in the solid catalyst component (A) was 64 wt%.

(3) Prepolymerization Into a reactor equipped with a stirrer with an internal volume of 210 liters, which was previously purged with nitrogen, 80 liters of butane was charged at room temperature, and then 88.8 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added. I put it in. Thereafter, the temperature in the reactor was increased to 50 ° C. and stirred for 2 hours. The temperature in the reactor was lowered to 30 ° C., and 0.1 kg of ethylene was added. Next, 697 g of the solid catalyst component (A) obtained in Example 1 (2) was added. Thereafter, 0.1 liter of hydrogen was introduced at normal temperature and pressure. After the system was stabilized, 263 mmol of triisobutylaluminum was added to start prepolymerization.
After the start of the prepolymerization, the polymerization temperature in the reactor was operated at 30 ° C. for 0.5 hour, then the temperature was raised to 50 ° C. over 30 minutes, and then the polymerization was carried out at 50 ° C. For the first 0.5 hours, ethylene is supplied at 0.8 kg / hour, hydrogen is supplied at room temperature and normal pressure at a rate of 0.8 liter / hour, and from 0.5 hours after the start of prepolymerization, ethylene is supplied. 4.45 kg / hour, hydrogen was supplied at a normal temperature and normal pressure at a rate of 13.5 liters / hour, and preliminary polymerization was carried out for a total of 6 hours. After completion of the prepolymerization, the reactor internal pressure was purged to 0.5 MPaG, the slurry prepolymerization catalyst was transferred to a dryer, and nitrogen circulation drying was performed to obtain a prepolymerization catalyst. The prepolymerization amount of the ethylene polymer in the prepolymerization catalyst was 28.0 g per 1 g of the cocatalyst support.

(4) Fluidized bed gas phase polymerization A circulating gas line has a temperature-controllable jacket, and a cyclone-type collector that can remove the collected fine powder polymer is installed. Using a fluidized bed type continuous gas phase polymerization reactor having a fluidized bed type polymerization reactor having a diameter of 50 cm, polymerization temperature: 85.9 ° C., pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: ethylene 90. Copolymerization of ethylene and 1-octene under polymerization conditions of 8 mol%, hydrogen 1.18 mol%, 1-octene 0.41 mol%, nitrogen 7.31 mol%, hexane 0.30 mol%, circulating gas flow rate: 34 cm / sec. went. During the polymerization, the prepolymerized catalyst obtained in Example 1 (1) was supplied at a supply amount of 36.4 g / hr. During the polymerization, triethylamine was fed to the polymerization reactor at a feed rate of 0.6 mmol / hr and triisobutylaluminum was fed at a rate of 21 mmol / hr, and an average of 22.0 kg / h of ethylene-1-octene copolymer was fed. A polymer was produced. The scattering rate of the fine powder particles collected by the collector for 8 hours before the end of the operation was 10 wtppm. The resulting ethylene-1-octene copolymer had a density of 919.0 kg / m ³ , an MFR of 0.73 g / 10 min, a cold xylene soluble content of 2.1 wt%, and a Q value of 13.2. there were.
Stable operation was possible, and the scattering rate of fine particles was at a considerably low level.

Example 2
(1) Fluidized bed gas phase polymerization Using the same fluidized bed continuous gas phase polymerization reactor as in Example 1, polymerization temperature: 86.0 ° C, pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: Ethylene 91.3 mol%, hydrogen 1.35 mol%, 1-octene 0.40 mol%, nitrogen 6.65 mol%, hexane 0.30 mol%, circulation gas flow rate: 34 cm / sec. Copolymerization was performed. During the polymerization, the prepolymerized catalyst obtained in Example 1 (3) was supplied at a supply amount of 36.4 g / hr. During the polymerization, triethylamine was supplied at a supply rate of 0.6 mmol / hr and triisobutylaluminum was supplied at a supply rate of 20 mmol / hr to the polymerization reactor, and an average of 20.3 kg / h of ethylene-1-octene copolymer was supplied. A polymer was produced. The scattering rate of the fine particles collected by the collector for 8 hours before the end of the operation was 5 wtppm. The resulting ethylene-1-octene copolymer had a density of 919.2 kg / m ³ , an MFR of 1.49 g / 10 min, a cold xylene soluble content of 2.2 wt%, and a Q value of 11.2. there were.
Stable operation was possible, and the scattering rate of fine particles was at a considerably low level.

Example 3
(1) Fluidized bed gas phase polymerization Using the same fluidized bed continuous gas phase polymerization reactor as in Example 1, polymerization temperature: 84.0 ° C, pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: Ethylene 94.0 mol%, hydrogen 1.02 mol%, 1-octene 0.37 mol%, nitrogen 4.31 mol%, hexane 0.30 mol%, circulating gas flow rate: 34 cm / sec between ethylene and 1-octene Copolymerization was performed. During the polymerization, the prepolymerized catalyst obtained in Example 1 (3) was supplied at a supply rate of 35.0 g / hr. During the polymerization, triethylamine was supplied at a supply rate of 0.6 mmol / hr and triisobutylaluminum was supplied at a supply rate of 20 mmol / hr to the polymerization reactor, and an average of 21.2 kg / h of ethylene-1-octene copolymer was supplied. A polymer was produced. The scattering rate of the fine particles collected by the collector for 8 hours before the end of the operation was 113 wtppm. The resulting ethylene-1-octene copolymer had a density of 921.2 kg / m ³ , an MFR of 0.35 g / 10 min, a cold xylene soluble content of 1.6 wt%, and a Q value of 10.2. there were.
Stable operation was possible, and the scattering rate of fine particles was at a relatively low level.

Example 4
(1) Fluidized bed type gas phase polymerization Using the same fluidized bed type continuous gas phase polymerization reactor as in Example 1, polymerization temperature: 80.0 ° C, pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: Ethylene 93.5 mol%, hydrogen 1.19 mol%, 1-octene 0.44 mol%, nitrogen 4.57 mol%, hexane 0.30 mol%, circulating gas flow rate: 34 cm / sec between ethylene and 1-octene Copolymerization was performed. During the polymerization, the prepolymerized catalyst obtained in Example 1 (3) was supplied at a supply rate of 29.7 g / hr. During the polymerization, triethylamine was fed to the polymerization reactor at a feed rate of 0.6 mmol / hr and triisobutylaluminum was fed at a feed rate of 20 mmol / hr, and an average of 21.7 kg / h of ethylene-1-octene copolymer was fed. A polymer was produced. The scattering rate of the fine particles collected by the collector for 8 hours before the end of the operation was 31 wtppm. The resulting ethylene-1-octene copolymer had a density of 913.8 kg / m ³ , an MFR of 0.55 g / 10 min, a cold xylene soluble content of 2.5 wt%, and a Q value of 8.1. there were.
Stable operation was possible, and the scattering rate of fine particles was at a considerably low level.

Example 5
(1) Fluidized bed gas phase polymerization Using the same fluidized bed continuous gas phase polymerization reactor as in Example 1, polymerization temperature: 90.1 ° C, pressure: 2.0 MPaG, holdup amount: 80 kg, gas composition: Ethylene 92.0 mol%, hydrogen 1.39 mol%, 1-octene 0.32 mol%, nitrogen 5.99 mol%, hexane 0.30 mol%, circulating gas flow rate: 36 cm / sec between ethylene and 1-octene under polymerization conditions Copolymerization was performed. During the polymerization, the prepolymerized catalyst obtained in Example 1 (3) was supplied at a supply rate of 23.4 g / hr. During the polymerization, triethylamine was supplied at a supply rate of 0.6 mmol / hr and triisobutylaluminum was supplied at a supply rate of 20 mmol / hr to the polymerization reactor, and an average of 18.6 kg / h of ethylene-1-octene copolymer was supplied. A polymer was produced. The scattering rate of fine particles collected by the collector in 8 hours before the end of the operation was 64 wtppm. The resulting ethylene-1-octene copolymer had a density of 923.7 kg / m ³ , an MFR of 0.40 g / 10 min, a cold xylene soluble content of 1.2 wt%, and a Q value of 9.7. there were.
Stable operation was possible, and the scattering rate of fine particles was at a low level.

Example 6
(1) Fluidized bed gas phase polymerization Using the same fluidized bed continuous gas phase polymerization reactor as in Example 1, polymerization temperature: 83.7 ° C., pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: Polymerization conditions of ethylene 91.6 mol%, hydrogen 1.29 mol%, 1-octene 0.25 mol%, 1-butene 1.58 mol%, nitrogen 4.98 mol%, hexane 0.30 mol%, circulating gas flow rate: 34 cm / sec Then, ethylene, 1-butene and 1-octene were copolymerized. During the polymerization, the prepolymerized catalyst obtained in Example 1 (3) was fed at a feed rate of 34.6 g / hr. During the polymerization, triethylamine was fed to the polymerization reactor at a feed rate of 0.6 mmol / hr and triisobutylaluminum was fed at a feed rate of 21 mmol / hr, and an average of 18.6 kg / h of ethylene-1-butene- A 1-octene copolymer was produced. The scattering rate of the fine particles collected by the collector for 8 hours before the end of the operation was 75 wtppm. The resulting ethylene-1-butene-1-octene copolymer had a density of 923.7 kg / m ³ , an MFR of 0.40 g / 10 min, a cold xylene soluble content of 1.2 wt%, and a Q value of It was 9.7.
Stable operation was possible, and the scattering rate of fine particles was at a low level.

Example 7
(1) Fluidized bed gas phase polymerization Using the same fluidized bed continuous gas phase polymerization reactor as in Example 1, polymerization temperature: 86.0 ° C, pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: Ethylene, 1-butene and 1 under polymerization conditions of ethylene 91.5 mol%, hydrogen 1.50 mol%, 1-octene 0.56 mol%, nitrogen 6.14 mol%, hexane 0.30 mol%, circulation gas flow rate: 34 cm / sec. -Copolymerization with octene was carried out. During the polymerization, the prepolymerized catalyst obtained in Example 1 (3) was supplied at a supply rate of 45.0 g / hr. During the polymerization, triethylamine was fed to the polymerization reactor at a feed rate of 0.6 mmol / hr and triisobutylaluminum was fed at a feed rate of 21 mmol / hr, and an average of 19.1 kg / h of ethylene-1-octene copolymer was fed. A polymer was produced. The scattering rate of fine particles collected by the collector in 8 hours before the end of the operation was 2.0 wtppm. The resulting ethylene-1-hexene copolymer had a density of 911.4 kg / m ³ , an MFR of 3.58 g / 10 min, a cold xylene soluble content of 5.1 wt%, and a Q value of 15.5. there were.
Stable operation was possible, and the scattering rate of fine particles was at a low level.

Comparative Example 1
(1) Fluidized bed type gas phase polymerization Using the same fluidized bed type continuous gas phase polymerization reactor as in Example 1, polymerization temperature: 80.0 ° C, pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: Ethylene 92.8 mol%, hydrogen 1.37 mol%, 1-hexene 1.57 mol%, nitrogen 3.96 mol%, hexane 0.30 mol%, circulating gas flow rate: 31 cm / sec between ethylene and 1-octene Copolymerization was performed. During the polymerization, the prepolymerized catalyst obtained in Example 1 (3) was supplied at a supply rate of 38.9 g / hr. During the polymerization, triethylamine was supplied to the polymerization reactor at a supply rate of 0.6 mmol / hr and triisobutylaluminum was supplied at a rate of 21 mmol / hr, and an average of 20.1 kg / h of ethylene-1-hexene was added. A polymer was produced. The scattering rate of the fine particles collected by the collector for 8 hours before the end of the operation was 1273 wtppm. The resulting ethylene-1-hexene copolymer had a density of 913.6 kg / m ³ , an MFR of 0.49 g / 10 min, a cold xylene soluble content of 2.85 wt%, and a Q value of 7.2. there were.
Although stable operation was possible for a short period of time, the scattering rate of fine particles was quite high.

Comparative Example 2
(1) Fluidized bed type gas phase polymerization Using the same fluidized bed type continuous gas phase polymerization reactor as in Example 1, polymerization temperature: 86.1 ° C, pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: Polymerization conditions of ethylene 89.5 mol%, hydrogen 1.34 mol%, 1-butene 2.31 mol%, 1-hexene 0.71 mol%, nitrogen 5.84 mol%, hexane 0.30 mol%, circulating gas flow rate: 29 cm / sec The copolymerization of ethylene, 1-butene and 1-hexene was carried out. During the polymerization, the prepolymerized catalyst obtained in Example 1 (3) was supplied at a supply rate of 45.0 g / hr. During the polymerization, triethylamine was fed to the polymerization reactor at a feed rate of 0.6 mmol / hr and triisobutylaluminum was fed at a feed rate of 21 mmol / hr, and an average of 22.5 kg / h of ethylene-1-butene- A 1-hexene copolymer was produced. The scattering rate of the fine particles collected by the collector for 8 hours before the end of the operation was 454 wtppm. The resulting ethylene-1-hexene copolymer had a density of 918.8 kg / m ³ , an MFR of 0.85 g / 10 min, a cold xylene soluble content of 2.0 wt%, and a Q value of 12.1. there were.
Although stable operation was possible for a short time, the scattering rate of fine particles was high.

Comparative Example 3
(1) Fluidized bed gas phase polymerization Using the same fluidized bed continuous gas phase polymerization reactor as in Example 1, polymerization temperature: 86.0 ° C, pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: Ethylene 91.5 mol%, hydrogen 1.32 mol%, 1-octene 1.2 mol%, nitrogen 6.18 mol%, hexane 0.30 mol%, circulating gas flow rate: 34 cm / sec between ethylene and 1-octene under polymerization conditions Copolymerization was performed. Supply of the prepolymerized catalyst obtained in Example 1 (3) was started at a supply amount of 35.0 g / hr. At the same time, when the triethylamine was supplied to the polymerization reactor at a supply rate of 0.6 mmol / hr and triisobutylaluminum was supplied at a rate of 21 mmol / hr, the wall temperature of the reaction vessel in which the flow state in the system deteriorated Fluctuations, and the pressure gauge malfunctioned. Stable operation was not possible.

Claims (3)

  A method for producing an olefin polymer in which at least ethylene and 1-octene are copolymerized using a gas phase polymerization reactor, wherein the concentration of 1-octene in a gas contained in the gas phase polymerization reactor is 0.01 mol. % To 1.1 mol% of olefin polymer production method (however, the total amount of gas contained in the gas phase polymerization reactor is 100 mol%).   The process for producing an olefin polymer according to claim 1, wherein the concentration of 1-octene in the gas contained in the gas phase polymerization reactor is in the range of 0.1 mol% to 0.6 mol%.   The method for producing an olefin polymer according to claim 1 or 2, wherein the olefin polymerization catalyst used is a metallocene catalyst.