JP2008044978A - Method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an olefin polymer with a fluidized bed type reactor by which formation of massive materials is suppressed. <P>SOLUTION: The method for producing the olefin polymer comprises feeding an olefin and a catalyst for olefin polymerization to the fluidized bed type reactor equipped with a gas distributor plate in the interior and carrying out the polymerization of the olefin while forming a fluidized bed of solid particles containing the catalyst for the olefin polymerization on the gas distributor plate. Furthermore, in the method for producing the olefin polymer, the gas distributor plate is a swirling stream type gas distributor plate and the catalyst for the olefin polymerization is fed to a swirling stream region of the fluidized bed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing an olefin polymer using a fluidized bed reactor.

The method for producing an olefin polymer using a fluidized bed reactor does not need to have a polymer precipitation step and a solvent separation step after polymerization, as compared with a solution polymerization method or a slurry polymerization method. It is known that it can be simplified. The method for producing an olefin polymer using the fluidized bed reactor is such that an olefin and a solid olefin polymerization catalyst are supplied to a fluidized bed reactor, and the olefin polymer particles, catalyst particles, etc. are fluidized in a suspended state. In the polymerization process (while forming a so-called fluidized bed), but in the polymerization method, a lump such as a polymer lump or plate may be generated, and the lump is olefin. By inhibiting the flow of polymer particles and catalyst particles, the mixed state of the fluidized bed becomes non-uniform, and when the olefin polymer particles are extracted from the fluidized bed reactor, the lump blocks the outlet. There was something to do.
Various methods for suppressing the generation of the agglomerates have been studied. For example, a method of performing a polymerization reaction at a temperature having a specific relationship with the melting point of the obtained polymer (see, for example, Patent Document 1) has been proposed. ing.

JP 2003-82007 A

However, the above method is not always satisfactory from the viewpoint of suppressing the generation of a lump.
Under such circumstances, the problem to be solved by the present invention is to provide a method for producing an olefin polymer using a fluidized bed reactor, and to provide a method for producing an olefin polymer in which the generation of a lump is suppressed. is there.

  That is, the present invention supplies an olefin and an olefin polymerization catalyst to a fluidized bed reactor having a gas dispersion plate therein, and forms a fluidized bed of solid particles containing the olefin polymerization catalyst on the gas dispersion plate. A process for producing an olefin polymer, wherein the gas dispersion plate is a swirl type gas dispersion plate, and the olefin polymerization catalyst is supplied to the swirl region of the fluidized bed. It relates to the manufacturing method.

  INDUSTRIAL APPLICABILITY According to the present invention, there can be provided a method for producing an olefin polymer using a fluidized bed reactor, in which the production of lumps is suppressed.

  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 cylindrical 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 swirl type gas dispersion plate is used as the gas dispersion plate installed inside the fluidized bed reactor. The gas dispersion plate is a type of gas dispersion plate that generates a swirl flow on the gas dispersion plate. For example, JP-A-1-284509, JP-A-3-153704, JP-A-6-136003, etc. Can be used.

  In the present invention, an olefin and an olefin polymerization catalyst are supplied to a fluidized bed reactor having the swirl type gas dispersion plate therein, and a fluidized bed of solid particles containing the olefin polymerization catalyst on the gas dispersion plate. To form an olefin.

  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. 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.

  In the present invention, the olefin polymerization catalyst is supplied to the swirl flow region of the fluidized bed. The height of the swirl flow region of the fluidized bed is obtained by changing the height of the fluidized bed and observing the moving direction of the solid particles from the upper part of the reactor to the fluidized bed powder surface. The height can be changed depending on the shape of the gas dispersion plate, the circulating gas flow rate, the pressure in the reactor, and the like. Usually, the higher the circulating gas flow rate, the higher the higher the reactor pressure.

  As a position for supplying the olefin polymerization catalyst to the swirl flow region of the fluidized bed, the inner diameter of the fluidized bed reactor is set to D from the upper direction of the fluidized bed reactor from the viewpoint of further suppressing the generation of agglomerates. (Unit: cm) is preferably a position of 1 cm to (0.5 D-1 cm) in the center direction from the inner wall of the fluidized bed reactor, and is preferably a position of 5 cm to (0.5 D-5 cm). More preferred.

  The supply direction (blow-out direction) when the olefin polymerization catalyst is supplied to the swirl flow region of the fluidized bed is as follows: the catalyst supply position and the center of the reactor as viewed from above the fluidized bed reactor. An angle X formed by a line connecting the points and the catalyst supply direction is preferably −10 ° to 90 ° (where X is a positive flow direction of the swirl flow), and −5 ° to 45 °. More preferably.

  The supply of the olefin polymerization catalyst is usually performed by providing a catalyst supply nozzle in a fluidized bed reactor and blowing it out to the swirl flow region of the fluidized bed using the carrier gas. As the carrier gas, a gas inert to the catalyst is used, and examples thereof include olefin gas, nitrogen gas, and gas containing these. The flow rate of the carrier gas when supplying the catalyst is usually 0.05 to 50 m / sec.

  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 thereof include scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom. , Samarium atoms, ytterbium atoms and the like. M 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, dimethylsilylene bis (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).

  Examples of the olefin used in the method for producing an olefin polymer of the present invention include α-olefins having 2 to 20 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, etc. Olefin can also be used.

  Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1-octene and 1-nonene. Α-olefins such as 1-decene; 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl- 1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl- 2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydro Diolefins such as phthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene; norbornene, 5-methylnorbornene, 5- Ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8 -Ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonor Cyclic olefins such as bornene, 8-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- Dimethyl styrene, 3,4-dimethyl styrene, 3,5-dimethyl styrene, 3-methyl-5-ethyl styrene, p-tertiary butyl styrene, p-secondary butyl styrene, etc.), bisalkenylbenzene (divinylbenzene) Etc.), alkenylnaphthalene (1-vinylnaphthalene, etc.) Alkenyl aromatic hydrocarbons; α, such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid β-unsaturated carboxylic acid compounds; metal salts of α, β-unsaturated carboxylic acid compounds with sodium, potassium, lithium, zinc, magnesium, calcium, etc .; methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic Α, β-unsaturation such as isopropyl acetate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Carboxylic acid ester compounds; unsaturated dicarbox such as maleic acid and itaconic acid Acid compounds: Vinyl acetate compounds such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. And unsaturated carboxylic acid glycidyl ester compounds.

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

  The olefin polymer produced in the present invention is particularly preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and among them, ethylene having a polyethylene crystal structure and α having 3 to 20 carbon atoms. -Copolymers with olefins are preferred. The α-olefin is more preferably an α-olefin having 3 to 8 carbon atoms, and specific examples include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.

  Moreover, this invention is used suitably for manufacture of the olefin polymer whose molecular weight distribution (Mw / Mn) is 3-30.

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) Coarse Grain Ratio The polymer particles were sieved with a sieve having a mesh size of 5 mm, and the weight ratio of the polymer particles that did not pass through the sieve was determined.

Example 1
(1) Preparation of prepolymerization catalyst 80 liters of butane was introduced at room temperature into a reactor with an internal volume of 210 liters, which had been purged with nitrogen in advance, and then 142 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide. Was introduced. 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, 715 g of a co-catalyst carrier prepared by the same method as the synthesis of component (A) in Examples 1 (1), (2) and (3) of JP-A-2005-68170 was added. Thereafter, 0.1 liter of hydrogen was introduced at normal temperature and pressure. After the system was stabilized, 280 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 a rate of 0.7 kg / hour, hydrogen is supplied at a normal temperature and a normal pressure at a rate of 0.7 liter / hour. Hydrogen was supplied at a rate of 10.5 liters / hour at a normal temperature and a normal pressure of 0.5 kg / hour, and preliminary polymerization was carried out for a total of 4 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 16.2 g per 1 g of the promoter support.

(2) Fluidized bed type gas phase polymerization Fluidized bed type continuous gas phase polymerization reactor having a fluidized bed type polymerization reactor having a swirl type gas dispersion plate having an opening ratio of 2.4% and an inner diameter of 50 cm. Polymerization temperature: 85 ° C., pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: ethylene 91.4 mol%, hydrogen 1.6 mol%, 1-hexene 1.1 mol%, nitrogen 5.9 mol%, Circulating gas flow rate: Copolymerization of ethylene and 1-hexene was performed under polymerization conditions of 25 cm / sec. During the polymerization, the prepolymerized catalyst obtained in Example 1 (1) was 13.2 g / hr from a position where the height from the gas dispersion plate was 8 cm and the distance from the inner wall of the reactor toward the center was 12 cm. The amount supplied was toward the center. 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 supply rate of 20 mmol / hr. In addition, in this circulation gas flow velocity, this pressure, this temperature, and this gas composition, it confirmed separately that the height of the swirl | flow area | region of a fluidized bed was 40 cm. The density of the obtained ethylene-1-hexene copolymer was 920 kg / m ³ , MFR was 0.57 g / 10 min, and the coarse particle ratio was 100 wtppm or less.

Comparative Example 1
(1) Preparation of prepolymerization catalyst 80 liters of butane was charged at room temperature into a reactor with an internal volume of 210 liters, which had been purged with nitrogen in advance, and then 144 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide. Was introduced. 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, 702 g of a promoter support prepared by the same method as the synthesis of component (A) in Examples 1 (1), (2) and (3) of JP-A-2005-68170 was added. Thereafter, 0.1 liter of hydrogen was introduced at normal temperature and pressure. After the system was stabilized, 280 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 0.7 kg / hour, hydrogen is supplied at a normal pressure and normal pressure at a rate of 0.7 liter / hour, and from 0.5 hours after the start of prepolymerization, ethylene is supplied. Hydrogen was supplied at a rate of 10.5 liters / hour at a normal temperature and pressure of 3.5 kg / hour, and preliminary polymerization was carried out for a total of 4 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 15.4 g per 1 g of the promoter support.

(2) Fluidized bed type gas phase polymerization Fluidized bed type continuous gas phase polymerization reactor having a fluidized bed type polymerization reactor having a swirl type gas dispersion plate having an opening ratio of 2.4% and an inner diameter of 50 cm. Polymerization temperature: 85 ° C., pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: ethylene 91.5 mol%, hydrogen 1.2 mol%, 1-hexene 0.9 mol%, nitrogen 6.4 mol%, Circulation gas flow rate: Copolymerization of ethylene and 1-hexene was carried out under polymerization conditions of 28 cm / sec. During the polymerization, the prepolymerized catalyst obtained in Example 2 (1) was 13.0 g / hr from a position where the height from the gas dispersion plate was 58 cm and the distance from the inner wall of the reactor toward the center was 12 cm. The amount supplied was toward the center. 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 supply rate of 20 mmol / hr. In addition, in this circulation gas flow velocity, this pressure, this temperature, and this gas composition, it confirmed separately that the height of the swirl | flow area | region of a fluidized bed was 40 cm. The density of the obtained ethylene-1-hexene copolymer was 919 kg / m ³ , the MFR was 0.43 g / 10 min, and the coarse particle ratio was about 300 wtppm.

Claims (3)

  An olefin polymer produced by supplying an olefin and an olefin polymerization catalyst to a fluidized bed reactor having a gas dispersion plate therein, and forming a fluidized bed of solid particles containing the olefin polymerization catalyst on the gas dispersion plate. A method for producing an olefin polymer, wherein the gas dispersion plate is a swirl type gas dispersion plate, and the olefin polymerization catalyst is supplied to a swirl flow region of the fluidized bed.   When viewed from the top of the fluidized bed reactor, when the inner diameter of the fluidized bed reactor is D (unit: cm), 1 cm to (0.5 D-1 cm) from the inner wall of the fluidized bed reactor toward the center. The angle X formed by a line connecting the supply position of the catalyst and the center point of the reactor and the supply direction of the catalyst is -10 ° to 90 ° (provided that 2. The method for producing an olefin polymer according to claim 1, wherein X is a flow direction of the swirling flow. The method for producing an olefin polymer according to claim 1 or 2, wherein the olefin polymerization catalyst is a metallocene catalyst.