JP4967301B2 - Process for producing olefin polymer - Google Patents

Description

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

The production method of olefin polymer by gas phase polymerization method does not need to be equipped with a polymer precipitation step after polymerization and a solvent separation step, compared to solution polymerization method and slurry polymerization method, simplifying the production process It is known that it can be done. In the gas phase polymerization method, a solid polymerization catalyst and an olefin are supplied to a gas phase fluidized bed reactor, and the polyolefin particles and the catalyst particles are flowed in a suspended state (while forming a so-called fluidized bed). In the gas phase polymerization method, a lump such as a polymer lump or plate-like material may be generated, and the lump inhibits the flow of polyolefin particles or catalyst particles. As a result, the mixed state of the fluidized bed may become non-uniform, and when the polyolefin particles are extracted from the fluidized bed reactor, the lump may block the outlet.
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, even in the above method, the suppression of the generation of the lump was not sufficiently satisfactory.
Under such circumstances, the problem to be solved by the present invention is to provide a method for producing an olefin polymer using a gas phase fluidized bed reactor, and to provide a method for producing an olefin polymer in which the generation of lumps is suppressed. It is in.

That is, the present invention introduces an olefin gas and seed polymer particles into a gas phase fluidized bed reactor, forms a fluidized bed of the seed polymer particles, and then supplies an olefin polymerization catalyst into the reactor. Olefin polymer particles are produced, and the olefin polymer particles in the reactor are extracted from the reactor, the method comprising the steps of introducing seed polymer particles and introducing the olefin polymer particles in the reactor. Until the extraction is started, the temperature in the reactor is related to the method for producing an olefin polymer that satisfies the following formula (1).
70 × X ^−0.2 ≦ T ≦ Z (1)
T: Temperature in the reactor (° C)
X: Cold xylene soluble part of seed polymer (wt%)
Z: Melting point of seed polymer (° C)

  According to the present invention, it is possible to provide a method for producing an olefin polymer using a gas phase fluidized bed reactor, wherein the production of an olefin polymer with suppressed generation of a lump.

  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 gas phase fluidized bed reactor, 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.

In the gas phase polymerization of olefin, various polymer particles are used as seed polymer particles used in the fluidized bed to be formed in advance in the gas phase fluidized bed reactor, but preferably the same as the olefin polymer to be produced. Or polymer particles comprising similar components are preferred. Usually, olefin polymer particles are used. Further, the weight average particle diameter of the seed polymer particles is usually 350 to 3000 μm, preferably 400 to 2000 μm, and the bulk specific gravity is usually 0.25 to 0.50 g / cm ³ , preferably 0.8. 30 to 0.45 g / cm ³ . The weight average particle diameter is measured by a laser diffraction particle size distribution measuring apparatus (for example, HELOS & RODOS manufactured by JEOL Ltd.), and the bulk specific gravity is measured by using a bulk specific gravity measuring apparatus according to JIS K6721-1977.

  The molecular weight distribution (Mw / Mn) of the polymer constituting the seed polymer particles is preferably 3 to 30, and more preferably 3.5 to 20. The molecular weight distribution is a ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn), and is measured by gel permeation chromatography.

  The amount of the cold xylene soluble part of the polymer constituting the seed polymer particles is preferably 3 to 15% by weight, more preferably 4 to 10% by weight. The amount of the cold xylene soluble part is measured according to the method defined in § 177.1520 of Code of federal regulations, Food and Drugs Administration, USA. As a method of increasing the amount of the cold xylene soluble part, a method of increasing the hydrogen concentration in the polymerization gas at the time of producing the seed polymer, a method of increasing the comonomer ratio in the monomer of the polymerization gas (for example, ethylene and 1-hexene). In the copolymerization, the concentration of 1-hexene relative to ethylene is increased.

  Examples of the method for producing seed polymer particles include a known polymerization method using a known olefin polymerization catalyst, such as a slurry polymerization method and a gas phase polymerization method.

  The production of the olefin polymer using the gas phase fluidized bed reactor of the present invention, after introducing the olefin gas and seed polymer particles into the gas phase fluidized bed reactor to form a fluidized bed of the seed polymer particles, An olefin polymerization catalyst is supplied into the reactor to polymerize the olefin, to produce olefin polymer particles, and the olefin polymer particles in the reactor are extracted from the reactor. More specifically, (a) seed polymer particles are introduced into the reactor to form a fluidized bed of the seed polymer particles, and (b) olefin gas is introduced into the reactor before or after introduction of the seed polymer particles. (C) supplying an olefin polymerization catalyst into the reactor and polymerizing the olefin to produce olefin polymer particles, (d) reaction so that the fluidized bed height is in a substantially constant range. It is carried out by a process comprising withdrawing the olefin polymer particles in the reactor from the reactor.

  In the production of an olefin polymer using the gas phase fluidized bed reactor according to the present invention, the seed polymer particles are fluidized by introducing seed polymer particles into the reactor and then circulating the gas in the reactor. The particles may be formed by flowing, or may be formed by introducing seed polymer particles into a reactor in which a gas has been circulated in advance and flowing the seed polymer particles simultaneously with the introduction of the seed polymer particles. Good. The olefin to be subjected to the polymerization reaction may be circulated in the reactor as a circulating gas when forming the fluidized bed, and after forming the fluidized bed with a circulating gas composed of an inert gas or the like, Olefin may be introduced into the reactor and circulated in the reactor.

  In the production of an olefin polymer using the gas phase fluidized bed reactor of the present invention, the olefin polymerization reaction is carried out by supplying a catalyst for olefin polymerization into the reactor in which the olefin is circulated, preferably in the fluidized bed. The olefin polymer particles are produced by the polymerization reaction of the olefin. Usually, an amount of polymer particles commensurate with the amount produced is withdrawn from the reactor so that the fluidized bed height falls within a certain range. The olefin polymerization reaction is usually a continuous polymerization reaction, and the supply of the olefin polymerization catalyst and the extraction of the olefin polymer particles are usually performed continuously or intermittently. The extracted olefin polymer particles also contain seed polymer particles used for fluidized bed formation at the start of polymerization, that is, a mixture of both polymer particles, but there is no problem.

In the production of the olefin polymer, the temperature in the reactor is set to a temperature satisfying the following formula (1), and at least the seed polymer particles are introduced into the gas phase fluidized bed reactor, and then the olefin polymer is introduced into the reactor. The polymerization catalyst is supplied to produce olefin polymer particles, and the olefin polymer particles in the reactor (hereinafter sometimes referred to as polymer particles) are adjusted until they start to be extracted.
70 × X ^−0.2 ≦ T ≦ Z (1)
T: Temperature in the reactor (° C)
X: Cold xylene soluble part of seed polymer (wt%)
Z: Melting point of seed polymer (° C)
Here, the melting point of the seed polymer is obtained from the melting curve of the seed polymer measured with a differential scanning calorimeter at a temperature rising rate of 5 ° C./min. The endothermic peak having the maximum height in the melting curve is obtained. The peak temperature is taken as the melting point.

  Furthermore, the temperature in the reactor is changed from the above equation until the average residence time of the polymer particles in the reactor reaches the amount of polymer particles withdrawn to 12 hours or less after the extraction of the polymer particles in the reactor is started. It is preferable to adjust the temperature to satisfy (1), and after the extraction of the polymer particles in the reactor is started, the average residence time of the polymer particles in the reactor is 8 hours or less. In the meantime, it is more preferable to adjust the temperature in the reactor to a temperature that satisfies the above formula (1). Here, the average residence time is a value obtained by dividing the total weight (unit: kg) of the polymer particles in the fluidized bed by the average extraction rate (unit: kg / hour) of the polymer particles. The average residence time in the steady state is not particularly limited, but is generally about 0.5 to about 6 hours.

The temperature that satisfies the above formula (1) is preferably a temperature that satisfies the following formula (2).
70 × X ^−0.2 ≦ T ≦ Y (2)
T: Temperature in the reactor (° C)
X: cold xylene soluble part ratio of seed polymer (wt%)
Y: Vicat softening point of seed polymer (° C)
Here, the Vicat softening point of the seed polymer is measured under the conditions of a test load of 1 kg and a heating rate of 50 ° C./hour according to the liquid heating method specified in JIS K7206-1991, and when the needle-like indenter enters 1 mm. Temperature.

Further, the temperature satisfying the above formula (1) or the above formula (2) is preferably a temperature of 80 × X ^−0.2 or more, more preferably 90 × X ^−0.2 or more from the viewpoint of further suppressing the generation of a lump. Is more preferable, and a temperature of 95 × X ^−0.2 or more is more preferable.

  The circulating gas flow rate in the reactor is such that the seed polymer particles begin to be introduced into the gas-phase fluidized bed reactor, the olefin polymerization catalyst is supplied into the reactor, and the polymer particles in the reactor are withdrawn from the reactor. Until the start, it is preferably 50 cm / second or less. Furthermore, the above-mentioned circulation gas flow rate is set from the start of extracting the polymer particles in the reactor until the average residence time of the polymer particles in the reactor reaches the extraction amount of the polymer particles of 12 hours or less. More preferably, the flow rate of the circulating gas is from the time when the polymer particles in the reactor start to be extracted from the reactor until the average residence time of the polymer particles in the reactor reaches the amount of polymer particles withdrawn to 8 hours or less. More preferably. The circulating gas flow rate in the reactor when introducing the seed polymer particles into the gas phase fluidized bed reactor is preferably equal to or higher than the flow start rate of the particles.

  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.

The metallocene compound is preferably a transition metal compound represented by the following general formula [1] or a μ-oxo type transition metal compound dimer thereof.
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, 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 Denenyl-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.

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.

The particulate carrier is preferably a porous material, and is an inorganic oxide 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 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).

  In the production of an olefin polymer using the gas phase fluidized bed reactor of the present invention, the polymerization is performed under known polymerization conditions after the olefin polymerization is started. The internal pressure of the reactor may be within a range in which olefins 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.

The supply amount of the olefin polymerization catalyst into the reactor is usually 0.01 to 100 mmol / hr · as the amount of transition metal atoms in the olefin polymerization catalyst per unit time and unit volume of the fluidized bed. m ³ h.

  Examples of the olefin polymerized in the production of the olefin polymer using the gas phase fluidized bed reactor of the present invention include α-olefins having 2 to 20 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, polar monomers, etc. Two or more monomers can be used at the same time.

  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. 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-endomethylenehexahydronaphth Diolefins such as len, 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-cyanonorbo Cyclic olefins such as nene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; styrene, 2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene Alkenylbenzene, 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, alkyl styrene such as p-secondary butyl styrene, bisalkenyl benzene such as divinylbenzene, Alkene such as alkenylnaphthalene such as 1-vinylnaphthalene Nyl aromatic hydrocarbons; 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 acids and their metal salts such as sodium, potassium, lithium, zinc, magnesium, calcium, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, t-butyl acrylate, acrylic acid Such as 2-ethylhexyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, α, β-unsaturated carboxylic acid esters, maleic acid, itaconic acid, etc. Unsaturated dicarboxylic acid, vinyl acetate, vinyl propionate, capro Polar monomers such as vinyl esters such as vinyl acid, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. Is given.

  The present invention is applied to homopolymerization or copolymerization of these monomers. Specific examples of the monomer 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, it is preferable to use for manufacture of the olefin polymer whose molecular weight distribution (Mw / Mn) is 3-30 from a viewpoint of improving the effect of this invention.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The physical properties in the examples were measured by the following methods.
(1) Density (Unit: kg / m ³ )
After annealing described in JIS K6760-1995, the measurement was performed according to the underwater substitution method described in JIS K7112-1980.
(2) Melt flow rate (MFR, unit: g / 10 minutes)
According to the method defined in JIS K7210-1995, the measurement was performed under conditions of a temperature of 190 ° C. and a load of 21.18N.
(3) Amount of cold xylene soluble part (CXS, unit: wt%)
It was measured according to the method specified in § 177.1520 of Code of federal regulations, Food Drugs Administration, USA.
(4) Melting point (unit: ° C)
Using a differential scanning calorimeter (DSC, [DiamondDSC manufactured by PerkinElmer Co., Ltd.]), a melting curve was measured under the condition of a heating rate of 5 ° C./min, and the peak temperature of the endothermic peak having the maximum height was taken as the melting point.
(5) Vicat softening point (unit: ° C)
According to the liquid heating method defined in JIS K7206-1991, H. Toyo Seiki Co., Ltd. D. T & V. S. P. Using TTESTER, the temperature of the electric heating medium was measured when 1 mm of the needle-like indenter vertically invaded the test piece perpendicular to the heating bath under the conditions of a test load of 1 kg and a heating rate of 50 ° C./hour. The test piece was filled with about 16 g of polymer in a 60 mm × 60 mm × 5 mm mold using a hot press machine, preheated at 150 ° C. for 5 minutes without pressure, and pressure of 5 MPa at 150 ° C. For 5 minutes, and then cooled at 30 ° C. at a pressure of 3 MPa for 5 minutes. A Shinto F type hydraulic press manufactured by Shindo Metal Industry Co., Ltd. was used as the press machine.
(6) 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: Millipore Waters 150C type column: TSK-GEL GMH-HT 7.5 × 600 Two measuring temperature: 140 ° C.
Solvent: orthodichlorobenzene,
Measurement concentration: 5 mg / 5 ml
Detector: Differential refractometer

[Example 1]
(A) Preparation of seed polymer particles (1) Preparation of catalyst for production of seed polymer particles In an autoclave with a stirrer having an internal volume of 210 liters, which had been previously purged with nitrogen, 100% of butane containing triisobutylaluminum at a concentration of 3.54 mmol / liter was added. After charging 1 liter, 0.3 kg of 1-butene and 6 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 30 ° C. After ethylene was charged by 0.15 MPa as the gas phase pressure in the autoclave and the system was stabilized, 146.3 mmol of triisobutylaluminum, 48.75 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide, Subsequently, 325.7 g of a solid catalyst component obtained by a method similar to the synthesis of component (A) in Example 10 (1) and (2) of JP-A No. 2003-171415 was added to initiate polymerization. The temperature in the reactor was 30 ° C., and during the first hour from the start of polymerization, ethylene was supplied at a rate of 5.0 liter / hour as 1.5 kg / hour of hydrogen and hydrogen at room temperature and normal pressure. From the time, prepolymerization was carried out for a total of 4 hours by supplying ethylene at 3.0 kg / hour and hydrogen at normal temperature and pressure at a rate of 18.0 liters / hour. After completion of the polymerization, ethylene, butane and hydrogen gas were purged and the solvent was filtered. The resulting solid was vacuum-dried at room temperature to give 33.1 g of ethylene-1-butene copolymer per gram of the solid catalyst component. A catalyst for producing seed polymer particles in which the polymer was prepolymerized was obtained.
(2) Production of seed polymer particles Using a gas phase fluidized bed polymerization reactor, the pressure in the reactor: 2.0 MPaG, the temperature in the reactor: 85 ° C., the linear velocity of the circulating gas: 28 cm / sec, the hold-up amount: 80 kg, supply amount of the catalyst for producing seed polymer particles obtained in the above (1): 108 g / hour, supply amount of triisobutylaluminum: 22 mmol / hour, gas composition: ethylene 87.7 mol%, hydrogen 0.4 mol%, 1 -Copolymerization of ethylene and 1-hexene was carried out under conditions of 1.2 mol% hexene and 10.7 mol% nitrogen to obtain seed polymer particles.
The density of the obtained seed polymer particles is 920 kg / m ³ , MFR is 0.56 g / 10 min, molecular weight distribution is 13.6, CXS is 2.2% by weight, melting point is 114 ° C., Vicat softening point is 95 ° C. there were.

(B) Production of Olefin Polymer (1) Synthesis of Prepolymerized Polymerization Catalyst Into an autoclave with a stirrer having an internal volume of 210 liters, which was previously purged with nitrogen, was added 100% butane containing triisobutylaluminum at a concentration of 5.7 mmol / liter. After charging 1 liter, 0.3 kg of 1-butene and 6 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 30 ° C. After ethylene was charged by 0.12 MPa at the gas phase pressure in the autoclave and the system was stabilized, 180 mmol of triisobutylaluminum, 60 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide, Polymerization was started by adding 400 g of the solid catalyst component obtained in the same manner as in the synthesis of component (A) in Example 10 (1) and (2) of 2003-171415. The temperature in the reactor was 30 ° C., and during the first hour after the start of polymerization, ethylene was supplied at a rate of 7.5 liters / hour as ethylene at 2.2 kg / hour and hydrogen at room temperature and normal pressure. From the time, ethylene was 4.5 kg / hour and hydrogen was supplied at normal temperature and pressure as hydrogen at a rate of 25 liters / hour to carry out preliminary polymerization for a total of 4 hours. After the completion of the polymerization, ethylene, butane and hydrogen gas were purged and the solvent was filtered. The resulting solid was vacuum-dried at room temperature to give 34.3 g of ethylene-1-butene copolymer per gram of the solid catalyst component. A prepolymerized polymerization catalyst in which the polymer was prepolymerized was obtained.
(2) Gas phase polymerization After replacing the inside of the gas phase fluidized bed polymerization reactor with a nitrogen atmosphere, nitrogen gas was set at 28 cm / cm as the linear velocity in the reactor under the conditions of a reactor internal pressure of 0.23 MPaG and a temperature of 85 ° C. Circulated in seconds. Thereafter, 96.1 kg of seed polymer particles were pumped from the stock drum to the gas phase fluidized bed polymerization reactor with nitrogen. Next, pressure was increased with ethylene, 1-hexene, hydrogen and nitrogen, and the pressure was increased to 2.0 MPaG in the reactor. After completion of the pressurization, 116 g / hour of prepolymerized polymerization catalyst and 26 mmol / hour of triisobutylaluminum were supplied, the reactor temperature was 85 ° C., the reactor pressure was 2.0 MPaG, the holdup was 80 kg, The gas composition was adjusted to 90.8 mol% ethylene, 0.6 mol% hydrogen, 1.4 mol% 1-hexene, and 7.2 mol% nitrogen, and ethylene and 1-hexene were copolymerized. In this state, stable operation was performed for 2 days.
The density of the ethylene-1-hexene copolymer obtained by the polymerization was 914 kg / m ³ , the MFR was 1.39 g / 10 min, the molecular weight distribution was 8.2, and CXS was 4.4% by weight.

[Example 2]
(A) Preparation of seed polymer particles (1) Preparation of catalyst for production of seed polymer particles In an autoclave with a stirrer with an internal volume of 210 liters previously purged with nitrogen, 80 liters of butane, 0.15 kg of 1-butene, hydrogen Was charged with 3 liters of hydrogen at room temperature and normal pressure, and then the autoclave was heated to 45 ° C. After the system was stabilized, 315 mmol of triisobutylaluminum, 105 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide, and then Examples 10 (1) and (2) of JP-A No. 2003-171415 ) 760 g of a solid catalyst component obtained by the same method as in the synthesis of component (A) was added to initiate polymerization. The reactor internal temperature was raised from 45 ° C. to 50 ° C. over 30 minutes from the start of polymerization, and then adjusted to 50 ° C. For the first 0.5 hours from the start of the polymerization, ethylene was supplied at a rate of 12.0 liters / hour as 1.5 kg / hour of hydrogen and hydrogen at room temperature and normal pressure. Was supplied at a rate of 48 liters / hour as 6 kg / hour of hydrogen and hydrogen at normal temperature and pressure, and prepolymerization was carried out for a total of 2 hours. After completion of the polymerization, a catalyst for producing seed polymer particles in which ethylene, butane, and hydrogen gas were purged, nitrogen flow drying was performed, and 12.3 g of ethylene-1-butene copolymer was prepolymerized per 1 g of the solid catalyst component. Obtained.
(2) Production of seed polymer particles Using a gas phase fluidized bed polymerization reactor, the pressure in the reactor: 2.0 MPaG, the temperature in the reactor: 75 ° C., the linear velocity of the circulating gas: 28 cm / second, the hold-up amount: 80 kg, supply amount of seed polymer particle production catalyst obtained in (1) above: 28 g / hour, supply amount of triisobutylaluminum: 13 mmol / hour, gas composition: ethylene 92.9 mol%, hydrogen 1.0 mol%, 1 -Copolymerization of ethylene and 1-hexene was carried out under the conditions of 1.1 mol% hexene and 5 mol% nitrogen to obtain seed polymer particles.
The density of the obtained seed polymer particles is 920 kg / m ³ , MFR is 1.26 g / 10 min, molecular weight distribution is 15.7, CXS is 3.7 wt%, melting point is 111 ° C., Vicat softening point is 93 ° C. there were.

(B) Production of Olefin Polymer (1) Synthesis of Prepolymerized Polymerization Catalyst After charging 80 liters of butane into an autoclave with a stirrer with an internal volume of 210 liters that has been previously purged with nitrogen, JP-A-2003-171415 730 g of a solid catalyst component obtained by the same method as in the synthesis of component (A) in Example 10 (1) and (2) was added. Thereafter, 8 g of 1-butene, 4 liters of hydrogen at normal temperature and normal pressure, and 0.3 kg of ethylene were charged, and then the autoclave was heated to 40 ° C. After the system was stabilized, 225 mmol of triisobutylaluminum and 75 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The reactor internal temperature was raised from 40 ° C. to 50 ° C. over 30 minutes from the start of polymerization, and then adjusted to 50 ° C. For the first 0.5 hours from the start of the polymerization, ethylene was supplied at a rate of 5.0 liters / hour as 0.6 kg / hour of hydrogen and hydrogen at room temperature and normal pressure. Was supplied at a rate of 20 liters / hour as hydrogen at normal temperature and pressure, and prepolymerization was carried out for a total of 6 hours. After completion of the polymerization, a prepolymerized polymerization catalyst in which ethylene, butane, hydrogen gas was purged, nitrogen circulation drying was performed, and 12.3 g of ethylene-1-butene copolymer was prepolymerized per 1 g of the solid catalyst component. Obtained.
(2) Gas phase polymerization After replacing the inside of the gas phase fluidized bed polymerization reactor with a nitrogen atmosphere, nitrogen gas was used as a linear velocity in the reactor at 28 cm / min under the conditions of a reactor internal pressure of 0.23 MPaG and a temperature of 75 ° C. Circulated in seconds. Thereafter, 84.7 kg of seed polymer particles were pumped from the stock drum to a gas phase fluidized bed polymerization reactor with nitrogen. Next, pressure was increased with ethylene, 1-hexene, hydrogen and nitrogen, and the pressure was increased to 2.0 MPaG in the reactor. After completion of pressurization, 41.3 g / hour of prepolymerized polymerization catalyst and 21 mmol / hour of triisobutylaluminum were supplied, the reactor temperature was 75 ° C., the reactor pressure was 2.0 MPaG, and the holdup was 80 kg. The inside gas composition was adjusted to ethylene 87.7 mol%, hydrogen 1.7 mol%, 1-butene 6.1 mol%, and nitrogen 4.5 mol%, and ethylene and 1-butene were copolymerized. In this state, stable operation was performed for 4 days.
The density of the ethylene-1-butene copolymer obtained by polymerization was 912 kg / m ³ , MFR was 1.53 g / 10 min, molecular weight distribution was 8.1, and CXS was 10.9 wt%.

[Comparative Example 1]
(A) Preparation of seed polymer particles (1) Preparation of solid catalyst component A 5-liter four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was dried under reduced pressure, and then purged with nitrogen. 346 g of heat-treated silica (Debison # 948; average particle size = 64 μm; pore volume = 1.62 ml / g; specific surface area = 312 m ² / g; heat treatment at 300 ° C. under nitrogen flow) into flask Was introduced. Next, 3 liters of toluene was added to form a slurry, which was cooled to 5 ° C. using an ice bath, and then 368 ml of a toluene solution of trimethylaluminum whose concentration was adjusted to 2.3 mmol / ml was gradually added dropwise. After stirring at 5 ° C. for 30 minutes and at 80 ° C. for 2 hours, the supernatant was filtered, and the remaining solid component was washed with 3 liters of toluene four times. Thereafter, 3 liters of toluene was added again to form a slurry. After cooling the slurry to 5 ° C. using an ice bath, 380 ml of a toluene solution of pentafluorophenol adjusted to a concentration of 2 mmol / ml was slowly added. After stirring at 5 ° C. for 30 minutes and at 80 ° C. for 2 hours, the supernatant was filtered, and the remaining solid components were washed 4 times with 3 liters of toluene and twice with 3 liters of hexane. Thereafter, the solid component was dried under reduced pressure to obtain 440 g of a solid catalyst component.
(2) Preparation of catalyst for production of seed polymer particles An autoclave with a stirrer with an internal volume of 210 liters previously purged with nitrogen was adjusted to a reactor internal temperature of 10 ° C, and then 65 g of the solid catalyst component prepared in (1) above was prepared. And 93.7 liters of butane containing 550 mmol of triisobutylaluminum and 37.5 liters of hydrogen as hydrogen at room temperature and normal pressure, and then ethylene is charged by 0.3 MPa at the gas phase pressure in the autoclave. Next, 1.05 liter of norbornadiene was charged. Thereafter, 9.7 mmol of bisnormalbutylcyclopentadienylzirconium dichloride was charged to initiate polymerization. During the polymerization, ethylene was fed at 5.3 kg / hour. In addition, the temperature in the reactor was increased from 30 ° C. to 40 ° C. over 1.5 hours from the start of polymerization, and then adjusted to 40 ° C. to carry out preliminary polymerization for a total of 2.7 hours. After completion of the polymerization, the solvent was filtered, and the resulting solid was vacuum-dried at room temperature to obtain a seed polymer particle production catalyst in which 183 g of ethylene polymer was prepolymerized per 1 g of the solid catalyst component.
(3) Production of seed polymer particles Using a gas phase fluidized bed polymerization reactor, the pressure in the reactor: 2.0 MPaG, the temperature in the reactor: 70 ° C., the linear velocity of the circulating gas: 34 cm / second, the hold-up amount: 60 kg, supply amount of the catalyst for producing seed polymer particles obtained in the above (1): 245 g / hour, supply amount of triisobutylaluminum: 51 mmol / hour, gas composition: ethylene 87.1 mol%, hydrogen 0.02 mol%, 1 -Copolymerization of ethylene and 1-butene was performed under conditions of 5.6 mol% butene and 7.28 mol% nitrogen to obtain seed polymer particles.
The density of the obtained seed polymer particles is 924 kg / m ³ , MFR is 2.6 g / 10 min, molecular weight distribution is 2.1, CXS is 0.5 wt%, melting point is 112 ° C., Vicat softening point is 102 ° C. there were.

(B) Production of Olefin Polymer (1) Synthesis of Prepolymerized Polymerization Catalyst An autoclave with a stirrer having an internal volume of 210 liters, which had been purged with nitrogen in advance, was adjusted to 30 ° C., and (A) (1) and 203 g of the solid catalyst component obtained in the same manner, 100 liters of butane containing 600 mmol of triisobutylaluminum, 15 liters of hydrogen at room temperature and atmospheric pressure, 0.3 kg of ethylene, bisnormalbutylcyclopentadienylzirconium dichloride 30.7 mmol was charged to initiate polymerization. During the polymerization, ethylene was fed at 3.0 kg / hour. In addition, the temperature in the reactor was increased from 30 ° C. to 40 ° C. over 0.4 hours from the start of polymerization, and then adjusted to 40 ° C. to carry out preliminary polymerization for a total of 5.4 hours. After completion of the polymerization, the solvent was filtered, and the resulting solid was vacuum dried at room temperature to obtain a prepolymerized polymerization catalyst in which 47 g of ethylene polymer per 1 g of the solid catalyst component was prepolymerized.
(2) Gas phase polymerization After replacing the inside of the gas phase fluidized bed polymerization reactor with a nitrogen atmosphere, nitrogen gas was set at 28 cm / cm as the linear velocity in the reactor under the conditions of a reactor internal pressure of 0.23 MPaG and a temperature of 70 ° C. Circulated in seconds. Thereafter, 60 kg of seed polymer particles were pumped from the stock drum to the gas phase fluidized bed polymerization reactor with nitrogen. Next, pressure was increased with ethylene, 1-hexene, hydrogen and nitrogen, and the pressure was increased to 2.0 MPaG in the reactor. After completion of the pressurization, the linear velocity of the circulating gas in the reactor is set to 34 cm / second, the prepolymerized polymerization catalyst is supplied at 20 g / hour, and triisobutylaluminum is supplied at 101 mmol / hour. In-vessel pressure 2.0 MPaG, hold-up 60 kg, gas composition during operation: ethylene 88.5 mol%, hydrogen 0.01 mol%, 1-butene 5.4 mol%, butane 3.7 mol%, nitrogen 2.39 mol% And ethylene and 1-butene were copolymerized. However, 19 hours after the start of the polymerization, the polymerization particle was removed from the reactor, so the polymerization was stopped. When the inside of the reactor was opened, a sheet-like lump was generated inside the reactor.

Claims (6)

After introducing gaseous olefin and seed polymer particles into a gas phase fluidized bed reactor and forming a fluidized bed of the seed polymer particles, an olefin polymerization catalyst is supplied into the reactor to polymerize the olefin, A method for producing an olefin polymer comprising producing polymer particles and extracting the olefin polymer particles in the reactor from the reactor,
The seed polymer particles are made of an olefin polymer, and the amount of the cold xylene soluble part of the olefin polymer is 2.2 to 8% by weight,
A process for producing an olefin polymer in which the temperature in the reactor satisfies the following formula (1) from the introduction of the seed polymer particles to the start of extraction of the olefin polymer particles in the reactor.
95 × X ^−0.2 ≦ T ≦ Z (1)
T: Temperature in the reactor (° C)
X: Cold xylene soluble part of seed polymer (wt%)
Z: Melting point of seed polymer (° C)   From the start of the extraction of the olefin polymer particles in the reactor until the average residence time of the olefin polymer particles in the reactor reaches 12 hours, the temperature in the reactor is a temperature that satisfies the equation (1) The method for producing an olefin polymer according to claim 1. The method for producing an olefin polymer according to claim 1 or 2, wherein the temperature that satisfies the formula (1) is a temperature that further satisfies the following formula (2).
95 × X ^−0.2 ≦ T ≦ Y (2)
T: Temperature in the reactor (° C)
X: Cold xylene soluble part of seed polymer (wt%)
Y: Vicat softening point of seed polymer (° C)   The olefin weight according to any one of claims 1 to 3, wherein the circulation gas flow rate in the reactor is 50 cm / sec or less from the introduction of the seed polymer particles to the start of the extraction of the olefin polymer particles in the reactor. Manufacturing method of coalescence. Process for producing an olefin polymer according to claim 1 the molecular weight distribution of the olefin polymer molecular weight distribution (Mw / Mn) Ru 3-30 der constituting the seed polymer particles.   The method for producing an olefin polymer according to any one of claims 1 to 5, wherein the olefin polymerization catalyst is a metallocene catalyst.