JP4984443B2 - Process for producing olefin polymer - Google Patents

Description

  The present invention relates to a method for producing an olefin polymer.

The production method of the olefin polymer by the fluidized bed gas phase polymerization method does not need to have a polymer precipitation step after the polymerization and a solvent separation step as compared with the production method by the solution polymerization method or the slurry polymerization method. It is known that can be simplified. In the fluidized bed gas phase polymerization method, a solid phase polymerization catalyst particle and an olefin gas are supplied to a gas phase fluidized bed reactor filled with polyolefin particles, and the polyolefin particles and the catalyst particles are floated and fluidized. This is a method of polymerizing olefins (by forming a so-called fluidized bed), but agglomerates such as particle aggregates and plate-like materials may be generated during the polymerization, and the agglomerates may be polyolefin particles or catalysts. By inhibiting the flow of particles, the mixed state of the fluidized bed becomes non-uniform, and when the polyolefin particles are extracted from the gas phase fluidized bed reactor, the agglomerates sometimes block the outlet.
Various methods for suppressing the generation of the agglomerated materials 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 (for example, see Patent Document 1) is proposed. ing.

JP 2003-82007 A

However, even in the above method, the suppression of the generation of agglomerates 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 agglomerates is suppressed. It is in.

The present invention is a method for producing an olefin polymer in which solid particles for olefin polymerization using a metallocene compound are supplied to a gas phase fluidized bed reactor, and the olefin is polymerized in the gas phase fluidized bed reactor, The agglomeration parameter χ represented by the following formula (I) relates to a method for producing an olefin polymer in which olefin polymerization is performed under the polymerization conditions satisfying the following formula (II).
χ = 19.5 × α + 10.5 × β−1.48 × γ + 2.70 × ε (I)
240 ≦ χ ≦ 330 (II)
α: Cold xylene of olefin polymer particles withdrawn from the gas phase fluidized bed reactor
Soluble component (wt%)
β: amount of cold xylene-soluble component of solid particles for olefin polymerization (wt%)
γ: Gas flow rate in the gas-phase fluidized bed reactor (cm / sec)
ε: Polymerization temperature (° 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, which suppresses the generation of agglomerates.

  Examples of the olefin used in this production method include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene, cyclohexene and the like. These can be used alone or in combination of two or more, preferably ethylene alone, or a combination of olefins other than ethylene and ethylene, more preferably ethylene alone or ethylene and α-olefin. More preferably, at least one α-olefin selected from 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene and ethylene are used in combination.

In this production method, the olefin is polymerized in the gas phase fluidized bed reactor under the polymerization conditions in which the agglomeration parameter χ represented by the following formula (I) satisfies the following formula (II).
χ = 19.5 × α + 10.5 × β−1.48 × γ + 2.70 × ε (I)
240 ≦ χ ≦ 330 (II)
α: Cold xylene of olefin polymer particles withdrawn from the gas phase fluidized bed reactor
Soluble component (wt%)
β: amount of cold xylene-soluble component of solid particles for olefin polymerization (wt%)
γ: Gas flow rate in the gas-phase fluidized bed reactor (cm / sec)
ε: Polymerization temperature (° C)
If the agglomeration parameter χ is too small or too large, the effect of suppressing the generation of agglomerates may be reduced. The agglomeration parameter χ is preferably in the range of 250 to 320, and more preferably in the range of 260 to 310.

  In formula (I), α is the cold xylene soluble component amount (CXS) of the olefin polymer particles withdrawn from the gas phase fluidized bed reactor, and is §177 of Code of federal regulations, Food and Drugs Administration, USA. Measured by the method specified in 1520. CXS represents the weight of the polymer in the olefin polymer particles extracted from the gas phase fluidized bed reactor as 100% by weight. As a method of increasing the α, a method of increasing the hydrogen concentration in the polymerization gas, a method of increasing the comonomer ratio in the monomer of the polymerization gas (for example, in the copolymerization of ethylene and 1-hexene, 1-hexene is In the case of a comonomer, the concentration of 1-hexene with respect to ethylene is increased.

  In the formula (I), β is CXS of the solid particles for olefin polymerization, and represents the weight of the polyolefin in the solid particles for olefin polymerization as 100% by weight. The solid particles for olefin polymerization are obtained by polymerizing an olefin in a step before the polymerization of olefin in the gas phase fluidized bed reactor (hereinafter referred to as pre-stage polymerization) using a solid catalyst component described later. The obtained particles are particles containing a solid catalyst component and a polyolefin. Examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene, cyclohexene and the like. These can be used alone or in combination of two or more, preferably ethylene alone, or a combination of olefins other than ethylene and ethylene, more preferably ethylene alone or ethylene and α-olefin. More preferably, at least one α-olefin selected from 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene and ethylene are used in combination.

  The polyolefin content in the solid particles for olefin polymerization is appropriately determined depending on each polymerization type, but is usually 1 to 20000 g, preferably 5 to 5000 g, more preferably 5 to 200 g, per 1 g of the solid catalyst component. It is.

  The pre-polymerization is usually performed by suspension polymerization, gas phase polymerization, or the like. The pre-stage polymerization may use any of batch, semi-batch, and continuous processes, and may be single-stage polymerization or multi-stage polymerization.

  In the case where the former polymerization is carried out by suspension polymerization, examples of the solvent include hydrocarbons having 20 or less carbon atoms. Examples include saturated aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane and decane, and aromatic hydrocarbons such as toluene and xylene, which are used alone or in combination of two or more. Used in combination. Normal butane, hexane, heptane and toluene are preferred, and normal butane and hexane are more preferred.

  When pre-stage polymerization is performed by a suspension polymerization method, the polymerization temperature is usually −10 to 100 ° C., preferably 0 to 70 ° C. The polymerization pressure of the former stage polymerization is usually normal pressure to 4 MPaG.

  On the other hand, when the pre-stage polymerization is performed by a fluidized bed gas phase polymerization method, polymerization conditions described later are employed.

  The pre-stage polymerization may be performed using another catalyst component such as an organoaluminum compound, an organoaluminooxy compound, or a boron compound, or may be performed by adding a chain transfer agent such as hydrogen.

  The weight average particle diameter of the solid particles for olefin polymerization is usually 20 to 2000 μm, and preferably 50 to 1000 μm. From the viewpoint of further suppressing the generation of agglomerates, the content of particles having a particle size of 30 μm or less is preferably 10% by weight or less, and the content of particles having a particle size of 50 μm or less is 10% by weight or less. It is more preferable that

  CXS of polyolefin in solid particles for olefin polymerization is obtained by the same method as α described above (method defined in § 177.1520 of Code of federal regulations, Food and Drugs Administration in the United States). After measuring the amount of the cold xylene-soluble component, it is calculated as a value where the polyolefin in the solid particles for olefin polymerization is 100% by weight. The CXS value can be determined by, for example, changing the amount of chain transfer agent such as hydrogen or the polymerization temperature in the pre-stage polymerization by changing the molecular weight or copolymer composition of the polyolefin, and the olefin used in the pre-stage polymerization. It can be prepared by a method of changing the composition.

  Solid catalyst components used for the preparation of solid particles for olefin polymerization include solid catalyst components containing titanium, magnesium and halogen (hereinafter referred to as solid catalyst component (A)); organoaluminum compounds, organoaluminum oxy compounds. , A solid catalyst component (hereinafter referred to as solid catalyst component (B)) in which a promoter component such as a boron compound or an organic zinc compound is supported on a particulate carrier; an organoaluminum compound, an organoaluminum oxy compound, a boron compound, or the like A solid catalyst component (hereinafter referred to as a solid catalyst component (C)) obtained by supporting a cocatalyst component and a metallocene compound on a particulate carrier can be used.

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.

  Examples of the solid catalyst component (A) include JP-A 63-142008, JP-A-4-227604, JP-A-5-339319, JP-A-6-179720, JP-B-7- 116252, JP-A-8-134124, JP-A-9-31119, JP-A-11-228628, JP-A-11-80234, JP-A-11-322833, and the like. Examples of the catalyst component. In the pre-stage polymerization using the solid catalyst component (A), an organoaluminum compound is usually used in combination, and an electron donating compound is used in combination as necessary.

Examples of the solid catalyst component (B) include solid catalyst components described in JP-A No. 2003-171212, that is, the following component (a), the following component (b), the following component (c), and the like. The solid catalyst component obtained by making the following component (d) contact is mentioned.
(A): Compound represented by the following general formula [1] M ¹ L ¹ _m [1]
(B): Compound represented by the following general formula [2] R ¹ _t-1 TH [2]
(C): Compound represented by the following general formula [3] R ² _t-2 TH ₂ [3]
(D): particulate carrier (in the above general formulas [1] to [3], M ¹ represents a metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table, and m represents an atom of M ¹ ) L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when a plurality of L ¹ are present, they may be the same or different from each other, R ¹ is an electron withdrawing When a plurality of R ¹ are present, they may be the same or different from each other, and R ² represents a hydrocarbon group or a halogenated hydrocarbon group. T represents each independently a non-metal atom of Group 15 or 16 of the periodic table, and t represents a number corresponding to the valence of T of each compound.)
In the pre-stage polymerization using the solid catalyst component (B), when the pre-stage polymerization is carried out by single-stage polymerization, catalyst components such as metallocene compounds and organoaluminum compounds are usually used in combination. Further, when the pre-stage polymerization is carried out by multi-stage polymerization, in the pre-stage polymerization of the multi-stage polymerization, a catalyst component such as a metallocene compound or an organoaluminum compound is usually used together. In the post-stage polymerization of the multi-stage polymerization, if necessary, the metallocene is used. Catalyst components such as system compounds and organoaluminum compounds are used in combination.

  Examples of the solid catalyst component (C) include, for example, JP-A-61-108610, JP-A-61-276805, JP-A-61-296008, JP-A-63-89505, Examples thereof include solid catalyst components described in, for example, Kaihei 3-234709. In the pre-stage polymerization using the solid catalyst component (C), catalyst components such as an organoaluminum compound and a boron compound are used in combination as necessary.

  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.

  Solid particles for olefin polymerization include solid particles for olefin polymerization obtained by pre-polymerizing a solid catalyst component prepared using a metallocene compound, and olefins obtained by pre-polymerization using a solid catalyst component and a metallocene compound. Solid particles for olefin polymerization using a metallocene compound such as solid particles for polymerization are preferred.

  In the formula (I), γ is a gas flow rate (unit: cm / second) in the gas-phase fluidized bed reactor, and the gas flow rate γ in the gas-phase fluidized bed reactor is usually 20 cm / second or more. Preferably, it is 30 cm / second or more. The upper limit of the gas flow rate is preferably 100 cm / second or less.

  In the formula (1), ε is a polymerization temperature (unit: ° C), and the polymerization temperature is usually 50 to 110 ° C, preferably 60 to 100 ° C.

  Note that χ in the present invention is an index that represents the degree of particle cohesion due to particle stickiness or static electricity in the gas-phase fluidized bed reactor, and if the value is small, the particle aggregation due to static electricity increases, and the value is Larger values indicate greater particle aggregation due to particle stickiness. More specifically, in the present invention, in the polymerization of olefin in the gas-phase fluidized bed reactor, the particles in the gas-phase fluidized bed reactor are agglomerated by aggregation due to particle adhesion and aggregation due to static electricity. In order to reduce the aggregation due to the stickiness of the particles, (1) lower the CXS or polymerization temperature of the particles in the gas-phase fluidized bed reactor (lower α, β and ε). (2) Decrease particle stickiness, (2) Increase gas flow rate in gas-phase fluidized bed reactor (increase γ), and dispersibility of particles in gas-phase fluidized bed reactor In order to reduce the aggregation caused by static electricity, the number of contact and the contact area of particles / particles, particle / reactor inner wall, etc. are reduced to suppress the generation of static electricity. (3) Increasing the CXS or polymerization temperature of the particles in the gas phase fluidized bed reactor (α , Β and ε are increased) to increase the stickiness of particles and adhere particles to each other to reduce the apparent particle surface area per unit weight, and (4) the gas flow rate in the gas phase fluidized bed reactor. It has been found that it is effective to reduce the number of contacts by lowering (lowering γ). That is, lowering α, β, ε and increasing γ is reducing χ, increasing the aggregation of particles due to static electricity, increasing α, β, ε, and lowering γ increases χ. This is to increase the aggregation due to the stickiness of the particles.

  In this production method, the polymerization pressure may be within a range in which olefin can exist as a gas phase in the fluidized bed reactor, and is usually normal pressure to 5.0 MPaG, preferably 1.5 to 3.0 MPaG. .

  The average residence time of the olefin polymer in the gas-phase fluidized bed reactor (value obtained by dividing the total weight of powder in the fluidized bed (unit: kg) by the average polymer withdrawal rate (unit: kg / hour)) is usually 1 to 20 hours, preferably 2 to 10 hours.

  The polymerization in the gas phase fluidized bed reactor may be performed using other promoters such as an organoaluminum compound or an organoaluminooxy compound in addition to the solid particles for olefin polymerization. Moreover, you may carry out in presence of additives, such as a fluidization aid and a static elimination additive, and you may carry out in presence of chain transfer agents, such as hydrogen. When using an organoaluminum compound or an organoaluminooxy compound, the amount of the compound used is usually 1 to 2000 moles per mole of transition metal in the solid particles for olefin polymerization, in terms of the aluminum atomic weight of the compound, preferably Is 5 to 1000 mol, more preferably 10 to 500 mol.

  As the gas phase fluidized bed reactor of this production method, a known reactor, for example, a reactor described in JP-A-58-201802, JP-A-59-126406, JP-A-2-233708, or the like is used. Can be used. A plurality of these gas phase fluidized bed reactors may be used. In this production method, a reactor other than the gas phase fluidized bed reactor may be used in combination with the gas phase fluidized bed reactor.

  This production method is suitable for production of a polymer having monomer units based on ethylene, so-called ethylene-based polymer, and more suitable for production of ethylene homopolymer and ethylene-α-olefin copolymer. -The α-olefin copolymer is particularly preferably used. Among the ethylene-α-olefin copolymers, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4 -Methyl-1-pentene copolymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer and ethylene-1-butene-1-octene copolymer are preferred.

The density of the ethylene polymer is usually 895 to 965 kg / m ³ , preferably 900 to 940 kg / m ³ . The density is measured by an underwater substitution method described in JIS K7112-1980 after annealing described in JIS K6760-1995.

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 The obtained olefin polymer particles were roll-kneaded at 150 ° C. for 5 minutes, and then subjected to hot press molding as a sample. The sample was annealed according to JIS K6760-1995, and then measured by an underwater displacement method described in JIS K7112-1980. The unit is kg / m ³ .
(2) Melt flow rate (MFR)
The obtained olefin polymer particles were roll kneaded at 150 ° C. for 5 minutes, and measured according to JIS K7210-1995 under conditions of a temperature of 190 ° C. and a load of 21.18N. The unit is g / 10 minutes.
(3) Amount of cold xylene soluble component (CXS)
It was measured by the method specified in § 177.1520 of Code of federal regulations, Food Drugs Administration, USA. The unit is% by weight.
(4) Evaluation of polymerization status The polymerization status of olefins in a fluidized bed reactor was evaluated as follows.
A: Almost no agglomerates were observed.
Δ: A small amount of agglomerated material was observed.
X: Many agglomerates were recognized.

[Preparation of solid catalyst components]
A solid product (hereinafter referred to as solid catalyst component (I)) was obtained in the same manner as in Example 10 (1) and (2) of JP-A No. 2003-171415.

Example 1
[Preliminary polymerization]
A solid catalyst component (I) 760 g was charged into an autoclave with a stirrer having an internal volume of 210 liters that had been purged with nitrogen in advance, and then 80 liters of butane containing triisobutylaluminum at a concentration of 3.9 mmol / liter was charged. -After charging 150 g of butene and 3 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 47 ° C. After 0.77 MPa of ethylene was charged at a gas phase pressure in the autoclave and the system was stabilized, 315 mmol of triisobutylaluminum and 105 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The polymerization temperature in the tank was raised from 47 ° C. to 48 ° C. over 0.5 hours after the start of polymerization, during which ethylene was 1.2 kg / hour and hydrogen was 9.9 liters / hour as hydrogen at normal temperature and pressure. Supplied in time. Thereafter, ethylene was fed at 4.6 kg / hour and hydrogen at normal temperature and pressure at 36.8 liter / hour, and polymerization was carried out at 48 ° C. for 1.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and the solid particles for olefin polymerization having 11.2 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component. (Hereinafter referred to as solid particles for olefin polymerization (II-1)). CXS of the obtained solid particles for olefin polymerization (II-1) was 3.2% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, olefin polymerization solid particles (II-1) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (in the tank) Pressure) 2.0 MPaG, gas flow rate in gas phase fluidized bed reactor 28 cm / sec, polymerization temperature 75.3 ° C., powder hold-up 80 kg, supply amount of solid particles (II-1) for olefin polymerization 36 g / hour, tri The supply amount of isobutylaluminum is 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization is ethylene 92.54 mol%, 1-hexene 1.23 mol%, hydrogen 0.93 mol%, nitrogen 5.3 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During the polymerization, almost no agglomerates were observed, and stable operation was continued.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 922 kg / m ³ , MFR was 1.4 g / 10 min, and CXS was 2.9 wt%. The agglomeration parameter χ of this polymerization was 252 and the average residence time was 6.9 hours.

Example 2
[Preliminary polymerization]
A solid catalyst component (I) (720 g) was charged into an autoclave with a stirrer having an internal volume of 210 liters, which had been previously purged with nitrogen, and then charged with 80 liters of butane containing triisobutylaluminum at a concentration of 2.8 mmol / liter. -After charging 10 g of butene and 4 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 49 ° C. Ethylene was charged at 0.60 MPa as the gas phase pressure in the autoclave, and 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 polymerization temperature in the tank was raised from 45 ° C. to 50 ° C. over 0.5 hours after the start of the polymerization, during which ethylene was 0.6 kg / hour and hydrogen was 3.8 liters / hour as hydrogen at normal temperature and pressure. Supplied in time. Thereafter, ethylene was fed at 1.7 kg / hour and hydrogen at normal temperature and pressure as 13.5 liter / hour, and polymerization was carried out at 50 ° C. for 5.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and solid particles for olefin polymerization having 13.0 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component. (Hereinafter referred to as solid particles for olefin polymerization (II-2)). CXS of the obtained solid particles for olefin polymerization (II-2) was 2.8% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, olefin polymerization solid particles (II-2) and triisobutylaluminum were fed into the reactor, and polymerization pressure (in the tank) Pressure) 2.0 MPaG, gas flow rate in gas phase fluidized bed reactor 28 cm / sec, polymerization temperature 75.5 ° C., powder hold-up 80 kg, supply amount of solid particles (II-2) for olefin polymerization 38 g / hr, tri The supply amount of isobutylaluminum was 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization was ethylene 91.83 mol%, 1-hexene 0.84 mol%, hydrogen 0.73 mol%, nitrogen 6.6 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During the polymerization, almost no agglomerates were observed, and stable operation was continued.
The density of the olefin polymer particles obtained by extracting from the gas phase fluidized bed reactor was 918 kg / m ³ , MFR was 0.9 g / 10 min, and CXS was 3.7 wt%. The agglomeration parameter χ of this polymerization was 264, and the average residence time was 3.7 hours.

Example 3
[Preliminary polymerization]
700 g of the solid catalyst component (I) was charged into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, and then 80 liters of butane containing triisobutylaluminum at a concentration of 4.5 mmol / liter was charged. -After charging 30 g of butene and 11 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 47 ° C. Ethylene was charged at 0.74 MPa at the gas phase pressure in the autoclave, and after the system was stabilized, 315 mmol of triisobutylaluminum and 105 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The polymerization temperature in the tank was raised from 47 ° C. to 50 ° C. over 0.5 hours after the start of the polymerization, during which ethylene was 1.0 kg / hour and hydrogen was 18.6 liters / hour as hydrogen at normal temperature and pressure. Supplied in time. Thereafter, ethylene was supplied at 2.6 kg / hour and hydrogen was supplied at 38.5 liter / hour as hydrogen at room temperature and normal pressure, and polymerization was carried out at 50 ° C. for 3.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and solid particles for olefin polymerization having 13.0 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component. (Hereinafter referred to as solid particles for olefin polymerization (II-3)). CXS of the obtained solid particles for olefin polymerization (II-3) was 5.4% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, olefin polymerization solid particles (II-3) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (in the tank) Pressure) 2.0 MPaG, gas flow rate 28 cm / sec in the gas phase fluidized bed reactor, polymerization temperature 74.9 ° C., powder hold-up 80 kg, supply amount of solid particles (II-3) for olefin polymerization 71 g / hr, tri The supply amount of isobutylaluminum was 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization was ethylene 90.10 mol%, 1-hexene 1.01 mol%, hydrogen 1.09 mol%, nitrogen 7.8 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During the polymerization, almost no agglomerates were observed, and stable operation was continued.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 928 kg / m ³ , MFR was 0.9 g / 10 min, and CXS was 3.3% by weight. The agglomeration parameter χ of this polymerization was 282, and the average residence time was 3.6 hours.

Example 4
[Preliminary polymerization]
After putting 330 g of the solid catalyst component (I) into an autoclave with a stirrer having an internal volume of 210 liters, which was previously purged with nitrogen, 80 liters of butane containing triisobutylaluminum at a concentration of 5.0 mmol / liter was charged. -After charging 300 g of butene and 6 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 32 ° C. Ethylene was charged at 0.70 MPa as the gas phase pressure in the autoclave, and after the system was stabilized, 500 mmol of triisobutylaluminum and 49 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. During 0.5 hour after the start of polymerization, ethylene was supplied at 1.2 kg / hour and hydrogen was supplied at 4.0 liter / hour as hydrogen at normal temperature and pressure. Thereafter, ethylene was fed at 2.6 kg / hour, hydrogen at 14.2 liters / hour as hydrogen at room temperature and normal pressure, and polymerization was carried out at 32 ° C. for 3.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and solid particles for olefin polymerization having 33.1 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component. (Hereinafter referred to as solid particles for olefin polymerization (II-4)). CXS of the obtained solid particles for olefin polymerization (II-4) was 6.4% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, olefin polymerization solid particles (II-4) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (in the tank) Pressure) 2.0 MPaG, gas flow rate 28 cm / second in gas phase fluidized bed reactor, polymerization temperature 75.3 ° C., powder holdup 80 kg, supply amount of solid particles (II-4) for olefin polymerization 87 g / hour, tri The supply amount of isobutylaluminum is 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization is ethylene 92.10 mol%, 1-hexene 1.21 mol%, hydrogen 0.89 mol%, nitrogen 5.8 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During the polymerization, almost no agglomerates were observed, and stable operation was continued.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 921 kg / m ³ , MFR was 1.3 g / 10 min, and CXS was 3.0 wt%. The agglomeration parameter χ of this polymerization was 288, and the average residence time was 5.0 hours.

Example 5
[Preliminary polymerization]
690 g of solid catalyst component (I) was charged into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, and then 80 liters of butane containing triisobutylaluminum at a concentration of 4.1 mmol / liter was charged. -After charging 20 g of butene and 4 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 30 ° C. Ethylene was charged at 0.70 MPa as the gas phase pressure in the autoclave, and after the system was stabilized, 329 mmol of triisobutylaluminum and 103 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The polymerization temperature in the tank was raised from 30 ° C. to 34 ° C. over 0.5 hours after the start of the polymerization, during which ethylene was 1.4 kg / hour and hydrogen was 7.5 liter / hour as hydrogen at normal temperature and normal pressure. Supplied in time. Thereafter, ethylene was fed at 3.8 kg / hour and hydrogen at normal temperature and pressure at 25.9 liters / hour, and polymerization was conducted at 34 ° C. for 3.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and 19.1 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component is used for olefin polymerization solid particles. (Hereinafter referred to as solid particles for olefin polymerization (II-5)). CXS of the obtained solid particles for olefin polymerization (II-5) was 3.3% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, olefin polymerization solid particles (II-5) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (inside the tank) Pressure) 2.0 MPaG, gas flow rate 34 cm / second in the gas phase fluidized bed reactor, polymerization temperature 85.0 ° C., powder hold-up 80 kg, supply amount of solid particles for olefin polymerization (II-5) 80 g / hour, tri The supply amount of isobutylaluminum was 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization was ethylene 89.70 mol%, 1-hexene 1.34 mol%, hydrogen 0.96 mol%, nitrogen 8.0 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During the polymerization, almost no agglomerates were observed, and stable operation was continued.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 919 kg / m ³ , MFR was 1.7 g / 10 min, and CXS was 4.3 wt%. Further, the agglomeration parameter χ of this polymerization was 298, and the average residence time was 3.5 hours.

Example 6
[Preliminary polymerization]
A solid catalyst component (I) (600 g) was charged into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, and then 80 liters of butane containing triisobutylaluminum at a concentration of 10.5 mmol / liter was charged. -After charging 120 g of butene and 5 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 28 ° C. Ethylene was charged at a gas phase pressure in the autoclave of 0.67 MPa, and after the system was stabilized, 1050 mmol of triisobutylaluminum and 90 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The polymerization temperature in the tank was raised from 28 ° C. to 30 ° C. over 0.5 hours after the start of the polymerization, during which ethylene was 1.0 kg / hour and hydrogen was 10.0 liter / hour as hydrogen at normal temperature and pressure. Supplied in time. Thereafter, ethylene was supplied at 5.3 kg / hour and hydrogen was supplied at 33.2 liter / hour as hydrogen at normal temperature and normal pressure, and polymerization was carried out at 30 ° C. for 3.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and solid particles for olefin polymerization having 34.4 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component. (Hereinafter referred to as solid particles for olefin polymerization (II-6)). CXS of the obtained solid particles for olefin polymerization (II-6) was 3.8% by weight.

[Gas phase polymerization]
Using a gas phase fluidized bed reactor having a diameter of 50 cm, ethylene, 4-methyl-1-pentene, hydrogen, nitrogen, solid particles for olefin polymerization (II-6) and triisobutylaluminum are fed into the reactor, and polymerization is performed. Pressure (inside tank pressure) 2.0 MPaG, gas flow rate in the gas-phase fluidized bed reactor 34 cm / sec, polymerization temperature 85.2 ° C., powder holdup 80 kg, supply amount 196 g of solid particles for olefin polymerization (II-6) / Hour, supply amount of triisobutylaluminum 20 mmol / hour, gas composition in the gas phase fluidized bed reactor during polymerization is 87.79 mol% ethylene, 2.31 mol% 4-methyl-1-pentene, 0.60 mol hydrogen % And nitrogen were 9.3 mol%, and ethylene and 4-methyl-1-pentene were copolymerized. During the polymerization, almost no agglomerates were observed, and stable operation was continued.
The density of the olefin polymer particles obtained by extracting from the gas phase fluidized bed reactor was 919 kg / m ³ , MFR was 1.4 g / 10 min, and CXS was 4.1 wt%. The agglomeration parameter χ of this polymerization was 300, and the average residence time was 2.4 hours.

Example 7
[Gas phase polymerization]
The polymerization temperature is 90.0 ° C., the supply amount of solid particles for olefin polymerization (II-5) is 72 g / hour, the gas composition in the gas phase fluidized bed reactor during polymerization is ethylene 88.88 mol%, 1-hexene Copolymerization of ethylene and 1-hexene was performed in accordance with the gas phase polymerization of Example 5 except that 45 mol%, hydrogen 0.67 mol%, and nitrogen 9.0 mol% were used. During the polymerization, almost no agglomerates were observed, and stable operation was continued.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 920 kg / m ³ , MFR was 1.6 g / 10 min, and CXS was 4.1 wt%. The agglomeration parameter χ of this polymerization was 307, and the average residence time was 3.5 hours.

Example 8
[Preliminary polymerization]
700 g of solid catalyst component (I) was charged into an autoclave with a stirrer having an internal volume of 210 liters, which had been purged with nitrogen in advance, and then charged with 80 liters of butane containing triisobutylaluminum at a concentration of 2.6 mmol / liter. -After charging 10 g of butene and 12 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 44 ° C. After ethylene was charged at 0.48 MPa in the gas phase pressure in the autoclave and the system was stabilized, 210 mmol of triisobutylaluminum and 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The polymerization temperature in the tank was raised from 44 ° C. to 49 ° C. over 0.5 hours after the start of polymerization, and during that time, ethylene was 0.5 kg / hour and hydrogen was hydrogen at normal temperature and normal pressure to 4.3 liters / hour. Supplied in time. Thereafter, ethylene was fed at 1.7 kg / hour and hydrogen at normal temperature and pressure at 13.9 liter / hour, and polymerization was carried out at 49 ° C. for 5.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane, and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and 11.8 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component is used for olefin polymerization solid particles. (Hereinafter referred to as solid particles for olefin polymerization (II-7)). CXS of the obtained solid particles for olefin polymerization (II-7) was 2.8% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, olefin polymerization solid particles (II-7) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (in the tank) Pressure) 2.0 MPaG, gas flow rate in the gas phase fluidized bed reactor 28 cm / sec, polymerization temperature 75.2 ° C., powder hold-up 80 kg, supply amount of solid particles (II-7) for olefin polymerization 38 g / hour, tri The supply amount of isobutylaluminum was 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization was ethylene 91.60 mol%, 1-hexene 1.36 mol%, hydrogen 0.74 mol%, nitrogen 6.3 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During the polymerization, almost no agglomerates were observed, and stable operation was continued.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 912 kg / m ³ , MFR was 1.0 g / 10 min, and CXS was 6.4 wt%. The agglomeration parameter χ of this polymerization was 316, and the average residence time was 4.0 hours.

Example 9
[Preliminary polymerization]
A solid catalyst component (I) (690 g) was charged into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, and then 80 liters of butane containing triisobutylaluminum at a concentration of 3.9 mmol / liter was charged. -After charging 120 g of butene and 1 liter of hydrogen at normal temperature and pressure, the autoclave was heated to 47 ° C. Ethylene was charged in an autoclave at a gas phase pressure of 0.72 MPa, and after the system was stabilized, 315 mmol of triisobutylaluminum and 105 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The polymerization temperature in the tank was raised from 47 ° C. to 49 ° C. over 0.5 hours after the start of the polymerization, during which time ethylene was 0.8 kg / hour and hydrogen was 3.0 liter / hour as hydrogen at normal temperature and pressure. Supplied in time. Thereafter, ethylene was fed at 4.6 kg / hour and hydrogen at normal temperature and pressure at 23.7 liter / hour, and polymerization was carried out at 49 ° C. for 1.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and 13.7 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component is used for olefin polymerization solid particles. (Hereinafter referred to as solid particles for olefin polymerization (II-8)). CXS of the obtained solid particles for olefin polymerization (II-8) was 3.1% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, olefin polymerization solid particles (II-8) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (in the tank) Pressure) 2.0 MPaG, gas flow rate in gas phase fluidized bed reactor 39 cm / sec, polymerization temperature 75.5 ° C., powder hold-up 80 kg, supply amount of solid particles (II-8) for olefin polymerization 81 g / hour, tri The supply amount of isobutylaluminum is 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization is 91.53 mol% of ethylene, 1.20 mol% of 1-hexene, 1.17 mol% of hydrogen and 6.1 mol% of nitrogen. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During polymerization, a small amount of agglomerates was observed, but stable operation was continued.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 919 kg / m ³ , MFR was 1.0 g / 10 min, and CXS was 3.5 wt%. The agglomeration parameter χ of this polymerization was 247, and the average residence time was 3.6 hours.

Example 10
[Preliminary polymerization]
A solid catalyst component (I) (690 g) was charged into an autoclave with a stirrer having an internal volume of 210 liters, which had been previously purged with nitrogen, and then charged with 80 liters of butane containing triisobutylaluminum at a concentration of 4.6 mmol / liter. -After charging 20 g of butene and 4 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 22 ° C. Ethylene was charged at a gas phase pressure in the autoclave at 0.56 MPa, and after the system was stabilized, 367 mmol of triisobutylaluminum and 105 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The polymerization temperature in the tank was raised from 22 ° C. to 28 ° C. over 0.5 hours after the start of polymerization, during which ethylene was 1.4 kg / hour and hydrogen was 7.5 liter / hour as hydrogen at normal temperature and pressure. Supplied in time. Thereafter, ethylene was supplied at 4.4 kg / hour and hydrogen at normal temperature and pressure at 37.9 liter / hour, and polymerization was carried out at 28 ° C. for 1.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and solid particles for olefin polymerization having 11.3 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component. (Hereinafter referred to as solid particles for olefin polymerization (II-9)). CXS of the obtained solid particles for olefin polymerization (II-9) was 2.6% by weight.

[Gas phase polymerization]
Using a gas phase fluidized bed reactor having a diameter of 50 cm, ethylene, 1-hexene, hydrogen, nitrogen, solid particles for olefin polymerization (II-9) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (in the tank) Pressure) 2.0 MPaG, gas flow rate in gas phase fluidized bed reactor 25 cm / sec, polymerization temperature 75.2 ° C., powder hold-up 80 kg, supply amount of solid particles (II-9) for olefin polymerization 37 g / hour, tri The supply amount of isobutylaluminum was 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization was ethylene 90.50 mol%, 1-hexene 1.65 mol%, hydrogen 0.65 mol%, nitrogen 7.2 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During polymerization, a small amount of agglomerates was observed, but stable operation was continued.
The density of the olefin polymer particles obtained by extracting from the gas phase fluidized bed reactor was 904 kg / m ³ , MFR was 0.4 g / 10 min, and CXS was 6.7 wt%. Further, the agglomeration parameter χ of this polymerization was 324, and the average residence time was 3.2 hours.

Comparative Example 1
[Gas phase polymerization]
Gas flow rate in the gas-phase fluidized bed reactor 24 cm / sec, polymerization temperature 75.2 ° C., supply amount of solid particles for olefin polymerization (II-2) 30 g / hour, gas in the gas-phase fluidized bed reactor during polymerization Except for the composition being ethylene 92.74 mol%, 1-hexene 0.48 mol%, hydrogen 0.18 mol%, and nitrogen 6.6 mol%, in accordance with the gas phase polymerization of Example 2, ethylene and 1-hexene were co-polymerized. Polymerization was performed. During polymerization, a plate-like agglomerate was generated.
The density of the olefin polymer particles obtained by extracting from the gas phase fluidized bed reactor was 926 kg / m ³ , MFR was 0.2 g / 10 min, and CXS was 0.6 wt%. The agglomeration parameter χ of this polymerization was 209, and the average residence time was 4.3 hours.

Comparative Example 2
[Gas phase polymerization]
The polymerization temperature is 84.8 ° C., the supply amount of the solid particles for olefin polymerization (II-2) is 28 g / hour, the gas composition in the gas phase fluidized bed reactor during polymerization is 92.68 mol% ethylene, 1-hexene According to the gas phase polymerization of Example 2, copolymerization of ethylene and 1-hexene was performed except that 44 mol%, hydrogen 0.08 mol%, and nitrogen 6.8 mol% were used. During polymerization, a plate-like agglomerate was generated.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 927 kg / m ³ , MFR was 0.02 g / 10 min, and CXS was 0.2 wt%. Further, the agglomeration parameter χ of this polymerization was 221 and the average residence time was 4.3 hours.

Comparative Example 3
[Gas phase polymerization]
Gas flow rate in the gas-phase fluidized bed reactor 23 cm / sec, polymerization temperature 75.7 ° C., supply amount of solid particles for olefin polymerization (II-9) 69 g / hour, gas in the gas-phase fluidized bed reactor during polymerization Except for the composition being ethylene 91.29 mol%, 1-hexene 0.35 mol%, hydrogen 0.36 mol%, and nitrogen 8.0 mol%, in accordance with the gas phase polymerization of Example 10, the copolymer of ethylene and 1-hexene was used. Polymerization was performed. During polymerization, a plate-like agglomerate was generated.
The density of the olefin polymer particles obtained by extracting from the gas phase fluidized bed reactor was 935 kg / m ³ , the MFR was 1.2 g / 10 min, and the CXS was 1.2% by weight. Further, the agglomeration parameter χ of this polymerization was 221 and the average residence time was 3.3 hours.

Comparative Example 4
[Preliminary polymerization]
A solid catalyst component (I) (680 g) was charged into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, and then 80 liters of butane containing triisobutylaluminum at a concentration of 9.2 mmol / liter was charged. -After charging 80 g of butene and 3 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 27 ° C. Ethylene was charged at 0.60 MPa as the gas phase pressure in the autoclave, and after the system was stabilized, 735 mmol of triisobutylaluminum and 105 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The polymerization temperature in the tank was raised from 27 ° C. to 29 ° C. over 0.5 hours after the start of polymerization, during which ethylene was 1.1 kg / hour and hydrogen was 4.4 liters / hour at room temperature and normal pressure. Supplied in time. Thereafter, ethylene was supplied at 4.4 kg / hour and hydrogen was supplied at 22.5 liters / hour as hydrogen at room temperature and normal pressure, and polymerization was carried out at 29 ° C. for 1.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, the resulting solid is vacuum dried at room temperature, and 12.2 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component is used for olefin polymerization solid particles. (Hereinafter referred to as solid particles for olefin polymerization (II-10)). CXS of the obtained solid particles for olefin polymerization (II-10) was 1.2% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, solid particles for olefin polymerization (II-10) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (inside the tank) Pressure) 2.0 MPaG, gas flow rate 28 cm / second in the gas phase fluidized bed reactor, polymerization temperature 75.0 ° C., powder holdup 80 kg, supply amount of solid particles (II-10) for olefin polymerization 82 g / hour, tri The supply amount of isobutylaluminum was 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization was ethylene 89.65 mol%, 1-hexene 0.58 mol%, hydrogen 1.07 mol%, nitrogen 8.7 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During polymerization, a plate-like agglomerate was generated.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 924 kg / m ³ , MFR was 2.7 g / 10 min, and CXS was 2.7 wt%. The agglomeration parameter χ of this polymerization was 226, and the average residence time was 3.8 hours.

Comparative Example 5
[Preliminary polymerization]
A solid catalyst component (I) (300 g) was charged into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, and then 80 liters of butane containing triisobutylaluminum at a concentration of 1.3 mmol / liter was charged. -After charging 10 g of butene and 12 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 45 ° C. Ethylene was charged at a gas phase pressure in the autoclave at 0.58 MPa, and after the system was stabilized, 108 mmol of triisobutylaluminum and 36 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The polymerization temperature in the tank was raised from 45 ° C. to 49 ° C. over 0.5 hours after the start of polymerization, during which ethylene was 0.4 g / hour and hydrogen was 3.3 liter / hour with hydrogen at normal temperature and pressure. Supplied in time. Thereafter, ethylene was supplied at 1.1 kg / hour and hydrogen was supplied at 9.2 liter / hour as hydrogen at room temperature and normal pressure, and polymerization was carried out at 49 ° C. for 5.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and 18.9 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component is used for olefin polymerization solid particles. (Hereinafter referred to as solid particles for olefin polymerization (II-11)). CXS of the obtained solid particles for olefin polymerization (II-11) was 2.8% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, solid particles for olefin polymerization (II-11) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (in the tank) Pressure) 2.0 MPaG, gas flow rate in the gas phase fluidized bed reactor 28 cm / sec, polymerization temperature 75.0 ° C., powder holdup 80 kg, supply amount of solid particles for olefin polymerization (II-11) 33 g / hr, tri The supply rate of isobutylaluminum is 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization is ethylene 92.23 mol%, 1-hexene 1.06 mol%, hydrogen 0.71 mol%, nitrogen 6.0 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During polymerization, a plate-like agglomerate was generated.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 921 kg / m ³ , MFR was 1.1 g / 10 min, and CXS was 2.3 wt%. In addition, the agglomeration parameter χ of this polymerization was 235, and the average residence time was 3.9 hours.

Comparative Example 6
[Preliminary polymerization]
A solid catalyst component (I) (690 g) was charged into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, and then 80 liters of butane containing triisobutylaluminum at a concentration of 3.9 mmol / liter was charged. -After charging 120 g of butene and 1 liter of hydrogen at normal temperature and pressure, the autoclave was heated to 48 ° C. Ethylene was charged at 0.73 MPa at a gas phase pressure in the autoclave, and after the system was stabilized, 315 mmol of triisobutylaluminum and 105 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The polymerization temperature in the tank was raised from 48 ° C. to 50 ° C. over 0.5 hours after the start of polymerization, and during that time, ethylene was 0.7 g / hour and hydrogen was hydrogen at room temperature and normal pressure to 3.1 liters / hour. Supplied in time. Thereafter, ethylene was supplied at 4.5 kg / hour and hydrogen was supplied at 23.7 liter / hour as hydrogen at ordinary temperature and pressure, and polymerization was carried out at 50 ° C. for 1.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the produced solid is vacuum-dried at room temperature, and 13.5 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component is used for olefin polymerization solid particles. (Hereinafter referred to as solid particles for olefin polymerization (II-12)). CXS of the obtained solid particles for olefin polymerization (II-12) was 2.3% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, solid particles for olefin polymerization (II-12) and triisobutylaluminum were fed into the reactor, and polymerization pressure (inside the tank) Pressure) 2.0 MPaG, gas flow rate 28 cm / sec in the gas phase fluidized bed reactor, polymerization temperature 75.4 ° C., powder hold-up 80 kg, supply amount of solid particles (II-12) for olefin polymerization 52 g / hour, tri The supply amount of isobutylaluminum is 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization is ethylene 90.92 mol%, 1-hexene 1.23 mol%, hydrogen 0.85 mol%, nitrogen 7.0 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During polymerization, a plate-like agglomerate was generated.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 919 kg / m ³ , MFR was 0.7 g / 10 min, and CXS was 2.6 wt%. Further, the agglomeration parameter χ of this polymerization was 237, and the average residence time was 4.2 hours.

Comparative Example 7
[Gas phase polymerization]
The polymerization temperature is 94.3 ° C., the supply amount of solid particles for olefin polymerization (II-5) is 80 g / hour, the gas composition in the gas phase fluidized bed reactor during polymerization is ethylene 89.72 mol%, 1-hexene Except for 66 mol%, hydrogen 0.92 mol%, and nitrogen 7.7 mol%, the copolymerization of ethylene and 1-hexene was performed according to the gas phase polymerization of Example 5. During the polymerization, an agglomerate in which the particles were aggregated was generated.
The density of the olefin polymer particles obtained by extracting from the gas phase fluidized bed reactor was 920 kg / m ³ , MFR was 5.7 g / 10 min, and CXS was 5.2 wt%. Further, the agglomeration parameter χ of this polymerization was 340, and the average residence time was 4.0 hours.

Comparative Example 8
[Preliminary polymerization]
A solid catalyst component (I) 250 g was charged into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, and then 80 liters of butane containing triisobutylaluminum at a concentration of 5.0 mmol / liter was charged. -After charging 300 g of butene and 7 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 31 ° C. Ethylene was charged at a gas phase pressure in the autoclave of 0.67 MPa, and after the system was stabilized, 500 mmol of triisobutylaluminum and 38 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. During 0.5 hour after the start of polymerization, ethylene was supplied at 1.5 g / hour and hydrogen was supplied at normal temperature and normal pressure at 6.9 liter / hour. Thereafter, ethylene was fed at 2.6 kg / hour and hydrogen at normal temperature and pressure at 17.9 liter / hour, and polymerization was carried out at 31 ° C. for 3.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and 41.1 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component is used for olefin polymerization solid particles. (Hereinafter referred to as solid particles for olefin polymerization (II-13)). CXS of the obtained solid particles for olefin polymerization (II-13) was 7.1% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-butene, hydrogen, nitrogen, olefin polymerization solid particles (II-13) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (in the tank) Pressure) 2.0 MPaG, gas flow rate in gas phase fluidized bed reactor 28 cm / second, polymerization temperature 84.4 ° C., powder holdup 80 kg, supply amount of solid particles for olefin polymerization (II-13) 210 g / hour, tri The supply amount of isobutylaluminum was 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization was ethylene 84.43 mol%, 1-butene 4.80 mol%, hydrogen 0.67 mol%, nitrogen 10.1 mol%. Under the conditions, copolymerization of ethylene and 1-butene was performed. During the polymerization, an agglomerate in which the particles were aggregated was generated.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 920 kg / m ³ , MFR was 1.8 g / 10 min, and CXS was 5.0 wt%. Further, the agglomeration parameter χ of this polymerization was 358, and the average residence time was 3.3 hours.

Comparative Example 9
[Preliminary polymerization]
A solid catalyst component (I) (600 g) was charged into an autoclave with a stirrer having an internal volume of 210 liters, which had been previously purged with nitrogen, and then charged with 80 liters of butane containing triisobutylaluminum at a concentration of 12.9 mmol / liter. -After charging 100 g of butene and 5 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 31 ° C. Ethylene was charged at 0.72 MPa at the gas phase pressure in the autoclave, and after the system was stabilized, 900 mmol of triisobutylaluminum and 88 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. The polymerization temperature in the tank is lowered from 31 ° C. to 30 ° C. over 0.5 hours after the start of the polymerization, during which ethylene is 1.4 kg / hour and hydrogen is 13.3 liter / hour with hydrogen at normal temperature and pressure. Supplied with. Thereafter, ethylene was fed at 2.6 kg / hour and hydrogen at normal temperature and pressure at 18.9 liter / hour, and polymerization was carried out at 30 ° C. for 3.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the resulting solid is vacuum-dried at room temperature, and 16.7 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component is used for olefin polymerization solid particles. (Hereinafter referred to as solid particles for olefin polymerization (II-14)). CXS of the obtained solid particles for olefin polymerization (II-14) was 2.3% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, olefin polymerization solid particles (II-14) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (in the tank) Pressure) 2.0 MPaG, gas flow rate in the gas phase fluidized bed reactor 37 cm / second, polymerization temperature 84.9 ° C., powder holdup 80 kg, supply amount of solid particles for olefin polymerization (II-14) 100 g / hour, tri The supply amount of isobutylaluminum is 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization is ethylene 89.41 mol%, 1-hexene 1.30 mol%, hydrogen 0.99 mol%, nitrogen 8.3 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During the polymerization, an agglomerate in which the particles were aggregated was generated.
The density of the olefin polymer particles obtained by extraction from the gas phase fluidized bed reactor was 921 kg / m ³ , MFR was 8.8 g / 10 min, and CXS was 9.3 wt%. In addition, the agglomeration parameter χ of this polymerization was 380, and the average residence time was 2.6 hours.

Comparative Example 10
[Preliminary polymerization]
After charging 730 g of the solid catalyst component (I) into an autoclave with a stirrer having an internal volume of 210 liters, which was previously purged with nitrogen, 80 liters of butane containing triisobutylaluminum at a concentration of 2.8 mmol / liter was charged. -After charging 10 g of butene and 4 liters of hydrogen at normal temperature and pressure, the autoclave was heated to 46 ° C. Ethylene was charged at 0.57 MPa at a gas phase pressure in the autoclave, and 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 polymerization temperature in the tank was raised from 46 ° C. to 50 ° C. over 0.5 hours after the start of polymerization, and during that time, ethylene was 0.5 g / hour and hydrogen was 3.9 liters / hour as hydrogen at normal temperature and pressure. Supplied in time. Thereafter, ethylene was supplied at 1.7 kg / hour and hydrogen was supplied at 18.3 liters / hour as hydrogen at room temperature and normal pressure, and polymerization was carried out at 50 ° C. for 5.5 hours to carry out pre-stage polymerization. After completion of the polymerization, ethylene, butane and hydrogen gas are purged, and the produced solid is vacuum-dried at room temperature, and 12.3 g of ethylene-1-butene copolymer per 1 g of the solid catalyst component is used for olefin polymerization solid particles. (Hereinafter referred to as solid particles for olefin polymerization (II-15)). CXS of the obtained solid particles for olefin polymerization (II-15) was 4.0% by weight.

[Gas phase polymerization]
A gas phase fluidized bed reactor having a diameter of 50 cm was used, and ethylene, 1-hexene, hydrogen, nitrogen, solid particles for olefin polymerization (II-15) and triisobutylaluminum were fed into the reactor, and the polymerization pressure (in the tank) Pressure) 2.0 MPaG, gas flow rate 28 cm / sec in the gas phase fluidized bed reactor, polymerization temperature 70.5 ° C., powder hold-up 80 kg, supply amount of solid particles for olefin polymerization (II-15) 49 g / hr, tri The supply rate of isobutylaluminum is 20 mmol / hour, and the gas composition in the gas phase fluidized bed reactor during polymerization is ethylene 91.20 mol%, 1-hexene 1.37 mol%, hydrogen 1.63 mol%, nitrogen 5.8 mol%. Under the conditions, copolymerization of ethylene and 1-hexene was performed. During the polymerization, an agglomerate in which the particles were aggregated was generated.
The density of the olefin polymer particles obtained by extracting from the gas phase fluidized bed reactor was 907 kg / m ³ , MFR was 4.6 g / 10 min, and CXS was 12.3% by weight. In addition, the agglomeration parameter χ of this polymerization was 431, and the average residence time was 3.7 hours.

Claims (1)

Solid particles for olefin polymerization using a metallocene compound whose central metal is zirconium are supplied to a gas phase fluidized bed reactor, and ethylene is homopolymerized or ethylene and α-olefin are produced in the gas phase fluidized bed reactor. A method for producing an olefin polymer to be copolymerized, wherein the agglomeration parameter χ represented by the following formula (I) satisfies the following formula (II) :
Under polymerization conditions in which the gas flow rate (γ) in the gas phase fluidized bed reactor is 20 to 100 cm / sec and the polymerization temperature (ε) is 60 to 100 ° C. , ethylene is homopolymerized or ethylene and α-olefin are mixed. A method for producing an olefin polymer to be copolymerized.
χ = 19.5 × α + 10.5 × β−1.48 × γ + 2.70 × ε (I)
240 ≦ χ ≦ 330 (II)
α: Cold xylene of olefin polymer particles withdrawn from the gas phase fluidized bed reactor
Soluble component (wt%)
β: amount of cold xylene-soluble component of solid particles for olefin polymerization (wt%)
γ: Gas flow rate in the gas-phase fluidized bed reactor (cm / sec)
ε: Polymerization temperature (° C)