JP2015124285A - Method for producing polyethylene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing polyethylene that can produce polyethylene excellent in powder properties while suppressing the adhesion of polyethylene to a reactor and the like and the production of a massive polymer.SOLUTION: The method for producing polyethylene has a polymerization step of subjecting ethylene to homopolymerization or subjecting ethylene and olefin to copolymerization using a polyolefin polymerization catalyst to produce polyethylene. The polyolefin polymerization catalyst has as constituent components [A] a silica carrier, [B] a transition metal compound component, [C] an activator and [D] a liquid component in which the silica carrier [A] has an average particle size D50 of not less than 5 μm to not more than 50 μm, a specific surface area of not less than 300 m/g to not more than 700 m/g and a pore volume of not less than 1.5 mL/g to not more than 2.0 mL/g; the transition metal compound component [B] includes (B-1) a predetermined transition metal compound; the activator [C] includes (C-1) a predetermined borate compound reacting with the transition metal compound component [B] to form a metal complex having a catalytic activity; and the liquid component [D] is synthesized by reacting [E] a predetermined organomagnesium compound and [F] a compound selected from among an amine compound, an alcohol compound and a siloxane compound.

Description

  The present invention relates to a method for producing polyethylene.

  The catalysts proposed in the prior art are often soluble in the reaction system. An olefin polymer obtained by slurry polymerization or gas phase polymerization using a catalyst that is soluble in the reaction system has extremely poor particle properties such as an indefinite particle shape, a small bulk density, and a large amount of fine powder. In addition, a part of the olefin polymer obtained adheres to the wall surface of the reactor, the stirring blade, etc., and there is a problem that it cannot be used industrially. Therefore, the process for producing an olefin polymer is usually limited to the solution polymerization method. However, when a high molecular weight polymer is produced using the solution polymerization method, there is a problem that the viscosity of the solution containing the olefin polymer is remarkably increased and the productivity is greatly reduced, which is a preferable method in terms of cost. Absent. Therefore, performing a solution polymerization method using a conventional catalyst has a big problem in industrial application.

  In addition, the amorphous polymer described above grows greatly while taking in the surrounding powder, thereby generating a block polymer. In the case of a continuous process, when such a bulk polymer is generated, the polymer extraction pipe from the polymerization reactor is blocked, so that the polymer cannot be extracted and the continuous operation is hindered. As a result, production efficiency is further reduced, and as a result, commercial scale manufacturing is difficult to implement.

  For such problems, Patent Document 1 uses a polymerization catalyst capable of polymerizing a polymer having excellent powder properties in slurry polymerization or gas phase polymerization without causing adhesion to a reactor, and the like. Olefin polymerization methods have been reported. Patent Document 2 discloses promotion of adsorption of a catalyst on a carrier using a Lewis acid-base interaction between a metallocene compound and a cocatalyst. Furthermore, Patent Document 3 reports a catalyst preparation method using a porous carrier treated with an ionic compound and a polyolefin production method.

JP 2006-273976 A JP-T-2007-519781 Special table 2011-515555 gazette Special table 2007-524721 gazette

  The disclosed contents of Patent Documents 1-3 are intended to improve the polymer powder properties and the polymerization activity by devising the catalyst adjustment method. Generation is seen.

  The present invention has been made in view of the above problems, and provides a method for producing polyethylene capable of producing polyethylene having excellent powder properties while suppressing the adhesion of polyethylene to a reactor and the like, and the formation of bulk polymer. The purpose is to provide.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be achieved by using a predetermined polyolefin polymerization catalyst, and have completed the present invention. That is, the present invention is as follows.

[1]
Using a polyolefin polymerization catalyst, having a polymerization step of homopolymerizing ethylene or copolymerizing ethylene and olefin to obtain polyethylene,
The polyolefin polymerization catalyst has a silica carrier [A], a transition metal compound component [B], an activator [C], and a liquid component [D] as constituent components,
The silica carrier [A] is, 5 [mu] m or more 50μm or less of the average particle diameter D50,300m ² / g or more 700 meters ² / g or less in specific surface area, and the volume of pores 1.5 mL / g or more 2.0 mL / g Have
The transition metal compound component [B] includes a transition metal compound (B-1) represented by the following general formula (1),
The activator [C] includes a borate compound (C-1) represented by the following general formula (2) that reacts with the transition metal compound component [B] to form a metal complex having catalytic activity,
The liquid component [D] is synthesized by reacting an organomagnesium compound [E] represented by the following general formula (3) with a compound [F] selected from amine compounds, alcohol compounds, and siloxane compounds.
A method for producing polyethylene.
(In the above general formula (1),
M ¹ represents a transition metal selected from the group consisting of titanium, zirconium, and hafnium, and has a formal oxidation number of +2, +3, or +4,
R ¹ is each independently one or more selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a composite group thereof. Represents a substituent having 20 or less non-hydrogen atoms, wherein when the substituent R is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, or a germyl group, two adjacent substituents R ¹ is bonded to each other to form a divalent group, and thus, the ring is formed by cooperating with a bond between two carbon atoms of the cyclopentadienyl ring bonded to each of the two adjacent substituents R ^1. May form,
X ¹ is each independently a halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, or 1 carbon atom. 1 or more and 20 or less selected from the group consisting of a hydrocarbyl amide group having 18 or less, a hydrocarbyl phosphide group having 1 to 18 carbons, a hydrocarbyl sulfide group having 1 to 18 carbons, and a composite group thereof. Represents a substituent having a non-hydrogen atom, wherein the two substituents X ¹ may cooperate to form a neutral conjugated diene or a divalent group having 4 to 30 carbon atoms,
Y represents —O—, —S—, —NR ² —, or —PR ² —, wherein R ² represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or 1 to 8 carbon atoms. The following hydrocarbyloxy group, silyl group, halogenated alkyl group having 1 to 8 carbon atoms, halogenated aryl group having 6 to 20 carbon atoms, or a composite group thereof,
Z represents Si (R ³ ) ₂ , C (R ³ ) ₂ , Si (R ³ ) ₂ —Si (R ³ ) ₂ , C (R ³ ) —C (R ³ ) ₂ , C (R ³ ) = C (R ³ ), C (R ³ ) ₂ —Si (R ³ ) ₂ , Si (R ³ ) ₂ —C (R ³ ) ₂ , or Ge (R ³ ) ₂ , where R ³ is Hydrogen atom, hydrocarbon group having 1 to 12 carbon atoms, hydrocarbyloxy group having 1 to 8 carbon atoms, silyl group, halogenated alkyl group having 1 to 8 carbon atoms, halogenation having 6 to 20 carbon atoms Represents an aryl group or a composite group thereof;
x is 1, 2 or 3.
[A−H] ⁺ [BQ ¹ ₄ ] ⁻ (2)
(In the above general formula (2),
[A-H] ⁺ represents a monovalent proton-donating Bronsted acid,
A represents a neutral Lewis base,
[BQ ¹ ₄ ] ⁻ represents a compatible non-coordinating anion,
B represents a boron element,
Q ¹ represents a substituted aryl group having 6 to 20 carbon atoms. )
(M ² ) _a (Mg) _b (R ⁴ ) _c (R ⁵ ) _d (3)
(In the above general formula (3),
M ² represents a metal atom belonging to Group 1, Group 2, Group 12, and Group 13 of the Periodic Table;
R ⁴ and R ⁵ represent a hydrocarbon group having 2 to 20 carbon atoms,
a, b, c, and d are real numbers that satisfy the following relationship. 0 ≦ a, 0 <b, 0 ≦ c, 0 ≦ d, c + d> 0, e × a + 2b = c + d (where e is the valence of M ² ))
[2]
The method for producing polyethylene according to [1] above, wherein the silica support [A] has an average particle diameter D50 of 9 μm or more and 41 μm or less.
[3]
The pore diameter determined by the following formula of the silica support [A] is from 120 to 210 mm.
Pore diameter = pore volume / specific surface area × 40000
The method for producing polyethylene according to [1] or [2] above.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of polyethylene which can manufacture the polyethylene excellent in powder property can be provided, suppressing the adhesion to the reactor etc. of polyethylene, and the production | generation of a block polymer.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.

[Method for producing polyethylene]
The method for producing polyethylene according to the present embodiment includes a polymerization step of obtaining polyethylene by homopolymerizing ethylene or copolymerizing ethylene and olefin using a polyolefin polymerization catalyst.

[Polyolefin polymerization catalyst]
The polyolefin polymerization catalyst used in this embodiment has a silica carrier [A], a transition metal compound component [B], an activator [C], and a liquid component [D] as constituent components. Among these, a component having a silica carrier [A], a transition metal compound component [B], and an activator [C] as constituent components is called a solid catalyst for olefin polymerization.

[Silica support [A]]
First, the silica carrier [A] will be described. Silica carrier [A] has a 5μm or 50μm or less of the average particle diameter D50,300m ² / g or more 700 meters ² / g or less in specific surface area, and 1.5 mL / g or more 2.0 mL / g volume of pores .

(Average particle size D50)
The average particle diameter D50 of the silica support [A] is 5 μm or more and 50 μm or less, preferably 9 μm or more and 41 μm or less, more preferably 9 μm or more and 30 μm or less. When the average particle diameter D50 of the silica support [A] is 5 μm or more, the silica support [A] can be further prevented from adhering to the inside of the polymerization vessel or the pipe, and the polymerization of polyethylene is more stable. Moreover, when the average particle diameter D50 of the silica support [A] is 50 μm or less, the production of a bulk polymer due to poor heat removal can be further suppressed. The average particle diameter D50 of the silica support [A] can be measured with a laser type particle size distribution measuring apparatus, and more specifically can be measured by the method described in the examples.

(Specific surface area)
The specific surface area of the silica support [A] is 300 m ² / g or more and 700 m ² / g, preferably 350 m ² / g or more and 700 m ² / g, more preferably 500 m ² / g or more and 700 m ² / g. . When the specific surface area of the silica support [A] is 300 m ² / g or more, the active sites are not dispersed and agglomerated without aggregation, and the formation of a bulk polymer due to poor heat removal can be further suppressed. Moreover, when the specific surface area of the silica support [A] is 700 m ² / g or less, the strength reduction of the silica support [A] can be suppressed, and the crushed silica support [A] can be introduced into the polymerization vessel or into the piping. Adhesion can be further suppressed, and the polymerization of polyethylene is more stable. The specific surface area of the silica support [A] is E. T.A. (Brunauer-Emmett-Teller) can be measured by a nitrogen gas adsorption method, and more specifically, can be measured by the method described in Examples.

(Pore volume)
The pore volume of the silica support [A] is 1.5 mL / g or more and 2.0 mL / g or less, preferably 1.6 mL / g or more and 2.0 mL / g or less, more preferably 1.6 mL / g. g to 1.9 mL / g. When the pore volume of the silica support [A] is 1.5 mL / g or more, the active sites do not enter the pores but aggregate on the surface of the silica support [A], and a bulk polymer is generated due to poor heat removal. This can be further suppressed. In addition, when the pore volume of the silica support [A] is 2.0 mL / g or less, the strength reduction of the silica support [A] can be suppressed, and the crushed silica support [A] is inside the polymerization vessel or in the piping. Adhesion to polyethylene can be further suppressed, and the polymerization of polyethylene becomes more stable. The pore volume of the silica support [A] E. T.A. (Brunauer-Emmett-Teller) can be measured by a nitrogen gas adsorption method, and more specifically, can be measured by the method described in Examples.

(Pore diameter)
The pore diameter of the silica support [A] is preferably from 120 to 210 mm, more preferably from 120 to 200 mm, and still more preferably from 130 to 200 mm. When the pore diameter of the silica support [A] is 120 mm or more, the active sites do not enter into the pores and the surface of the silica support [A] is agglomerated and the formation of a bulk polymer due to poor heat removal is further suppressed. It tends to be possible. In addition, since the pore diameter of the silica support [A] is 210 mm or less, the strength reduction of the silica support [A] can be suppressed, and the crushed silica support [A] can be adhered to the inside of the polymerization vessel or piping. It can suppress more and it exists in the tendency for the superposition | polymerization of polyethylene to become more stable. The pore diameter of the silica support [A] can be determined by the following formula based on the pore volume and specific surface area.
Pore diameter = pore volume / specific surface area × 40000

  The silica support [A] is preferably capable of adsorbing a Lewis acidic compound. The silica support [A] capable of adsorbing the Lewis acidic compound is that the Lewis acidic compound is adsorbed on the surface of the silica support [A] by physical adsorption or chemical adsorption when treated with the Lewis acidic compound. It is a simple silica support. By using such a silica carrier [A], the dispersibility in a solvent during catalyst preparation tends to be further improved.

  Note that the Lewis acidic compound in the present embodiment refers to an organometallic compound containing a metal element belonging to the group consisting of Groups 2 to 13 of the periodic table. Although it does not specifically limit as a Lewis acidic compound, For example, an organoaluminum compound or an organomagnesium compound is preferable.

(Organic aluminum compound)
Among the preferable organoaluminum compounds, a compound represented by the following general formula (4) is more preferable.
Al (R ⁶ ) _v (X ² ) _(3-v) (4)
(In General Formula (4), each R ⁶ independently represents a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms, X ² each independently represents a halide, hydride, or an alkoxide group having 1 to 10 carbon atoms, and v is a real number having 1 to 3).

The group R ⁶ in the general formula (4) is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, and a tolyl group. .

The group X ² in the general formula (4) is not particularly limited, for example, a methoxy group, an ethoxy group, a butoxy group, a hydrogen atom, a chlorine atom.

  Although it does not specifically limit as an organoaluminum compound represented by the said General formula (4), For example, Trialkylaluminum compounds, such as a trimethylaluminum, a triethylaluminum, a tributylaluminum, a trihexylaluminum, a trioctylaluminum, a tridecylaluminum; And reaction products of these trialkylaluminum compounds and alcohols. Here, although it does not specifically limit as alcohol, For example, methanol, ethanol, 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, 1-decanol is mentioned.

  The reaction product of the trialkylaluminum compound and alcohol is not particularly limited, and examples thereof include methoxydimethylaluminum, ethoxydiethylaluminum, and butoxydibutylaluminum. In the case of producing such a reaction product, the molar ratio of trialkylaluminum to alcohol is preferably 0.3 or more and 20 or less, more preferably 0.5 or more and 5 or less, and further preferably 0.8 or more and 3 or less. In addition, these organoaluminum compounds may be used alone, or two or more kinds of organoaluminum compounds may be mixed and used.

(Organic magnesium compound)
Among the above preferred organomagnesium compounds, compounds represented by the following general formula (5) are more preferred.
Mg (R ⁷ ) w (X ³ ) _(2-w) (5)
(In General Formula (5), each R ⁷ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and ³ each independently represents a halide, hydride or an alkoxy group having 1 to 10 carbon atoms, and w is a real number having 1 to 2).

The group R ⁷ in the general formula (5) is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, and a tolyl group. It is done.

X ³ in the general formula (5) is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a butoxy group, a hydroxy group, and a chloro group.

  Specific examples of the organic magnesium compound represented by the general formula (5) are not particularly limited, and examples thereof include diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, and butyl octyl magnesium. These organomagnesium compounds may be used alone or in combination of two or more kinds of organomagnesium compounds.

  In addition, the organoaluminum compound and the organomagnesium compound represented by the general formula (4) and the general formula (5) may be used in combination.

(Method for producing silica support [A])
The silica support [A] capable of adsorbing the Lewis acidic compound used in the present embodiment is produced from a silica product (hereinafter also referred to as “precursor of support [A]”) by the method described below. Is possible.
1) First, water (crystal water, adsorbed water, etc.) present on the surface is removed by heat-treating the precursor of the silica support [A].
2) Thereafter, the saturated adsorption amount of the Lewis acidic compound adsorbed on the precursor of the silica support [A] is quantified.
3) Finally, an amount of Lewis acidic compound smaller than the saturated adsorption amount is adsorbed on the precursor of the silica support [A].

  “Saturated adsorption amount of Lewis acidic compound” refers to the amount of surface hydroxyl group (mmol / g) of the precursor of the silica support [A] under stirring in the hexane slurry of the precursor of the silica support [A] after the heat treatment. Calculated based on the molar amount of Lewis acidic compound in the supernatant of the slurry after adding and reacting 1.4 mol times the Lewis acidic compound with respect to the total molar amount of surface hydroxyl groups contained in the slurry. It is the calculated amount of adsorption. The amount of surface hydroxyl group (mmol / g) of the precursor of the silica support [A] is determined by reacting ethoxydiethylaluminum with the surface hydroxyl group of the precursor of the silica support [A] to generate ethane gas, and quantifying the amount of ethane gas generated. This can be calculated.

  Before quantifying the saturated adsorption amount of the Lewis acidic compound or adsorbing the Lewis acidic compound in an amount less than the saturated adsorption amount, water (crystal water) present on the surface of the precursor of the silica support [A] by heat treatment is used. It is preferable to remove adsorbed water and the like. The heating temperature is preferably 150 ° C. or higher and 1,000 ° C. or lower, more preferably 250 ° C. or higher and 800 ° C. or lower. The heating time is preferably 1 hour or more and 50 hours or less. Furthermore, the atmosphere of the heat treatment is preferably an inert atmosphere or a non-reducing atmosphere. Here, “under a non-reducing atmosphere” means an oxygen atmosphere or an air atmosphere that substantially does not contain moisture, and an air atmosphere that is sufficiently dried by circulating in a desiccant such as molecular sieves. Below is preferred. In this non-reducing atmosphere, an inert gas such as nitrogen or argon may coexist. In addition, when the saturated adsorption amount of the Lewis acidic compound as a precursor of the silica support [A] becomes 0.01 mmol / g or more and 0.4 mmol / g or less by this heat treatment, the Lewis acidic compound is adsorbed. The precursor of the silica support [A] can be used as the silica support [A].

  The shape of the silica product used as the precursor of the silica support [A] is not particularly limited, and may be any shape such as a granular shape, a spherical shape, an agglomerated shape, and a fume shape. Although it does not specifically limit as a commercial item of the precursor of a silica support | carrier [A], For example, SD3216.30, SP-9-633, Devison 948, or Devison 952 [all or more, Grace Devison (WR Devison, Inc.) (US branch office)], ES70W [PQ Corporation (USA)], P6 [Fuji Silysia (Japan)], L123, M202 [AGC S-Tech (Japan)] and the like. .

(Adsorption amount of Lewis acidic compounds)
The amount of Lewis acidic compound adsorbed on the silica support [A] is preferably 0.01 mmol / g or more and 0.4 mmol / g or less, more preferably 0.02 mmol / g or more and 0.35 mmol / g or less, Preferably they are 0.03 mmol / g or more and 0.3 mmol / g or less. When the amount of the Lewis acidic compound adsorbed on the silica support [A] is 0.01 mmol / g or more, it is possible to further suppress the elution of the transition metal compound component [B] and the activator [C] from the catalyst. Thus, the catalyst preparation step and the catalyst washing step before using the catalyst can be omitted. Moreover, it exists in the tendency which can suppress a fall of catalyst activity more because the adsorption amount of the Lewis acidic compound of a silica support [A] is 0.4 mmol / g or less.

(Saturated adsorption amount of Lewis acidic compound to precursor of silica support [A])
In this embodiment, the saturated adsorption amount of the Lewis acidic compound with respect to the precursor of the silica support [A] is preferably 0.01 mmol / g or more and 5.0 mmol / g or less, more preferably 0.01 mmol / g or more. It is 4.0 mmol / g or less, More preferably, it is 0.01 mmol / g or more and 3.0 mmol / g or less. When the saturated adsorption amount of the Lewis acidic compound is 0.01 mmol / g or more, it is possible to further suppress the elution of the transition metal compound component [B] and the activator [C]. The previous catalyst washing step can be omitted. In addition, when the saturated adsorption amount of the Lewis acidic compound is 5 mmol / g or less, the catalyst activity tends to be further suppressed. The saturated adsorption amount of the Lewis acidic compound with respect to the precursor of the silica carrier [A] can be controlled by the heat treatment conditions of the precursor of the silica carrier [A] described above.

[Transition metal compound component [B]]
Next, the transition metal compound component [B] will be described. Transition metal compound component [B] contains the transition metal compound (B-1) represented by General formula (1).
(In the above general formula (1),
M ¹ represents a transition metal selected from the group consisting of titanium, zirconium, and hafnium, and has a formal oxidation number of +2, +3, or +4,
R ¹ is each independently one or more selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a composite group thereof. Represents a substituent having 20 or less non-hydrogen atoms, wherein when the substituent R is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, or a germyl group, two adjacent substituents R ¹ is bonded to each other to form a divalent group, and thus, the ring is formed by cooperating with a bond between two carbon atoms of the cyclopentadienyl ring bonded to each of the two adjacent substituents R ^1. May form,
X ¹ is each independently a halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, or 1 carbon atom. 1 or more and 20 or less selected from the group consisting of a hydrocarbyl amide group having 18 or less, a hydrocarbyl phosphide group having 1 to 18 carbons, a hydrocarbyl sulfide group having 1 to 18 carbons, and a composite group thereof. Represents a substituent having a non-hydrogen atom, wherein the two substituents X ¹ may cooperate to form a neutral conjugated diene or a divalent group having 4 to 30 carbon atoms,
Y represents —O—, —S—, —NR ² —, or —PR ² —, wherein R ² represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or 1 to 8 carbon atoms. The following hydrocarbyloxy group, silyl group, halogenated alkyl group having 1 to 8 carbon atoms, halogenated aryl group having 6 to 20 carbon atoms, or a composite group thereof,
Z represents Si (R ³ ) ₂ , C (R ³ ) ₂ , Si (R ³ ) ₂ —Si (R ³ ) ₂ , C (R ³ ) —C (R ³ ) ₂ , C (R ³ ) = C (R ³ ), C (R ³ ) ₂ —Si (R ³ ) ₂ , Si (R ³ ) ₂ —C (R ³ ) ₂ , or Ge (R ³ ) ₂ , where R ³ is Hydrogen atom, hydrocarbon group having 1 to 12 carbon atoms, hydrocarbyloxy group having 1 to 8 carbon atoms, silyl group, halogenated alkyl group having 1 to 8 carbon atoms, halogenation having 6 to 20 carbon atoms Represents an aryl group or a composite group thereof;
x is 1, 2 or 3.

  The transition metal compound (B-1) is not particularly limited. For example, [(Nt-butylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [(N -T-Butylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-methylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-phenyl Amido) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-benzylamido) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium dimethyl, [(Nt-butylamide) ) (Η5-cyclopentadienyl) -1,2-ethanediyl Titanium dimethyl, [(N-t-butylamide) (η5-cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-methylamido) (η5-cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, (N-methylamido) (η5-cyclopentadienyl) dimethylsilane] titanium dimethyl, [(Nt-butylamido) (η5-indenyl) dimethylsilane] titanium dimethyl, and [(N-benzylamido) (η5-indenyl) ) Dimethylsilane] titanium dimethyl and the like.

Further, as a further specific example of the transition metal compound (B-1), a part of “dimethyl” in the names of the zirconium and titanium compounds listed above as specific examples of the transition metal compound (B-1) , The last part of the name of each compound, that is, the part appearing immediately after the part of “zirconium” or “titanium”, and the name corresponding to the part of X ^{1 in} the general formula (1)), A compound having a name formed by replacing a functional group other than dimethyl may also be mentioned.

  The functional group other than dimethyl is not particularly limited. For example, “1,3-pentadiene”, “dibenzyl”, “2- (N, N-dimethylamino) benzyl”, “2-butene-1,4- “Diyl”, “s-trans-η4-1,4-diphenyl-1,3-butadiene”, “s-trans-η4-3-methyl-1,3-pentadiene”, “s-trans-η4-1, 4-dibenzyl-1,3-butadiene ”,“ s-trans-η4-2,4-hexadiene ”,“ s-trans-η4-1,3-pentadiene ”,“ s-trans-η4-1,4- “Ditolyl-1,3-butadiene”, “s-trans-η4-1,4-bis (trimethylsilyl) -1,3-butadiene”, “s-cis-η4-1,4-diphenyl-1,3-butadiene” ”,“ S-cis-η4- -Methyl-1,3-pentadiene "," s-cis-η4-1,4-dibenzyl-1,3-butadiene "," s-cis-η4-2,4-hexadiene "," s-cis-η4 " -1,3-pentadiene "," s-cis-η4-1,4-ditolyl-1,3-butadiene "," s-cis-η4-1,4-bis (trimethylsilyl) -1,3-butadiene " , Etc.

  Of these, [(Nt-butylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene is preferable as the transition metal compound (B-1).

  These transition metal compounds (B-1) may be used alone or in combination of two or more.

  In the present embodiment, it is preferable that the transition metal compound (B-1) is used as a mixture with an organomagnesium compound (B-2) soluble in a hydrocarbon solvent.

Although it does not specifically limit as an organomagnesium compound (B-2) used in this embodiment, For example, what is represented by following General formula (6) is mentioned.
(M ³ ) _p (Mg) _q (R ⁸ ) _r (R ⁹ ) _s (OR ¹⁰ ) _t (6)
(In General Formula (6), M ³ is each independently a metal atom belonging to the group consisting of Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 2 to 20 carbon atoms, and p, q, r, s, and t are numbers satisfying the following relationship: 0 ≦ p, 0 <Q, 0 ≦ r, 0 ≦ s, 0 ≦ t, r + s> 0, 0 ≦ t / (r + s) ≦ 2, p × u + 2q = r + s + t (where u is the valence of M ³ ) )

The organomagnesium compound (B-2) is shown as a complex form of organomagnesium soluble in a hydrocarbon solvent, but all of (R ⁸ ) ₂ Mg and complexes of these with other metal compounds It is included. The relational expression p × u + 2q = r + s + t of the symbols p, q, r, s, and t represents the stoichiometry between the valence of the metal atom and the substituent.

In the general formula (6), the hydrocarbon group represented by R ⁸ and R ⁹ is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group. Such a hydrocarbon group is not particularly limited, and examples thereof include an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, a 1-methylpropyl group, a 1,1-dimethylethyl group, a pentyl group, and a hexyl group. Group, 2-methylpentyl group, 2-ethylbutyl group, 2-ethylpentyl group, 2-ethylhexyl group, 2-ethyl-4-methylpentyl group, 2-propylheptyl group, 2-ethyl-5-methyloctyl group, Examples include octyl group, nonyl group, decyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, phenyl group, and tolyl group. Of these, an alkyl group is preferable, and a primary alkyl group is particularly preferable.

In the general formula (6), when 0 <p, the metal atom M ³ includes a metal element belonging to the group consisting of Group 1, Group 2, Group 12, and Group 13 of the Periodic Table. Such M ³ is not particularly limited, and examples thereof include lithium, sodium, potassium, beryllium, zinc, boron, and aluminum. Of these, aluminum, boron, beryllium, and zinc are particularly preferable. In the present embodiment, the molar ratio q / p of magnesium to the metal atom M ³ is preferably 0.1 or more and 30 or less, more preferably 0.5 or more and 10 or less.

In the general formula (6), when p = 0, an organomagnesium compound that is soluble in a hydrocarbon solvent is preferable, and R ⁸ and R ⁹ are represented by the following three groups (1), (2), (3 More preferably, it belongs to any one of (1).
Group (1) At least one of R ⁸ and R ⁹ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably both R ⁸ and R ⁹ have 4 to 6 carbon atoms. Yes, at least one of which is a secondary or tertiary alkyl group.
Group (2) R ⁸ and R ⁹ are alkyl groups having different carbon numbers, preferably R ⁸ is an alkyl group having 2 or 3 carbon atoms, and R ⁹ is an alkyl group having 4 to 20 carbon atoms. Be a group.
It group (3) at least one of R ⁸ and R ⁹ is a hydrocarbon group having 6 to 20 carbon atoms, preferably that R ⁸ and R ⁹ are both alkyl groups having 6 to 20 carbon atoms.

Next, R ⁸ and R ⁹ are specifically shown.
In the group (1), examples of the secondary or tertiary alkyl group having 4 to 6 carbon atoms include 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, 2-methylbutyl group, 2-ethylpropyl group, 2,2-dimethylpropyl group, 2-methylpentyl group, 2-ethylbutyl group, 2,2-dimethylbutyl group, 2-methyl-2-ethylpropyl group and the like are used, and 2-methyl A pentyl group is particularly preferred.
In group (2), examples of the alkyl group having 2 or 3 carbon atoms include an ethyl group and a propyl group, and an ethyl group is particularly preferable. Examples of the alkyl group having 4 to 20 carbon atoms include a butyl group, an amyl group, a hexyl group, and an octyl group, and a butyl group and a hexyl group are particularly preferable.
In the group (3), examples of the alkyl group having 6 to 20 carbon atoms include a hexyl group, an octyl group, a decyl group, a phenyl group, an alkyl group is preferable, and a hexyl group is particularly preferable.

  In general, increasing the number of carbon atoms in the alkyl group facilitates dissolution in a hydrocarbon solvent, but the viscosity of the solution tends to increase, and it is preferable in terms of handling to use a long-chain alkyl group having an appropriate length. The organomagnesium compound is used by being dissolved in a hydrocarbon solution, but the solution may contain a slight amount of a complexing agent such as ether, ester or amine, or may be used even if it remains. Can do.

Next, the alkoxy group (OR ¹⁰ ) of the above formula (6) will be described. The hydrocarbon group represented by R ¹⁰ is preferably an alkyl group or aryl group having 3 to 10 carbon atoms. Examples of such R ¹⁰ include, but are not limited to, propyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, hexyl group, 2-methyl group. Pentyl group, 2-ethylbutyl group, 2-ethylpentyl group, 2-ethylhexyl group, 2-ethyl-4-methylpentyl group, 2-propylheptyl group, 2-ethyl-5-methyloctyl group, n-octyl group, An n-decyl group, a phenyl group, etc. are mentioned, A butyl group, 1-methylpropyl, 2-methylpentyl group, and 2-ethylhexyl group are preferable.

These organomagnesium compounds (organomagnesium complexes) are organic magnesium compounds represented by the following general formula (7) or general formula (8) and organic compounds represented by the following general formula (9) or general formula (10). Reaction with a metal compound in an inert hydrocarbon medium such as hexane, heptane, cyclohexane, benzene, toluene, etc. in the range of 10 ° C. or higher and 150 ° C. or lower, followed by hydrocarbon represented by R ¹⁰ when necessary. It can be synthesized by a method of reacting with a hydrocarbyloxymagnesium compound having a hydrocarbon group represented by R ¹⁰ and / or a hydrocarbyloxyaluminum compound soluble in an alcohol having a group or a hydrocarbon solvent.
R ⁸ MgX ⁴ , (7)
(In general formula (7), R ⁸ is as defined in general formula (6) above, and X ⁴ is halogen.)
(R ⁸ ) ₂ Mg (8)
(In General Formula (8), R ⁸ is as defined in General Formula (6) above.)
M ³ (R ⁹ ) _u (9)
(In the general formula (9), M ³ , R ⁹ and u are as defined in the general formula (6).)
M ³ (R ⁹ ) _(u-1) H (10)
(In the general formula (10), M ³ , R ⁹ and u are as defined in the general formula (6).)

  When the organic magnesium component soluble in hydrocarbon and the alcohol are reacted, the order of the reaction is not particularly limited, a method of adding the alcohol to the organic magnesium component, a method of adding the organic magnesium component to the alcohol, or Any method of adding both at the same time is preferred. In the present embodiment, the reaction ratio between the organic magnesium component soluble in hydrocarbon and the alcohol is not particularly limited, but as a result of the reaction, the molar composition ratio of alkoxy groups to all metal atoms in the resulting alkoxy group-containing organomagnesium component. The range of t / (p + q) is preferably 0 ≦ t / (p + q) ≦ 2, and more preferably 0 ≦ t / (p + q) <1.

  The method of mixing the transition metal compound (B-1) and the organomagnesium compound (B-2) is not particularly limited, and the method of adding the organomagnesium compound (B-2) to the transition metal compound (B-1). Alternatively, a method of adding the transition metal compound (B-1) to the organomagnesium compound (B-2) or a method of adding both at the same time, and any of these methods are preferred.

  The molar ratio of the organomagnesium compound (B-2) / transition metal compound (B-1) is not particularly limited, but is preferably 0.005 or more and 5 or less, and more preferably 0.01 or more and 2 or less. preferable. There is a problem that the organic magnesium compound (B-2) may be deficient in activity due to the organomagnesium compound (B-2) / transition metal compound (B-1) molar ratio being 0.005 or more. Is preferably 5 or less, the organomagnesium compound (B-2) is excessive, and the transition metal compound component [B] and the activator [C] are eluted. This is preferable in order to avoid the problem that a catalyst washing step may be required before using the catalyst.

The content of the transition metal compound (B-1) is preferably used in an amount of 5.0 × 10 ⁻⁶ mol or more and 1.0 × 10 ⁻² mol or less with respect to 1 g of the silica support [A]. More preferably, it is used in an amount of 1.0 × 10 ⁻⁵ mol or more and 1.0 × 10 ⁻³ mol or less. When the content of the transition metal compound (B-1) is 5 × 10 ⁻⁶ mol or more, the activity per 1 g of the polyolefin polymerization catalyst tends to be further improved. Moreover, it can suppress that a transition metal compound (B-1) elutes from a polyolefin polymerization catalyst because content of a transition metal compound (B-1) is 10 ^<-2> mol or less, and a catalyst preparation process or catalyst use The previous catalyst washing step can be omitted.

[Activator [C]]
Next, the activator [C] will be described. The activator [C] includes a borate compound (C-1) represented by the following general formula (2) that reacts with the transition metal compound component [B] to form a metal complex having catalytic activity.
[A−H] ⁺ [BQ ¹ ₄ ] ⁻ (2)
(In general formula (2),
[A-H] ⁺ represents a monovalent proton-donating Bronsted acid,
A represents a neutral Lewis base,
[BQ ¹ ₄ ] ⁻ represents a compatible non-coordinating anion,
B represents a boron element,
Q ¹ represents a substituted aryl group having 6 to 20 carbon atoms. )

In the general formula (2), the compatible non-coordinating anion represented by [BQ ¹ ₄ ] ⁻ is not particularly limited, and examples thereof include tetrakisphenyl borate, tri (p-tolyl) (phenyl) borate, Tris (pentafluorophenyl) (phenyl) borate, tris (2,4-dimethylphenyl) (hydrphenyl) borate, tris (3,5-dimethylphenyl) (phenyl) borate, tris (3,5-di-trifluoromethyl) Phenyl) (phenyl) borate, tris (pentafluorophenyl) (cyclohexyl) borate, tris (pentafluorophenyl) (naphthyl) borate, tetrakis (pentafluorophenyl) borate, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxy) Phenyl) borate, tri Phenyl (2,4-dihydroxyphenyl) borate, tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, Tris (3,5-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-di-trifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris ( Pentafluorophenyl) (4-hydroxybutyl) borate, tris (pentafluorophenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4′-hydroxyphenyl) phenyl) borate , Tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate, and tris (pentafluorophenyl) (4-hydroxyphenyl) borate. Of these, tris (pentafluorophenyl) (4-hydroxyphenyl) borate is preferable.

In the general formula (2), the monovalent proton-providing Bronsted acid represented by [AH] ⁺ is not particularly limited, and examples thereof include bis (hydrogenated tallow alkyl) methylammonium and triethyl. Trialkyl group-substituted ammonium cations such as ammonium, tripropylammonium, tributylammonium, trimethylammonium, tributylammonium and trioctylammonium; N, N-dimethylanilinium, N, N-diethylanilinium, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium, N, N-dimethylbenzylanilinium and the like; dialkylammonium such as bis- (1-methylethyl) ammonium, dicyclohexylammonium and the like Kachio Triarylphosphonium cations such as triphenylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium and the like; and dimethylsulfonium, diethylfuronium, diphenylsulfone Ni and the like can be mentioned.

  These borate compounds (C-1) may be used alone or in combination of two or more.

  Moreover, it is preferable to mix and use a borate compound (C-1) and an organoaluminum compound (C-2). The organoaluminum compound (C-2) is not particularly limited, and examples thereof include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; Reaction products of an aluminum compound and alcohols such as methanol, ethanol, 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, 1-decanol and the like can be mentioned. Here, the reaction product is not particularly limited, but for example, dimethylmethoxyaluminum, diethylethoxyaluminum, and dibutylbutoxyaluminum are also preferable. Al / OH is preferably 0.3 to 20, more preferably 0.5 to 5, and still more preferably 0.8 to 3 as the molar ratio of the alkylaluminum to the alcohols in producing the reaction product.

  In the present invention, the amount of the organoaluminum compound (C-2) used is preferably 0.01 to 1000 mol times, preferably 0.1 to 100 mol times the amount of the borate compound (C-1) used. More preferred is 0.5 to 10 mole times.

  The reaction method of the borate compound (C-1) and the organoaluminum compound (C-2) is not particularly limited, and is inert such as aliphatic hydrocarbons such as hexane and heptane, and aromatic hydrocarbons such as benzene and toluene. The reaction can be carried out in a reaction medium between room temperature and 150 ° C. The order of the reaction is not particularly limited, and the method of adding the organoaluminum compound (C-2) to the borate compound (C-1), the borate compound (C-1) being added to the organoaluminum compound (C-2) Any of the method of adding or adding both at the same time can be used.

[Method for producing solid catalyst for olefin polymerization]
Next, a method for producing a solid catalyst for olefin polymerization from the silica support [A], the transition metal compound component [B], and the activator [C] will be described.

  In the presence of the silica support [A], the transition metal compound component [B] and the activator [C] are added simultaneously to produce a solid catalyst for olefin polymerization. More specifically, an inert reaction solvent is added to a reactor sufficiently purged with nitrogen, and silica support [A] is added thereto to form a slurry, thereby obtaining a slurry. A polyolefin polymerization catalyst is produced by adding the transition metal compound component [B] and the activator [C] to the resulting slurry separately and simultaneously into the reactor. As a result, an equal amount of the transition metal compound component [B] and the activator [C] react and are supported on the silica support [A].

  The inert reaction solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene. Among these, linear or branched hydrocarbon compounds such as isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, and kerosene are preferable.

  “To add transition metal compound component [B] and activator [C] simultaneously” means that the time difference between the start time of addition of transition metal compound component [B] and the start time of addition of activator [C], And the time difference between the addition end time of the transition metal compound component [B] and the addition end time of the activator [C] averages both addition times of the transition metal compound component [B] and the activator [C]. The average value is within 10%. The time difference between the addition start time and the addition end time is preferably within 5% with respect to the average value of both addition times of the transition metal compound component [B] and the activator [C], preferably within 3%. More preferably, the addition of both is most preferably initiated or terminated simultaneously. The time difference between the addition start time of the transition metal compound component [B] and the addition start time of the activator [C], and the addition end time of the transition metal compound component [B] and the addition end time of the activator [C] Of the transition metal compound component [B] and the activation agent [C] is within 10% of the average value of both addition times of the transition metal compound component [B], The adhesion of the reaction product of the agent [C] or the transition metal compound component [B] and the activator [C] can be prevented, and the generation of coarse particles due to the aggregation of the solid catalyst for olefin polymerization tends to be suppressed. It is in. In addition, when the transition metal compound component [B] or the activator [C] is present alone in the reactor, the single component adheres to the reactor wall, whereby the solid catalyst component for olefin polymerization is converted into the reactor. It is thought to adhere to the wall.

Content of the transition metal compound component [B], to the silica carrier [A] 1 g, preferably from 5 × ¹⁰ -6 ~1.0 × ^{10 -2} mol, more preferably 1.0 × 10 ^{- 5 to} 1.0 × 10 ⁻³ mol.

[Liquid component [D]]
Next, the liquid component [D] will be described. The liquid component [D] is synthesized by reacting an organomagnesium compound [E] represented by the following general formula (3) with a compound [F] selected from amine compounds, alcohol compounds, and siloxane compounds. is there. Although it does not specifically limit as liquid component [D], For example, it is preferable that it is the hydrocarbon solution which melt | dissolved the organic magnesium compound soluble in a hydrocarbon solvent.
(M ² ) _a (Mg) _b (R ⁴ ) _c (R ⁵ ) _d (3)
(In the above general formula (3),
M ² represents a metal atom belonging to Group 1, Group 2, Group 12, and Group 13 of the Periodic Table;
R ⁴ and R ⁵ represent a hydrocarbon group having 2 to 20 carbon atoms,
a, b, c, and d are real numbers that satisfy the following relationship. 0 ≦ a, 0 <b, 0 ≦ c, 0 ≦ d, c + d> 0, e × a + 2b = c + d (where e is the valence of M ² ))

  The reaction between the organomagnesium compound [E] and the compound [F] is not particularly limited, but in an inert reaction medium such as aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, etc. It is preferable to carry out by reacting between 150 degreeC. Further, the order of the reaction is not particularly limited, but the method of adding the compound [F] to the organomagnesium compound [E], the method of adding the organomagnesium compound [E] to the compound [F], or both simultaneously Any method of adding is preferred. Furthermore, the reaction ratio between the organomagnesium compound [E] and the compound [F] is not particularly limited, but the molar ratio of the compound [F] to all metal atoms contained in the liquid component [D] synthesized by the reaction is It is preferable that it is 0.01-2, and it is further more preferable that it is 0.1-1.

  The liquid component [D] may be used alone or in combination of two or more.

  The liquid component [D] can be used as an impurity scavenger. Since the liquid component [D] hardly reduces the polymerization activity even at a high concentration, the liquid component [D] can exhibit a high polymerization activity in a wide concentration range. For this reason, the polymerization activity of the polyolefin polymerization catalyst containing the liquid component [D] can be easily controlled.

  The molar concentration of all metal atoms contained in the liquid component [D] when used for polymerization is preferably 0.001 mmol / L or more and 10 mmol / L or less, more preferably 0.01 mmol / L or more and 5 mmol / L or less. It is. When the molar concentration of all metal atoms contained in the liquid component [D] is 0.001 mmol / L or more, the effect of impurities as a scavenger tends to be further improved. Further, when the molar concentration of all metal atoms contained in the liquid component [D] is 10 mmol / L or less, the polymerization activity tends to be further improved.

[Organic magnesium compound [E]]
Next, the organomagnesium compound [E] will be described. The organomagnesium compound [E] is represented by the general formula (3). In the above general formula (3), it is shown as a form of a complex compound of organomagnesium soluble in a hydrocarbon solvent, but all of (R ³ ) ₂ Mg and complexes of these with other metal compounds are included. It is included. The relational expression e × a + 2b = c + d of the symbols a, b, c, and d indicates the stoichiometry between the valence of the metal atom and the substituent.

In the general formula (3), the hydrocarbon group represented by R ⁴ and R ⁵ is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group. Such a hydrocarbon group is not particularly limited, and for example, methyl group, ethyl group, propyl group, 1-methylethyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1- Examples include dimethylethyl group, pentyl group, hexyl group, octyl group, decyl group, phenyl group, and tolyl group. Among these, an alkyl group is preferable, and a primary alkyl group is more preferable.

In the general formula (3), when a> 0, the metal atom M ² is not particularly limited, and examples thereof include lithium, sodium, potassium, beryllium, zinc, boron, and aluminum. Of these, aluminum, boron, beryllium, and zinc are particularly preferable. The molar ratio b / a of magnesium to the metal atom M ² is not particularly limited, but is preferably 0.1 or more and 50 or less, and more preferably 0.5 or more and 10 or less.

In the general formula (3), when a = 0, the organomagnesium compound [E] is preferably an organomagnesium compound soluble in a hydrocarbon solvent, and R ^{4 in the} above formula (3) and More preferably, R ⁵ is any one of the following three groups (1), (2), and (3).
Group (1) At least one of R ⁴ and R ⁵ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably R ⁴ and R ⁵ are both 4 to 6 carbon atoms, One is a secondary or tertiary alkyl group.
Group (2) R ⁴ and R ⁵ are alkyl groups having different carbon numbers, preferably R ⁴ is an alkyl group having 2 or 3 carbon atoms, and R ⁵ is an alkyl group having 4 or more carbon atoms. about.
Group (3) at least one of R ⁴ and R ⁵ is a hydrocarbon group having 6 or more carbon atoms, preferably that R ⁴ and R ⁵ are both alkyl groups having 6 or more carbon atoms.

These groups are specifically shown below.
The secondary or tertiary alkyl group having 4 to 6 carbon atoms in the group (1) is not particularly limited, and examples thereof include 1-methylpropyl group, 1,1-dimethylethyl group, 1-methylbutyl group, 1 -Ethylpropyl group, 1,1-dimethylpropyl group, 1-methylpentyl group, 1-ethylbutyl group, 1,1-dimethylbutyl group, 1-methyl-1-ethylpropyl group, etc. A propyl group is particularly preferred.
In the group (2), the alkyl group having 2 or 3 carbon atoms is not particularly limited, and examples thereof include an ethyl group and a propyl group, and an ethyl group is particularly preferable. Examples of the alkyl group having 4 or more carbon atoms include a butyl group, an amyl group, a hexyl group, and an octyl group, and a butyl group and a hexyl group are particularly preferable.
In group (3), the alkyl group having 6 or more carbon atoms is not particularly limited, and examples thereof include a hexyl group, an octyl group, a decyl group, and a phenyl group, and an alkyl group is preferable, and a hexyl group is particularly preferable.

  In general, increasing the number of carbon atoms in the alkyl group facilitates dissolution in a hydrocarbon solvent, but the viscosity of the solution tends to increase, and it is preferable in handling to use an alkyl group having an appropriate length. In addition, although the said organomagnesium compound is used as a hydrocarbon solution, even if a trace amount of complexing agents, such as ether, ester, and amine, are contained or remain in the solution, it can be used without any problem.

[Compound [F]]
Next, compound [F] is demonstrated. Compound [F] is a compound belonging to the group consisting of an amine compound, an alcohol compound, and a siloxane compound.

  Although it does not specifically limit as an amine compound, For example, an aliphatic, alicyclic thru | or aromatic amine is preferable. Specifically, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, hexylamine, dihexylamine, trihexylamine, octylamine, dioctylamine, trioctylamine, aniline, N -Methylaniline, N, N-dimethylaniline, toluidine and the like.

  Although it does not specifically limit as an alcohol compound, For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1,1-dimethylethanol, pentanol, hexanol, 2-methylpentanol, 2-ethyl-1-butanol, 2-ethyl-1-pentanol, 2-ethyl-1-hexanol, 2-ethyl-4-methyl-1-pentanol, 2-propyl-1-heptanol, 2-ethyl- Examples include 5-methyl-1-octanol, 1-octanol, 1-decanol, cyclohexanol, and phenol. Of these, 1-butanol, 2-butanol, 2-methyl-1-pentanol and 2-ethyl-1-hexanol are preferable.

Although it does not specifically limit as a siloxane compound, For example, the siloxane compound which has a structural unit represented by following General formula (11) is preferable.
(In the general formula (11), R ¹¹ and R ¹² are groups selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms.)

In the general formula (11), the unsubstituted hydrocarbon group represented by R ¹¹ and R ¹² is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, A 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, hexyl group, octyl group, decyl group, phenyl group, tolyl group and vinyl group are preferred. In the general formula (11), the substituted hydrocarbon group represented by R ¹¹ and R ¹² is not particularly limited, but a trifluoropropyl group is preferable.

  The siloxane compound can be used in the form of a dimer or higher chain or cyclic compound composed of one type or two or more types of structural units.

  The siloxane compound is not particularly limited. For example, symmetric dihydrotetramethyldisiloxane, hexamethyldisiloxane, hexamethyltrisiloxane, pentamethyltrihydrotrisiloxane, cyclic methylhydrotetrasiloxane, cyclic methylhydropentasiloxane, cyclic dimethyl Tetrasiloxane, cyclic methyltrifluoropropyltetrasiloxane, cyclic methylphenyltetrasiloxane, cyclic diphenyltetrasiloxane, (terminal methyl capping) methylhydropolysiloxane, dimethylpolysiloxane, (terminal methyl capping) phenylhydropolysiloxane, methylphenyl Polysiloxane is mentioned.

[Production method of polyolefin polymerization catalyst]
The polyolefin polymerization catalyst comprises a component having a silica carrier [A], a transition metal compound component [B], and an activator [C] as constituent components, a solid catalyst for olefin polymerization, a liquid component [D], It can be manufactured by mixing.

  The polyolefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.

[Polymerization process]
Next, the polymerization process will be described. The polymerization step is a step of obtaining polyethylene by homopolymerizing ethylene or copolymerizing ethylene and olefin using a polyolefin polymerization catalyst. In this embodiment, polyethylene contains an ethylene homopolymer and an ethylene copolymer. The density and physical properties of polyethylene can be controlled by copolymerization of ethylene and the olefin (comonomer).

The olefin is not particularly limited, for example, the number 3 to 20 of the α- olefin carbon number of 3 or more carbon atoms and 20 or less of the cyclic olefin of the general formula _CH 2 = ^{CHR 13 (wherein, R 13} is 6 or more carbon atoms And at least one selected from the group consisting of straight-chain, branched or cyclic dienes having 4 to 20 carbon atoms.

  The α-olefin having 3 to 20 carbon atoms is not particularly limited. For example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, Examples include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene.

  In addition, the cyclic olefin having 3 to 20 carbon atoms is not particularly limited. For example, cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1.4. , 5.8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

Furthermore, the compound represented by the general formula CH ₂ = CHR ¹³ (wherein R ¹³ is an aryl group having 6 to 20 carbon atoms) is not particularly limited, and examples thereof include styrene and vinylcyclohexane. .

  Moreover, the linear, branched or cyclic diene having 4 to 20 carbon atoms is not particularly limited, and examples thereof include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1, 4-hexadiene and cyclohexadiene are mentioned.

  The polymerization method is not particularly limited, and examples thereof include a suspension polymerization method and a gas phase polymerization method. In the suspension polymerization method, an inert hydrocarbon solvent can be used as a suspension polymerization medium, and the olefin itself can also be used as a solvent. Examples of the inert hydrocarbon solvent include, but are not limited to, aliphatic hydrocarbons such as propane, butane, 2-methylpropane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, And alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethyl chloride, chlorobenzene and dichloromethane. Of these, propane, butane, 2-methylpropane, pentane, hexane, and heptane are particularly preferable. Moreover, an inert hydrocarbon solvent can be used independently, or 2 or more types can be mixed and used for it.

  A method for adding the polyolefin polymerization catalyst to the polymerization vessel is not particularly limited, but a method of adding the polyolefin polymerization catalyst to the polymerization vessel as a slurry of the above inert hydrocarbon solvent is preferable. Although it does not specifically limit as an inert hydrocarbon solvent to be used, For example, butane, 2-methylpropane, pentane, hexane, and heptane are preferable.

  The amount of the catalyst added in the polymerization step is not particularly limited, but it is preferably adjusted so that the weight of the catalyst with respect to the weight of polyethylene obtained per hour is 0.001 wt% or more and 1 wt% or less. The polymerization temperature is not particularly limited, but is preferably 0 ° C. or higher, more preferably 50 ° C. or higher, and still more preferably 60 ° C. or higher. The polymerization temperature is preferably 150 ° C. or lower, more preferably 110 ° C. or lower, and further preferably 100 ° C. or lower. The polymerization pressure is not particularly limited, but is preferably 0.1 MPa or more and 10 MPa or less, more preferably 0.2 MPa or more and 5 MPa, and further preferably 0.3 MPa or more and 3 MPa or less. The type of this polymerization reaction is not particularly limited, and any of batch, semi-continuous and continuous methods can be preferably performed. It is also possible to carry out the polymerization in two or more stages having different reaction conditions.

  The molecular weight of the polyethylene obtained in this embodiment can be adjusted by changing the concentration of hydrogen in the polymerization vessel or the polymerization temperature, as described in DE31273133.2.

  Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

  In the present invention, ethylene and hexane used in Examples and Comparative Examples were dehydrated using MS-3A (manufactured by Showa Union), and hexane was further used after deoxygenation by performing vacuum degassing using a vacuum pump. did.

(Average particle size D50)
The average particle diameter D50 of the precursor of the silica support [A] and the silica support [A] in the examples was measured using a laser type particle size distribution measuring apparatus (SALD-2100 manufactured by Shimadzu Corporation). The average particle diameter D50 of the precursor of the silica support [A] and the average particle diameter D50 of the silica support [A] were in agreement.

(Specific surface area and pore volume)
The specific surface area and pore volume of the precursor of the silica support [A] and the silica support [A] in the examples were measured by the BET method (Brunauer-Emmett-Teller) using an autosorb 3MP apparatus manufactured by Yuasa Ionics. The measurement was performed using nitrogen as the adsorption gas.

(Pore diameter)
The pore diameter of the silica support [A] in the examples was calculated by the following formula.
Pore diameter of silica support [A] = pore volume of silica support [A] / specific surface area of silica support [A] × 40000

(Mole amount of surface hydroxyl group of precursor of silica support [A])
In the examples, the molar amount (mol / g) of the surface hydroxyl group of the precursor of the silica support [A] is obtained by reacting 10 mL of neat ethoxydiethylaluminum with the surface hydroxyl group of the precursor of the silica support [A]. Then, ethane gas was generated, and the amount of ethane gas generated was calculated by quantifying it using a gas burette.

(Measurement of saturated adsorption amount of Lewis acidic compound to precursor of silica support [A])
In the examples, the saturated adsorption amount of the Lewis acidic compound was 50 g / L hexane slurry of the silica support [A] precursor in a nitrogen atmosphere and the silica support [A] precursor at 20 ° C. with stirring. After adding a Lewis acidic compound having a molar number of 1.4 times the total molar amount of surface hydroxyl groups contained in the whole slurry calculated from the surface hydroxyl amount of the slurry and reacting for 2 hours, This was calculated from the molar reduction amount of the Lewis acidic compound.

(Polymerization activity)
The polymerization activity in the examples represents the amount of polymer produced (g) per hour per 1 g of the solid catalyst component. The bulk density in the examples was measured according to JIS K-6721 after the obtained polyethylene powder was dried at 90 ° C. for 1 hour.

(Stable operation: Evaluation of polymer adhesion to the reactor)
The evaluation of the polymer adhesion to the reactor was a measure of the stable operability at the time of scale-up, and was evaluated as ◯ when there was no polymer adhesion at the reactor, and x when there was even a slight adhesion.

(Stable operability: Evaluation of formation of bulk polymer)
The evaluation of the bulk polymer was a measure of stable operation at the time of scale-up, and it was evaluated as “◯” when there was no bulk polymer in the polymerization vessel, and “X” when there was a little.

[Example 1]
(Measurement of saturated adsorption amount of Lewis acidic compound to precursor of silica support [A])
Silica M202 (manufactured by AGC S-Itech) was used as a precursor of the silica carrier [A]. Triethylaluminum was used as the Lewis acidic compound.

Silica M202 was heat-treated at 600 ° C. for 4 hours under a nitrogen atmosphere. The specific surface area of the silica M202 after the heat treatment was 537 m ² / g, the average particle diameter D50 was 22.2 μm, and the pore volume was 1.80 mL / g.

  The surface hydroxyl group amount of the silica M202 after the heat treatment was calculated by reacting ethoxydiethylaluminum with the surface hydroxyl group of the precursor of the silica carrier [A] to generate ethane gas, and quantifying the amount of ethane gas generated. The surface hydroxyl group content of the silica after the heat treatment was 1.42 mmol / g.

  Under a nitrogen atmosphere, silica M202 (4 g) after this heat treatment was added to a 0.2 L glass container, and 80 mL of hexane was added and dispersed to obtain a silica slurry. 8 mL of a hexane solution of triethylaluminum (concentration 1M) was added to the resulting slurry at 20 ° C. with stirring. Then, it stirred for 2 hours and made triethylaluminum and the surface hydroxyl group of the silica M202 react. As a result of quantifying the amount of triethylaluminum in the supernatant of the hexane slurry after the reaction and calculating the molar reduction amount, the saturated adsorption amount of triethylaluminum on silica M202 was 1.58 mmol / g.

(Preparation of silica support [A])
Silica M202 (130 g) after heat treatment was dispersed in 2500 mL of hexane in a nitrogen-substituted 8 L autoclave to obtain a slurry. To the obtained slurry, 195 mL of a hexane solution of triethylaluminum (concentration 1M) was added at 20 ° C. with stirring. Thereafter, the mixture was stirred for 2 hours, and triethylaluminum was reacted with the surface hydroxyl group of silica M202 to prepare 2695 mL of a hexane slurry of silica support [A] on which triethylaluminum was adsorbed.

The specific surface area of silica M202 of the silica support [A] is 537 m ² / g, the average particle diameter D50 is 22.2 μm, the pore volume is 1.80 mL / g, and the pore diameter is 134.1 mm. there were. Further, the adsorption amount of triethylaluminum was 1.50 mmol / g.

(Preparation of transition metal compound component [B])
As the transition metal compound (B-1), [(Nt-butylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter abbreviated as “complex 1”) It was used. Further, as the organomagnesium compound (B-2), a composition formula Mg (C ₂ H ₅ ) (C ₄ H ₉ ) (hereinafter abbreviated as “Mg1”) was used.

  200 mmol of Complex 1 is dissolved in 1000 mL of Isopar E, 40 mL of hexane solution of Mg1 (concentration 1M) is added, and further hexane is added to adjust the concentration of Complex 1 to 0.1 M, thereby obtaining a transition metal compound component [B]. It was.

(Preparation of activator [C])
As the borate compound (C-1), bis (hydrogenated tallow alkyl) methylammonium-tetrakis (pentafluorophenyl) borate (hereinafter abbreviated as “borate 1”) was used. 17.8 g of borate 1 was added and dissolved in 156 mL of toluene, and further hexane was added to adjust the concentration of borate 1 in the toluene solution to 80 mM to prepare activator [C].

(Preparation of solid catalyst for olefin polymerization)
To 2695 mL of the slurry of silica support [A] obtained by the above operation, 219 mL of the activator [C] obtained by the above operation and 175 mL of the transition metal compound component [B], while stirring at 25 ° C. The solid component [A] was prepared by adding simultaneously from another line using a metering pump and then continuing the reaction for 3 hours. The addition time at this time was 30 minutes for both the activator [C] and the transition metal compound component [B], and the number of stirring was 400 rpm.

(Preparation of liquid component [D])
As the organomagnesium compound [E], a composition formula AlMg6 (C2H5) 3 (C4H9) 12 (hereinafter abbreviated as “Mg2”) was used. As compound [F], methylhydropolysiloxane (viscosity at 25 ° C., 20 centistokes, hereinafter abbreviated as “siloxane compound 1”) was used.

  To a 200 mL flask, 40 mL of hexane and Mg1 were added while stirring and 38.0 mmol of Mg and Al as a total amount. At 20 ° C., 40 mL of hexane containing 2.27 g (37.8 mmol) of methylhydropolysiloxane was stirred. Then, the temperature was raised to 80 ° C., and the mixture was reacted for 3 hours with stirring to prepare liquid component [D].

(Ethylene polymerization)
800 mL of hexane was put into a 1.5 L autoclave, and 0.25 mmol of the above liquid component [D] was added as a total amount of Mg and Al. Pressurized ethylene was added to the autoclave to increase the internal pressure of the autoclave to 0.8 MPaG. Next, the internal temperature of the autoclave was increased to 75 ° C., and the polymerization of ethylene was started by adding the slurry of the solid catalyst for olefin polymerization to the autoclave so that the weight of the solid catalyst for olefin polymerization was 10 mg. Polymerization was carried out for 1 hour while adding ethylene to the autoclave so that the internal pressure of the autoclave was maintained at 0.8 MPaG. After completion of the polymerization, the reaction mixture (polymer slurry) was extracted from the autoclave, and the olefin polymerization catalyst was deactivated with methanol. Thereafter, the reaction mixture was filtered, washed and dried to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, no polymer deposits and bulk polymer were observed on the inner wall of the autoclave. The polymerization activity of the olefin polymerization catalyst was 6000 g / g / h. The resulting polymer powder had a bulk density of 0.32 g / cm ³ . These results are shown in Table 1.

[Example 2]
(Preparation of solid catalyst for olefin polymerization)
As borate compound (C-1), instead of borate 1, bis (hydrogenated tallow alkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter abbreviated as “borate 2”) is used. And ethoxydiethylaluminum (hereinafter abbreviated as “aluminum 1”) was used as the organoaluminum compound (C-2). 17.8 g of borate 2 was added and dissolved in 156 mL of toluene to obtain a 100 mM toluene solution of borate 2. 15.6 mL of a hexane solution (concentration 1 M) of aluminum 1 was added to the toluene solution of borate 2 at 25 ° C., and further hexane was added to adjust the concentration of borate 2 in the toluene solution to 80 mM. Then, activator [C] was prepared by stirring at 25 degreeC for 1 hour. Otherwise, a solid catalyst for olefin polymerization was prepared under the same conditions as in Example 1.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, no polymer deposits and bulk polymer were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 6900 g / g / h. The bulk density of the obtained polymer powder was 0.34 g / cm ³ . These results are shown in Table 1.

[Example 3]
(Preparation of solid catalyst for olefin polymerization)
A solid catalyst for olefin polymerization was prepared under the same conditions as in Example 2 except that the silica shown in Example 3 of Table 1 was used. The adsorption amount of triethylaluminum was 1.50 mmol / g.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, no polymer deposits and bulk polymer were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 4520 g / g / h. The bulk density of the obtained polymer powder was 0.35 g / cm ³ . These results are shown in Table 1.

[Example 4]
(Preparation of solid catalyst for olefin polymerization)
A solid catalyst for olefin polymerization was prepared under the same conditions as in Example 2 except that the silica shown in Example 4 of Table 1 was used. The adsorption amount of triethylaluminum was 1.60 mmol / g.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, no polymer deposits and bulk polymer were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 3370 g / g / h. The bulk density of the obtained polymer powder was 0.22 g / cm ³ . These results are shown in Table 1.

[Example 5]
(Preparation of solid catalyst for olefin polymerization)
A solid catalyst for olefin polymerization was prepared under the same conditions as in Example 2 except that the silica shown in Example 5 of Table 1 was used. The adsorption amount of triethylaluminum was 3.69 mmol / g.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, no polymer deposits and bulk polymer were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 6300 g / g / h. The bulk density of the obtained polymer powder was 0.31 g / cm ³ . These results are shown in Table 1.

[Example 6]
(Preparation of solid catalyst for olefin polymerization)
A solid catalyst for olefin polymerization was prepared under the same conditions as in Example 2 except that the silica shown in Example 6 of Table 1 was used. The adsorption amount of triethylaluminum was 1.48 mmol / g.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, no polymer deposits and bulk polymer were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 4880 g / g / h. The bulk density of the obtained polymer powder was 0.30 g / cm ³ . These results are shown in Table 1.

[Comparative Example 1]
(Preparation of solid catalyst for olefin polymerization)
A solid catalyst for olefin polymerization was prepared under the same conditions as in Example 2 except that the silica shown in Comparative Example 1 in Table 1 was used. The adsorption amount of triethylaluminum was 1.80 mmol / g.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, polymer deposits were observed on the inner wall of the autoclave, and bulk polymer was observed. The polymerization activity of the catalyst was 6460 g / g / h. The bulk density of the obtained polymer powder was 0.29 g / cm ³ . These results are shown in Table 1.

[Comparative Example 2]
(Preparation of solid catalyst for olefin polymerization)
A solid catalyst for olefin polymerization was prepared under the same conditions as in Example 2 except that the silica shown in Comparative Example 2 in Table 1 was used. The adsorption amount of triethylaluminum was 3.00 mmol / g.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, polymer deposits were observed on the inner wall of the autoclave, and no bulk polymer was observed. The polymerization activity of the catalyst was 5250 g / g / h. The bulk density of the obtained polymer powder was 0.30 g / cm ³ . These results are shown in Table 1.

[Comparative Example 3]
(Preparation of solid catalyst for olefin polymerization)
A solid catalyst for olefin polymerization was prepared under the same conditions as in Example 2 except that the silica shown in Comparative Example 3 in Table 1 was used. The adsorption amount of triethylaluminum was 1.39 mmol / g.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, polymer deposits were observed on the inner wall of the autoclave, and bulk polymer was observed. The polymerization activity of the catalyst was 3500 g / g / h. The bulk density of the obtained polymer powder was 0.38 g / cm ³ . These results are shown in Table 1.

[Comparative Example 4]
(Preparation of solid catalyst for olefin polymerization)
A solid catalyst for olefin polymerization was prepared under the same conditions as in Example 2 except that the silica shown in Comparative Example 4 in Table 1 was used. The adsorption amount of triethylaluminum was 1.80 mmol / g.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, polymer deposits were observed on the inner wall of the autoclave, and bulk polymer was observed. The polymerization activity of the catalyst was 7690 g / g / h. The bulk density of the obtained polymer powder was 0.25 g / cm ³ . These results are shown in Table 1.

[Comparative Example 5]
(Preparation of solid catalyst for olefin polymerization)
A solid catalyst for olefin polymerization was prepared under the same conditions as in Example 2 except that the silica shown in Comparative Example 5 in Table 1 was used. The adsorption amount of triethylaluminum was 2.38 mmol / g.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, polymer deposits were observed on the inner wall of the autoclave, and bulk polymer was observed. The polymerization activity of the catalyst was 4000 g / g / h. The bulk density of the obtained polymer powder was 0.25 g / cm ³ . These results are shown in Table 1.

[Comparative Example 6]
(Preparation of solid catalyst for olefin polymerization)
A solid catalyst for olefin polymerization was prepared under the same conditions as in Example 2 except that the silica shown in Comparative Example 6 in Table 1 was used. The adsorption amount of triethylaluminum was 2.30 mmol / g.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, polymer deposits were observed on the inner wall of the autoclave, and no bulk polymer was observed. The polymerization activity of the catalyst was 10,000 g / g / h. The bulk density of the obtained polymer powder was 0.23 g / cm ³ . These results are shown in Table 1.

[Comparative Example 7]
(Preparation of solid catalyst for olefin polymerization)
A solid catalyst for olefin polymerization was prepared under the same conditions as in Example 2 except that the silica shown in Comparative Example 7 in Table 1 was used. The adsorption amount of triethylaluminum was 1.80 mmol / g.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, no polymer deposits were observed on the inner wall of the autoclave, and bulk polymer was observed. The polymerization activity of the catalyst was 8000 g / g / h. The bulk density of the obtained polymer powder was 0.30 g / cm ³ . These results are shown in Table 1.

[Comparative Example 8]
(Preparation of solid catalyst for olefin polymerization)
Except for using silica shown in Example 1 of Table 1 and using bis (n-butylcyclopentadienyl) zirconium dimethyl (hereinafter abbreviated as “complex 2”) as the transition metal compound (B-1). Prepared a solid catalyst for olefin polymerization under the same conditions as in Example 2.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, polymer deposits were observed on the inner wall of the autoclave, and bulk polymer was observed. The polymerization activity of the catalyst was 3200 g / g / h. The bulk density of the obtained polymer powder was 0.28 g / cm ³ . These results are shown in Table 1.

[Comparative Example 9]
(Preparation of solid catalyst for olefin polymerization)
Example 1 except that silica shown in Example 1 of Table 1 was used and bis (cyclopentadienyl) titanium dimethyl (hereinafter abbreviated as “complex 3”) was used as the transition metal compound (B-1). A solid catalyst for olefin polymerization was prepared under the same conditions as in No. 2.

(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. When the inside of the autoclave was inspected, polymer deposits were observed on the inner wall of the autoclave, and bulk polymer was observed. The polymerization activity of the catalyst was 5000 g / g / h. The bulk density of the obtained polymer powder was 0.30 g / cm ³ . These results are shown in Table 1.

  The polyethylene production method of the present invention can polymerize a polymer having excellent powder properties without causing adhesion to the reactor or the like, and without producing a bulk polymer, thus improving production efficiency by continuous operation. Therefore, it is extremely effective industrially and can be widely used.

Claims (3)

Using a polyolefin polymerization catalyst, having a polymerization step of homopolymerizing ethylene or copolymerizing ethylene and olefin to obtain polyethylene,
The polyolefin polymerization catalyst has a silica carrier [A], a transition metal compound component [B], an activator [C], and a liquid component [D] as constituent components,
The silica carrier [A] is, 5 [mu] m or more 50μm or less of the average particle diameter D50,300m ² / g or more 700 meters ² / g or less in specific surface area, and the volume of pores 1.5 mL / g or more 2.0 mL / g Have
The transition metal compound component [B] includes a transition metal compound (B-1) represented by the following general formula (1),
The activator [C] includes a borate compound (C-1) represented by the following general formula (2) that reacts with the transition metal compound component [B] to form a metal complex having catalytic activity,
The liquid component [D] is synthesized by reacting an organomagnesium compound [E] represented by the following general formula (3) with a compound [F] selected from amine compounds, alcohol compounds, and siloxane compounds.
A method for producing polyethylene.
(In the above general formula (1),
M ¹ represents a transition metal selected from the group consisting of titanium, zirconium, and hafnium, and has a formal oxidation number of +2, +3, or +4,
R ¹ is each independently one or more selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a composite group thereof. Represents a substituent having 20 or less non-hydrogen atoms, wherein when the substituent R is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, or a germyl group, two adjacent substituents R ¹ is bonded to each other to form a divalent group, and thus, the ring is formed by cooperating with a bond between two carbon atoms of the cyclopentadienyl ring bonded to each of the two adjacent substituents R ^1. May form,
X ¹ is each independently a halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, or 1 carbon atom. 1 or more and 20 or less selected from the group consisting of a hydrocarbyl amide group having 18 or less, a hydrocarbyl phosphide group having 1 to 18 carbons, a hydrocarbyl sulfide group having 1 to 18 carbons, and a composite group thereof. Represents a substituent having a non-hydrogen atom, wherein the two substituents X ¹ may cooperate to form a neutral conjugated diene or a divalent group having 4 to 30 carbon atoms,
Y represents —O—, —S—, —NR ² —, or —PR ² —, wherein R ² represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or 1 to 8 carbon atoms. The following hydrocarbyloxy group, silyl group, halogenated alkyl group having 1 to 8 carbon atoms, halogenated aryl group having 6 to 20 carbon atoms, or a composite group thereof,
Z represents Si (R ³ ) ₂ , C (R ³ ) ₂ , Si (R ³ ) ₂ —Si (R ³ ) ₂ , C (R ³ ) —C (R ³ ) ₂ , C (R ³ ) = C (R ³ ), C (R ³ ) ₂ —Si (R ³ ) ₂ , Si (R ³ ) ₂ —C (R ³ ) ₂ , or Ge (R ³ ) ₂ , where R ³ is Hydrogen atom, hydrocarbon group having 1 to 12 carbon atoms, hydrocarbyloxy group having 1 to 8 carbon atoms, silyl group, halogenated alkyl group having 1 to 8 carbon atoms, halogenation having 6 to 20 carbon atoms Represents an aryl group or a composite group thereof;
x is 1, 2 or 3.
[A−H] ⁺ [BQ ¹ ₄ ] ⁻ (2)
(In the above general formula (2),
[A-H] ⁺ represents a monovalent proton-donating Bronsted acid,
A represents a neutral Lewis base,
[BQ ¹ ₄ ] ⁻ represents a compatible non-coordinating anion,
B represents a boron element,
Q ¹ represents a substituted aryl group having 6 to 20 carbon atoms. )
(M ² ) _a (Mg) _b (R ⁴ ) _c (R ⁵ ) _d (3)
(In the above general formula (3),
M ² represents a metal atom belonging to Group 1, Group 2, Group 12, and Group 13 of the Periodic Table;
R ⁴ and R ⁵ represent a hydrocarbon group having 2 to 20 carbon atoms,
a, b, c, and d are real numbers that satisfy the following relationship. 0 ≦ a, 0 <b, 0 ≦ c, 0 ≦ d, c + d> 0, e × a + 2b = c + d (where e is the valence of M ² ))   The method for producing polyethylene according to claim 1, wherein an average particle diameter D50 of the silica support [A] is 9 µm or more and 41 µm or less. The pore diameter determined by the following formula of the silica support [A] is from 120 to 210 mm.
Pore diameter = pore volume / specific surface area × 40000
The manufacturing method of the polyethylene of Claim 1 or 2.