JP2017071741A - Olefin polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst which has high activity, suppresses polymer adhesion to a reactor or the like and generation of bulk polymers, and allows production of a polyolefin excellent in powder characteristics.SOLUTION: An olefin polymerization solid catalyst comprises a silica carrier [A] with an average particle diameter D50 of 1-20 μm and a compressive strength of 1-30 MPa, and a metal complex [X] having a transition metal compound (B-1) represented by general formula (1) and a borate compound (C-1) represented by general formula (2) defined by [A-H][BQ].SELECTED DRAWING: None

Description

  The present invention relates to an olefin polymerization catalyst.

Conventionally, metallocene catalysts using transition metal metallocene compounds have been used as olefin polymerization catalysts in addition to so-called Ziegler-Natta catalysts. It is known that when an olefin is polymerized using a metallocene catalyst, an olefin polymer having a narrow molecular weight distribution can be obtained with high activity.
A typical process for polymerizing olefins using a metallocene catalyst is a solution polymerization method in which an olefin polymer is obtained in a form dissolved in a solvent using a reaction solvent, and so-called particle form polymerization, that is, olefin weight in particle form. There are methods for producing coalescence. Examples of particle morphology polymerization include slurry polymerization and gas phase polymerization.

Conventional metallocene catalysts are often soluble in the reaction system. However, when slurry polymerization or gas phase polymerization is performed using a catalyst that is soluble in the reaction system, the particle shape of the resulting olefin polymer becomes indefinite and the bulk density decreases, and a large amount of fine powder is generated. There is a problem. There is also a problem that a part of the obtained olefin polymer adheres to the wall surface of the reactor. In addition, the solution polymerization method has a problem that the viscosity of the solution increases remarkably with an increase in the molecular weight of the polymer, and it is difficult to produce a high molecular weight polymer.
Therefore, in order to produce a high molecular weight olefin polymer using a metallocene catalyst, it is necessary to adopt a particle morphology polymerization method after making the catalyst insoluble in the reaction system by a method such as supporting the catalyst on a carrier. It becomes.

  On the other hand, supported metallocene catalysts tend to have the following problems. In general, a metallocene-based catalyst is more active when the active site is released from the catalyst particles. Therefore, when a metallocene catalyst is used in particle form polymerization, a small amount of the released metallocene catalyst produces a large amount of amorphous polymer. As a result, the amorphous polymer grows large while taking in the surrounding powder, and a bulk polymer is formed. In the case of a continuous process, when such a bulk polymer is formed, the extraction pipe from the polymerization reactor may be blocked, which may hinder the extraction of the polymer. For this reason, continuous operation is hindered and production efficiency is lowered, making it difficult to carry out manufacturing on a commercial scale.

  In order to solve such a problem, Patent Document 1 discloses a polymer having excellent powder properties (high bulk density, high fluidity, narrow particle size distribution) in slurry polymerization or gas phase polymerization. A polymerization catalyst that can be polymerized without causing adhesion or the like is disclosed. Patent Documents 2 to 7 disclose a catalyst carrier that utilizes a Lewis acid-base interaction between a metallocene compound and a cocatalyst.

JP 2006-273976 A JP-A-11-310612 JP 2000-038419 A JP 2002-284808 A JP 2006-316160 A JP 2006-342326 A JP 2012-126084 A

In Patent Document 1, improvement of polymerization activity, polymer powder properties, and the like are devised by devising a catalyst adjustment method, but in an actual polymerization reaction, generation of an amorphous polymer due to crushing of catalyst particles is observed. Further, the catalytic activity is not sufficient, and there is a problem in industrial productivity.
In Patent Documents 2 to 7, the use of a specific carrier suppresses crushing during polymerization and generation of fine powder to improve the powder properties, but it is still not sufficient.
The present invention has been made in view of the above problems, and has a high activity, and can produce a polyolefin excellent in powder properties while suppressing the adhesion of a polymer to a reactor or the like and the formation of a bulk polymer. An object is to provide a possible olefin polymerization catalyst.

As a result of intensive studies on the above problems, the inventors of the present invention are supported olefin polymerization catalysts in which a specific metal complex is supported on a silica support, and the compression strength of the silica support is smaller than that generally used. The inventors have found that the above-described problems can be achieved by using a specific range, and have completed the present invention.
That is, the present invention is as follows.

（上記一般式（１）中、
Ｍ^１は、チタン、ジルコニウム、及びハフニウムからなる群より選ばれる遷移金属であって、形式酸化数が＋２、＋３、又は＋４である遷移金属を表し、
Ｒ^１は、各々独立して、水素原子、炭素数１以上８以下の炭化水素基、シリル基、ゲルミル基、シアノ基、ハロゲン原子、及びこれらの複合基からなる群より選ばれる、１個以上２０個以下の非水素原子を有する置換基を表し、ここで、前記置換基Ｒが炭素数１以上８以下の炭化水素基、シリル基、又はゲルミル基である場合、２つの隣接する前記置換基Ｒ^１が互いに結合して２価の基を形成し、これにより前記２つの隣接する置換基Ｒ^１にそれぞれ結合するシクロペンタジエニル環の２つの炭素原子間の結合と共働して環を形成してもよく、
Ｘ^１は、各々独立して、ハライド、炭素数１以上２０以下の炭化水素基、炭素数１以上１８以下のヒドロカルビルオキシ基、炭素数１以上１８以下のヒドロカルビルアミノ基、シリル基、炭素数１以上１８以下のヒドロカルビルアミド基、炭素数１以上１８以下のヒドロカルビルフォスフィド基、炭素数１以上１８以下のヒドロカルビルスルフィド基、及びこれらの複合基からなる群より選ばれる、１個以上２０個以下の非水素原子を有する置換基を表し、ここで、２つの前記置換基Ｘ^１が共働して炭素数４以上３０以下の中性共役ジエン又は２価の基を形成してもよく、
Ｙは、−Ｏ−、−Ｓ−、−ＮＲ^２−、又は−ＰＲ^２−を表し、ここで、Ｒ^２は、水素原子、炭素数１以上１２以下の炭化水素基、炭素数１以上８以下のヒドロカルビルオキシ基、シリル基、炭素数１以上８以下のハロゲン化アルキル基、炭素数６以上２０以下のハロゲン化アリール基、又はこれらの複合基を表し、
Ｚは、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、又はＧｅ（Ｒ^３）_２を表し、ここで、Ｒ^３は、水素原子、炭素数１以上１２以下の炭化水素基、炭素数１以上８以下のヒドロカルビルオキシ基、シリル基、炭素数１以上８以下のハロゲン化アルキル基、炭素数６以上２０以下のハロゲン化アリール基、又はこれらの複合基を表し、
ｘは、１、２、又は３である）。
［Ａ−Ｈ］^＋［ＢＱ^１ _４］⁻ （２）
（上記一般式（２）中、
［Ａ−Ｈ］^＋は、１価のプロトン供与性のブレンステッド酸を表し、
Ａは、中性のルイス塩基を表し、
［ＢＱ^１ _４］⁻は、相溶性の非配位性アニオンを表し、
Ｂは、硼素元素を表し、
Ｑ^１は、炭素数６以上２０以下の置換アリール基を表す。）
［２］前記金属錯体が、シリカ担体［Ａ］に担持されている、［１］に記載のオレフィン重合用固体触媒。
［３］前記シリカ担体［Ａ］の比表面積が３００ｍ^２／ｇ以上８００ｍ^２／ｇ以下である、［１］又は［２］に記載のオレフィン重合用固体触媒。
［４］前記シリカ担体［Ａ］の細孔容積が、０．５ｍＬ／ｇ以上３．０ｍＬ／ｇ以下である、請求項１〜３いずれか一項に記載のオレフィン重合用固体触媒。
［５］［１］〜［４］いずれか一項に記載のオレフィン重合用固体触媒、及び、有機溶媒を含む液体成分［Ｄ］を含む、オレフィン重合触媒。
［６］［５］に記載のオレフィン重合触媒を用いて、エチレンを単独重合、又はエチレンとエチレン以外のオレフィンを共重合することを特徴とする、ポリオレフィンの製造方法。 [1] A silica carrier [A] having an average particle diameter D50 of 1 μm to 20 μm and a compressive strength of 1 MPa to 30 MPa, and
Metal complex having a structure derived from a transition metal compound (B-1) represented by the following general formula (1) and a structure derived from a borate compound (C-1) represented by the following general formula (2) [ X]
A solid catalyst for olefin polymerization.

(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. )
[2] The solid catalyst for olefin polymerization according to [1], wherein the metal complex is supported on a silica support [A].
[3] The solid catalyst for olefin polymerization according to [1] or [2], wherein the silica support [A] has a specific surface area of 300 m ² / g or more and 800 m ² / g or less.
[4] The solid catalyst for olefin polymerization according to any one of claims 1 to 3, wherein the silica carrier [A] has a pore volume of 0.5 mL / g or more and 3.0 mL / g or less.
[5] An olefin polymerization catalyst comprising the solid catalyst for olefin polymerization according to any one of [1] to [4] and a liquid component [D] containing an organic solvent.
[6] A method for producing a polyolefin, characterized in that ethylene is homopolymerized or ethylene and an olefin other than ethylene are copolymerized using the olefin polymerization catalyst according to [5].

  ADVANTAGE OF THE INVENTION According to this invention, polyolefin excellent in powder property can be manufactured, suppressing the adhesion of the polymer to a reactor etc. 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.

[Olefin polymerization catalyst]
The polymerization catalyst of this embodiment contains a silica support [A] and a metal complex [X] as constituent components.
Among these, the solid component containing the silica support [A] and the metal complex [X] is referred to as a solid catalyst for olefin polymerization.

[Silica support [A]]
First, the silica carrier [A] will be described.
The silica support [A] is a particle having an average particle diameter D50 of 1 μm to 20 μm and a compressive strength of 1 MPa to 30 MPa.
The specific surface area is preferably 300 m ² / g or more and 800 m ² / g or less, and the pore volume is preferably 0.5 mL / g or more and 3.0 mL / g or less.

(Average particle size D50)
The average particle diameter D50 of the silica support [A] is 1 μm or more and 20 μm or less, preferably 2 μm or more and 15 μm or less, more preferably 3 μm or more and 10 μm or less.
When the average particle diameter D50 of the silica carrier [A] is 1 μm or more, the silica carrier [A] can be easily handled. In addition, it is possible to suppress the adhesion of the polymer in the polymerization vessel or in the piping due to the separation of the active species from the carrier, and the polymerization becomes more stable. Further, a powder having a high bulk density and fluidity and a narrow particle size distribution can be obtained. Furthermore, it is possible to prevent the formation of a bulk polymer due to the aggregation of the catalyst.
Moreover, when the average particle diameter D50 of the silica support [A] is 20 μm or less, the production of coarse powder (particles that do not pass through a standard sieve having an opening of 1180 μm) can be 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.

(Compressive strength)
The compressive strength of the silica carrier [A] is 1 MPa or more and 30 MPa or less, preferably 2 MPa or more and 20 MPa or less, more preferably 3 MPa or more and 15 MPa or less, and further preferably 5 MPa or more and less than 10 MPa. In general, a carrier having a high strength is preferred as a carrier for the polymerization catalyst, and usually a carrier having a compressive strength of about 100 MPa is used. However, according to the study by the present inventors, in the supported olefin polymerization catalyst in which the metal complex [X] is supported on a silica support, the coarse powder is not generated at the time of polyolefin polymerization if the compression strength of the silica support is not too high. It was found that it was not generated.
When the compression strength of the silica support [A] is 1 MPa or more, the solid catalyst can be prevented from being pulverized during the polymerization, and the polymer can be prevented from adhering to the inside of the polymerization vessel or the pipe. This makes the polymerization more stable. In addition, since the polymer powder grows by the replica effect (the shape of the powder is similar to the shape of the catalyst), the generation of distorted powder can be suppressed by suppressing the pulverization of the catalyst, A powder with a high bulk density is obtained.
Further, when the compressive strength of the silica support [A] is 30 MPa or less, the aggregation of the catalyst can be suppressed, and the formation of coarse powder can be prevented. The reason why the aggregation of the catalyst is suppressed as the compressive strength of the silica support [A] is smaller is not clear, but in the catalyst in which the metal complex is supported on the silica support [A], the metal complex supported on the surface is changed. It is considered that the aggregation of the catalyst occurs between the catalyst, and when the compression strength of the silica support [A] is high, the number of pores in the support [A] decreases, so that the metal complex does not enter the inside of the pores. This is considered to be due to the presence of more on the surface of the silica support [A]. However, the mechanism does not depend on this.
The compressive strength of the silica support [A] can be measured by a micro compression tester, and more specifically, can be measured by the method described in the examples.

(Specific surface area)
The specific surface area of the silica carrier [A], 300m ² / g or more 800 m ² / g or less, more preferably not more than 350 meters ² / g or more 700 meters ² / g, more preferably from 400 meters ² / g or more 600 meters ² / g or less. When the specific surface area of the silica support [A] is 300 m ² / g or more, the activity of the catalyst can be enhanced.
Moreover, when the specific surface area of the silica support [A] is 800 m ² / g or less, crushing due to the strength reduction of the silica support [A] can be suppressed. Thereby, the adhesion of the polymer in the polymerization vessel or in the piping is suppressed, and the polymerization is more stable. Furthermore, it is possible to prevent the formation of a bulk polymer due to the aggregation of the catalyst.
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 silica support [A] is preferably porous, and its pore volume is preferably 0.5 mL / g or more and 3.0 mL / g or less, more preferably 1.0 mL / g or more and 2.5 mL / g. It is below, More preferably, they are 1.2 mL / g or more and 2.0 mL / g or less. When the pore volume of the silica support [A] is 0.5 mL / g or more, the active sites of the metal complex [X] can be accommodated in the pores without aggregating on the surface of the silica support [A]. it can. Thereby, the production | generation of a block polymer can be prevented.
Moreover, when the pore volume of the silica support [A] is 3.0 mL / g or less, crushing due to the strength reduction of the silica support [A] can be suppressed. As a result, the polymer can be prevented from adhering to the inside of the polymerization vessel or the piping, and the polymerization is 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.

The silica support [A] is preferably a Lewis acidic compound adsorbed on a silanol group. In this case, when the silica carrier [A] is treated with the Lewis acidic compound, the Lewis acidic compound is adsorbed on the surface of the silica carrier [A] by physical adsorption or chemical adsorption. By using such a silica support [A], the dispersibility in a solvent during catalyst preparation tends to be further improved, and the metal complex [X] can be prevented from being deactivated by a silanol group. .
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 and 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 organoaluminum compounds preferable as the Lewis acidic compound, 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 organic magnesium compounds preferable as the Lewis acidic compound, a compound represented by the following general formula (5) is more preferable.
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.

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

(Method for producing silica support [A])
The silica carrier [A] adsorbing the Lewis acidic compound can be produced from a silica product (hereinafter also referred to as “precursor of carrier [A]”) by the method described below.
1) First, the water (crystal water, adsorbed water, etc.) existing on the surface is removed by heat-treating the precursor of the silica carrier [A] as necessary.
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” in step 2) is the amount of surface hydroxyl group (mmol) 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. / G) The molar amount of Lewis acidic compound in the supernatant of the slurry after addition and reaction of 1.4 mol times the total molar amount of surface hydroxyl groups contained in the slurry calculated based on It is the amount of adsorption calculated from the amount of decrease. In addition, the amount of surface hydroxyl groups (mmol / g) of the precursor of the silica support [A] is such that ethane gas is generated by reacting ethoxydiethylaluminum with the surface hydroxyl groups of the precursor of the silica support [A]. Can be calculated by quantifying.

Before quantifying the saturated adsorption amount of the Lewis acidic compound (before Step 2)) or before adsorbing a less amount of Lewis acidic compound than the saturated adsorption amount (before Step 3)), the silica support [ It is preferable to remove water (crystal water, adsorbed water, etc.) existing on the surface of the precursor A] (step 1)).
Water can be removed by heat treatment. In this case, 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.
When the saturated adsorption amount of the Lewis acidic compound as the 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 metal complex [X] is lost. Since the amount of silanol groups that may be activated is not large, the step 3) for adsorbing the Lewis acidic compound is omitted, and the Lewis acidic compound is not adsorbed on the precursor of the silica support [A]. It can be used as it is as a silica carrier [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)], ES70W [PQ Corporation (USA)], P10, P6, Q6 [Fuji Silysia (Japan)], L123, M202, H122, H52, H32 [AGC S-Tech Co., Ltd. (Made in Japan)].

(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, the transition metal compound component [B] and the activator [C] described below are eluted from the catalyst during catalyst preparation. 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.
The adsorption amount of the Lewis acidic compound on the silica carrier [A] is the saturation adsorption amount of the Lewis acidic compound with respect to the precursor of the silica carrier [A] and the Lewis acidic compound adsorbed on the precursor of the silica carrier [A]. It can be controlled by the amount.

(Saturated adsorption amount of Lewis acidic compound to precursor of silica support [A])
In this embodiment, when the precursor of the silica support [A] adsorbs the Lewis acidic compound, 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 to 5.0 mmol / g, more preferably 0.01 mmol / g to 4.0 mmol / g, and still more preferably 0.01 mmol / g to 3.0 mmol / g. 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], which will be described later, during catalyst preparation. The preparation step and the catalyst washing step before using the catalyst 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.

[Metal complex [X]]
Next, metal complex [X] is demonstrated.
The metal complex [X] is derived from the structure derived from the transition metal compound (B-1) represented by the following general formula (1) and the borate compound (C-1) represented by the following general formula (2). It is a metal complex having a structure.

(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,
Each R ¹ is independently selected from the group consisting of a hydrogen atom or 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 the substituent R ¹
Is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, or a germyl group, two adjacent substituents R ¹ are bonded to each other to form a divalent group, whereby the two adjacent groups A ring may be formed by cooperating with a bond between two carbon atoms of the cyclopentadienyl ring each bonded to the substituent R ¹ to be
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 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. )

  The metal complex [X] is produced, for example, by reacting the transition metal compound component [B] containing the transition metal compound (B-1) with the activator [C] containing the borate compound (C-1). be able to.

  The transition metal compound component [B] includes a transition metal compound (B-1) represented by the general formula (1). The transition metal compound component [B] may be in any form as long as it contains the transition compound (B-1) represented by the general formula (1), and is represented by the general formula (1). The transition compound (B-1) alone may be used, or the transition compound (B-1) represented by the general formula (1) may be dissolved in an organic solvent such as a hydrocarbon solvent. Further, the transition metal compound component [B] preferably contains an organomagnesium compound (B-2) described later.

Although it does not specifically limit as a transition metal compound (B-1), For example,
[(Nt-butylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl,
[(Nt-butylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium dimethyl,
[(N-methylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium dimethyl,
[(N-phenylamido) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium dimethyl,
[(N-benzylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium dimethyl,
[(Nt-butylamide) (η5-cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl,
[(Nt-butylamide) (η5-cyclopentadienyl) dimethylsilane] titanium dimethyl,
[(N-methylamido) (η5-cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl,
[(N-methylamido) (η5-cyclopentadienyl) dimethylsilane] titanium dimethyl,
[(Nt-butylamide) (η5-indenyl) dimethylsilane] titanium dimethyl, [(N-benzylamide) (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” at the end of the names of the zirconium and titanium compounds listed above as specific examples of the transition metal compound (B-1) ( This appears immediately after the last part of the name of each compound, that is, the part of “zirconium” or “titanium”, and is the name corresponding to the part of X ^{1 in} the general formula (1)) In addition, a compound having a name formed by substituting with a functional group other than dimethyl is also included.

The functional group other than dimethyl is not particularly limited.
“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-η4-3-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” and the like.

Among these, as the transition metal compound (B-1), [(Nt-butylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene is preferable.
These transition metal compounds (B-1) may be used alone or in combination of two or more.

In this embodiment, it is preferable that the transition metal compound (B-1) is used as a mixture with the organomagnesium compound (B-2).
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 Groups 12 and 13 of the Periodic Table, and R ⁸ , R ⁹ and R ¹⁰ are each independently 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 ))
In the general formula (6), the organomagnesium compound (B-2) is shown as a complex form of organomagnesium, but is represented by (R ⁸ ) ₂ Mg or the general formula (6). And a complex of the above compound and another metal compound.
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. Among these, an alkyl group is preferable, and a primary alkyl group is particularly preferable.

In the general formula (6), when 0 <p, examples of the metal atom M ³ include metal elements belonging to the group consisting of Group 12 and Group 13. Such M ³ is not particularly limited, and examples thereof include zinc, boron, and aluminum. Among these, aluminum 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, the compound represented by the general formula (6) is preferably soluble in a hydrocarbon solvent, and R ⁸ and R ⁹ are represented by the following three groups (1 More preferably, it belongs to any one of (2) and (3).
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 (B-2) rarely contains a complexing agent such as a small amount of ether, ester or amine, but the transition metal compound component [B] is added to the hydrocarbon solution. Even when the complexing agent such as a small amount of ether, ester, amine or the like elutes from the organomagnesium compound (B-2) in the transition metal compound component [B] in the solution, The activity of the metal complex [X] obtained by reacting the compound component [B] with the activator [C] is not affected.

Next, the alkoxy group (OR ¹⁰ ) of the general 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.

The organomagnesium compound (organomagnesium complex) represented by the general formula (6) is composed of the organomagnesium compound represented by the following general formula (7) or the general formula (8) and the following general formula (9) or the general formula ( 10) is reacted in an inert hydrocarbon medium such as hexane, heptane, cyclohexane, benzene, toluene and the like in the range of 10 ° C. to 150 ° C., and if necessary (t ≠ 0 in the case of a) followed hydrocarbyloxy magnesium compound having a hydrocarbon group represented by soluble above R ¹⁰ alcohol or a hydrocarbon solvent having a hydrocarbon group represented by R ^10, and / or hydrocarbyloxy It can be synthesized by a method of reacting with an aluminum compound.

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 organomagnesium component and the alcohol having a hydrocarbon group represented by R ¹⁰ are reacted, there is no particular limitation on the order of the reaction, a method of adding alcohol to the organomagnesium component, an organomagnesium component in the alcohol Any of the method of adding, or the method of adding both simultaneously is preferable. In the present embodiment, the reaction ratio of the organomagnesium component and the alcohol is not particularly limited, but as a result of the reaction, the molar composition ratio t / (p + q) of alkoxy groups to all metal atoms in the resulting alkoxy group-containing organomagnesium component. The range 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. If the molar ratio of the organomagnesium compound (B-2) / transition metal compound (B-1) is 0.005 or more, the organomagnesium compound (B-2) may be insufficient and the activity may be reduced. Is preferably 5 or less, since the organomagnesium compound (B-2) is excessive and the transition metal compound component [B] and the activator [C] are eluted during catalyst preparation. This is preferable for avoiding a problem that a catalyst washing step may be required before the preparation step or the catalyst use.

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 ^{x10 −5} mol to 1.0 × 10 ⁻³ mol. When the content of the transition metal compound (B-1) is 5 × 10 ⁻⁶ mol or more with respect to 1 g of the silica support [A], the activity per 1 g of the olefin polymerization catalyst tends to be further improved. Moreover, when the content of the transition metal compound (B-1) is 1.0 × 10 ⁻² mol or less with respect to 1 g of the silica support [A], the transition metal compound (B-1) is converted from the olefin polymerization catalyst. Elution can be suppressed, and the catalyst preparation step and the catalyst washing step before using the catalyst can be omitted.

  The activator [C] includes the borate compound (C-1) represented by the general formula (2) that reacts with the transition metal compound component [B] to form the metal complex [X] having catalytic activity. . The activator [C] may be in any form as long as it contains the borate (C-1) represented by the general formula (2), and the borate compound (C) represented by the general formula (2) -1) It may be a simple substance, or the borate compound (C-1) represented by the general formula (2) is dissolved in an organic solvent (for example, an inert reaction medium such as aliphatic hydrocarbon or aromatic hydrocarbon). It may be made. Furthermore, activator [C] may contain the organoaluminum compound (C-2) mentioned later.

In the general formula (2), the compatibility represented by [BQ ¹ ₄ ] ⁻ , that is, it cannot form a coordinate bond with the transition metal of the transition metal compound (B-1), or the transition Non-coordinating anions that can only form weak coordination bonds with metals and are easily replaced with neutral Lewis bases such as α-olefins are not particularly limited,
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-trifluoromethylphenyl) (phenyl) borate,
Tris (pentafluorophenyl) (cyclohexyl) borate,
Tris (pentafluorophenyl) (naphthyl) borate,
Tetrakis (pentafluorophenyl) borate, triphenyl (hydroxyphenyl) borate,
Diphenyl-di (hydroxyphenyl) borate,
Triphenyl (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. Among these, tris (pentafluorophenyl) (4-hydroxyphenyl) borate is preferable.

Further, in the general formula (2), the monovalent proton-providing Bronsted acid represented by [A-H] ⁺ is not particularly limited.
Bis (hydrogenated tallow alkyl) methylammonium,
Triethylammonium,
Tripropylammonium,
Tributylammonium,
Trimethylammonium,
Trialkyl group-substituted ammonium cations such as tributylammonium and trioctylammonium;
N, N-dimethylanilinium,
N, N-diethylanilinium,
N, N-2,4,6-pentamethylanilinium,
N, N-dialkylanilinium cations such as N, N-dimethylbenzylanilinium and the like;
Bis- (1-methylethyl) ammonium,
Dialkylammonium cations such as dicyclohexylammonium;
Triphenylphosphonium,
Tri (methylphenyl) phosphonium,
A triarylphosphonium cation such as tri (dimethylphenyl) phosphonium;
Dimethylsulfonium,
Diethylfuronium,
Examples thereof include diphenylsulfonium.

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

Moreover, it is preferable to mix and react the borate compound (C-1) and the 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.
A solid catalyst for olefin polymerization can be produced by simultaneously adding the transition metal compound component [B] and the activator [C] in the presence of the silica support [A].
For example, 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. The transition metal compound component [B] and the activator [C] are separately added to the obtained slurry simultaneously and simultaneously to the reactor to produce a solid catalyst for olefin polymerization. As a result, an equivalent amount of the transition metal compound component [B] reacts with the activator [C] to produce a metal complex [X] having catalytic activity, which is 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, both additions are particularly preferably initiated or terminated at the same time, most preferably both additions are initiated simultaneously and terminated at the same time.
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], 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 solid catalyst for olefin polymerization aggregates to perform olefin polymerization. In this case, the generation of coarse particles tends to be suppressed. 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, and thus the generated solid catalyst component for olefin polymerization. Will adhere to the reactor wall and agglomerate.

The addition amount of the transition metal compound component [B] and the activator [C] is preferably such that the transition metal compound (B-1) and the borate compound (C-1) are equimolar, More specifically, the transition metal compound (B-1) and the borate compound (C-1) are both 5 × 10 ^{−6 to} 1.0 × 10 ⁻² mol per 1 g of the silica support [A]. It is preferable that the amount is 1.0 × 10 ^{−5 to} 1.0 × 10 ⁻³ mol.

[Liquid component [D]] In this embodiment, the olefin polymerization catalyst can be used in a form containing the above-mentioned solid catalyst for olefin polymerization and the liquid component [D] containing an organic solvent.
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 an amine compound, an alcohol compound, and a siloxane compound. It is preferable that the compound is included.
Although liquid component [D] is not specifically limited, Specifically, it is preferable that the compound synthesize | combined by making organic magnesium compound [E] and compound [F] react, and an organic solvent are included. For example, the liquid component [D] can be obtained by reacting the organomagnesium compound [E] and the compound [F] in an inert solvent common to the organomagnesium compound [E] and the compound [F]. .
Since the organomagnesium compound [E] and the compound [F] are soluble in the hydrocarbon solvent, the liquid component [D] is obtained by dissolving both in the hydrocarbon solvent and reacting in the hydrocarbon solvent. It is preferable to do.
As the hydrocarbon solvent, the same solvent as used as a polymerization solvent can be used, and an inert hydrocarbon solvent, among which butane, 2-methylpropane, pentane, hexane and heptane are preferable.

(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 Groups 12 and 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.

One type of liquid component [D] may be used alone, or two or more types may be mixed and used.
The liquid component [D] can be used as a scavenger for impurities in the polymerization system. In the polymerization system, even when the liquid component [D] itself is used at a high concentration (even when used in a large amount), the polymerization activity is hardly lowered, so that a high polymerization activity can be expressed in a wide concentration range. For this reason, by using the olefin polymerization catalyst containing the liquid component [D] to remove impurities that adversely affect the polymerization activity and performing olefin polymerization, the polymerization activity can be easily controlled.

  The molar concentration of all metal atoms contained in the liquid component [D] 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. 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), the organomagnesium compound [E] is shown as a form of a complex compound of organomagnesium, but (R ³ ) ₂ Mg or a compound represented by the general formula (3) And complexes of other metal compounds.
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, a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, a 1-methylpropyl group, a 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 zinc, boron, and aluminum. Among these, aluminum 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 general formula (3). And R ⁵ is more preferably 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, At least one is a secondary or tertiary alkyl group.
Group (2): R ⁴ and R ⁵ are alkyl groups different from each other in carbon number, 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. There is.
Group (3): that it at least one of R ⁴ and R ⁵ is a hydrocarbon group having 6 or more carbon atoms, preferably R ⁴ and R ⁵ are both alkyl group 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, when the number of carbon atoms of these alkyl groups is increased, the compound represented by the general formula (3) is easily dissolved in a hydrocarbon solvent. However, the viscosity of the obtained hydrocarbon solution tends to increase. It is preferable in terms of handling to use an alkyl group. When the organomagnesium compound [E] is used as a hydrocarbon solution, it may be used even if a slight amount of a complexing agent such as ether, ester or amine is contained or remains in the solution. Can do.

[Compound [F]]
Next, compound [F] is demonstrated. The compound [F] is a compound selected from 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. Among these, 1-butanol, 2-butanol, 2-methyl-1-pentanol and 2-ethyl-1-hexanol are preferable.

（上記一般式（１１）中、Ｒ^１１及びＲ^１２は、水素、及び炭素数１〜４０の置換又は無置換の炭化水素基なる群より選ばれる基である。）
一般式（１１）中、Ｒ^１１及びＲ^１２で表される無置換の炭化水素基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、１−メチルエチル基、ブチル基、１−メチルプロピル基、２−メチルプロピル基、１，１−ジメチルエチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、フェニル基、トリル基、ビニル基が好ましい。また、一般式（１１）中、Ｒ^１１及びＲ^１２で表される置換された炭化水素基としては特に限定されないが、トリフルオロプロピル基が好ましい。
シロキサン化合物は１種類又は２種類以上の構成単位から成る２量体以上の鎖状又は環状の化合物の形で用いることができる。
シロキサン化合物としては、特に限定されないが、例えば、対称ジヒドロテトラメチルジシロキサン、ヘキサメチルジシロキサン、ヘキサメチルトリシロキサン、ペンタメチルトリヒドロトリシロキサン、環状メチルヒドロテトラシロキサン、環状メチルヒドロペンタシロキサン、環状ジメチルテトラシロキサン、環状メチルトリフルオロプロピルテトラシロキサン、環状メチルフェニルテトラシロキサン、環状ジフェニルテトラシロキサン、（末端メチル封塞）メチルヒドロポリシロキサン、ジメチルポリシロキサン、（末端メチル封塞）フェニルヒドロポリシロキサン、メチルフェニルポリシロキサンが挙げられる。 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.

[Method for producing olefin polymerization catalyst]
In this embodiment, the olefin polymerization catalyst can be synthesized by reacting a silica carrier [A] with a metal complex [X] (for example, a transition metal compound component [B] and an activator [C]. Can be produced by mixing the solid catalyst for olefin polymerization containing the liquid component [D].
Here, the ratio of the total amount (g) of the silica carrier [A], the transition metal compound component [B] and the activator [C] to the amount (mol) of the liquid component [D] is not particularly limited. For example, ([A] + [B] + [C]) / [D] can be set to 100 g / mol to 500 g / mol.
The olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.

[Production method of polyolefin]
The method for producing a polyolefin of the present embodiment includes a polymerization step of obtaining a polyolefin by homopolymerizing or copolymerizing the olefin using the olefin polymerization catalyst of the present embodiment.
The olefin polymerization catalyst of this embodiment is particularly suitable for the production of polyethylene and copolymers of ethylene and other olefins.

[Polymerization process]
The polymerization process will be described.
In the present embodiment, the polyolefin refers to an olefin homopolymer or copolymer, and an ethylene homopolymer or a copolymer of ethylene and another olefin is particularly preferable. The density and physical properties of polyethylene can be controlled by copolymerization of ethylene and another olefin (comonomer). Other olefins to be copolymerized with ethylene 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 an aryl group having 6 to 20 carbon atoms.) And at least one selected from the group consisting of linear, branched or cyclic dienes having 4 to 20 carbon atoms. Can be mentioned.
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. Among 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.

The method for adding the olefin polymerization catalyst of the present embodiment to the polymerization vessel is not particularly limited. Even if the solid catalyst for olefin polymerization and the liquid component [D] are simultaneously added to the polymerization vessel, they are added separately to the polymerization vessel. However, it is preferable to add them separately.
The olefin polymerization solid catalyst is preferably added to the polymerization vessel as a slurry using an organic solvent as a dispersion medium. The organic solvent used in this case is not particularly limited. For example, the above-described inert hydrocarbon solvent used as a polymerization medium can be used, and among these, butane, 2-methylpropane, pentane, hexane, and heptane are preferable. .
The amount of catalyst added in the polymerization step is not particularly limited, but it is preferable that the mass of the polyolefin polymerization solid catalyst with respect to the mass of polyolefin obtained per hour is adjusted to 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 polyolefin obtained in the present embodiment can be adjusted by changing the concentration of hydrogen in the polymerization vessel or the polymerization temperature, as described in DE31273133.2 and the like.

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 are dehydrated using MS-3A (Molecular sieve manufactured by Showa Union Co., Ltd.), and hexane is further deoxygenated by performing vacuum degassing using a vacuum pump. Used after.

(Average particle size D50)
The average particle diameter D50 of the silica carrier [A] was measured using a laser particle size distribution measuring apparatus (SALD-2100 manufactured by Shimadzu Corporation). Integration was performed from the smaller particle size side to the larger side.

(Compressive strength)
The compressive strength of the silica support [A] in the examples was measured using a micro compressive strength tester MCT-510 (manufactured by Shimadzu Corporation). The load speed was 1.4873 mN / sec, and the maximum load was 19.6 mN. The crushing strength of 10 or more particles arbitrarily selected was measured, and the average value was adopted.

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

(Mole amount of surface hydroxyl group of precursor of silica support [A])
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 (stock solution) 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])
Included in the entire slurry calculated from the surface hydroxyl amount of the precursor of the silica support [A] under stirring with respect to 80 mL of the 50 g / L hexane slurry of the precursor of the silica support [A] in a nitrogen atmosphere at 20 ° C. The Lewis acidic compound (triethylaluminum) having a molar number 1.4 times the total molar amount of the surface hydroxyl group to be added was added and reacted for 2 hours. Thereafter, the amount of Lewis acidic compound in the supernatant of the slurry was measured, the difference (decrease amount) between the addition amount and the residual amount was determined, and the saturated adsorption amount was calculated from this decrease amount (mol).

(Polymerization activity)
The polymerization activity was evaluated by the amount of polymer produced per hour (g) per gram of the solid catalyst component.

(The bulk density)
The bulk density was measured according to JIS K-6721 after drying the obtained polyolefin powder at 90 ° C. for 1 hour.
(Coarse powder ratio)
The coarse powder ratio was calculated from the amount of powder that did not pass through classification of polyolefin powder using a standard sieve having an opening of 1180 μm.

(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]
(Preparation of silica support [A1])
As a precursor of the silica carrier [A1], silica having an average particle diameter of 7 μm, a specific surface area of 660 m ² / g, a pore volume of 1.4 mL / g, and a compressive strength of 7 MPa (hereinafter referred to as silica 1) was used.
Silica 1 (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 (concentration 1 M) of triethylaluminum, which is a Lewis acidic compound, was added at 20 ° C. with stirring. Thereafter, the mixture was stirred for 2 hours, and triethylaluminum and the surface hydroxyl group of silica 1 were reacted to prepare 2695 mL of a hexane slurry of silica support [A1] on which triethylaluminum was adsorbed.
(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 isoparaffin hydrocarbon (Isopar E manufactured by ExxonMobil), 40 mL of hexane solution of Mg1 (concentration 1M) is added thereto, and further hexane is added to adjust the concentration of complex 1 to 0.1M. As a result, a transition metal compound component [B] was obtained.
(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)
Activating agent [C] 219 mL obtained by the above operation and 175 mL of transition metal compound component [B] were added to 2695 mL of the slurry of silica support [A1] obtained by the above operation while stirring at 25 ° C. A solid catalyst for olefin polymerization was prepared by simultaneous addition using a metering pump from another line 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 AlMg ₆ (C ₂ H ₅ ) ₃ (C ₄ H ₉ ) ₁₂ (hereinafter abbreviated as “Mg 2”) 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 0.2 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 slurry of the solid catalyst for olefin polymerization was added to the autoclave so that the mass of the solid catalyst for olefin polymerization (mass of solid content) was 10 mg. Polymerization of was started. 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 16,000 g / g / h. The bulk density of the obtained polymer powder was 0.33 g / cm ³ . These results are shown in Table 1.

[Example 2]
(Preparation of solid catalyst for olefin polymerization)
As a silica support, silica having an average particle size of 4 μm, a specific surface area of 570 m ² / g, a pore volume of 1.9 mL / g, and a compressive strength of 6 MPa (hereinafter referred to as silica 2) is used for olefin polymerization under the same conditions as in Example 1. A solid catalyst was prepared.
(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 25,000 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 3]
(Preparation of solid catalyst for olefin polymerization)
Olefin polymerization was carried out under the same conditions as in Example 1, using silica having an average particle size of 10 μm, a specific surface area of 550 m ² / g, a pore volume of 1.5 mL / g, and a compression strength of 15 MPa (hereinafter referred to as silica 3). A solid catalyst was prepared.
(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 14,000 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 4]
(Copolymerization of ethylene and 1-butene)
Using a vessel type 300 L polymerization reactor equipped with a stirrer, dehydrated normal hexane as a solvent was 40 L / hour, the solid catalyst for olefin polymerization used in Example 1 was 0.6 g / hour, and the liquid component [D] was Mg The total amount of Al was supplied at 4 mmol / hour. Copolymerization of ethylene and 1-butene by supplying hydrogen for molecular weight adjustment at 0.25 mol% relative to the gas phase concentration of ethylene and 1-butene at 0.38 molL% relative to the gas phase concentration of ethylene. Was subjected to continuous polymerization under the conditions of a polymerization temperature of 75 ° C., a polymerization pressure of 1.0 MPaG, and an average residence time of 1.6 hours. The polymerization slurry in the polymerization reactor was led to a flash tank having a pressure of 0.05 MPaG and a temperature of 60 ° C. so that the level in the polymerization reactor was kept constant, and unreacted ethylene, 1-butene and hydrogen were separated. Next, the ethylene-1-butene copolymer slurry is continuously sent to a centrifugal separator to separate the polymer and the solvent, and the separated copolymer powder is continuously sent to an 80 ° C. dryer and blown with nitrogen. While drying.
The polymerization activity of the catalyst was 17,900 g / gs, MFR measured at 190 ° C. was 2.5, density was 943 kg / m ³ , and bulk density was 0.26 g / cm ³ .

[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 1 except that silica 4 having the physical properties shown in Comparative Example 1 in Table 1 was used.
(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. The polymerization activity of the catalyst was 5,500 g / g / h, which was lower than in the examples. The bulk density of the obtained polymer powder was 0.34 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 1 except that silica 5 having physical properties shown in Comparative Example 2 in Table 1 was used.
(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. The polymerization activity of the catalyst was 12,000 g / g / h. The bulk density of the obtained polymer powder was 0.33 g / cm ³ , but the coarse powder ratio was as high as 3.0 wt%. 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 1 except that silica 6 having physical properties shown in Comparative Example 3 in Table 1 was used.
(Ethylene polymerization)
Ethylene was polymerized in the same manner as in Example 1 to obtain a dry powder of the polymer. The polymerization activity of the catalyst was 10,000 g / g / h, which was lower than in the examples. The bulk density of the obtained polymer powder was 0.31 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 silica 7 having physical properties shown in Comparative Example 4 in Table 1 was used.
(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 28,000 g / g / h. The bulk density of the obtained polymer powder was 0.08 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 1 except that silica 8 having the physical properties shown in Comparative Example 5 in Table 1 was used.
(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 20,000 g / g / h. The bulk density of the obtained polymer powder was 0.13 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 1 except that silica 9 having the physical properties shown in Comparative Example 6 in Table 1 was used.
(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, but the coarse powder ratio was as high as 2.0 wt%. The polymerization activity of the catalyst was 13,000 g / g / h. The bulk density of the obtained polymer powder was 0.31 g / cm ³ . These results are shown in Table 1.

[Comparative Example 7]
(Copolymerization of ethylene and 1-butene)
Using a solid catalyst for olefin polymerization using silica 5 having the physical properties shown in Comparative Example 2 in Table 1, ethylene and 1-butene were continuously polymerized in the same manner as in Example 4. When the inside of the polymerization reactor was inspected after the operation was completed, no polymer deposits were observed on the inner wall of the autoclave, but a bulk polymer was observed. The polymerization activity of the catalyst was 12,400 g / g. The bulk density of the obtained polymer powder was 0.31 g / cm ³ . These results are shown in Table 1.

[Comparative Example 8]
(Polymerization of ethylene and 1-butene)
Using a solid catalyst for olefin polymerization using silica 6 having physical properties shown in Comparative Example 3 in Table 1, ethylene and 1-butene were continuously polymerized in the same manner as in Example 4. After completion of the operation, the inside of the polymerization reactor was inspected, and many polymer deposits were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 11,600 g / g. The resulting polymer powder had a bulk density of 0.32 g / cm ³ . These results are shown in Table 1.

  The olefin polymerization catalyst of the present invention has high activity, and can suppress the adhesion of the polymer to the reactor and the formation of a bulk polymer. For this reason, the production efficiency by continuous operation improves. Furthermore, since an olefin polymer having excellent powder properties can be produced, it is very useful industrially.

Claims (6)

Silica carrier [A] having an average particle diameter D50 of 1 μm or more and 20 μm or less and a compressive strength of 1 MPa or more and 30 MPa or less, and
Metal complex having a structure derived from a transition metal compound (B-1) represented by the following general formula (1) and a structure derived from a borate compound (C-1) represented by the following general formula (2) [ X]
A solid catalyst for olefin polymerization.

(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. )   The solid catalyst for olefin polymerization according to claim 1, wherein the metal complex is supported on a silica support [A]. The solid catalyst for olefin polymerization according to claim 1 or 2, wherein the silica support [A] has a specific surface area of 300 m ² / g or more and 800 m ² / g or less.   The solid catalyst for olefin polymerization according to any one of claims 1 to 3, wherein a pore volume of the silica support [A] is 0.5 mL / g or more and 3.0 mL / g or less. Liquid component [D] containing the solid catalyst for olefin polymerization as described in any one of Claims 1-4, and an organic solvent.
An olefin polymerization catalyst.   A method for producing a polyolefin, wherein the olefin polymerization catalyst according to claim 5 is used to homopolymerize ethylene or copolymerize ethylene and an olefin other than ethylene.