JP7410461B2 - Method for producing olefin polymer - Google Patents

Description

The present invention relates to a method for producing an olefin polymer and an olefin polymer. More specifically, the present invention relates to a method for producing an olefin polymer in which the molecular weight distribution can be narrowed by adjusting the supply amount of a specific component during polymerization, and an olefin polymer obtained by this production method.

As a method to improve the moldability of metallocene polyolefins, which generally have poor moldability, there is a method of blending high-pressure low-density polyethylene with metallocene polyolefins, and a method of adding long chain branching to polyolefins through a polymerization reaction using a specific metallocene. There are known ways to introduce it. The former requires a blending process, which increases manufacturing costs. Further, although the obtained blend has excellent moldability, the mechanical strength, which is an advantage of metallocene polyolefins, is reduced.
On the other hand, a method is known in which a crosslinked pentadienyl indenyl compound is used as a specific metallocene catalyst for introducing the latter long chain branch (see Patent Documents 1 to 3). By using these metallocene catalysts, it is possible to produce olefinic polymers with a developed long chain branched structure. However, with this method, the molecular weight distribution of the polymer tends to be wide, which may lead to breakage of the molten resin, poor appearance due to surface elastic roughness, and deterioration of mechanical strength due to melt orientation, resulting in poor molding process. It is still not enough to achieve both performance and product characteristics. Therefore, there is a need for a production method that can produce an olefin polymer with a narrow molecular weight distribution without changing the long chain branched structural characteristics of the resulting polymer.

JP2013-227271A JP 2017-020019 Publication Japanese Patent Application Publication No. 2016-017039

An object of the present invention is to provide a method for producing an olefin polymer that can narrow the molecular weight distribution while maintaining the long chain branched structural characteristics of the olefin polymer.
Another object of the present invention is to provide an olefin polymer having a narrow molecular weight distribution while maintaining long chain branched structure characteristics.

In order to solve the above problems, the present inventors have conducted extensive research and found that the molecular weight distribution can be narrowed by adjusting the supply amount of specific components during polymerization.Based on this knowledge, the present invention I was able to complete it.

That is, the first aspect of the present invention is to add an olefin polymerization catalyst containing the following essential components (A) and (B) and the following component (D) to a polymerization reactor in which an olefin monomer and a polymerization medium exist under the following conditions. A method for producing an olefin polymer having a long chain branched structure, which is carried out by supplying the olefin polymer so as to satisfy (1) to (3), the supply amount ratio (mol/ mol) is 1.5 to 100 times the ratio (mol/mol) in the following condition (1), and is a method for producing an olefin polymer with a narrow molecular weight distribution.
However, the following condition (1) is such that "the supply amount ratio (mol/mol) of the component (D) to the component (A) is 1.5 times to 100 times the ratio (mol/mol) in the following condition (1). This is a prerequisite used to calculate the requirement that "the number is doubled," and it is not necessary to satisfy condition (1) alone.

Component (A): a crosslinked biscyclopentadienyl compound represented by the following general formula (1) containing transition metal element ^M1

［式（１）中、Ｍ^１は、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１およびＸ^２は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、酸素原子若しくは窒素原子を含む炭素数１～２０の炭化水素基、炭素数１～２０の炭化水素基置換アミノ基または炭素数１～２０のアルコキシ基を示す。Ｑ^１とＱ^２は、各々独立して、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１は、それぞれ独立して、水素原子または炭素数１～１０の炭化水素基を示し、４つのＲ^１のうち少なくとも２つが結合して、Ｑ^１およびＱ^２と一緒に環を形成していてもよい。ｍは、０または１であり、ｍが０の場合、Ｑ^１は、Ｒ^２およびＲ^３を含む共役５員環と直接結合している。Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、ケイ素数１～６を含む炭素数１～１８のケイ素含有炭化水素基、炭素数１～２０のハロゲン含有炭化水素基、酸素原子または硫黄原子を含む炭素数１～４０の炭化水素基または炭素数１～４０の炭化水素基置換シリル基を示し、２つのＲ^２と２つのＲ^３のうち少なくとも１つは水素原子ではなく、４つのＲ^４のうち少なくとも１つは水素原子ではない。Ｒ^２、Ｒ^３およびＲ^４のうち、隣接するＲ^３同士または隣接するＲ^２とＲ^３のいずれか１組のみは結合している炭素原子と一緒に環を形成していてもよい。］

成分（Ｂ）：成分（Ａ）の化合物と反応してカチオン性メタロセン化合物を生成させる化合物

成分（Ｄ）：一般式Ｍ^２Ｌ^１ _ｎで示される化合物
（Ｍ^２は周期表第１族、２族、１２～１５族の典型金属原子を表し、
Ｌ^１は水素原子、ハロゲン原子、炭化水素基であり、
ｎはＭ^２の原子価に相当する数である）

条件（１）Ｍ^１に対するＭ^２の比（ｍｏｌ／ｍｏｌ）が１１６０～１８００
条件（２）重合媒体に対するＭ^１の比（μｍｏｌ／ｋｇ）が０．００１～１２
条件（３）重合媒体に対するＭ^２の比（ｍｍｏｌ／ｋｇ）が０．０１～１００

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms; represents a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ¹ and Q ² each independently represent a carbon atom, a silicon atom, or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of the four R ^1s are bonded to form a ring together with Q ¹ and Q ² . It's okay. m is 0 or 1, and when m is 0, Q ¹ is directly bonded to the conjugated 5-membered ring containing R ² and R ³ . R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, Indicates a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a silyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms, and two R ² and 2 At least one of the three R ³ is not a hydrogen atom, and at least one of the four R ⁴ is not a hydrogen atom. Among R ² , R ³ and R ⁴ , only one pair of adjacent R ³ or adjacent R ² and R ³ may form a ring together with the carbon atoms to which they are bonded. ]

Component (B): a compound that reacts with the compound of component (A) to produce a cationic metallocene compound

Component (D): a compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Groups 1, 2, and 12 to 15 of the periodic table,
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group,
n is a number corresponding to the valence of ^M2 )

Condition (1) The ratio of M ² to M ¹ (mol/mol) is 1160 to 1800
Condition (2) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12
Condition (3) The ratio of ^M2 to the polymerization medium (mmol/kg) is 0.01 to 100

The second aspect of the present invention is to add an olefin polymerization catalyst containing the following essential components (A) and (B) and the following component (D) to a polymerization reactor in which an olefin monomer and a polymerization medium exist under the following conditions (1a). ) to (3a) are supplied to satisfy the following conditions:

Component (A): a crosslinked biscyclopentadienyl compound represented by the following general formula (1) containing transition metal element ^M1

［式（１）中、Ｍ^１は、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１およびＸ^２は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、酸素原子若しくは窒素原子を含む炭素数１～２０の炭化水素基、炭素数１～２０の炭化水素基置換アミノ基または炭素数１～２０のアルコキシ基を示す。Ｑ^１とＱ^２は、各々独立して、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１は、それぞれ独立して、水素原子または炭素数１～１０の炭化水素基を示し、４つのＲ^１のうち少なくとも２つが結合して、Ｑ^１およびＱ^２と一緒に環を形成していてもよい。ｍは、０または１であり、ｍが０の場合、Ｑ^１は、Ｒ^２およびＲ^３を含む共役５員環と直接結合している。Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、ケイ素数１～６を含む炭素数１～１８のケイ素含有炭化水素基、炭素数１～２０のハロゲン含有炭化水素基、酸素原子または硫黄原子を含む炭素数１～４０の炭化水素基または炭素数１～４０の炭化水素基置換シリル基を示し、２つのＲ^２と２つのＲ^３のうち少なくとも１つは水素原子ではなく、４つのＲ^４のうち少なくとも１つは水素原子ではない。Ｒ^２、Ｒ^３およびＲ^４のうち、隣接するＲ^３同士または隣接するＲ^２とＲ^３のいずれか１組のみは結合している炭素原子と一緒に環を形成していてもよい。］

成分（Ｂ）：成分（Ａ）の化合物と反応してカチオン性メタロセン化合物を生成させる化合物

成分（Ｄ）：一般式Ｍ^２Ｌ^１ _ｎで示される化合物
（Ｍ^２は周期表第１族、２族、１２～１５族の典型金属原子を表し、
Ｌ^１は水素原子、ハロゲン原子、炭化水素基であり、
ｎはＭ^２の原子価に相当する数である）

条件（１ａ）Ｍ^１に対するＭ^２の比（ｍｏｌ／ｍｏｌ）が１８００～１８００００
条件（２ａ）重合媒体に対するＭ^１の比（μｍｏｌ／ｋｇ）が０．００１～１２
条件（３ａ）重合媒体に対するＭ^２の比（ｍｍｏｌ／ｋｇ）が０．０１～１００

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms; represents a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ¹ and Q ² each independently represent a carbon atom, a silicon atom, or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of the four R ^1s are bonded to form a ring together with Q ¹ and Q ² . It's okay. m is 0 or 1, and when m is 0, Q ¹ is directly bonded to the conjugated 5-membered ring containing R ² and R ³ . R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, Indicates a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a silyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms, and two R ² and 2 At least one of the three R ³ is not a hydrogen atom, and at least one of the four R ⁴ is not a hydrogen atom. Among R ² , R ³ and R ⁴ , only one pair of adjacent R ³ or adjacent R ² and R ³ may form a ring together with the carbon atoms to which they are bonded. ]

Component (B): a compound that reacts with the compound of component (A) to produce a cationic metallocene compound

Component (D): a compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Groups 1, 2, and 12 to 15 of the periodic table,
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group,
n is a number corresponding to the valence of ^M2 )

Condition (1a) The ratio of M ² to M ¹ (mol/mol) is 1800 to 180000
Condition (2a) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12
Condition (3a) The ratio of M ² to the polymerization medium (mmol/kg) is 0.01 to 100

A third invention of the present invention is the method for producing an olefin polymer according to the first or second invention, characterized in that the obtained olefin polymer satisfies the following physical properties (i) and (ii). be.

Physical properties (i) Value of molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) and olefin obtained when the supply amount ratio of the component (D) to the component (A) is not increased. The ratio ([Mw _/ Mn]/[Mw 0 /Mn ₀ ]) to the molecular weight distribution (Mw ₀ /Mn ₀ ) of the polymer is 0.50 to 0.95.

Physical properties (ii) The value (g' _m ) of the branching index g' at a molecular weight of 100,000 measured by a GPC measuring device that combines a differential refractometer, a viscosity detector, and a light scattering detector, and the above component (A ) to the value (g' _m0 ) at a molecular weight of 100,000 of the branching index g' of the olefin polymer obtained when the supply ratio of the above component (D) to ) is not increased (g' _m /g' _m0 ) is 0.90 to 1.10.

A fourth invention of the present invention is the production of an olefin polymer according to any one of the first to third inventions, characterized in that the obtained olefin polymer satisfies the following physical properties (iii) and (iv). It's a method.

Physical properties (iii) The Mw/Mn is 2.0 to 7.0.
Physical properties (iv) The g' _m is 0.50 to 0.95.

A fifth invention of the present invention is the method for producing an olefin polymer according to any one of the first to fourth inventions, characterized in that the olefin monomer is ethylene.

A sixth invention of the present invention is the method for producing an olefin polymer according to the fifth invention, wherein the obtained olefin polymer satisfies the following physical properties (v) and (vi).
Physical properties (v) MFR is 0.001 to 1000 g/10 minutes.
Physical properties (vi) Density is 0.895 to 0.970 g/cm ³ .

A seventh invention of the present invention is the method for producing an olefin polymer according to any one of the first to sixth inventions, wherein the polymerization medium is a hydrocarbon solvent or a polyolefin (particles or pellets). be.

An eighth invention of the present invention is the method for producing an olefin polymer according to any one of the first to seventh inventions, wherein the polymerization reactor is a slurry polymerization reactor or a gas phase polymerization reactor. It is.

A ninth invention of the present invention is the method for producing an olefin polymer according to any one of the first to eighth inventions, characterized in that the polymerization reaction is carried out at a temperature of 60 to 110°C.

A tenth invention of the present invention is the method for producing an olefin polymer according to any one of the first to ninth inventions, characterized in that the polymerization reaction is carried out at an olefin partial pressure of 0.2 to 1.9 MPa. be.

An eleventh invention of the present invention is any one of the first to tenth inventions, wherein component (D) has the general formula AlL ¹ ₃ (L ¹ is a hydrogen atom, a halogen atom, or a hydrocarbon group). This is a method for producing an olefin polymer according to the invention.

A twelfth invention of the present invention is the olefin polymer according to any one of the first to eleventh inventions, wherein the olefin polymerization catalyst further contains an inorganic compound carrier (component (C)). This is a manufacturing method.

A thirteenth invention of the present invention is an olefin polymer obtained by the method for producing an olefin polymer according to any one of the first to twelfth items.

According to the method for producing an olefin polymer of the present invention, the molecular weight distribution can be narrowed while maintaining the long chain branched structural characteristics of the olefin polymer.
The olefin polymer of the present invention has a narrow molecular weight distribution while maintaining long chain branched structural characteristics.

It is a graph showing the baseline and interval of a chromatogram used in gel permeation chromatography (GPC) method. 1 is a graph showing the relationship between branching index (g') calculated from GPC-VIS measurement (branched structure analysis) and molecular weight (M). FIG. 2(a) shows Comparative Example 2. FIG. 2(b) shows Example 7.

Below, the method for producing an olefin polymer of the present invention will be specifically and detailedly explained for each item.

1. Method for producing olefin polymer (first production method)
(1) Method for producing an olefin polymer The method for producing an olefin polymer of the present invention involves adding an olefin polymerization catalyst containing the following essential components (A) and (B) to a polymerization reactor in which an olefin monomer and a polymerization medium are present. This is a method for producing an olefin polymer having a long chain branched structure, which is carried out by supplying the following component (D) so as to satisfy the following conditions (1) to (3). It is characterized in that the supply amount ratio (mol/mol) of component (D) to component (A) is 1.5 to 100 times the ratio (mol/mol) in the following condition (1). This feature is also called a characteristic requirement.

Component (A): a crosslinked biscyclopentadienyl compound represented by the following general formula (1) containing transition metal element ^M1

［式（１）中、Ｍ^１は、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１およびＸ^２は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、酸素原子若しくは窒素原子を含む炭素数１～２０の炭化水素基、炭素数１～２０の炭化水素基置換アミノ基または炭素数１～２０のアルコキシ基を示す。Ｑ^１とＱ^２は、各々独立して、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１は、それぞれ独立して、水素原子または炭素数１～１０の炭化水素基を示し、４つのＲ^１のうち少なくとも２つが結合して、Ｑ^１およびＱ^２と一緒に環を形成していてもよい。ｍは、０または１であり、ｍが０の場合、Ｑ^１は、Ｒ^２およびＲ^３を含む共役５員環と直接結合している。Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、ケイ素数１～６を含む炭素数１～１８のケイ素含有炭化水素基、炭素数１～２０のハロゲン含有炭化水素基、酸素原子または硫黄原子を含む炭素数１～４０の炭化水素基または炭素数１～４０の炭化水素基置換シリル基を示し、２つのＲ^２と２つのＲ^３のうち少なくとも１つは水素原子ではなく、４つのＲ^４のうち少なくとも１つは水素原子ではない。Ｒ^２、Ｒ^３およびＲ^４のうち、隣接するＲ^３同士または隣接するＲ^２とＲ^３のいずれか１組のみは結合している炭素原子と一緒に環を形成していてもよい。］

成分（Ｂ）：成分（Ａ）の化合物と反応してカチオン性メタロセン化合物を生成させる化合物

成分（Ｄ）：一般式Ｍ^２Ｌ^１ _ｎで示される化合物
（Ｍ^２は周期表第１族、２族、１２～１５族の典型金属原子を表し、
Ｌ^１は水素原子、ハロゲン原子、炭化水素基であり、
ｎはＭ^２の原子価に相当する数である）

条件（１）Ｍ^１に対するＭ^２の比（ｍｏｌ／ｍｏｌ）が１１６０～１８００
条件（２）重合媒体に対するＭ^１の比（μｍｏｌ／ｋｇ）が０．００１～１２
条件（３）重合媒体に対するＭ^２の比（ｍｍｏｌ／ｋｇ）が０．０１～１００

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms; represents a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ¹ and Q ² each independently represent a carbon atom, a silicon atom, or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of the four R ^1s are bonded to form a ring together with Q ¹ and Q ² . It's okay. m is 0 or 1, and when m is 0, Q ¹ is directly bonded to the conjugated 5-membered ring containing R ² and R ³ . R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, Indicates a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a silyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms, and two R ² and 2 At least one of the three R ³ is not a hydrogen atom, and at least one of the four R ⁴ is not a hydrogen atom. Among R ² , R ³ and R ⁴ , only one pair of adjacent R ³ or adjacent R ² and R ³ may form a ring together with the carbon atoms to which they are bonded. ]

Component (B): a compound that reacts with the compound of component (A) to produce a cationic metallocene compound

Component (D): a compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Groups 1, 2, and 12 to 15 of the periodic table,
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group,
n is a number corresponding to the valence of ^M2 )

Condition (1) The ratio of M ² to M ¹ (mol/mol) is 1160 to 1800
Condition (2) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12
Condition (3) The ratio of M ² to the polymerization medium (mmol/kg) is 0.01 to 100

(2) Olefin Monomer The olefin monomer is not particularly limited, and examples include ethylene and other α-olefins. The method for producing an olefin polymer of the present invention can be suitably used for either homopolymerization of ethylene or copolymerization of ethylene and α-olefin.
The α-olefins used as comonomers include those having 3 to 30 carbon atoms, preferably 3 to 8 carbon atoms, and specifically include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl- Examples include 1-pentene. Regarding α-olefins, it is also possible to copolymerize two or more types of α-olefins with ethylene. The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. When copolymerizing ethylene and other α-olefins, the amount of the other α-olefins can be arbitrarily selected within the range of 90 mol% or less of the total monomers, but generally it is 40 mol%. The content is preferably selected within the range of 30 mol% or less, more preferably 10 mol% or less. Of course, it is also possible to use small amounts of comonomers other than ethylene and α-olefins, and in this case, styrenes such as styrene, 4-methylstyrene, 4-dimethylaminostyrene, 1,4-butadiene, 1,5- Contains polymerizable double bonds such as dienes such as hexadiene, 1,4-hexadiene, and 1,7-octadiene, cyclic compounds such as norbornene and cyclopentene, and oxygen-containing compounds such as hexenol, hexenoic acid, and methyl octenoate. Compounds can be mentioned.

(3) Polymerization medium Conventionally known polymerization media can be used and are not particularly limited, but hydrocarbon solvents or polyolefins (particles or pellets) are preferably used.
As the hydrocarbon solvent, conventionally known ones can be used, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, heptane, octane, decane, dodecane, cyclohexane, etc. linear, branched, or cyclic hydrocarbons, inert hydrocarbons such as benzene, toluene, and xylene, and mixtures classified as liquid paraffins, isoparaffinic solvents, and mixed aliphatic hydrocarbon solvents. For example, commercially available products such as IP solvent, ISOPAR, kerosene, etc. may be used alone or in mixtures, and α-olefins such as liquefied ethylene, liquefied propylene, 1-butene, 1-hexene, 1-octene, etc. It is also possible to use liquid monomers such as aromatic monomers such as , styrene, and internal olefin monomers such as 2-butene and cyclopentene. Among these, straight chain, branched chain or cyclic hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, Liquid paraffins, isoparaffinic solvents, mixed aliphatic hydrocarbon solvents, such as IP solvent, ISOPAR, and other commercially available products, as well as liquefied ethylene, liquefied propylene, 1-butene, 1-hexene, and 1-octene. α-olefins such as α-olefins are preferably used alone or in mixtures. Propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, IP solvent, ISOPAR, liquefied ethylene, liquefied propylene, 1-butene, 1- Hexene, 1-octene alone or a mixture is more preferably used, and isobutane, isopentane, n-hexane, isohexane, heptane, cyclopentane, cyclohexane, IP solvent, ISOPAR alone or a mixture is even more preferably used.
As the polyolefin, conventionally known ones can be used, such as polyethylene (ethylene homopolymer or copolymer with other monomers. The same applies to the following polyolefins), polypropylene, polybutene, polyhexene, Polyisobutene, polystyrene, etc. are preferably used, but it is more preferable to use a polyolefin containing an olefin copolymer obtained by copolymerizing the same type of comonomer as the olefin polymer to be produced. Although polymer particles (also referred to as polymer powder or polymer granules) may be so-called pellets obtained through a melt-kneading machine, these polymer particles are preferable, and the average particle size of the polymer particles is about 100 to 3000 μm. More preferably, they are particles.

(4) Component (A)
Component (A) is a crosslinked biscyclopentadienyl compound represented by the following general formula (1) containing a transition metal element ^M1 .

［式（１）中、Ｍ^１は、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１およびＸ^２は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、酸素原子若しくは窒素原子を含む炭素数１～２０の炭化水素基、炭素数１～２０の炭化水素基置換アミノ基または炭素数１～２０のアルコキシ基を示す。Ｑ^１とＱ^２は、各々独立して、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１は、それぞれ独立して、水素原子または炭素数１～１０の炭化水素基を示し、４つのＲ^１のうち少なくとも２つが結合して、Ｑ^１およびＱ^２と一緒に環を形成していてもよい。ｍは、０または１であり、ｍが０の場合、Ｑ^１は、Ｒ^２およびＲ^３を含む共役５員環と直接結合している。Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、ケイ素数１～６を含む炭素数１～１８のケイ素含有炭化水素基、炭素数１～２０のハロゲン含有炭化水素基、酸素原子または硫黄原子を含む炭素数１～４０の炭化水素基または炭素数１～４０の炭化水素基置換シリル基を示し、２つのＲ^２と２つのＲ^３のうち少なくとも１つは水素原子ではなく、４つのＲ^４のうち少なくとも１つは水素原子ではない。Ｒ^２、Ｒ^３およびＲ^４のうち、隣接するＲ^３同士または隣接するＲ^２とＲ^３のいずれか１組のみは結合している炭素原子と一緒に環を形成していてもよい。］

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms; represents a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ¹ and Q ² each independently represent a carbon atom, a silicon atom, or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of the four R ^1s are bonded to form a ring together with Q ¹ and Q ² . It's okay. m is 0 or 1, and when m is 0, Q ¹ is directly bonded to the conjugated 5-membered ring containing R ² and R ³ . R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, Indicates a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a silyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms, and two R ² and 2 At least one of the three R ³ is not a hydrogen atom, and at least one of the four R ⁴ is not a hydrogen atom. Among R ² , R ³ and R ⁴ , only one pair of adjacent R ³ or adjacent R ² and R ³ may form a ring together with the carbon atoms to which they are bonded. ]

In the above general formula (1), M ¹ of the metallocene compound represents Ti, Zr or Hf, M ¹ of the metallocene compound preferably represents Zr or Hf, and M ¹ of the metallocene compound more preferably represents Zr. represent. Furthermore, X ¹ and X ² are each independently a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i -Butyl group, t-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, benzyl group, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i- Propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, acetyl group, 1-oxopropyl group, 1-oxo-n-butyl group, 2- Methyl-1-oxopropyl group, 2,2-dimethyl-1-oxo-propyl group, phenylacetyl group, diphenylacetyl group, benzoyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-furyl group, 2-tetrahydrofuryl group, dimethylaminomethyl group, diethylaminomethyl group, di-i-propylaminomethyl group, bis(dimethylamino)methyl group, bis(di-i-propylamino)methyl group, (dimethylamino) )(phenyl)methyl group, methylimino group, ethylimino group, 1-(methylimino)ethyl group, 1-(phenylimino)ethyl group, 1-[(phenylmethyl)imino]ethyl group, methoxy group, ethoxy group, n- Propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, phenoxy group, dimethylamino group, diethylamino group, di-n-propylamino group, di-i-propylamino group, di-n- Examples include butylamino group, di-i-butylamino group, di-t-butylamino group, diphenylamino group, and the like.
Preferred specific examples of X ¹ and X ² include chlorine atom, bromine atom, methyl group, n-butyl group, i-butyl group, methoxy group, ethoxy group, i-propoxy group, n-butoxy group, phenoxy group, Examples include dimethylamino group and di-i-propylamino group. Among these specific examples, a chlorine atom, a methyl group, and a dimethylamino group are particularly preferred.

Moreover, Q ¹ and Q ² represent a carbon atom, a silicon atom, or a germanium atom. Preferably it is a carbon atom or a silicon atom. More preferably a silicon atom.
Furthermore, R ¹ each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, , neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, etc. In addition, when R ¹ forms a ring together with Q ¹ and Q ² , examples include a cyclobutylidene group, a cyclopentylidene group, a cyclohexylidene group, a silacyclobutyl group, a silacyclopentyl group, a silacyclohexyl group, etc. can be mentioned.
Preferred specific examples of R ¹ include hydrogen atom, methyl group, ethyl group, phenyl group, ethylene group, and cyclobutylidene group when ^{Q 1} and/or Q ² are carbon atoms; When Q ² is a silicon atom, examples thereof include a methyl group, an ethyl group, a phenyl group, and a silacyclobutyl group.

m is 0 or 1, and when m is 0, Q ¹ is directly bonded to the conjugated 5-membered ring containing R ² and R ³ .

R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, Indicates a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a silyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms, and two R ² and 2 At least one of the three R ³ is not a hydrogen atom, and at least one of the four R ⁴ is not a hydrogen atom.
Preferred specific examples of R ² , R ³ and R ⁴ include a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, n-propyl group, -hexyl group, cyclohexyl group, phenyl group, 2-methylfuryl group, and trimethylsilyl group. Among these specific examples, hydrogen atom, methyl group, n-butyl group, t-butyl group, phenyl group, and trimethylsilyl group are more preferred, and hydrogen atom, methyl group, t-butyl group, phenyl group, and trimethylsilyl group are particularly preferred. preferable.
Among R ² , R ³ and R ⁴ , only one pair of adjacent R ³ or adjacent R ² and R ³ may form a ring together with the carbon atoms to which they are bonded.

As component (A), it is preferable that m=0 in the general formula (1), and specifically, it is more preferable that it is the following general formula (2).

Here, M ¹ , X ¹ , X ² , Q ¹ , R ¹ , R ² , R ³ and R ⁴ follow the description of general formula (1). Adjacent ^R3s preferably form a 5- to 7-membered ring structure together with the carbon atoms to which they are bonded, and specifically, 5-membered ring structures such as a thiophene ring and a pyrrole ring, a benzene ring, a cyclohexene ring, It is more preferable to form a 6-membered ring structure such as a cyclohexane ring, a 7-membered ring structure such as a heptadiene ring, and even more preferably a benzene ring, that is, a bridged cyclopentadienyl/indenyl compound represented by the following general formula. .

Here, M ¹ , X ¹ , X ² , Q ¹ , R ¹ , R ² and R ⁴ follow the description of general formula (1). R ³¹ , R ³² , R ³³ , and R ³⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon having 1 to 18 carbon atoms containing 1 to 6 silicon atoms. group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a nitrogen atom, or a sulfur atom, or a silyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms. Adjacent R ³¹ , R ³² , R ³³ , and R ³⁴ may form a ring together with the carbon atoms to which they are bonded.

As a specific example of the case where R ² and R ³ do not form a ring in general formula (2), M ¹ , X ¹ , X ² , Q ¹ , R ¹ , R in the following general formula (2') Examples include compounds in which R ² , R ² ′, R ³ , R ³ ′, and R ⁴ are shown in the table below. However, component (A) is not limited to these.

In general formula (2), as an example of a case where R ² and R ³ form a ring, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (4-methyl-5-phenyl- cyclopentathiophene) zirconium dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (4-methyl-5-phenyl-cyclopentathiophene) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) ( 4-Methyl-5-phenyl-cyclopentathiophene) zirconium dichloride, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-methyl-5-(5-methyl-2-furyl)- cyclopentathiophene) zirconium dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (3-methyl-5-(5-methyl-2-furyl)-cyclopentathiophene) zirconium dichloride, dimethylsilylene (3,4 -dimethylcyclopentadienyl) (3-methyl-5-(5-methyl-2-furyl)-cyclopentathiophene) zirconium dichloride, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) ( 2-Methyl-4-phenyl-4H-azulenyl) zirconium dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl) zirconium dichloride, dimethylsilylene (3,4 -dimethylcyclopentadienyl)(2-methyl-4-phenyl-4H-azulenyl)zirconium dichloride, and the like, as well-known crosslinked cyclopentadienyl/indenyl compounds included in general formula (3), All exemplified compounds of JP-A No. 2013-227482, [Chemical formula 1] of JP-A-2013-227271, all exemplified compounds of general formula (1c) in which at least one of R ^4c is not H, [Chemical formula 1] General of JP-A-2014-70029 All exemplified compounds when at least one of R ⁴ is not H in formula (1), [Chemical formula 1] of JP-A-2015-63515 All exemplified compounds when at least one of R ⁵ is not H in general formula (1) , All exemplified compounds of [Chemical Formula 1] General Formula (1) in JP-A No. 2015-172037 when at least one of R ⁷ to R ¹⁰ is not H, [Chemical Formula 1] General Formula (1) in JP-A No. 2012-25664 All exemplified compounds in ^which at least one of ^{R 11} to R ¹⁴ is not H; Exemplified compounds, all exemplified compounds of [Chemical formula 1] in JP-A-2016-145190, where at least one of R ⁸ to R ¹¹ is not H, all exemplified compounds of JP-A-2016-051152, JP-A-2007 -308486, and the like.

Specifically, the compounds of JP-A-2013-227271 are all exemplified compounds of the following general formula (1c) in which at least one of R ^4c is not H.

Specifically, the compounds of JP-A-2014-70029 are all exemplified compounds in the following general formula (1) where at least one of R ⁴ is not H.

Specifically, the compounds of JP-A-2015-63515 are all exemplified compounds in which at least one of R ⁵ is not H in the following general formula (1).

Specifically, the compounds of JP-A-2015-172037 are all exemplified compounds of the following general formula (1) in which at least one of R ⁷ to R ¹⁰ is not H.

Specifically, the compounds of JP-A No. 2012-25664 are all exemplified compounds of the following general formula (1) in which at least one of R ¹¹ to R ¹⁴ is not H.

Specifically, the compounds of JP-A-2016-141635 are all exemplified compounds of the following general formula (1) in which at least one of R ⁸ to R ¹¹ is not H.

Specifically, the compounds of JP-A-2016-145190 are all exemplified compounds of the following general formula (1) in which at least one of R ⁸ to R ¹¹ is not H.

All the exemplified compounds of JP-A No. 2007-308486 are specifically exemplified by the following compounds.
(1) Dichloro {1,1'-dimethylsilylene (2,3-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (2) Dichloro {1,1'-dimethylsilylene (3,4-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (3) dichloro {1,1'-dimethylsilylene (2,5-dimethylcyclopentadienyl) ( 2-methyl-4-phenyl-4H-azulenyl)}hafnium(4)dichloro{1,1'-dimethylsilylene(2,3-di-t-butylcyclopentadienyl)(2-methyl-4-phenyl-4H -azlenyl)} hafnium (5) dichloro {1,1'-dimethylsilylene (3,4-di t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (6) dichloro {1,1'-dimethylsilylene (2,5-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (7) dichloro {1,1'-dimethylsilylene ( 2,3-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (8) dichloro {1,1'-dimethylsilylene (3,4-diphenylcyclopentadienyl) (2 -Methyl-4-phenyl-4H-azulenyl)} Hafnium (9) dichloro{1,1'-dimethylsilylene (2,5-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} Hafnium (10) dichloro {1,1'-dimethylsilylene (2-methyl-4-ethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (11) dichloro {1,1' -dimethylsilylene (2-ethyl-4-methylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (12) dichloro {1,1'-dimethylsilylene (4-t-butyl- 2-methylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (13) dichloro {1,1'-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2 -Methyl-4-phenyl-4H-azulenyl)}hafnium(14)dichloro{1,1'-dimethylsilylene(2,3,4-trimethylcyclopentadienyl)(2-methyl-4-phenyl-4H-azulenyl) )} hafnium (15) dichloro {1,1'-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (16) dichloro {1, 1'-dimethylsilylene (2,3-dimethyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (17) dichloro {1,1'-dimethylsilylene (2, 3-dimethyl-5-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium

(18) Dichloro {1,1'-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azulenyl)} hafnium (19) dichloro {1,1'- Dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azulenyl)} hafnium (20) dichloro {1,1'-dimethylsilylene (2-methyl-4-phenyl) cyclopentadienyl) (4-phenyl-2-i-propyl-4H-azulenyl)} hafnium (21) dichloro {1,1'-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (4- t-phenyl-2-i-propyl-4H-azulenyl)}hafnium

(22) Dichloro {1,1'-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (4-(4-chlorophenyl)-2-methyl-4H-azulenyl)} hafnium (23) dichloro {1 , 1'-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (4-(4-chlorophenyl)-2-methyl-4H-azulenyl)} hafnium (24) dichloro {1,1'-dimethylsilylene (2-Methyl-4-phenylcyclopentadienyl) (2-methyl-4-(3-methylphenyl)-4H-azulenyl)} hafnium (25) dichloro {1,1'-dimethylsilylene (2,4, 5-trimethylcyclopentadienyl) (2-methyl-4-(3-methylphenyl)-4H-azulenyl)} hafnium (26) dichloro {1,1'-dimethylsilylene (2-methyl-4-phenylcyclopenta dienyl) (4-(4-t-butylphenyl)-2-methyl-4H-azulenyl)} hafnium (27) dichloro {1,1'-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (4-(4-t-butylphenyl)-2-methyl-4H-azulenyl)}hafnium

(28) Dichloro {1,1'-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-(2-naphthyl)-4H-azulenyl)} hafnium (29) dichloro {1 , 1'-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-(2-naphthyl)-4H-azulenyl)} hafnium

(30) Dichloro {1,1'-methylphenylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (31) dichloro {1,1' -silacyclobutenyl (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (32) dichloro {1,1'-silacyclopropenyl (2,4 ,5-trimethylcyclopentadienyl)(2-methyl-4-phenyl-4H-azulenyl)}hafnium(33)dichloro{1,1′-silafluorenyl(2,4,5-trimethylcyclopentadienyl)(2 -Methyl-4-phenyl-4H-azulenyl)}hafnium

(34) Dichloro {1,1'-methylphenylgermylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (35) dichloro {1,1 '-Gelmacyclobutenyl (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (36) dichloro {1,1'-Gelmacyclopropenyl (2, 4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} hafnium (37) dichloro {1,1'-germafluorenyl (2,4,5-trimethylcyclopentadienyl) enyl)(2-methyl-4-phenyl-4H-azulenyl)}hafnium

(5) Component (B)
The olefin polymerization catalyst has as an essential component, in addition to the above component (A), a cationic metallocene compound that reacts with a metallocene compound (component (A), hereinafter sometimes simply referred to as A) as component (A). (component (B), hereinafter sometimes simply referred to as B).

An organoaluminumoxy compound is one of the compounds (B) that reacts with the metallocene compound (A) to form a cationic metallocene compound.
The organoaluminumoxy compound has an Al--O--Al bond in its molecule, and the number of such bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminumoxy compound is usually a product obtained by reacting an organoaluminum compound with water.
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As inert hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene can be used, but aliphatic hydrocarbons or Preference is given to using aromatic hydrocarbons.

As the organoaluminum compound used for preparing the organoaluminumoxy compound, any compound represented by the following general formula (4) can be used, but trialkylaluminum is preferably used.
R ⁶ tAlX ³ _3-t ...Formula (4)
(In formula (4), R ⁶ represents a hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and X ³ is a hydrogen atom or a halogen represents an atom, and t represents an integer of 1≦t≦3.)

The alkyl group of trialkylaluminum can be any of the following: methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. It is particularly preferable that
Two or more of the above organoaluminum compounds can also be used in combination.

The reaction ratio between water and the organoaluminum compound (water/Al molar ratio) is preferably 0.25/1 to 1.2/1, particularly 0.5/1 to 1/1, and the reaction temperature is , usually in the range of -70 to 100°C, preferably in the range of -20 to 20°C. The reaction time is usually selected within the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As the water required for the reaction, not only water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate, etc., and components that can generate water in the reaction system can also be used. Among the organoaluminoxane compounds mentioned above, those obtained by reacting aluminum alkyl with water are usually called aluminoxanes, and in particular, methylaluminoxane (including those consisting essentially of methylaluminoxane (MAO)). is suitable as an organoaluminumoxy compound.
Of course, it is also possible to use a combination of two or more of the above-mentioned organoaluminumoxy compounds as the organoaluminumoxy compound, or a solution or dispersion of the above-mentioned organoaluminumoxy compound in the above-mentioned inert hydrocarbon solvent. You may also use the following.

It is preferable to use an organoaluminumoxy compound as the component (B) of the olefin polymerization catalyst because the strain hardening degree (λmax) of the resulting ethylene polymer increases and the polymerization activity increases.

Other specific examples of the compound (B) that reacts with the metallocene compound (A) to form a cationic metallocene compound include borane compounds and borate compounds. More specifically, the above borane compounds include triphenylborane, tri(o-tolyl)borane, tri(p-tolyl)borane, tri(m-tolyl)borane, tri(o-fluorophenyl)borane, tris( p-fluorophenyl)borane, tris(m-fluorophenyl)borane, tris(2,5-difluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-trifluoromethylphenyl)borane, tris (3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl), tris( Examples include perfluoroanthryl)borane and tris(perfluorobinaphthyl)borane.

Among these, tris(3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluoromethylphenyl)borane, biphenyl)borane, tris(perfluoroanthryl)borane, and tris(perfluorobinaphthyl)borane are more preferred, and even more preferred are tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, and tris( Preferred examples include perfluoronaphthyl)borane and tris(perfluorobiphenyl)borane.

Further, specifically representing the borate compound, a first example is a compound represented by the following general formula (5).
[L ¹ −H]+[BR ⁷ R ⁸ X ⁴ X ⁵ ]--Formula (5)

In formula (5), L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium, or phosphonium. Examples of ammonium include trialkyl-substituted ammoniums such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, and tri(n-butyl)ammonium, and dialkylammoniums such as di(n-propyl)ammonium and dicyclohexylammonium.

Examples of anilinium include N,N-dialkylanilinium such as N,N-dimethylanilinium, N,N-diethylanilinium, and N,N-2,4,6-pentamethylanilinium. Furthermore, examples of the phosphonium include triarylphosphoniums and trialkylphosphoniums such as triphenylphosphonium, tributylphosphonium, tri(methylphenyl)phosphonium, and tri(dimethylphenyl)phosphonium.

Furthermore, in formula (5), R ⁷ and R ⁸ are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and are connected to each other via a bridging group. The substituent of the substituted aromatic hydrocarbon group is preferably an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a halogen such as fluorine, chlorine, bromine, or iodine. Furthermore, X ^{4 and} It is a hydrogen group.

Specific examples of the compound represented by the above general formula (5) include tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, and tributylammonium tetra(3,5- ditrifluoromethylphenyl)borate, tributylammonium tetra(2,6-difluorophenyl)borate, tributylammoniumtetra(perfluoronaphthyl)borate, dimethylaniliniumtetra(pentafluorophenyl)borate, dimethylaniliniumtetra(2,6- ditrifluoromethylphenyl)borate, dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl)borate, dimethylaniliniumtetra(2,6-difluorophenyl)borate, dimethylaniliniumtetra(perfluoronaphthyl)borate, triphenyl Phosphonium tetra(pentafluorophenyl)borate, triphenylphosphoniumtetra(2,6-ditrifluoromethylphenyl)borate, triphenylphosphoniumtetra(3,5-ditrifluoromethylphenyl)borate, triphenylphosphoniumtetra(2,6- difluorophenyl)borate, triphenylphosphoniumtetra(perfluoronaphthyl)borate, trimethylammoniumtetra(2,6-ditrifluoromethylphenyl)borate, triethylammoniumtetra(pentafluorophenyl)borate, triethylammoniumtetra(2,6-ditrifluorophenyl)borate, fluoromethylphenyl)borate, triethylammonium tetra(perfluoronaphthyl)borate, tripropylammonium tetra(pentafluorophenyl)borate, tripropylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tripropylammonium tetra(perfluoro Examples include naphthyl)borate, di(1-propyl)ammoniumtetra(pentafluorophenyl)borate, and dicyclohexylammoniumtetraphenylborate.

Among these, tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tributylammonium tetra(3,5-ditrifluoromethylphenyl)borate, and tributylammonium tetra(perfluoromethylphenyl)borate. naphthyl)borate, dimethylaniliniumtetra(pentafluorophenyl)borate, dimethylaniliniumtetra(2,6-ditrifluoromethylphenyl)borate, dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl)borate, dimethylanilinium Tetra(perfluoronaphthyl)borate is preferred.

Further, a second example of the borate compound is represented by the following general formula (6).
[L ² ]+[BR ⁷ R ⁸ X ⁴ X ⁵ ]--Formula (6)

In formula (6), L ² is a carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium Examples include cations and protons. Moreover, R ⁷ , R ⁸ , X ⁴ and X ⁵ are the same as defined in the above general formula (5).

Specific examples of the above compounds include trityltetraphenylborate, trityltetra(o-tolyl)borate, trityltetra(p-tolyl)borate, trityltetra(m-tolyl)borate, trityltetra(o-fluorophenyl)borate, Trityltetra(p-fluorophenyl)borate, trityltetra(m-fluorophenyl)borate, trityltetra(3,5-difluorophenyl)borate, trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoro methylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, tropiniumtetraphenylborate, tropiniumtetra(o-tolyl)borate, tropiniumtetra(p- tolyl)borate, tropinium tetra(m-tolyl)borate, tropiniumtetra(o-fluorophenyl)borate, tropiniumtetra(p-fluorophenyl)borate, tropiniumtetra(m-fluorophenyl)borate, tropiniumtetra (3,5-difluorophenyl)borate, tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(3,5-ditrifluoromethylphenyl)borate, Tropinium tetra(perfluoronaphthyl)borate, NaBPh ₄ , NaB(o-CH ₃ -Ph) ₄ , NaB(p-CH ₃ -Ph) ₄ , NaB(m-CH ₃ -Ph) ₄ , NaB(o- F-Ph) ₄ , NaB(p-F-Ph) ₄ , NaB(m-F-Ph) ₄ , NaB(3,5-F ₂ -Ph) ₄ , NaB(C ₆ F ₅ ) ₄ , NaB( 2,6-(CF ₃ ) ₂ -Ph) ₄ , NaB(3,5-(CF ₃ ) ₂ -Ph) ₄ , NaB(C ₁₀ F ₇ ) ₄ , HBPh _4.2 diethyl ether, HB(3, 5-F ₂ -Ph) _4.2 diethyl ether, HB(C ₆ F ₅ ) 4.2 diethyl ether, HB(2,6-(CF ₃ ) ₂ -Ph) _4.2 diethyl ether, HB(3, Examples include 5-(CF ₃ ) ₂ -Ph) _4.2 diethyl ether and HB(C ₁₀ H ₇ ) _4.2 diethyl ether.

Among these, trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, Tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(3,5-ditrifluoromethylphenyl)borate, tropiniumtetra(perfluoronaphthyl)borate, NaB(C ₆ F ₅ ) ₄ , NaB(2,6-(CF ₃ ) ₂ -Ph) ₄ , NaB(3,5-(CF ₃ ) ₂ -Ph) ₄ , NaB(C ₁₀ F ₇ ) ₄ , HB(C ₆ F ₅ ) _4.2 diethyl ether, HB(2,6-(CF ₃ ) ₂ -Ph) _4.2 diethyl ether, HB(3,5-(CF ₃ ) ₂ -Ph) _4.2 Diethyl ether and HB(C ₁₀ H ₇ ) _4.2 diethyl ether are preferred.

Among these, trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(pentafluorophenyl)borate, tropiniumtetra(2,6-ditrifluoromethylphenyl)borate, and tropiniumtetra(2,6-ditrifluorophenyl)borate are more preferable among these. methylphenyl)borate, NaB(C ₆ F ₅ ) ₄ , NaB(2,6-(CF ₃ ) ₂ -Ph) ₄ , HB(C ₆ F ₅ ) _4.2 diethyl ether, HB(2,6-( Examples include CF ₃ ) ₂ -Ph) _{4.2 diethyl} ether, HB(3,5-(CF ₃ ) ₂ -Ph) 4.2 diethyl ether, and HB(C ₁₀ H ₇ ) _4.2 diethyl ether.

When a borane compound or a borate compound is used as component (B), the polymerization activity and copolymerizability are increased, so that the productivity of the ethylene polymer having long chain branches is improved. Further, as component (B), a mixture of the above-mentioned organoaluminumoxy compound and the above-mentioned borane compound or borate compound can also be used. Furthermore, two or more of the above borane compounds and borate compounds may be used in combination.

(6) Component (C)
The olefin polymerization catalyst may further contain an inorganic compound carrier (component (C)). As the inorganic support, metals, metal oxides, metal chlorides, metal carbonates, carbonaceous substances, or mixtures thereof can be used.
Suitable metals that can be used as the inorganic carrier include, for example, iron, aluminum, and nickel.

Examples of metal oxides include single oxides or composite oxides of elements in groups 1 to 14 of the periodic table, such as SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , TiO ₂ , _{ZrO2 , Fe2O3 , Al2O3.MgO , Al2O3.CaO , Al2O3.SiO2 , Al2O3.MgO.CaO , Al2O3.MgO.SiO2 , Al} Examples include various natural or synthetic single oxides or composite oxides such as ₂ O ₃ ·CuO, Al ₂ O ₃ ·Fe ₂ O ₃ , Al ₂ O ₃ ·NiO, and SiO ₂ ·MgO. Here, the above formula is not a molecular formula but represents only a composition, and the structure and component ratio of the composite oxide used in the present invention are not particularly limited. Further, the metal oxide used in the present invention may absorb a small amount of water or may contain a small amount of impurities.

As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferable, and specifically, MgCl ₂ , CaCl ₂ and the like are particularly preferable. As the metal carbonate, carbonates of alkali metals and alkaline earth metals are preferable, and specific examples thereof include magnesium carbonate, calcium carbonate, barium carbonate, and the like. Examples of the carbonaceous material include carbon black and activated carbon. Any of the above inorganic supports can be suitably used in the present invention, but metal oxides, silica, alumina, etc. are particularly preferably used.

These inorganic supports are usually calcined at 200 to 800°C, preferably 300 to 600°C, in air or in an inert gas such as nitrogen or argon, to reduce the amount of surface hydroxyl groups to 0.8 to 1.5 mmol/g. It is preferable to adjust the amount of water before use. There are no particular restrictions on the properties of these inorganic carriers, but the average particle size is usually 5 to 200 μm, preferably 10 to 150 μm, the average pore size is 20 to 1000 Å, preferably 50 to 500 Å, and the specific surface area is 150 to 1000 μm. ² /g, preferably 200 to 700 m ² /g, pore volume 0.3 to 2.5 cm ³ /g, preferably 0.5 to 2.0 cm ³ /g, apparent specific gravity 0.20 to 0. Preference is given to using an inorganic support having an amount of 0.50 g/cm ³ , preferably 0.25 to 0.45 g/cm ³ .

The above-mentioned inorganic carriers can of course be used as they are, but as a preliminary treatment, these carriers can be treated with trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, It can be used after being brought into contact with an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al-O-Al bond.

(7) Component (D)
The olefin polymerization catalyst of the present invention contains component (D), which is a compound represented by the following general formula, as an essential component.
General formula M ² L ¹ _n
( ^M2 represents a typical metal atom of Groups 1, 2, and 12 to 15 of the periodic table,
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group,
n is a number corresponding to the valence of ^M2 )

^M2 represents a typical metal atom of Groups 1, 2, and 12 to 15 of the periodic table, specifically Li, Be, B, Na, Mg, Al, K, Ca, Zn, Ga, and Ge. , preferably represents Li, B, Na, Mg, Al, K, and Zn, more preferably represents Mg, Al, and Zn, and still more preferably Al.
^L1 is a hydrogen atom, a halogen atom, a hydrocarbon group, and the halogen atom is specifically F, Cl, Br, I, and the hydrocarbon group is preferably a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, A hydrocarbon group having 1 to 30 carbon atoms that may contain a sulfur atom, more preferably a hydrocarbon group having 1 to 20 carbon atoms that may contain a nitrogen atom, an oxygen atom, or a silicon atom, and even more preferably an oxygen atom. It is a hydrocarbon group having 1 to 14 carbon atoms which may contain , and particularly preferably a hydrocarbon group having 1 to 11 carbon atoms which is composed only of carbon atoms and hydrogen atoms. L ¹ may be the same or different when the valence n of M ² is 2 or more, but it is preferable that at least one of the plurality of L ¹ is a hydrocarbon group, and the plurality of L ¹ More preferably, all of the groups are hydrocarbon groups.

Specific examples of component (D) include LiH, LiF, LiCl, LiBr, LiI, CH ₃ Li, C ₂ H ₅ Li, nC ₃ H ₇ Li, iC ₃ H ₇ Li, nC ₄ H ₉ Li, iC ₄ H ₉ Li, tC ₄ H ₉ Li, 1-C ₅ H ₁₁ Li, 2-C ₅ H ₁₁ Li, 3-C ₅ H ₁₁ Li, 2-CH ₃ -2-C ₄ H ₈ Li, 2- CH ₃ -3-C ₄ H ₈ Li, etc., 1-C ₆ H ₁₃ Li, 2-C ₆ H ₁₃ Li, 3-C ₆ H ₁₃ Li, 2-CH ₃ -1-C ₅ H ₁₀ Li, 2 -CH ₃ -2-C ₅ H ₁₀ Li, 2-CH ₃ -3-C ₅ H ₁₀ Li, 2,3-(CH ₃ ) ₂ -1-C ₄ H ₇ Li, etc., 1-C ₇ H ₁₅ Li, etc., 1-C ₈ H ₁₇ Li, etc., 1-C ₉ H ₁₉ Li, etc., 1-C ₁₀ H ₂₁ Li, etc., 1-C ₁₁ H ₂₃ Li, etc., 1-C ₁₂ H ₂₅ Li, etc., 1- C ₁₃ H ₂₇ Li etc., BeH ₂ , BeF ₂ , BeCl ₂ etc., (CH ₃ ) ₂ Be etc., BH ₃ , BF ₃ , BCl ₃ etc., (CH ₃ ) ₃ B, (CH ₃ ) ₂ BCl etc., NaH, NaF, NaCl, NaBr, etc., CH ₃ Na, C ₂ H ₅ Na, nC ₃ H ₇ Na, iC ₃ H ₇ Na, nC ₄ H ₉ Na, etc., 1-C ₅ H ₁₁ Na, 2-C ₅ H ₁₁ Na etc., MgH ₂ , MgF ₂ , MgCl ₂ etc., (CH ₃ ) ₂ Mg, (C ₂ H ₅ ) ₂ Mg, (nC ₃ H ₇ ) ₂ Mg, (iC ₃ H ₇ ) ₂ Mg etc. ( _{nC4H9 ) 2Mg etc.} , ( _CH3 )( _{C2H5 )} Mg _, ( _CH3 )( _{nC3H7 )} Mg etc., ( _C2H5 )( _nC4H9 )Mg etc. Mg compounds having a hydrocarbon group containing an unsaturated bond such as divinyl Mg, diallyl Mg, (hexenyl) ₂ Mg, (octenyl) ₂ Mg, diphenyl Mg, dibenzyl Mg, etc., AlH ₃ , AlF ₃ , AlCl _{3 ,} etc. CH ₃ ) ₃ Al, (C ₂ H ₅ ) ₃ Al, (nC ₃ H ₇ ) ₃ Al, (iC ₃ H ₇ ) ₃ Al, etc., (nC ₄ H ₉ ) ₃ Al, etc., (CH ₃ ) ₂ ( C ₂ H ₅ )Al, (CH ₃ ) ₂ (nC ₃ H ₇ )Al, etc., (C ₂ H ₅ ) ₂ (nC ₄ H ₉ )Al, etc., trivinyl Al, triallyl Al, (hexenyl) ₃ Al, ( Al compounds having a hydrocarbon group containing an unsaturated bond such as octenyl) ₃ Al, triphenyl Al, tribenzyl Al, etc., KH, KF, KCl, etc., CH ₃ K, C ₂ H ₅ K, nC ₃ H ₇ K, iC ₃ H ₇ K, nC ₄ H ₉ K, iC ₄ H ₉ K, tC ₄ H ₉ K, 1-C ₅ H ₁₁ K, etc., CaH ₂ , CaF ₂ , CaCl ₂ etc., (CH ₃ ) ₂ Ca, ( _CH3 )CaCl etc., _ZnH2 , _ZnF2 , _ZnCl2 etc., _{( CH3} ) _2Zn , ( _CH3 )ZnCl etc., _{( C2H5} ) _2Zn , ( _CH3 )( _C2H5 ) Zn, (nC ₃ H ₇ ) ₂ Zn, (iC ₃ H ₇ ) ₂ Zn, (nC ₄ H ₉ ) ₂ Zn, (iC ₄ H ₉ ) ₂ Zn, (tC ₄ H ₉ ) ₂ Zn, (nC ₅ H ₁₁ ) ₂ Zn, (nC ₆ H ₁₃ ) ₂ Zn, (nC ₇ H ₁₅ ) ₂ Zn, (nC ₈ H ₁₇ ) ₂ Zn, (nC ₉ H ₁₉ ) ₂ Zn, (nC ₁₀ H ₂₁ ) ₂ Zn Zn compounds having a hydrocarbon group containing an unsaturated bond such as divinyl Zn, diallyl Zn, (hexenyl) ₂ Zn, (octenyl) ₂ Zn, diphenyl Zn, dibenzyl Zn, etc., GaH ₃ , GaF ₃ , GaCl _{3 ,} etc. , (CH ₃ ) ₃ Ga, (C ₂ H ₅ ) ₃ Ga, (nC ₃ H ₇ ) ₃ Ga, (iC ₃ H ₇ ) ₃ Ga, etc., (nC ₄ H ₉ ) ₃ Ga, etc., (CH ₃ ) ₂ (C ₂ H ₅ )Ga, (CH ₃ ) ₂ (nC ₃ H ₇ )Ga, etc., (C ₂ H ₅ ) ₂ (nC ₄ H ₉ )Ga, etc., GeH ₄ , GeF ₄ , GeCl ₄ etc., ( CH ₃ ) ₄ Ge, (C ₂ H ₅ ) ₄ Ge, (nC ₃ H ₇ ) ₄ Ge, (iC ₃ H ₇ ) ₄ Ge, etc., (nC ₄ H ₉ ) ₄ Ge, etc., (CH ₃ ) ₃ ( C ₂ H ₅ )Ge, (CH ₃ ) ₃ (nC ₃ H ₇ )Ge, etc., (C ₂ H ₅ ) ₃ (nC ₄ H ₉ )Ge, etc., and paragraph [0034] of JP-A-2012-72229. - Exemplary compounds for MgX ¹ _m R ¹ _n (OR ² ) _2-m-n in general formula (a) described in [0038], general formula (c) described in paragraphs [0044] to [0046] of the same publication Exemplary compounds for AlX ³ _q R ⁴ _r (OR ⁵ ) _3-qr among others are mentioned. Furthermore, dinuclear metal compounds having the structure of the above compounds, such as (1,2-ethylene)di(ZnCl), (1,2-ethylene)di(ZnCH ₃ ), (1,2-ethylene)di(MgC ₂ H ₅ ), (1,4-butylene) di[Al(CH ₃ ) ₂ ], (1,4-butylene) di[Al(CH ₃ )Cl], and the like.

(8) Preparation of catalyst for olefin polymerization Olefin containing component (A) which is an essential component of the method for producing an olefin polymer of the present invention, component (B) which is an essential component, and component (C) which is an optional component. The method of contacting each component when obtaining a polymerization catalyst is not particularly limited, and, for example, the following methods can be arbitrarily adopted.

(I) After bringing component (A) into contact with component (B), component (C) is brought into contact as needed.
(II) After bringing component (A) into contact with component (C) as necessary, component (B) is brought into contact.
(III) Component (B) is brought into contact with component (C) if necessary, and then component (A) is brought into contact.

Among these contact methods, (I) and (III) are preferred, and (I) is most preferred. In either method of contacting, aromatic hydrocarbons (usually containing 6 to 12 carbon atoms) such as benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, dodecane, etc. A method is employed in which each component is brought into contact with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane. This contact is usually carried out at a temperature of -100°C to 200°C, preferably -50°C to 100°C, more preferably 0°C to 50°C, for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, and more preferably It is desirable to carry out the treatment for 30 minutes to 12 hours.

Furthermore, when contacting component (A), component (B), and optionally component (C), as described above, certain components are soluble or sparingly soluble in aromatic hydrocarbon solvents, and certain components are Any aliphatic or alicyclic hydrocarbon solvent in which these components are insoluble or sparingly soluble can be used.

In the case where the contact reaction between the components is carried out in stages, the solvent used in the first stage may be used as it is as a solvent for the second stage contact reaction without removing it. In addition, after the initial catalytic reaction using a soluble solvent, some components may be insoluble or poorly soluble liquid inert hydrocarbons (e.g., aliphatic hydrocarbons such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.). hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons) and recovering the desired product as a solid, or once some or all of the soluble solvent is removed by drying or other means to obtain the desired product. After removal of the product as a solid, subsequent catalytic reactions of the desired product can also be carried out using any of the inert hydrocarbon solvents mentioned above. In the present invention, the contact reaction of each component may be carried out multiple times.

In the present invention, the ratio of component (A) and component (B) used is not particularly limited, but is preferably in the following range.

When an organoaluminumoxy compound is used as the component (B) that reacts with component (A) to produce a cationic metallocene compound, the aluminum atom of the organoaluminumoxy compound relative to the transition metal (M ¹ ) in component (A) The ratio (Al/M ¹ ) is usually in the range of 1 to 100,000, preferably 5 to 10,000, more preferably 50 to 5,000, even more preferably 100 to 2,000, and a borane compound or a borate compound is used. In this case, the atomic ratio (B/M ¹ ) of boron to the transition metal (M ¹ ) in the metallocene compound is usually 0.01 to 100, preferably 0.1 to 50, more preferably 0.2 to 10. It is desirable to select within the range of . Furthermore, when a mixture of an organoaluminumoxy compound, a borane compound, and a borate compound is used as the compound (B) for producing a cationic metallocene compound, each compound in the mixture is added to the transition metal (M ¹ ). However, it is desirable to select the same usage ratio as above.

When component (C) is used, the amount of component (C) used is 1 g per 0.0001 to 5 mmol of transition metal in component (A), preferably 1 g per 0.001 to 0.1 mmol, more preferably 1 g per 0.002-0.05 mmol, more preferably 1 g per 0.003-0.02 mmol.

Component (A), component (B), and optionally component (C) are brought into contact with each other by any of the above contact methods (I) to (III), and then the solvent is removed. , an olefin polymerization catalyst can be obtained as a solid catalyst. It is desirable to remove the solvent under normal pressure or reduced pressure at 0 to 200°C, preferably 20 to 150°C, for 1 minute to 50 hours, preferably 10 minutes to 10 hours.

Note that the olefin polymerization catalyst can also be obtained by the following method.
(IV) Component (A) and component (C) are brought into contact to remove the solvent, and the resulting solid catalyst component is brought into contact with an organoaluminumoxy compound, a borane compound, a borate compound, or a mixture thereof under polymerization conditions. .
(V) Contacting an organoaluminumoxy compound, a borane compound, a borate compound, or a mixture thereof with component (C) to remove the solvent, turning this into a solid catalyst component, and contacting it with component (A) under polymerization conditions. .
In the case of the above contact methods (IV) and (V), the same component ratios, contact conditions, and solvent removal conditions as described above can be used.

In addition, a layered silicate is used as a component that also serves as a component (B) and a component (C) that reacts with component (A), which is an essential component of the method for producing an olefin polymer of the present invention, to produce a cationic metallocene compound. It can also be used. A layered silicate is a silicate compound that has a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with weak bonding force. Most layered silicates are produced naturally as the main component of clay minerals, but these layered silicates are not limited to natural products, and may be artificially synthesized.

Among these, the smectite group, vermiculite group, and mica group, such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, and taeniolite, are preferred.

In general, natural products often have non-ion exchange properties (non-swelling properties), and in that case, in order to have desirable ion exchange properties (or swelling properties), ion exchange properties (or swelling properties) should be adjusted. It is preferable to perform a process for imparting. Among such treatments, particularly preferred are the following chemical treatments. Here, the chemical treatment can be either a surface treatment for removing impurities adhering to the surface or a treatment for influencing the crystal structure and chemical composition of the layered silicate. Specifically, (i) acid treatment using hydrochloric acid, sulfuric acid, etc., (ii) alkali treatment using NaOH, KOH, NH3, etc., and (iii) treatment selected from Groups 2 to 14 of the periodic table. (iv) alcohol, hydrocarbon compound; , formamide, aniline, and other organic substance treatments. These processes may be performed alone or in combination of two or more processes.

The particle properties of the layered silicate can be controlled by pulverization, granulation, sizing, fractionation, etc. before, during, and after all steps. The method may be any suitable method. In particular, regarding granulation methods, for example, spray granulation method, rolling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation method. method, emulsion granulation method, submerged granulation method, and the like. Particularly preferred granulation methods are spray granulation, rolling granulation and compression granulation.

Of course, the above-mentioned layered silicates can be used as they are, but these layered silicates can be used as trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, It can be used in combination with an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al-O-Al bond.

In order to support component (A), which is an essential component of the method for producing an olefin polymer of the present invention, on a layered silicate, component (A) and the layered silicate may be brought into contact with each other, or component (A), an organic The aluminum compound and the layered silicate may be brought into contact with each other.
The method of contacting each component is not particularly limited, and, for example, the following methods can be arbitrarily adopted.
(VI) Component (A) is brought into contact with an organoaluminum compound and then brought into contact with a layered silicate support.
(VII) Component (A) is brought into contact with the layered silicate support, and then brought into contact with an organoaluminum compound.
(VIII) After bringing the organoaluminum compound into contact with the layered silicate support, the organic aluminum compound is brought into contact with component (A).

Among these contact methods, (VI) and (VIII) are preferred. In either method of contacting, aromatic hydrocarbons (usually containing 6 to 12 carbon atoms) such as benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, dodecane, etc. A method is employed in which each component is brought into contact with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane.

The proportions of component (A), organoaluminum compound, and layered silicate carrier are not particularly limited, but are preferably in the following ranges. The amount of component (A) supported is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, and more preferably 0.01 to 0.1 mmol per gram of the layered silicate carrier. Further, when an organoaluminum compound is used, the amount of Al supported is preferably in the range of 0.01 to 100 mol, preferably 0.1 to 50 mol, and more preferably 0.2 to 10 mol.

For the method of supporting and removing the solvent, the same conditions as those for the above-mentioned inorganic support can be used. When a layered silicate is used as a component that serves both as component (B) and component (C), the resulting olefin polymer has a narrow molecular weight distribution. Furthermore, the productivity of the olefin polymer having high polymerization activity and long chain branching is improved. The catalyst for olefin polymerization thus obtained may be used after prepolymerizing monomers, if necessary.

(9) Polymerization method The method for producing an olefin polymer of the present invention can be used for homopolymerization of ethylene or copolymerization of ethylene and α-olefin.

In the present invention, the polymerization reaction can be carried out in the presence of the above-mentioned supported catalyst, preferably by slurry polymerization or gas phase polymerization. In the case of slurry polymerization, aliphatic hydrocarbons such as isobutane, hexane, and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic polymers such as cyclohexane and methylcyclohexane are Ethylene or the like is polymerized in the presence or absence of an inert hydrocarbon solvent selected from group hydrocarbons and the like. It goes without saying that liquid monomers such as liquid ethylene and liquid propylene can also be used as solvents. In the case of gas phase polymerization, ethylene or the like is polymerized in a reactor into which a gas flow of ethylene or comonomer is introduced, circulated, or circulated. In the present invention, more preferred polymerization is gas phase polymerization. The polymerization conditions are not particularly limited, but the temperature is 0 to 250°C, preferably 60 to 110°C, more preferably 60 to 100°C, and the olefin partial pressure is normal pressure to 10 MPa, preferably normal pressure to 4 MPa, and more. Preferably 0.2 to 1.8 MPa, more preferably 0.2 to 1.5 MPa, even more preferably 0.2 to 1.3 MPa, particularly preferably 0.2 to 1.1 MPa, and most preferably 0.2 to 1.1 MPa. The pressure is in the range of 0.75 MPa, and the polymerization time is usually 5 minutes to 12 hours, preferably 20 minutes to 8 hours, more preferably 30 minutes to 5 hours.

Although the molecular weight of the resulting polymer can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, the molecular weight can be controlled more effectively by adding hydrogen to the polymerization reaction system. I can do it. Furthermore, a component for the purpose of removing water, a so-called scavenger, may be added to the polymerization system without any problem. Examples of such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, the above-mentioned organoaluminumoxy compounds, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethylzinc and dibutylzinc, diethylzinc, etc. Organomagnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferred, and triethylaluminum is particularly preferred. It is also possible to apply the present invention without any problem to a multi-stage polymerization system including two or more stages in which polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature are different from each other.

(10) Conditions for the first production method The first production method is a method for producing an olefin polymer having a long chain branched structure by supplying the olefin polymer so as to satisfy the following conditions (1) to (3). It is characterized in that the supply amount ratio (mol/mol) of component (D) to component (A) is 1.5 to 100 times the ratio (mol/mol) in the following condition (1).

Condition (1) The ratio of M ² to M ¹ (mol/mol) is 1160 to 1800
Condition (2) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12
Condition (3) The ratio of ^M2 to the polymerization medium (mmol/kg) is 0.01 to 100

Condition (1) is that the ratio of M ² to M ¹ (mol/mol) is 1160 to 1800, preferably 1350 to 1800, and more preferably 1500 to 1800.
Condition (2) is that the ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12, preferably 0.005 to 1.0, more preferably 0.01 to 0.38. be.
Condition (3) is such that the ratio of M ² to the polymerization medium (mmol/kg) is from 0.01 to 100, preferably from 0.02 to 10, and more preferably from 0.03 to 5.

In the first production method, the supply amount ratio (mol/mol) of component (D) to component (A) is 1.5 to 100 times the ratio (mol/mol) in the above condition (1), preferably 1.7 times to 70 times, more preferably 1.9 to 50 times.
When the above conditions are met, the molecular weight distribution can be narrowed while maintaining the long chain branched structure characteristics of the olefin polymer.

2. Method for producing olefin polymer (second production method)
In the second production method of the present invention, an olefin polymerization catalyst containing the following essential components (A) and (B) and the following component (D) are added to a polymerization reactor in which an olefin monomer and a polymerization medium are present under the following conditions ( This is a method for producing an olefin polymer having a long chain branched structure, which is carried out by supplying so as to satisfy 1a) to (3a).

Component (A): a crosslinked biscyclopentadienyl compound represented by the following general formula (1) containing transition metal element ^M1

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms; represents a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ¹ and Q ² each independently represent a carbon atom, a silicon atom, or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of the four R ^1s are bonded to form a ring together with Q ¹ and Q ² . It's okay. m is 0 or 1, and when m is 0, Q ¹ is directly bonded to the conjugated 5-membered ring containing R ² and R ³ . R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, Indicates a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a silyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms, and two R ² and 2 At least one of the three R ³ is not a hydrogen atom, and at least one of the four R ⁴ is not a hydrogen atom. Among R ² , R ³ and R ⁴ , only one pair of adjacent R ³ or adjacent R ² and R ³ may form a ring together with the carbon atoms to which they are bonded. ]

Component (B): a compound that reacts with the compound of component (A) to produce a cationic metallocene compound

Component (D): a compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Groups 1, 2, and 12 to 15 of the periodic table,
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group,
n is a number corresponding to the valence of ^M2 )

Condition (1a) The ratio of M ² to M ¹ (mol/mol) is 1800 to 180000
Condition (2a) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12
Condition (3a) The ratio of M ² to the polymerization medium (mmol/kg) is 0.01 to 100

The second manufacturing method of the present invention is characterized in that the characteristic requirements and various conditions (conditions (1), conditions (2), and conditions (3)) in the first manufacturing method are the following conditions (1a) and (2a). ) and condition (3a) are replaced, the conditions are the same, so detailed descriptions of conditions other than these will be omitted and the description in the first manufacturing method will be quoted as is.

Condition (1a) The ratio of M ² to M ¹ (mol/mol) is 1800 to 180000, preferably 2000 to 180000, more preferably 2000 to 50000, still more preferably 2500 to 50000, Particularly preferably 3,200 to 20,000.
Condition (2a) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12, preferably 0.001 to 2.0, more preferably 0.005 to 1.0. , more preferably 0.005 to 0.38, particularly preferably 0.01 to 0.38.
Condition (3a) The ratio of ^M2 to the polymerization medium (mmol/kg) is from 0.01 to 100, preferably from 0.02 to 20, more preferably from 0.03 to 15, even more preferably It is 0.04 to 10, particularly preferably 0.05 to 5.0.
When the above conditions are met, the molecular weight distribution can be narrowed while maintaining the long chain branched structural characteristics of the olefin polymer.

3. Physical Properties of Olefin Polymer The properties of the olefin polymer obtained by the method for producing an olefin polymer of the present invention are not particularly limited, but from the viewpoint of moldability and mechanical properties, it is preferable to have the following physical properties.
(1) Physical properties (i)
The value of the molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) and the molecular weight distribution ( The ratio ([Mw/Mn]/[Mw ₀ /Mn ₀ ]) to the value of Mw 0 /Mn ₀ ) is preferably 0.50 to 0.95, and preferably 0.55 to 0.94 _. is more preferable, and particularly preferably from 0.60 to 0.94. Within this range, the olefin polymer will have a narrow molecular weight distribution.
Here, "obtained when the supply ratio of component (D) to component (A) is not increased" means the following in the first manufacturing method. That is, it means a case where the supply amount ratio (mol/mol) of component (D) to component (A) is 1.0 times the ratio of the following condition (1). Specifically, if the ratio (M ² /M ¹ ) of condition (1) is 1160, it means that the supply amount ratio (D/A) is also 1160 (hereinafter, the same definition will apply). ).


Condition (1) The ratio of M ² to M ¹ (mol/mol) is 1160 to 1800

In addition, "obtained when the supply ratio of component (D) to component (A) is not increased" means the following in the second manufacturing method. Condition (1a) means a case where the ratio (mol/mol) of M ² to M ¹ is less than 1800 (hereinafter similarly defined).

(2) Physical properties (ii)
The value (g' _m ) of the branching index g' at a molecular weight of 100,000 measured by a GPC measuring device that combines a differential refractometer, a viscosity detector, and a light scattering detector, and the component (D) for the component (A). ), the ratio (g' _m /g' _m0 ) of the branching index g' of the olefin polymer obtained when the molecular weight is 100,000 (g' _m0 ) is 0.90 to 1. It is preferably .10, more preferably 0.90 to 1.08, even more preferably 0.90 to 1.07, and particularly preferably 0.93 to 1.07. Within this range, the long chain branched structure characteristics of the olefin polymer are maintained.

(3) Physical properties (iii)
Mw/Mn of the olefin polymer is preferably 2.0 to 7.0, more preferably 2.4 to 6.0, even more preferably 2.6 to 5.0, Particularly preferred is 2.6 to 4.0. Within this range, the olefin polymer will have a narrow molecular weight distribution.

(4) Physical properties (iv)
The _g'm of the olefin polymer is preferably from 0.50 to 0.95, more preferably from 0.50 to 0.90, even more preferably from 0.55 to 0.87. , 0.60 to 0.85 is particularly preferred. Within this range, the olefin polymer will have a sufficiently high melting tension and excellent product properties such as moldability and mechanical strength.

(5) Physical properties (v)
The MFR (melt flow rate, 190°C, 2.16 kg load) of the olefin polymer is preferably 0.001 to 1000 g/10 minutes, more preferably 0.005 to 100 g/10 minutes, and Particularly preferred is .05 to 50 g/10 minutes. Within this range, the olefin polymer will have good melt flowability and excellent product properties such as moldability and mechanical strength.

(6) Physical properties (vi)
The density of the olefin polymer is preferably 0.895 to 0.970 g/cm ³ , more preferably 0.900 to 0.965 g/cm ³ , and 0.905 to 0.960 g/cm ³ It is particularly preferable that Within this range, the olefin polymer will have good low-temperature processability and excellent moldability and product properties such as rigidity and transparency.

(7) Moldability The olefin polymer produced by the production method of the present invention has improved melt properties and excellent moldability compared to ordinary ethylene polymers.

EXAMPLES The present invention will be specifically explained below by showing Examples, but the present invention is not limited to these Examples. The evaluation method used in the examples is as follows. All of the following catalyst synthesis steps and polymerization steps were performed under a purified nitrogen atmosphere, and the solvent used was one that had been dehydrated and purified using molecular sieve 4A. was used.

1. Various evaluation (measurement) methods (1) MFR:
It was measured at 190° C. and a load of 2.16 kg in accordance with JIS K6760. FR (flow rate ratio) was calculated from the ratio of MFR10kg (=MFR10kg/MFR), which is the MFR similarly measured under the conditions of 190°C and 10kg load.

(2) Density: Density was measured in accordance with JIS K7112 by heat-treating the strand obtained during MFR measurement at 100° C. for 1 hour, and then allowing it to stand at room temperature for 1 hour, using a density gradient tube method.

(3) Measurement of molecular weight distribution:
In the present invention, weight average molecular weight (Mw) and number average molecular weight (Mn) refer to those measured by gel permeation chromatography (GPC). Conversion from retention capacity to molecular weight is performed using a standard polystyrene calibration curve prepared in advance. The standard polystyrene used is the following brand manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000. A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg/mL BHT) so that each sample is 0.5 mg/mL. The calibration curve uses a cubic equation obtained by approximation using the least squares method. The following numerical value is used for the viscosity formula [η]=K×M ^α used for conversion to molecular weight.
PS: K=1.38×10 ⁻⁴ , α=0.7
PE: K=3.92×10 ⁻⁴ , α=0.733
PP: K=1.03×10 ⁻⁴ , α=0.78

Note that the measurement conditions for GPC are as follows.
Equipment: Waters GPC (ALC/GPC 150C)
Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M/S (3 columns)
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140°C
Flow rate: 1.0ml/min Injection volume: 0.2ml
Preparation of sample: For the sample, a 1 mg/mL solution is prepared using ODCB (containing 0.5 mg/mL BHT) and dissolved at 140° C. for about 1 hour. Note that the baseline and interval of the obtained chromatogram are determined as illustrated in FIG. 1.

(4) Branched structure analysis by GPC-VIS As a GPC device equipped with a differential refractometer (RI) and a viscosity detector (Viscometer), Alliance GPCV2000 manufactured by Waters was used. Further, as a light scattering detector, a multi-angle laser light scattering detector (MALLS) DAWN-E manufactured by Wyatt Technology was used. The detectors were connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (added with antioxidant Irganox 1076 at a concentration of 0.5 mg/mL). The flow rate is 1 mL/min. The columns used were two Tosoh GMHHR-H(S)HT columns connected together. The temperature of the column, sample injection section, and each detector was 140°C. The sample concentration was 1 mg/mL. The injection volume (sample loop volume) is 0.2175 mL. To obtain the absolute molecular weight (M), square radius of inertia (Rg) obtained from MALLS, and limiting viscosity ([η]) obtained from Viscometer, the data processing software ASTRA (version 4.73.04) included with MALLS was used. , the calculations were made with reference to the following literature.

References:
1. Developments in polymer characterization, vol. 4. Essex: Applied Science; 1984. Chapter1.
2. Polymer, 45, 6495-6505 (2004)
3. Macromolecules, 33, 2424-2436 (2000)
4. Macromolecules, 33, 6945-6952 (2000)

[Calculation of branching index (g' m), etc.]
The branching index (g') is calculated as the ratio (ηbranch/ηlin) of the limiting viscosity (ηbranch) obtained by measuring the sample with the above Viscometer and the limiting viscosity (ηlin) obtained by separately measuring the linear polymer. do.
When long chain branches are introduced into a polymer molecule, the radius of gyration becomes smaller compared to a linear polymer molecule of the same molecular weight. Since the intrinsic viscosity decreases as the radius of inertia decreases, the ratio (ηbranch/ηlin) of the intrinsic viscosity of a branched polymer to the intrinsic viscosity (ηbranch) of a linear polymer of the same molecular weight (ηbranch/ηlin) decreases as long chain branches are introduced. It's becoming. Therefore, when the branching index (g'=ηbranch/ηlin) becomes a value smaller than 1, it means that branching has been introduced, and as the value decreases, the number of long chain branches introduced increases. It means that. In particular, in the present invention, the above g' at a molecular weight of 100,000 is calculated as g' _m as the absolute molecular weight obtained from MALLS.
FIGS. 2(a) and 2(b) show an example of the analysis results by the above GPC-VIS. FIGS. 2(a) and 2(b) represent the branching index (g') at the molecular weight (M) obtained from MALLS. Here, as the linear polymer, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) was used.

2. Examples and comparative examples [Reference example 1]
(1) Synthesis of crosslinked biscyclopentadienyl compound (component A) Dimethylsilylene (3-methyl-4-(2-(5-methyl)-furyl)-indenyl) (2,3,4, 5-Tetramethylcyclopentadienyl)zirconium dichloride was synthesized according to the following method. Note that this compound is referred to as metallocene compound A (see the chemical formula below).

(1-1) Synthesis of 1-methyl-7-(2-(5-methyl)-furyl)-indene (1-1-a) Synthesis of 2-bromophenyl-2-chloroethyl ketone In a 100 ml flask, add 2 - Bromobenzoic acid (5.30 g, 26.4 mmol) and 25 ml of thionyl chloride were added, and the mixture was refluxed for 2 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure, and 5.50 g of the resulting acid chloride was used in the next reaction without purification.
Acid chloride (5.00 g, 22.7 mmol) and 50 ml of dichloromethane were added to a 100 ml flask to form a solution, aluminum chloride (3.02 g, 22.7 mmol) was further added, and ethylene was bubbled in at 20° C. for 4 hours. After quenching the reaction with 4N hydrochloric acid and separating the organic and aqueous phases, the aqueous phase was washed three times with 50 ml of methyl-t-butyl ether, the combined organic phase was washed three times with 50 ml of water, and 100 ml of saturated sodium bicarbonate water. Then, it was washed with 100 ml of saturated saline. After drying with sodium sulfate, the solvent was distilled off under reduced pressure to obtain 4.80 g (yield: 85%) of Compound 3. It was used in the next reaction without further purification.
(1-1-b) Synthesis of 7-bromo-1-indanone Aluminum chloride (7.40 g, 55.6 mmol) and sodium chloride (2.15 g, 37.1 mmol) were added to a 100 ml flask and heated to 130°C. After that, 2-bromophenyl-2-chloroethylketone (4.60 g, 18.5 mmol) was slowly added and the mixture was stirred at 160° C. for 1 hour. After the reaction, it was cooled to 30°C and quenched with ice water. After adjusting the pH to 5 with concentrated hydrochloric acid, separate the organic phase and aqueous phase, wash the aqueous phase three times with 100 ml of dichloromethane, collect the organic phase, wash with 100 ml of water and 100 ml of saturated saline, and dry over sodium sulfate. Then, the solvent was distilled off under reduced pressure to obtain a crude product. Further purification was performed using a silica gel column (petroleum ether/ethyl acetate = 30/1) to obtain 1.60 g (yield: 33%) of 7-bromo-1-indanone.
(1-1-c) Synthesis of 7-(2-(5-methyl)-furyl)-1-indanone After adding 2-methylfuran (0.933 g, 11.4 mmol) and 10 ml of THF to a 100 ml flask and making a solution. , n-butyllithium/hexane solution (2.5M, 4.70ml, 11.4mmol) was added at -30°C, and the mixture was stirred at room temperature for 2 hours. Zinc chloride (1.55 g, 11.4 mmol) and 10 ml of THF were added to a separately prepared 100 ml flask, and then the above reaction solution was added at 0° C., followed by stirring at room temperature for 1 hour. Furthermore, in a separately prepared 100 ml flask, copper(I) iodide (90 mg, 0.473 mmol), Pd(dppf)Cl ₂ (177 mg, 0.236 mmol), and 7-bromo-1-indanone (2.00 g, 9.45 mmol) were added. ) and 10 ml of DMA, the above reaction product was added to the suspension, and the mixture was refluxed for 15 hours. The mixture was cooled to room temperature, added with 50 ml of water, and extracted twice with 50 ml of ethyl acetate. The organic phases were collected, washed twice with 50 ml of water and 50 ml of saturated brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. Further purification was performed using a silica gel column (petroleum ether/ethyl acetate = 20/1) to obtain 0.70 g (yield: 35%) of 7-(2-(5-methyl)-furyl)-1-indanone.
(1-1-d) Synthesis of 1-methyl-7-(2-(5-methyl)-furyl)-indene 7-(2-(5-methyl)-furyl)-1-indanone (1 After adding .40 g, 6.59 mmol) and 20 ml of THF to form a solution, methyllithium/diethyl ether solution (1.6 M, 7.5 ml, 11.9 mmol) was added at -78°C, and the mixture was stirred at room temperature for 10 hours. The reaction was quenched with 20 ml of saturated aqueous ammonium chloride solution and volatile components were removed under reduced pressure. The remaining solution was extracted twice with 50 ml of ethyl acetate, the organic phases were collected, washed with 50 ml of saturated brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. It was used in the next reaction without further purification.
The above crude product and 30 ml of toluene were added to a 100 ml flask to form a solution, then p-toluenesulfonic acid (62.0 mg, 0.330 mmol) was added and stirred at 130° C. for 2 hours. During stirring, water produced was removed using a Dean-Stark trap. The mixture was cooled to room temperature, 30 ml of saturated aqueous sodium bicarbonate solution was added, and the organic phase was separated. After the aqueous phase was extracted three times with 50 ml of ethyl acetate, the organic phase was collected, washed with 50 ml of saturated brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. Further purification was performed using a silica gel column (petroleum ether) to obtain 0.850 g (yield: 61%) of 1-methyl-7-(2-(5-methyl)-furyl)-indene.

(1-2) Synthesis of (2,3,4,5-tetramethylcyclopentadienyl)dimethylchlorosilane After adding 2.40 g (19.6 mmol) of tetramethylcyclopentadiene and 40 ml of THF to a 200 ml flask and making a solution, The mixture was cooled to −78° C., 12.0 ml (30.0 mmol) of n-butyllithium/hexane solution (2.5 M) was added, and the mixture was returned to room temperature and stirred for 3 hours. 5.00 g (38.7 mmol) of dimethyldichlorosilane and 20 ml of THF were added to a separately prepared 200 ml flask, cooled to -78°C, and the above reaction solution was added. The mixture was returned to room temperature and stirred for 12 hours. By removing the volatiles by distillation under reduced pressure, 4.00 g of a yellow liquid was obtained. The resulting yellow liquid was used in the next reaction without further purification.

(1-3) Synthesis of (3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)dimethylsilane In a 100 ml flask, Add 2.60 g (12.4 mmol) of 1-methyl-7-(2-(5-methyl)-furyl)-indene and 40 ml of THF to make a solution, then cool to -78°C and make an n-butyllithium/hexane solution. (2.5M) 5.2 ml (13.0 mmol) was added, the mixture was returned to room temperature, and stirred for 3 hours. 3.40 g (15.8 mmol) of the unpurified yellow liquid obtained in (1-2) and 10 ml of THF were added to a separately prepared 200 ml flask, cooled to -78° C., and the above reaction solution was added. The mixture was returned to room temperature and stirred for 12 hours. The reaction mixture was slowly added to 40 ml of ice water and extracted twice with 200 ml of ethyl acetate. The obtained organic phase was washed with 50 ml of saturated brine and dried over anhydrous sodium sulfate. The sodium sulfate was filtered, the solution was distilled off under reduced pressure, and purified with a silica gel column (petroleum ether) to give (3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3, 1.40 g (yield 25%) of a yellow oil of 4,5-tetramethylcyclopentadienyl)dimethylsilane was obtained.

(1-4) Synthesis of dimethylsilylene (3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride 200 ml flask , (3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)dimethylsilane 2.20 g (5.70 mmol), 30 ml of diethyl ether was added and the mixture was cooled to -78°C. 4.8 ml (11.9 mmol) of n-butyllithium/n-hexane solution (2.5 M) was added dropwise thereto, and the mixture was returned to room temperature and stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 60 ml of dichloromethane was added, and the mixture was cooled to -78°C. 1.40 g (6.01 mmol) of zirconium tetrachloride was added thereto, and the mixture was stirred overnight while gradually returning to room temperature. 3.0 g of yellow powder was obtained by distilling off the solvent under reduced pressure from the filtrate obtained by filtering the reaction solution. This powder was washed with 25 ml of toluene and dimethylsilylene(3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride was washed with 25 ml of toluene. 0.75 g (yield 26%) of yellow powder was obtained.

¹ H-NMR values (CDCl ₃ ): δ0.94 (s, 3H), δ1.19 (s, 3H), δ1.90 (s, 3H), δ1.95 (s, 3H), δ1.98 ( s, 3H), δ2.04 (s, 3H), δ2.28 (s, 3H), δ2.38 (s, 3H), δ5.52 (s, 1H), δ6.07 (d, 1H), δ6.38 (d, 1H), δ7.04 (dd, 1H), δ7.37 (d, 1H), δ7.45 (d, 1H).

(2) Synthesis of catalyst for olefin polymerization In a nitrogen atmosphere, 3.8 g of silica calcined at 400°C for 5 hours was placed in a 200ml two-necked flask, and the mixture was dried under reduced pressure using a vacuum pump for 1 hour while heating in a 150°C oil bath. 21 mg of metallocene compound A was placed in a separately prepared 100 ml two-necked flask under a nitrogen atmosphere, and dissolved in 21 ml of dehydrated toluene. 11 ml of a 20% methylaluminoxane/toluene solution manufactured by Albemarle was added to a toluene solution of metallocene compound A at room temperature and stirred for 30 minutes. A 200 ml two-necked flask containing vacuum-dried silica and 24 ml of dehydrated toluene was heated and stirred in an oil bath at 40° C., and the entire amount of the toluene solution of the reaction product of metallocene compound A and methylaluminoxane was added thereto. After stirring at 40°C for 1 hour, the toluene solvent was distilled off under reduced pressure while heating at 40°C to obtain a solid catalyst.

(3) Production of ethylene/1-hexene copolymer An ethylene/1-hexene copolymer was produced using the solid catalyst obtained in the above (2) Preparation of solid catalyst. That is, 30 ml of 1-hexene, 0.30 mmol of triethylaluminum, 40 ml of hydrogen, and 441 g of isobutane were added to a 2 L autoclave equipped with an induction stirring device, the temperature was raised to 85° C., and ethylene was introduced to maintain the ethylene partial pressure at 0.7 MPa. . Next, 25 mg of the solid catalyst obtained in the above (2) was introduced under pressure with nitrogen, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 0.7 MPa and a temperature of 85°C. During the polymerization reaction, hydrogen was additionally supplied at a supply rate proportional to the ethylene consumption rate. Polymerization was stopped by adding ethanol. The ethylene/1-hexene copolymer thus obtained weighed 140 g. The polymerization results are summarized in the table.

[Example 1]
(1) Synthesis of catalyst for olefin polymerization In a nitrogen atmosphere, 31.4 g of silica calcined at 400° C. for 5 hours was placed in a 500 ml two-necked flask, and the mixture was dried under reduced pressure using a vacuum pump for 1 hour while heating in a 150° C. oil bath. 87 mg of metallocene compound A was placed in a separately prepared 200 ml two-necked flask under a nitrogen atmosphere, and dissolved in 84 ml of dehydrated toluene. 88 ml of a 20% methylaluminoxane/toluene solution manufactured by Albemarle was added to a toluene solution of metallocene compound A at room temperature and stirred for 30 minutes. A 500 ml two-necked flask containing vacuum-dried silica and 204 ml of dehydrated toluene was heated and stirred in an oil bath at 40° C., and the entire amount of the toluene solution of the reaction product of metallocene compound A and methylaluminoxane was added thereto. After stirring at 40°C for 1 hour, the toluene solvent was distilled off under reduced pressure while heating at 40°C to obtain a solid catalyst.
(2) Production of ethylene/1-hexene copolymer In the same manner as in Reference Example 1(3), except that 25 mg of the solid catalyst obtained in (1) above was used and 0.30 mmol of triethylaluminum was used, ethylene/1-hexene copolymer was used. - A hexene copolymer was produced. As a result, 30 g of ethylene/1-hexene copolymer was produced. The polymerization results are summarized in the table.

[Example 2]
An ethylene/1-hexene copolymer was produced in the same manner as in Reference Example 1(3), except that 22 mg of the solid catalyst obtained in Reference Example 1 was used and 0.90 mmol of triethylaluminum was used. As a result, 61 g of ethylene/1-hexene copolymer was produced. The polymerization results are summarized in the table.

[Example 3]
An ethylene/1-hexene copolymer was produced in the same manner as in Reference Example 1 (3), except that 27 mg of the solid catalyst obtained in Example 1 was used and 0.90 mmol of triethylaluminum was used. As a result, 39 g of ethylene/1-hexene copolymer was produced. The polymerization results are summarized in the table.

[Comparative example 1]
(1) Crosslinked biscyclopentadienyl compound B; dimethylsilylene (3-methyl-4-(4-trimethylsilyl-phenyl)-indenyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride synthesis

(2-1) Synthesis of 7-bromo-1-indanone 7-bromo-1-indanone was synthesized in the same manner as in (1-1-a) and (1-1-b) of the metallocene compound A.

(2-2) Synthesis of 3-methyl-4-bromoindene 7.50 g (35.5 mmol) of 7-bromo-1-indanone and 100 ml of toluene were added to a 200 ml flask to form a solution, and then methylmagnesium bromide was added at 0°C. 17.77 ml (3M, 53.31 mmol) of /diethyl ether solution was added, and the mixture was stirred at 15° C. for 12 hours. The reaction solution was poured into 200 ml of ice water, and the precipitated solid was filtered and washed three times with 60 ml of ethyl acetate. After separating the organic phase from the filtrate, it was washed twice with 100 ml of water and dried over anhydrous sodium sulfate. The sodium sulfate was filtered and the solvent was distilled off under reduced pressure to obtain 8.00 g of a crude product of 7-bromo-1-methylindanol.
8.00 g (35.23 mmol) of the crude product of 7-bromo-1-methylindanol and 150 ml of toluene were added to a 300 ml flask to form a solution, and then 134.03 mg of p-toluenesulfonic acid monohydrate was prepared at 15°C. (704.60 μmol) was added and stirred at 110° C. for 2 hours. During stirring, water produced was removed using a Dean-Stark trap. The mixture was cooled to room temperature, 50 ml of saturated aqueous sodium bicarbonate solution was added, and the organic phase was separated. After the aqueous phase was extracted three times with 60 ml of ethyl acetate, the organic phase was collected, washed three times with 50 ml of saturated brine, and dried over sodium sulfate. A crude product was obtained by filtering the sodium sulfate and distilling off the solvent under reduced pressure. Further purification was performed using a silica gel column (petroleum ether) to obtain 5.00 g of 3-methyl-4-bromoindene (yield 67.8%).

(2-3) Synthesis of 3-methyl-4-(4-trimethylsilyl-phenyl)-indene 2.50 g (12.0 mmol) of 3-methyl-4-bromoindene and 40 ml of dimethoxyethane were added to a 200 ml flask to form a solution. After that, 2.79 g (14.4 mmol) of 4-trimethylphenylboronic acid, 343.77 mg (597.86 μmol) of Pd(dba) ₂ , 3.81 g (17.9 mmol) of tripotassium phosphate and 40 ml of water were heated at 15°C. were added and stirred under reflux for 16 hours. It was cooled to room temperature and 50 ml of water was poured into it. After separating the organic phase, the aqueous phase was extracted three times with 50 ml of ethyl acetate, mixed with the previous organic phase, and dried over anhydrous sodium sulfate. A crude product was obtained by filtering the sodium sulfate and distilling off the solvent under reduced pressure. Further purification was performed using a silica gel column (petroleum ether) to obtain 3.10 g (yield 92.8%) of 3-methyl-4-(4-trimethylsilyl-phenyl)-indene.

(2-4) Synthesis of (2,3,4,5-tetramethylcyclopentadienyl)dimethylchlorosilane 2,3,4,5-tetramethyl cyclopentadienyl)dimethylchlorosilane was synthesized.

(2-5) Synthesis of (3-methyl-4-(4-trimethylsilyl-phenyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)dimethylsilane 1-Methyl-7-(2 Using 3.10 g (11.1 mmol) of 3-methyl-4-(4-trimethylsilyl-phenyl)-indene instead of 2.60 g (12.4 mmol) of -(5-methyl)-furyl)-indene, a metallocene compound Synthesis was carried out in the same manner as in A(1-3) to obtain (3-methyl-4-(4-trimethylsilyl-phenyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)dimethylsilane. 1.00 g (yield 19.7%) of yellow liquid was obtained.

(2-6) Synthesis of dimethylsilylene (3-methyl-4-(4-trimethylsilyl-phenyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (3-methyl-4 -(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl) instead of 2.20 g (5.70 mmol) of Using 3.24 g (7.09 mmol) of -(4-trimethylsilyl-phenyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)dimethylsilane, the same as metallocene compound A (1-4) 1.20g of yellow powder of dimethylsilylene(3-methyl-4-(4-trimethylsilyl-phenyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride was synthesized using the following procedure. (yield 27.4%).

¹ H-NMR value (CDCl3): δ0.30 (s, 9H), δ0.93 (s, 3H), δ1.21 (s, 3H), δ1.89 (s, 3H), δ1.96 (s , 3H), δ1.98 (s, 3H), δ2.01 (s, 3H), δ2.06 (s, 3H), δ5.47 (s, 1H), δ7.07 (dd, 1H), δ7 .13 (dd, 1H), δ7.47 (d, 2H), δ7.53 (d, 3H).

Note that this compound is referred to as metallocene compound B (see the chemical formula below).

(2) Synthesis of catalyst for olefin polymerization In a nitrogen atmosphere, 3.2 g of silica calcined at 400° C. for 5 hours was placed in a 200 ml two-necked flask, and the mixture was dried under reduced pressure using a vacuum pump for 1 hour while heating in a 150° C. oil bath. 20 mg of metallocene compound B was placed in a separately prepared 100 ml two-necked flask under a nitrogen atmosphere, and dissolved in 9 ml of dehydrated toluene. 9 ml of a 20% methylaluminoxane/toluene solution manufactured by Albemarle was added to a toluene solution of metallocene compound B at room temperature and stirred for 30 minutes. A 200 ml two-necked flask containing vacuum-dried silica and 21 ml of dehydrated toluene was heated and stirred in an oil bath at 40° C., and the entire amount of the toluene solution of the reaction product of metallocene compound B and methylaluminoxane was added thereto. After stirring at 40°C for 1 hour, the toluene solvent was distilled off under reduced pressure while heating at 40°C to obtain a solid catalyst.

(3) Production of ethylene/1-hexene copolymer The same as in Reference Example 1 (3) except that 67 mg of the solid catalyst obtained in (2) above was used, 75 ml of hydrogen was used, and the ethylene partial pressure was 1.4 MPa. Then, an ethylene/1-hexene copolymer was produced. As a result, 126 g of ethylene/1-hexene copolymer was produced. The polymerization results are summarized in the table.

[Example 4]
An ethylene/1-hexene copolymer was produced in the same manner as in Comparative Example 1 (3) except that 22 mg of the solid catalyst obtained in Comparative Example 1 (2) was used. As a result, 14 g of ethylene/1-hexene copolymer was produced. The polymerization results are summarized in the table. In addition, in Table 7, _C2 partial pressure means ethylene partial pressure.

[Comparative example 2]
(1) Synthesis of catalyst for olefin polymerization A mixed slurry of 32.7 g of silica calcined at 480° C. for 6 hours and 213 ml of dehydrated toluene was prepared in a 1 L flask under a nitrogen atmosphere. 183 mg of metallocene compound A was placed in a separately prepared 200 ml two-necked flask under a nitrogen atmosphere, and dissolved in 90 ml of dehydrated toluene. 90 ml of a 20% methylaluminoxane/toluene solution manufactured by Albemarle was added to a toluene solution of metallocene compound A at room temperature and stirred for 30 minutes. While heating and stirring the 1 L flask containing the previously prepared toluene slurry of silica in an oil bath at 40°C, the entire amount of the toluene solution of the reaction product of metallocene compound A and methylaluminoxane was added, and the temperature was maintained at 40°C. The mixture was stirred for 1 hour. Stirring was stopped after 1 hour, and the mixture was allowed to stand for 10 minutes while being heated to 40°C, and then the supernatant was removed. After adding 600 ml of dehydrated hexane and stirring for 5 minutes, the mixture was allowed to stand for 10 minutes and the supernatant was removed. After washing the catalyst again with 700 ml of dehydrated hexane in the same manner, the hexane was distilled off under reduced pressure to obtain a powdered catalyst.
(2) Production of ethylene/1-hexene copolymer Using the powdered catalyst obtained in (1) above, continuous gas phase copolymerization of ethylene/1-hexene was carried out. That is, a gas phase continuous polymerization apparatus (inner volume 100 L) was prepared at a temperature of 85°C, a hexene/ethylene molar ratio of 2.5%, a hydrogen/ethylene molar ratio of 0.21%, a nitrogen concentration of 40 mol%, and an ethylene partial pressure of 0.45 MPa. Polymerization was carried out while keeping the gas composition and temperature constant while intermittently supplying the powdered catalyst at a rate of 56 mg/hour to a fluidized bed with a diameter of 10 cm and a fluidized bed polymer (dispersing agent) weighing 1.8 kg. . Further, 0.03 mol/L of a hexane diluted solution of triethylaluminum (D component) was supplied to the gas circulation line at 16.7 ml/hr. As a result, the average production rate of produced polyethylene was 274 g/hour. The MFR and density of the ethylene/1-hexene copolymer obtained after producing a cumulative weight of 5 kg or more of polyethylene were 0.5 g/10 min and 0.921 g/cm ³ , respectively. The results are shown in the table below.

[Example 5] to [Example 9] Production of ethylene/1-hexene copolymer;
Continuous gas phase copolymerization of ethylene and 1-hexene was carried out in the same manner as in Comparative Example 2 except for the conditions listed in the table below. However, in Examples 6 to 8, a 0.15 mol/L hexane diluted solution of triethylaluminum (D component) was used. The results are shown in the table below.

3. Evaluation As shown in Tables 5 to 8, in Examples 1, 2, and 3, the value of [Mw/Mn]/[Mw ₀ /Mn ₀ ] was lower than that in Reference Example 1. Similarly, in Example 4, the value of [Mw/Mn]/[Mw ₀ /Mn ₀ ] was lower than that in Comparative Example 1. Furthermore, in Examples 5 to 9, the value of [Mw/Mn]/[Mw ₀ /Mn ₀ ] was lower than that in Comparative Example 2.
On the other hand, the ratio of branching indexes (g' _m /g' _m0 ) was the same in Examples 1, 2, and 3 and Reference Example 1, and the same in Example 4 and Comparative Example 1. Further, the ratio of branching index (g' _m /g' _m0 ) was the same in Examples 5 to 9 and Comparative Example 2.
From these results, it was found that in the present invention, it is possible to narrow the molecular weight distribution without changing the long chain branched structural characteristics of the olefin polymer produced. By controlling the long chain branching structure and molecular weight distribution structure of olefin polymers, it is possible to control the melt viscoelastic properties of olefin polymers, which improves the moldability, mechanical properties, and transparency of olefin polymers in the molten state. It is considered to be useful for improving

The present invention is not limited to the embodiments detailed above, and various modifications and changes can be made within the scope of the claims of the present invention.

According to the present invention, an olefin polymer with a narrow molecular weight distribution without changing the long chain branching structure characteristics is provided. In this olefin polymer, by controlling the long chain branched structure and molecular weight distribution structure, it is possible to control the melt viscoelastic properties of the olefin polymer, and the moldability and mechanical properties of the olefin polymer in the molten state are improved. It is useful for improving transparency and has high industrial applicability.

Claims (12)

A catalyst for olefin polymerization containing the following essential components (A) and (B) and the following component (D) were added to a polymerization reactor containing an olefin monomer and a polymerization medium in such a manner that the following conditions (2) and (3) were satisfied. A method for producing an olefin polymer having a long chain branched structure, wherein the ratio (mol/mol) of the component (D) to the component (A) is adjusted to the ratio (mol/mol) under the following condition (1): A method for producing an olefin polymer with a narrow molecular weight distribution, characterized in that the molecular weight distribution is 1.9 to 100 times (mol/mol).

Component (A): a crosslinked biscyclopentadienyl compound represented by the following general formula (1) containing transition metal element ^M1

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms; represents a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ¹ and Q ² each independently represent a carbon atom, a silicon atom, or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of the four R ^1s are bonded to form a ring together with Q ¹ and Q ² . It's okay. m is 0 or 1, and when m is 0, Q ¹ is directly bonded to the conjugated 5-membered ring containing R ² and R ³ . R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, Indicates a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a silyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms, and two R ² and 2 At least one of the three R ³ is not a hydrogen atom, and at least one of the four R ⁴ is not a hydrogen atom. Among R ² , R ³ and R ⁴ , only one pair of adjacent R ³ or adjacent R ² and R ³ may form a ring together with the carbon atoms to which they are bonded. ]

Component (B): a compound that reacts with the compound of component (A) to produce a cationic metallocene compound

Component (D): a compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Groups 1, 2, and 12 to 15 of the periodic table,
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group,
n is a number corresponding to the valence of ^M2 )

Condition (1) The ratio of ^M2 to ^M1 (mol/mol) is 1500
Condition (2) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12
Condition (3) The ratio of ^M2 to the polymerization medium (mmol/kg) is 0.01 to 100
A catalyst for olefin polymerization containing the following essential components (A) and (B) and the following component (D) were added to a polymerization reactor containing an olefin monomer and a polymerization medium in such a manner that the following conditions (1a) to (3a) were satisfied. A method for producing an olefin polymer having a long chain branched structure, the method comprising: supplying an olefin polymer with a long chain branch structure.

Component (A): a crosslinked biscyclopentadienyl compound represented by the following general formula (1) containing transition metal element ^M1

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms; represents a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ¹ and Q ² each independently represent a carbon atom, a silicon atom, or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of the four R ^1s are bonded to form a ring together with Q ¹ and Q ² . It's okay. m is 0 or 1, and when m is 0, Q ¹ is directly bonded to the conjugated 5-membered ring containing R ² and R ³ . R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, Indicates a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a silyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms, and two R ² and 2 At least one of the three R ³ is not a hydrogen atom, and at least one of the four R ⁴ is not a hydrogen atom. Among R ² , R ³ and R ⁴ , only one pair of adjacent R ³ or adjacent R ² and R ³ may form a ring together with the carbon atoms to which they are bonded. ]

Component (B): a compound that reacts with the compound of component (A) to produce a cationic metallocene compound

Component (D): a compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Groups 1, 2, and 12 to 15 of the periodic table,
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group,
n is a number corresponding to the valence of ^M2 )

Condition (1a) The ratio of M ² to M ¹ (mol/mol) is 3200 to 180000
Condition (2a) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12
Condition (3a) The ratio of M ² to the polymerization medium (mmol/kg) is 0.01 to 100
The method for producing an olefin polymer according to claim 1 or 2, wherein the obtained olefin polymer satisfies the following physical properties (i) and (ii).

Physical properties (i) The value of molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) and the amount obtained when the supply amount ratio of the component (D) to the component (A) is 1160 to 1800. The ratio ([Mw/Mn]/[Mw ₀ /Mn ₀ ]) of the molecular weight distribution (Mw ₀ /Mn ₀ ) of the olefin polymer obtained is 0.50 to 0.95.

Physical properties (ii) The value (g' _m ) of the branching index g' at a molecular weight of 100,000 measured by a GPC measurement device that combines a differential refractometer, a viscosity detector, and a light scattering detector, and the above component (A ) to the value (g' _m0 ) at a molecular weight of 100,000 of the branching index g' of the olefin polymer obtained when the supply ratio of the component (D) is 1160 to 1800 (g' _m /g' _m0 ) is 0.90 to 1.10.
The method for producing an olefin polymer according to any one of claims 1 to 3, characterized in that the obtained olefin polymer satisfies the following physical properties (iii) and (iv).

Physical properties (iii) The Mw/Mn is 2.0 to 7.0.
Physical properties (iv) The g' _m is 0.50 to 0.95. The method for producing an olefin polymer according to any one of claims 1 to 4, wherein the olefin monomer is ethylene. The method for producing an olefin polymer according to claim 5, wherein the obtained olefin polymer satisfies the following physical properties (v) and (vi).

Physical properties (v) MFR is 0.001 to 1000 g/10 minutes.
Physical properties (vi) Density is 0.895 to 0.970 g/cm ³ . The method for producing an olefin polymer according to any one of claims 1 to 6, characterized in that the polymerization medium is a hydrocarbon solvent or a polyolefin (particles or pellets). The method for producing an olefin polymer according to any one of claims 1 to 7, wherein the polymerization reactor is a slurry polymerization reactor or a gas phase polymerization reactor. The method for producing an olefin polymer according to any one of claims 1 to 8, characterized in that the polymerization reaction is carried out at a temperature of 60 to 110°C. The method for producing an olefin polymer according to any one of claims 1 to 9, characterized in that the polymerization reaction is carried out at an olefin partial pressure of 0.2 to 1.9 MPa. The olefin polymer according to any one of claims 1 to 10, characterized in that component (D) has the general formula AlL ¹ ₃ (L ¹ is a hydrogen atom, a halogen atom, or a hydrocarbon group). manufacturing method. The method for producing an olefin polymer according to any one of claims 1 to 11, wherein the olefin polymerization catalyst further contains an inorganic compound carrier (component (C)).