JP2022095905A - Method of producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing an olefin polymer capable of narrowing a molecular weight distribution while maintaining long chain branch characteristics.

SOLUTION: A method of producing an olefin polymer includes feeding a catalyst for polymerizing olefin including essential constituents (A) and (B), and the following constituent (D). The feed amount ratio (mol/mol) of the constituent (D) to the constituent (A) is 1.5-100 times the ratio (mol/mol) in the following condition (1). The constituent (A) is a crosslinked biscyclopentadienyl compound containing a transition metal element M¹. The constituent (B) is a compound which generates a cationic metallocene compound by reacting with the constituent (A) compound. The constituent (D) is represented by a general formula: M² L¹ _n where M² is a typical metal atom of the group 1, 2, and 12-15 of the periodic table, and L¹ is a hydrogen atom, a halogen atom, or a hydrocarbon group. The condition (1) is a condition such that the ratio of M² to M¹ (mol/mol) is 1,160-1,800.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

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 capable of narrowing the molecular weight distribution by adjusting the supply amount of a specific component at the time of polymerization, and an olefin polymer obtained by this production method.

As a method for improving the moldability of metallocene-based polyolefins, which generally have poor moldability, a method of blending low-density polyethylene with a metallocene-based polyolefin by a high-pressure method and a polymerization reaction using a specific metallocene are used to branch long chains into the polyolefin. The method of introduction is known. The former requires a blending process, which increases the manufacturing cost. Further, although the obtained blend has excellent moldability, the mechanical strength, which is an advantage of the metallocene-based polyolefin, is lowered.
On the other hand, a method using a crosslinked pentadienylindenyl compound as a specific metallocene catalyst for introducing the latter long-chain branch is known (see Patent Documents 1 to 3). By using these metallocene catalysts, it is possible to produce an olefin-based polymer having a developed long-chain branched structure. However, in this method, the molecular weight distribution of the polymer tends to be wide, so that the molten resin is broken, the appearance is poor due to surface acoustic roughness, and the mechanical strength is deteriorated due to the melt orientation. It is still not enough to achieve both sex and product characteristics. Therefore, a production method capable of producing an olefin polymer having a narrow molecular weight distribution without changing the long-chain branched structure characteristics of the produced polymer is desired.

Japanese Unexamined Patent Publication No. 2013-227271 Japanese Unexamined Patent Publication No. 2017-020019 Japanese Unexamined Patent Publication No. 2016-0107039

An object of the present invention is to provide a method for producing an olefin polymer capable of narrowing the molecular weight distribution while maintaining the long-chain branched structure 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 structural properties.

As a result of intensive studies to solve the above problems, the present inventors have found that the molecular weight distribution can be narrowed by adjusting the supply amount of a specific component at the time of polymerization, and based on this finding, the present invention. Has been completed.

That is, in the first invention of the present invention, a catalyst for olefin polymerization containing the following essential components (A) and (B) and the following component (D) are provided in a polymerization reactor in which an olefin monomer and a polymerization medium are present, under the following conditions. A method for producing an olefin polymer having a long-chain branched structure, which is carried out by supplying (1) to (3) so as to satisfy the above, and the supply amount ratio (mol / mol /) of the component (D) to the component (A). It is a method for producing an olefin polymer having a narrow molecular weight distribution, wherein mol) is 1.5 to 100 times the ratio (mol / mol) under the following condition (1).
However, in the following condition (1), "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). It is a precondition used for the calculation of the requirement of "doubling", and it is not necessary to satisfy the condition (1) alone.

Component (A): Cross-linked biscyclopentadienyl compound represented by the following general formula (1) containing the transition metal element M ¹ .

［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 any transition metal of Ti, Zr or Hf. X ¹ and X ² independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, and 1 to 20 carbon atoms. A hydrogen group substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. ^Q1 and ^Q2 independently represent a carbon atom, a silicon atom, or a germanium atom. Each R ¹ 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 . You may. m is 0 or 1, and when m is 0, Q ¹ is directly attached to a conjugated 5-membered ring containing R ² and R ³ . ^{R2 ,} R3 and ^R4 are independently hydrogen atom, halogen atom, hydrogen group having 1 to 20 carbon atoms, and silicon-containing hydrocarbon group having 1 to 18 carbon atoms including silicon number 1 to 6. It shows a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrogen group having 1 to 40 carbon atoms including an oxygen atom or a sulfur atom, or a hydrogen group substituted silyl group having 1 to 40 carbon atoms, and has two ^R2 and 2. At least one of the ^four R3s is not a hydrogen atom and at least one of the ^four R4s is not a hydrogen atom. Of R ² , R ³ and R ⁴ , only one set of adjacent R ^3s or adjacent R ² and R ³ may form a ring together with the bonded carbon atom. ]

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

Component (D): Compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Group 1 Group 2 and Group 12 to 15 of the Periodic Table.
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group, and
n is a number corresponding to the valence of M ² )

Conditions (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
Conditions (3) The ratio of M ² to the polymerization medium (mmol / kg) is 0.01 to 100.

In the second invention of the present invention, a catalyst for olefin polymerization 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 (1a). )-(3a) is a method for producing an olefin polymer having a long-chain branched structure, which is carried out by supplying the polymer so as to satisfy the above conditions.

Component (A): Crosslinked biscyclopentadienyl compound represented by the following general formula (1) containing the transition metal element M ¹ .

［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 any transition metal of Ti, Zr or Hf. X ¹ and X ² independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, and 1 to 20 carbon atoms. A hydrogen group substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. ^Q1 and ^Q2 independently represent a carbon atom, a silicon atom, or a germanium atom. Each R ¹ 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 . You may. m is 0 or 1, and when m is 0, Q ¹ is directly attached to a conjugated 5-membered ring containing R ² and R ³ . ^{R2 ,} R3 and ^R4 are independently hydrogen atom, halogen atom, hydrogen group having 1 to 20 carbon atoms, and silicon-containing hydrocarbon group having 1 to 18 carbon atoms including silicon number 1 to 6. It shows a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrogen group having 1 to 40 carbon atoms including an oxygen atom or a sulfur atom, or a hydrogen group substituted silyl group having 1 to 40 carbon atoms, and has two ^R2 and 2. At least one of the ^four R3s is not a hydrogen atom and at least one of the ^four R4s is not a hydrogen atom. Of R ² , R ³ and R ⁴ , only one set of adjacent R ^3s or adjacent R ² and R ³ may form a ring together with the bonded carbon atom. ]

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

Component (D): Compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Group 1 Group 2 and Group 12 to 15 of the Periodic Table.
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group, and
n is a number corresponding to the valence of M ² )

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

Physical properties (i) An olefin obtained when the value of the molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) and the supply amount ratio of the component (D) to the component (A) are not increased. The ratio ([Mw / Mn] / [Mw ₀ / Mn ₀ ]) to the value of 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 branch index g'measured by a GPC measuring device combined with a differential refractometer, a viscosity detector, and a light scattering detector at a molecular weight of 100,000, and the above component (A). ) To the ratio ( _g'm / _g'm0 ) of the branch index g'of the olefin polymer obtained when the supply amount ratio of the above component (D) is not increased to the value ( _g'm0 ) at a molecular weight of 100,000. Is 0.90 to 1.10.

The fourth invention of the present invention is the production of the olefin polymer according to any one of the first to third inventions, wherein the obtained olefin polymer satisfies the following physical properties (iii) (iv). The 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 aspect of the present invention is the method for producing an olefin polymer according to any one of the first to fourth inventions, wherein the olefin monomer is ethylene.

The 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 characteristics (v) MFR is 0.001 to 1000 g / 10 minutes.
Physical properties (vi) The density is 0.895 to 0.970 g / cm ³ .

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

The 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. Is.

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

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

The eleventh invention of the present invention is any one of the first to tenth, characterized in that the component (D) is the general formula AlL ¹ ₃ (L ¹ is a hydrogen atom, a halogen atom, and a hydrocarbon group). The method for producing an olefin polymer according to the present invention.

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

The thirteenth invention of the present invention is an olefin polymer obtained by the method for producing an olefin polymer according to any one of items 1 to 12.

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 properties.

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

Hereinafter, the method for producing the olefin polymer of the present invention will be specifically and in detail described for each item.

1. 1. Method for producing olefin polymer (first method for producing)
(1) Method for Producing Olefin Polymer In the method for producing an olefin polymer of the present invention, a polymerization reactor in which an olefin monomer and a polymerization medium are present is used with a catalyst for olefin polymerization containing the following essential components (A) and (B). It 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 the component (D) to the component (A) is 1.5 to 100 times the ratio (mol / mol) under the following condition (1). This feature is also called a characteristic requirement.

Component (A): Cross-linked biscyclopentadienyl compound represented by the following general formula (1) containing the transition metal element M ¹ .

［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 any transition metal of Ti, Zr or Hf. X ¹ and X ² independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, and 1 to 20 carbon atoms. A hydrogen group substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. ^Q1 and ^Q2 independently represent a carbon atom, a silicon atom, or a germanium atom. Each R ¹ 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 . You may. m is 0 or 1, and when m is 0, Q ¹ is directly attached to a conjugated 5-membered ring containing R ² and R ³ . ^{R2 ,} R3 and ^R4 are independently hydrogen atom, halogen atom, hydrogen group having 1 to 20 carbon atoms, and silicon-containing hydrocarbon group having 1 to 18 carbon atoms including silicon number 1 to 6. It shows a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrogen group having 1 to 40 carbon atoms including an oxygen atom or a sulfur atom, or a hydrogen group substituted silyl group having 1 to 40 carbon atoms, and has two ^R2 and 2. At least one of the ^four R3s is not a hydrogen atom and at least one of the ^four R4s is not a hydrogen atom. Of R ² , R ³ and R ⁴ , only one set of adjacent R ^3s or adjacent R ² and R ³ may form a ring together with the bonded carbon atom. ]

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

Component (D): Compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Group 1 Group 2 and Group 12 to 15 of the Periodic Table.
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group, and
n is a number corresponding to the valence of M ² )

Conditions (1) The ratio of M ² to M ¹ (mol / mol) is 1160 to 1800.
Conditions (2) The ratio of M ¹ to the polymerization medium (μmol / kg) is 0.001 to 12
Conditions (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 thereof include ethylene and other α-olefins. The method for producing an olefin polymer of the present invention can be suitably used for both homopolymerization of ethylene and copolymerization of ethylene and α-olefin.
The α-olefins as comonomers include those having 3 to 30 carbon atoms, preferably 3 to 8 carbon atoms, and specifically, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-. 1-Pentene and the like are exemplified. The α-olefins can also be copolymerized with two or more kinds of α-olefins with ethylene. The copolymerization may be any of alternating copolymerization, random copolymerization and block copolymerization. When ethylene is copolymerized with another α-olefin, the amount of the other α-olefin can be arbitrarily selected within the range of 90 mol% or less of the total monomer, but generally 40 mol%. Hereinafter, it is preferably selected in the range of preferably 30 mol% or less, more preferably 10 mol% or less. Of course, it is also possible to use a small amount of comonomer other than ethylene or α-olefin. In this case, styrenes such as styrene, 4-methylstyrene and 4-dimethylaminostyrene, 1,4-butadiene, 1,5- It has a polymerizable double bond such as dienes such as hexadiene, 1,4-hexadiene and 1,7-octadien, cyclic compounds such as norbornene and cyclopentene, and oxygen-containing compounds such as hexenol, hexenoic acid and methyl octene. Compounds can be mentioned.

(3) Polymerization medium As the polymerization medium, conventionally known ones can be used and are not particularly limited, but a hydrocarbon solvent or polyolefin (particles or pellets) is preferably used.
Conventionally known hydrocarbon solvents can be used, for example, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, heptane, octane, decane, dodecane, cyclohexane and the like. Although it is a mixture classified as linear, branched or cyclic hydrocarbons, inert hydrocarbons such as benzene, toluene, and xylene, liquid paraffins, isoparaffin solvents, and mixed aliphatic hydrocarbon solvents. Examples thereof include commercially available products commercially available as IP solvent, ISOPAR, kerosene and the like, alone or in admixture, and further, α-olefins such as liquefied ethylene, liquefied propylene, 1-butene, 1-hexene and 1-octene. , Aromatic monomers such as styrene, and liquid monomers such as internal olefin monomers such as 2-butene and cyclopentene can also be used. Among these, straight chain, branched or cyclic hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, etc. Commercial products such as IP solvent and ISPAR, which are mixtures classified as liquid paraffins, isoparaffin solvents, and mixed aliphatic hydrocarbon solvents, as well as liquefied ethylene, liquefied propylene, 1-butene, 1-hexene, and 1-octene. Etc., alone or as a mixture of α-olefins and the like is preferably used. Propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, IP solvent, ISPPAR, liquefied ethylene, liquefied propylene, 1-butene, 1- Hexen, 1-octene alone or a mixture is more preferably used, and isopentane, isopentane, n-hexane, isohexane, heptane, cyclopentane, cyclohexane, IP solvent, ISOPAR alone or a mixture are more preferably used.
As the polyolefin, conventionally known ones can be used, for example, polyethylene (copolymer with an ethylene homopolymer or another monomer. The same applies to the following polyolefins), polypropylene, polybutene, polyhexene, and the like. Polyisobutene, polystyrene and the like are preferably used, but it is more preferable that the polyolefin contains an olefin copolymer obtained by copolymerizing the same type of comonomer as the olefin polymer to be produced, and the shape thereof is so-called obtained from a polymerization reactor. The polymerized particles (also referred to as polymerized powder or polymerized granule) may be so-called pellets obtained through a melt-kneader, but the polymerized particles are preferable, and the polymerization having an average particle size of about 100 to 3000 μm. More preferably, it is a particle.

(4) Ingredient (A)
The component (A) is a crosslinked biscyclopentadienyl compound represented by the following general formula ( ¹ ) containing the 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 any transition metal of Ti, Zr or Hf. X ¹ and X ² independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, and 1 to 20 carbon atoms. A hydrogen group substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. ^Q1 and ^Q2 independently represent a carbon atom, a silicon atom, or a germanium atom. Each R ¹ 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 . You may. m is 0 or 1, and when m is 0, Q ¹ is directly attached to a conjugated 5-membered ring containing R ² and R ³ . ^{R2 ,} R3 and ^R4 are independently hydrogen atom, halogen atom, hydrogen group having 1 to 20 carbon atoms, and silicon-containing hydrocarbon group having 1 to 18 carbon atoms including silicon number 1 to 6. It shows a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrogen group having 1 to 40 carbon atoms including an oxygen atom or a sulfur atom, or a hydrogen group substituted silyl group having 1 to 40 carbon atoms, and has two ^R2 and 2. At least one of the ^four R3s is not a hydrogen atom and at least one of the ^four R4s is not a hydrogen atom. Of R ² , R ³ and R ⁴ , only one set of adjacent R ^3s or adjacent R ² and R ³ may form a ring together with the bonded carbon atom. ]

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 further preferably represents Zr. show. Further, X ¹ and X ² are independently hydrogen atom, chlorine atom, bromine atom, iodine atom, or methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 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- Propylmethyl 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-Frill group, 2-Tetrahydrofuryl group, Dimethylaminomethyl group, diethylaminomethyl group, Di-propylaminomethyl group, Bis (dimethylamino) methyl group, Bis (di-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, din-propylamino group, di-propylamino group, din- Examples thereof include butylamino group, di-butylamino group, dit-butylamino group and diphenylamino group.
Specific examples of preferred 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 and phenoxy group. Examples thereof include a dimethylamino group and a di-propylamino group. Among these specific examples, a chlorine atom, a methyl group and a dimethylamino group are particularly preferable.

Further, Q ¹ and Q ² indicate a carbon atom, a silicon atom or a germanium atom. It is preferably a carbon atom or a silicon atom. More preferably, it is a silicon atom.
Further, as R ¹ , each independently has 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, and an n-pentyl group. , Neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group and the like. Further, as a case where R ¹ forms a ring together with Q ¹ and Q ² , a cyclobutylidene group, a cyclopentylidene group, a cyclohexylidene group, a silacyclobutyl group, a silacyclopentyl group, a silacyclohexyl group, etc. Can be mentioned.
Specific examples of preferred R ¹ include, when Q ¹ or / and Q ² are carbon atoms, a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an ethylene group, a cyclobutylidene group, and Q ¹ or /. When Q ² is a silicon atom, a methyl group, an ethyl group, a phenyl group, and a silacyclobutyl group can be mentioned.

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

^{R2 ,} R3 and ^R4 are independently hydrogen atom, halogen atom, hydrogen group having 1 to 20 carbon atoms, and silicon-containing hydrocarbon group having 1 to 18 carbon atoms including silicon number 1 to 6. It shows a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrogen group having 1 to 40 carbon atoms including an oxygen atom or a sulfur atom, or a hydrogen group substituted silyl group having 1 to 40 carbon atoms, and has two ^R2 and 2. At least one of the ^four R3s is not a hydrogen atom and at least one of the ^four R4s is not a hydrogen atom.
Preferred specific examples of ^{R2 ,} R3 and ^R4 are hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group and n. -Hexyl group, cyclohexyl group, phenyl group, 2-methylfuryl group, trimethylsilyl group can be mentioned. Among these specific examples, hydrogen atom, methyl group, n-butyl group, t-butyl group, phenyl group and trimethylsilyl group are more preferable, and hydrogen atom, methyl group, t-butyl group, phenyl group and trimethylsilyl group are particularly preferable. preferable.
Of R ² , R ³ and R ⁴ , only one set of adjacent R ^3s or adjacent R ² and R ³ may form a ring together with the bonded carbon atom.

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

Here, M ¹ , X ¹ , X ² , Q ¹ , R ¹ , R ² , R ³ , and R ⁴ follow the description of the general formula (1). Adjacent ^R3s preferably form a 5- to 7-membered ring structure together with bonded carbon atoms, specifically, a 5-membered ring structure such as a thiophene ring or a pyrrole ring, a benzene ring, a cyclohexene ring, or the like. It is more preferable to form a 6-membered ring structure such as a cyclohexane ring and a 7-membered ring structure such as a heptadiene ring, and further preferably a benzene ring, that is, a crosslinked 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 the general formula (1). R ³¹ , R ³² , R ³³ , and R ³⁴ are independent hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, and silicon-containing hydrocarbons having 1 to 18 carbon atoms including 1 to 6 carbon atoms. A group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrogen group having 1 to 40 carbon atoms including an oxygen atom, a nitrogen atom or a sulfur atom, or a hydrogen group substituted silyl group having 1 to 40 carbon atoms is shown. R ³¹ , R ³² , R ³³ , and R ³⁴ may form a ring with adjacent carbon atoms and carbon atoms bonded to each other.

Of the general formula (2), as a specific example when R ² and R ³ do not form a ring, M ¹ , X ¹ , X ² , Q ¹ , R ¹ , R of the following general formula (2') ² , R ² ', R ³ , R ³ ', R ⁴ can be mentioned as the compounds listed in the table below. However, the component (A) is not limited to these.

Of the general formula (2), dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (4-methyl-5-phenyl-) is an example of the case where R ² and R ³ form a ring. Cyclopentathiophene) zirconium dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (4-methyl-5-phenyl-cyclopentathiophene) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) ( 4-Methyl-5-Phenyl-Cyclopentatiophen) Zyroxide 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) -cyclopentatiophene) zirconium dichloride, dimethylsilylene (3,4) -Dimethylcyclopentadienyl) (3-Methyl-5- (5-methyl-2-furyl) -cyclopentatiophene) Zyroxide dichloride, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) ( 2-Methyl-4-phenyl-4H-azurenyl) zirconium dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl) zirconium dichloride, dimethylsilylene (3,4) -Dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl) In addition to zirconium dichloride, etc., known cross-linked cyclopentadienyl-indenyl compounds contained in the general formula (3) include Japanese Patent Laid-Open No. All Exemplified Compounds of 2013-227482, [Chemical 1] General Formula (1c) of Japanese Patent Laid-Open No. 2013-227482, All Exemplified Compounds When At least One of R ^4c is Not H, [Chemical No. 1] General of JP-A-2014-70029 All exemplary compounds in formula (1) where at least one of R ⁴ is not H, all exemplary compounds of Japanese Patent Application Laid-Open No. 2015-63515 when at least one of R ⁵ is not H in the general formula (1). , All exemplified compounds in the case where at least one of R ⁷ to R ¹⁰ is not H in the [Chemical formula 1] general formula (1) of JP-A-2015-172037, [Chemical formula 1] general formula (1) of JP-A-2012-25664. All examples when at least one of R ¹¹ to R ¹⁴ is not H All exemplified compounds in the case where at least one of R8 to R11 is not H ⁱⁿ the [Chemical formula ¹ ] general formula (1) of JP-A-2016-141635, [Chemical formula 1] general formula (1) of JP-A-2016-145190. ), All the exemplary compounds in the case where at least one of R ⁸ to R ¹¹ is not H, all the exemplary compounds of Japanese Patent Application No. 2016-051152, all the exemplary compounds of JP-A-2007-308486, and the like.

Specifically, the compounds of JP2013-227271A are all exemplary compounds in the following general formula (1c) when at least one of ^R4c is not H.

Specifically, the compounds of JP-A-2014-70029 are all exemplary compounds in the following general formula (1) when at least one of ^R4 is not H.

Specifically, the compounds of JP-A-2015-63515 are all exemplary compounds in the following general formula (1) when at ^least one of R5 is not H.

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

Specifically, the compounds of JP2012-25664A are all exemplary compounds in the following general formula (1) when at least one of R ¹¹ to R ¹⁴ is not H.

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

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

Specific examples of the all exemplified compounds of JP-A-2007-308486 include the following compounds.
(1) Dichloro {1,1'-dimethylsilylene (2,3-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (2) Dichloro {1,1'-dimethylsilylene (3,4-Dimethylcyclopentadienyl) (2-Methyl-4-phenyl-4H-azurenyl)} Hafnium (3) Dichloro {1,1'-dimethylsilylene (2,5-dimethylcyclopentadienyl) ( 2-Methyl-4-phenyl-4H-azurenyl)} Hafnium (4) Dichloro {1,1'-dimethylsilylene (2,3-dit-butylcyclopentadienyl) (2-methyl-4-phenyl-4H) -Azulenyl)} hafnium (5) dichloro {1,1'-dimethylsilylene (3,4-dit-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (6) dichloro {1,1'-dimethylsilylene (2,5-dit-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (7) dichloro {1,1'-dimethylsilylene (1,1'-dimethylsilylene ( 2,3-Diphenylcyclopentadienyl) (2-Methyl-4-phenyl-4H-azurenyl)} Hafnium (8) Dichloro {1,1'-dimethylsilylene (3,4-diphenylcyclopentadienyl) (2) -Methyl-4-phenyl-4H-azurenyl)} Hafnium (9) dichloro {1,1'-dimethylsilylene (2,5-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} Hafnium (10) dichloro {1,1'-dimethylsilylene (2-methyl-4-ethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (11) dichloro {1,1' -Dimethylsilylene (2-ethyl-4-methylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} Hafnium (12) Dichloro {1,1'-dimethylsilylene (4-t-butyl-) 2-Methylcyclopentadienyl) (2-Methyl-4-phenyl-4H-azurenyl)} Hafnium (13) Dichloro {1,1'-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2) -Methyl-4-phenyl-4H-azurenyl)} hafnium (14) dichloro {1,1'-dimethylsilylene (2,3,4-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-) Hafnium)} hafnium (15) dichloro {1,1'-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (16) dichloro {1 , 1'-dimethylsilylene (2,3-dimethyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (17) dichloro {1,1'-dimethylsilylene (2) , 3-Dimethyl-5-Phenylcyclopentadienyl) (2-Methyl-4-phenyl-4H-azurenyl)} Hafnium

(18) Dichloro {1,1'-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azurenyl)} Hafnium (19) Dichloro {1,1'- Dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azurenyl)} Hafnium (20) Dichloro {1,1'-dimethylsilylene (2-methyl-4-phenyl) Cyclopentadienyl) (4-Phenyl-2-i-propyl-4H-azurenyl)} Hafnium (21) Dichloro {1,1'-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (4- t-Phenyl-2-i-propyl-4H-azurenyl)} Hafnium

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

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

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

(34) Dichloro {1,1'-Methylphenylgelmylen (2-methyl-4-phenylcyclopentadienyl) (2-Methyl-4-phenyl-4H-azurenyl)} Hafnium (35) Dichloro {1,1 ´-Germacyclobutenyl (2,4,5-trimethylcyclopentadienyl) (2-Methyl-4-phenyl-4H-azurenyl)} Hafnium (36) Dichloro {1,1´-Germacyclopropenyl (2,) 4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (37) dichloro {1,1'-germafluorenyl (2,4,5-trimethylcyclopentadi) Enyl) (2-Methyl-4-phenyl-4H-azurenyl)} Hafnium

(5) Ingredient (B)
As an essential component, the catalyst for olefin polymerization reacts with the metallocene compound of the component (A) (component (A), hereinafter may be simply referred to as A) in addition to the above component (A) to form a cationic metallocene compound. (Component (B), hereinafter, may be simply referred to as B) is included.

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

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

The alkyl group of trialkylaluminum may be any of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and the like, but a methyl group. Is particularly preferable.
The above-mentioned organoaluminum compound may be used as a mixture of two or more kinds.

The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound 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 −20 to 20 ° C. The reaction time is usually selected in 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 crystalline water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like, and components capable of producing water in the reaction system can be used. Of the above-mentioned organoaluminum oxy compounds, those obtained by reacting alkylaluminum with water are usually called aluminoxane, and in particular, methylaluminoxane (including those substantially composed of methylaluminoxane (MAO)). Is suitable as an organoaluminum oxy compound.
Of course, as the organoaluminum oxy compound, two or more kinds of the above-mentioned organoaluminum oxy compounds can be used in combination, and a solution in which the above-mentioned organoaluminum oxy compound is dissolved or dispersed in the above-mentioned inert hydrocarbon solvent can also be used. May be used.

It is preferable to use an organoaluminum oxy compound as the component (B) of the catalyst for olefin polymerization because the strain hardening degree (λmax) of the obtained ethylene-based polymer is large and the polymerization activity is high.

Further, as another specific example of the compound (B) which reacts with the metallocene compound (A) to form a cationic metallocene compound, a borane compound and a borate compound can be mentioned. More specifically, the above borane compounds are 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 perfluoroanthril) borane and tris (perfluorobinaphthyl) borane.

Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenyl) borane, tris (perfluoroanthryl) borane, tris (perfluorobinaphthyl) borane are more preferred, and even more preferably tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris ( Perfluoronaphthyl) borane and tris (perfluorobiphenyl) borane are exemplified as preferred compounds.

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

In the 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, and phosphonium. Examples of the ammonium include trialkyl-substituted ammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.

Examples of the anilinium include N, N-dialkylaniliniums such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium. Further, examples of the phosphonium include triarylphosphonium such as triphenylphosphonium, tributylphosphonium, tri (methylphenyl) phosphonium, and tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

Further, in the 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, which are linked to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group and the like, and a halogen such as fluorine, chlorine, bromine and iodine are preferable. Further, ^X4 and ^X5 are hydride groups, halide groups, hydrocarbon groups containing 1 to 20 carbon atoms, and substituted hydrocarbons containing 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms. It is a hydrogen group.

Specific examples of the compound represented by the 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, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6- Ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluorophenyl) borate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenyl Phenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6- Difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (pentafluorophenyl) borate, triethylammonium tetra (2,6-ditri) Fluoromethylphenyl) borate, triethylammonium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoro) Examples thereof include naphthyl) borate, di (1-propyl) ammonium tetra (pentafluorophenyl) borate, and dicyclohexylammonium tetraphenyl borate.

Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro). Naftyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium Tetra (perfluoronaphthyl) borate is preferred.

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

In formula (6), L ² is 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. Further, R ⁷ , R ⁸ , X ⁴ and X ⁵ are the same as the definitions in the 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, and the like. Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluorophenyl) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) borate, tropiniumtetra (p- Trill) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m-fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (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-F2 _- Ph) _{4, NaB (C6F5) 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 , 5- (CF ₃ ) _{2 -} Ph) 4.2 diethyl ether, HB (C ₁₀ H ₇ ) _4.2 diethyl ether can be exemplified.

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, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (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, HB (C ₁₀ H ₇ ) _4.2 diethyl ether is preferred.

More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluorofluoro) 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- (2,6-( CF ₃ ) ₂ -Ph) 4.2 diethyl ether, HB (3,5- (CF ₃ ) _{2 -} Ph) 4.2 diethyl ether, HB ₍ C _{10H 7} ) _4.2 diethyl ether can be mentioned.

When a borane compound or a borate compound is used as the component (B), the polymerization activity and the copolymerizability are enhanced, so that the productivity of the ethylene-based polymer having a long-chain branch is improved. Further, as the component (B), a mixture of the above-mentioned organoaluminum oxy compound and the above-mentioned borane compound or borate compound can also be used. Further, the above-mentioned borane compound and borate compound can be used by mixing two or more kinds.

(6) Ingredient (C)
The catalyst for olefin polymerization may further contain an inorganic compound carrier (component (C)). As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous substance, or a mixture thereof can be used.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.

Examples of the metal oxide include single oxides or composite oxides of the elements of Groups 1 to 14 of the periodic table, for example, SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , TiO ₂ , and so on. ZrO ₂ , Fe ₂ O ₃ , Al ₂ O ₃ · MgO, Al ₂ O ₃ · CaO, Al ₂ O ₃ · SiO ₂ , Al ₂ O ₃ · MgO · CaO, Al ₂ O ₃ · MgO · SiO ₂ , Al 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, SiO ₂ · MgO can be exemplified. Here, the above formula represents only the composition, not the molecular formula, 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 and 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 and CaCl ₂ are particularly suitable. As the metal carbonate, an alkali metal or an alkaline earth metal carbonate is preferable, and specific examples thereof include magnesium carbonate, calcium carbonate, and barium carbonate. Examples of carbonaceous materials include carbon black and activated carbon. Any of the above inorganic carriers can be preferably used in the present invention, but it is particularly preferable to use metal oxides, silica, alumina and the like.

These inorganic carriers 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 to. The properties of these inorganic carriers are not particularly limited, but usually, the average particle size is 5 to 200 μm, preferably 10 to 150 μm, the average pore diameter is 20 to 1000 Å, preferably 50 to 500 Å, and the specific surface area is 150 to 1000 m. 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 surface area 0.20 to 0 It is preferable to use an inorganic carrier having a .50 g / cm ³ , preferably 0.25 to 0.45 g / cm ³ .

Of course, the above-mentioned inorganic carriers can be used as they are, but as a preliminary treatment, these carriers can be used as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, etc. It can be used after contacting with an organic aluminum compound such as diisobutylaluminum hydride or an organic aluminum oxy compound containing an Al—O—Al bond.

(7) Component (D)
The catalyst for olefin polymerization of the present invention contains a 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 Group 1, Group ² , Group 12 to 15 of the Periodic Table.
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group, and
n is a number corresponding to the valence of M ² )

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

Specific examples of the 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 et al., 1-C ₈ H ₁₇ Li et al., 1-C ₉ H ₁₉ Li et al., 1-C ₁₀ H ₂₁ Li et al., 1-C ₁₁ H ₂₃ Li et al., 1-C ₁₂ H ₂₅ Li et al., 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. (NC ₄ H ₉ ) ₂ Mg, etc., (CH ₃ ) (C ₂ H ₅ ) Mg, (CH ₃ ) (nC ₃ H ₇ ) Mg, etc., (C ₂ H ₅ ) (nC ₄ H ₉ ) Mg, etc. Divinyl Mg, diallyl Mg, (hexenyl) ₂ Mg, (octenyl) ₂ Mg, diphenyl Mg, dibenzyl Mg, etc. Mg compounds having a hydrocarbon group containing unsaturated bonds, 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, ( Octenyl) ₃ Al, Triphenyl Al, Tribenzyl Al and other Al compounds having a hydrocarbon group containing unsaturated bonds, 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, (CH ₃ ) CaCl, etc., ZnH ₂ , ZnF ₂ , ZnCl ₂ , etc., (CH ₃ ) ₂ Zn, (CH ₃ ) ZnCl, etc., (C ₂ H ₅ ) ₂ Zn, (CH ₃ ) (C ₂ H ₅ ) 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. Etc., Zn compounds having a hydrocarbon group containing unsaturated bonds 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 et al. And MgX ¹ _m R ¹ _n (OR ² ) _2- mn in the general formula (a) described in paragraphs [0034] to [0038] of JP2012-72229. Examples of the compound for AlX ³ _q R ⁴ _r (OR ⁵ ) _3-q-r in the general formula (c) described in paragraphs [0044] to [0046] of the same publication. Further, a dinuclear metal compound having the structure of the above compound, for example, (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 can also be mentioned.

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

(I) The component (A) and the component (B) are brought into contact with each other, and then the component (C) is brought into contact with the component (C) as necessary.
(II) The component (A) and the component (C) are brought into contact with each other, if necessary, and then the component (B) is brought into contact with the component (B).
(III) The component (B) is brought into contact with the component (C), if necessary, and then the component (A) is brought into contact with the component (A).

Among these contact methods, (I) and (III) are preferable, and (I) is most preferable. In either contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene (usually 6-12 carbon atoms), heptane, hexane, decane, dodecane. , A method of contacting each component with stirring or non-stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually 5 to 12 carbon atoms) such as cyclohexane is adopted. 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, still more preferably. It is desirable to do it in 30 minutes to 12 hours.

Further, upon contact between the component (A) and the component (B) and, if necessary, the component (C), as described above, a certain component is a soluble or sparingly soluble aromatic hydrocarbon solvent, and a certain kind. Any aliphatic or alicyclic hydrocarbon solvent in which the components of the above are insoluble or sparingly soluble can be used.

When the contact reaction between the components is carried out stepwise, the solvent used in the previous stage may be used as it is as the solvent for the contact reaction in the subsequent stage without removing the solvent or the like. In addition, after the contact reaction in the previous stage using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.) (Hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon) is added to recover the desired product as a solid, or once a part or all of the soluble solvent is removed by means such as drying, which is desired. After the product is taken out as a solid, the subsequent contact reaction of the desired product can also be carried out using any of the above-mentioned inert hydrocarbon solvents. In the present invention, it does not prevent the contact reaction of each component from being carried out a plurality of times.

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

When an organic aluminum oxy compound is used as the component (B) that reacts with the component (A) to form a cationic metallocene compound, the aluminum atom of the organic aluminum oxy compound with respect to the transition metal (M ¹ ) in the component (A). The ratio (Al / M ¹ ) is usually preferably in the range of 1 to 100,000, preferably 5 to 10000, more preferably 50 to 5000, still more preferably 100 to 2000, and a boron compound or a boron compound is used. In the 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, and more preferably 0.2 to 10. It is desirable to select within the range of. Further, when a mixture of an organoaluminum oxy 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 used as a transition metal (M ¹ ). On the other hand, it is desirable to select with the same usage ratio as above.

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

The component (A), the component (B), and the component (C), if necessary, are brought into contact with each other by any of the contact methods (I) to (III), and then the solvent is removed. , A catalyst for olefin polymerization 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.

The catalyst for olefin polymerization can also be obtained by the following method.
(IV) The component (A) and the component (C) are brought into contact with each other to remove the solvent, which is used as a solid catalyst component, and is brought into contact with an organoaluminum oxy compound, a borane compound, a borate compound or a mixture thereof under polymerization conditions. ..
(V) Organoaluminium oxy compound, borane compound, borate compound or a mixture thereof is brought into contact with the component (C) to remove the solvent, which is used as a solid catalyst component and is brought into contact with the component (A) under polymerization conditions. ..
Also in the case of the contact method of (IV) and (V), the same conditions as described above can be used as the component ratio, the contact condition and the solvent removal condition.

Further, as a component having both a component (B) and a component (C) for reacting with the component (A) which is an essential component of the method for producing an olefin polymer of the present invention to form a cationic metallocene compound, a layered silicate is used. It can also be used. The layered silicate is a silicate compound having a crystal structure in which planes composed of ionic bonds and the like are stacked in parallel with each other with a weak bonding force. Most layered silicates are naturally produced mainly as the main component of clay minerals, but these layered silicates are not limited to those naturally produced, and may be artificial compounds.

Among these, montmorillonite, saponite, byderite, nontronite, saponite, hectorite, stepnsite, bentonite, teniolite and other smectites, vermiculites and mica are preferred.

In general, natural products are often non-ion exchangeable (non-swellable), in which case they are ion-exchangeable (or swellable) in order to have preferable ion-exchangeable (or swellable) properties. It is preferable to carry out a process for imparting. Among such treatments, the following chemical treatments are particularly preferable. Here, as the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment for affecting the crystal structure and chemical composition of the layered silicate can be used. Specifically, it is selected from (i) acid treatment performed using hydrochloric acid, sulfuric acid, etc., (ii) alkaline treatment performed using NaOH, KOH, NH3, etc., and (iii) Group 2 to 14 of the Periodic Table. Salt treatment with salts consisting of at least one anion selected from the group consisting of cations containing at least one atom and anions derived from halogen atoms or inorganic acids, (iv) alcohols, hydrocarbon compounds. , Holmamide, treatment of organic substances such as aniline and the like. 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, granulation, separation, etc. at any time before, during, or after all the steps. The method can be arbitrary and purposeful. In particular, regarding the granulation method, for example, a spray granulation method, a rolling granulation method, a compression granulation method, a stirring granulation method, a briquetting method, a compacting method, an extrusion granulation method, and a fluidized bed granulation method. Examples thereof include a method, an emulsified granulation method, and an in-liquid granulation method. Among the above, particularly preferable granulation methods are the spray granulation method, the rolling granulation method and the compression granulation method.

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, etc. It can be used in combination with an organic aluminum compound such as diisobutylaluminum hydride or an organic aluminum oxy compound containing an Al—O—Al bond.

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

Among these contact methods, (VI) and (VIII) are preferable. In either contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene (usually 6-12 carbon atoms), heptane, hexane, decane, dodecane. , A method of contacting each component with stirring or non-stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually 5 to 12 carbon atoms) such as cyclohexane is adopted.

The ratio of the component (A), the organoaluminum compound, and the layered silicate carrier is not particularly limited, but the following range is preferable. The amount of the 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 1 g of the layered silicate carrier. When the organoaluminum compound is used, the amount of Al carried 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.

As the method of carrying and removing the solvent, the same conditions as those of the above-mentioned inorganic carrier can be used. When a layered silicate is used as a component that also serves as the component (B) and the component (C), the obtained olefin polymer has a narrow molecular weight distribution. Further, 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 prepolymerization of the 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 vapor 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 alicyclics such as cyclohexane and methylcyclohexane are substantially cut off. Ethylene and the like are polymerized in the presence or absence of an inert hydrocarbon solvent selected from group hydrocarbons and the like. Needless to say, liquid monomers such as liquid ethylene and liquid propylene can also be used as a solvent. Further, in the case of gas phase polymerization, ethylene or the like is polymerized in a reactor in which a gas stream of ethylene or comonomer is introduced, distributed or circulated. In the present invention, a more preferable polymerization is vapor 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. It is preferably 0.2 to 1.8 MPa, more preferably 0.2 to 1.5 MPa, still more preferably 0.2 to 1.3 MPa, particularly preferably 0.2 to 1.1 MPa, and most preferably 0.2 to 0.2 MPa. It is usually in the range of 0.75 MPa, and the polymerization time is usually 5 minutes to 12 hours, preferably 20 minutes to 8 hours, and more preferably 30 minutes to 5 hours.

The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system. Can be done. Further, even if a component for the purpose of removing water, a so-called scavenger, is added to the polymerization system, it can be carried out without any problem. Examples of such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, the organoaluminum oxy compound, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethylzinc and dibutylzinc, and diethyl. Organoaluminium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and glinal compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable. It can also be applied to a multi-step polymerization method having two or more steps in which polymerization conditions such as hydrogen concentration, amount of monomer, polymerization pressure, and polymerization temperature are different from each other without any problem.

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

Conditions (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
Conditions (3) The ratio of M ² to the polymerization medium (mmol / kg) is 0.01 to 100.

The condition (1) is that the ratio (mol / mol) of M ² to M ¹ is 1160 to 1800, preferably 1350 to 1800, and more preferably 1500 to 1800.
The 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, and more preferably 0.01 to 0.38. be.
The condition (3) is that the ratio of M ² to the polymerization medium (mmol / kg) is 0.01 to 100, preferably 0.02 to 10, and more preferably 0.03 to 5.

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

2. 2. Method for producing olefin polymer (second production method)
In the second production method of the present invention, a catalyst for olefin polymerization 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 ( It is a method for producing an olefin polymer having a long-chain branched structure, which is carried out by supplying 1a) to (3a) so as to satisfy them.

Component (A): Cross-linked biscyclopentadienyl compound represented by the following general formula (1) containing the transition metal element M ¹ .

[In formula (1), M ¹ represents any transition metal of Ti, Zr or Hf. X ¹ and X ² independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, and 1 to 20 carbon atoms. A hydrogen group substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. ^Q1 and ^Q2 independently represent a carbon atom, a silicon atom, or a germanium atom. Each R ¹ 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 . You may. m is 0 or 1, and when m is 0, Q ¹ is directly attached to a conjugated 5-membered ring containing R ² and R ³ . ^{R2 ,} R3 and ^R4 are independently hydrogen atom, halogen atom, hydrogen group having 1 to 20 carbon atoms, and silicon-containing hydrocarbon group having 1 to 18 carbon atoms including silicon number 1 to 6. It shows a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrogen group having 1 to 40 carbon atoms including an oxygen atom or a sulfur atom, or a hydrogen group substituted silyl group having 1 to 40 carbon atoms, and has two ^R2 and 2. At least one of the ^four R3s is not a hydrogen atom and at least one of the ^four R4s is not a hydrogen atom. Of R ² , R ³ and R ⁴ , only one set of adjacent R ^3s or adjacent R ² and R ³ may form a ring together with the bonded carbon atom. ]

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

Component (D): Compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Group 1 Group 2 and Group 12 to 15 of the Periodic Table.
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group, and
n is a number corresponding to the valence of M ² )

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.

In the second manufacturing method of the present invention, the characteristic requirements and various conditions (condition (1), condition (2), condition (3)) in the first manufacturing method are the following conditions (1a) and conditions (2a). ), Since they are the same except that they are replaced with the condition (3a), detailed description is omitted except for these conditions, and the description in the first manufacturing method is quoted as it is.

Condition (1a) The ratio (mol / mol) of M ² to M ¹ is 1800 to 180,000, preferably 2000 to 180000, more preferably 2000 to 50000, still more preferably 2500 to 50000. Particularly preferably, it is 3200 to 20000.
Condition (2a) The ratio of M ¹ to the polymerization medium (μmol / kg) is 0.001 to 12, preferably 0.001 to 2.0, and more preferably 0.005 to 1.0. It is more preferably 0.005 to 0.38, and particularly preferably 0.01 to 0.38.
Condition (3a) The ratio of M ² to the polymerization medium (mmol / kg) is 0.01 to 100, preferably 0.02 to 20, more preferably 0.03 to 15, and even more preferably 0.03 to 15. It is 0.04 to 10, and particularly preferably 0.05 to 5.0.
When the above conditions are satisfied, the molecular weight distribution can be narrowed while maintaining the long-chain branched structure characteristics of the olefin polymer.

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


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

Further, "obtained when the supply amount ratio of the component (D) to the component (A) is not increased" means the following items in the second production method. In the condition (1a), it means that the ratio (mol / mol) of M ² to M ¹ is less than 1800 (hereinafter, similarly defined).

(2) Physical characteristics (ii)
The value ( _g'm ) of the branch index g'at a molecular weight of 100,000 measured by a GPC measuring device combining a differential refractometer, a viscosity detector, and a light scattering detector, and a component (D) with respect to the component (A). ) The ratio ( _g'm / _g'm0 ) of the branching index g'of the olefin polymer obtained when the supply amount ratio is not increased to the value ( _g'm0 ) at a molecular weight of 100,000 is 0.90 to 1. It is preferably .10, more preferably 0.90 to 1.08, further preferably 0.90 to 1.07, and particularly preferably 0.93 to 1.07. Within this range, the long-chain branched structural properties of the olefin polymer are maintained.

(3) Physical characteristics (iii)
The Mw / Mn of the olefin polymer is preferably 2.0 to 7.0, more preferably 2.4 to 6.0, and even more preferably 2.6 to 5.0. It is particularly preferably 2.6 to 4.0. Within this range, the olefin polymer has a narrow molecular weight distribution.

(4) Physical characteristics (iv)
The _g'm of the olefin polymer is preferably 0.50 to 0.95, more preferably 0.50 to 0.90, and even more preferably 0.55 to 0.87. , 0.60 to 0.85 is particularly preferable. Within this range, the olefin polymer has a sufficiently high dissolution tension and is excellent in product characteristics such as formability and mechanical strength.

(5) Physical characteristics (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 0. It is particularly preferable that the amount is 0.05 to 50 g / 10 minutes. Within this range, the olefin polymer has good melt fluidity and excellent product characteristics such as formability and mechanical strength.

(6) Physical characteristics (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 more preferably 0.905 to 0.960 g / cm ³ . Is particularly preferable. Within this range, the olefin polymer has good low-temperature processing characteristics and excellent product characteristics such as molding processability, rigidity and transparency.

(7) Formability The olefin polymer produced by the production method of the present invention has improved melt properties as compared with ordinary ethylene-based polymers and has excellent formability.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The evaluation method used in the examples is as follows. The following catalyst synthesis steps and polymerization steps were all carried out in a purified nitrogen atmosphere, and the solvent used was dehydrated and purified with Molecular Sieve 4A. Was used.

1. 1. Various evaluation (measurement) methods (1) MFR:
Measured according to JIS K6760 at 190 ° C. and a load of 2.16 kg. The FR (flow rate ratio) was calculated from the ratio of MFR 10 kg to MFR (= MFR 10 kg / MFR), which was similarly measured under the conditions of 190 ° C. and 10 kg load.

(2) Density: The density was measured by the density gradient tube method after heat-treating the strands obtained at the time of MFR measurement at 100 ° C. for 1 hour and leaving them at room temperature for 1 hour in accordance with JIS K7112.

(3) Measurement of molecular weight distribution:
In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those measured by the gel permeation chromatography (GPC) method. The conversion from the holding capacity to the molecular weight is performed using a calibration curve made of standard polystyrene prepared in advance. The standard polystyrenes used are all the following brands 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 solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximating with the least squares method. The following numerical values are used for the viscosity formula [η] = K × M ^α used for conversion to the 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

The measurement conditions of 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)
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection amount: 0.2 ml
Sample Preparation: Samples are prepared with ODCB (containing 0.5 mg / mL BHT) to prepare a 1 mg / mL solution and dissolved at 140 ° C. for about 1 hour. The baseline and section of the obtained chromatogram are as illustrated in FIG.

(4) Branch structure analysis by GPC-VIS As a GPC device equipped with a differential refractometer (RI) and a viscosity detector (Viscometer), Waters GPCV2000 was used. Further, as the light scattering detector, a multi-angle laser light scattering detector (MALLS) DAWN-E manufactured by Waitt Technology was used. The detector was connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichrobendene (addition of the antioxidant Irganox 1076 at a concentration of 0.5 mg / mL). The flow rate is 1 mL / min. As the column, two MHHR-H (S) HTs manufactured by Tosoh Corporation were connected and used. The temperature of the column, the sample injection part and each detector is 140 ° C. The sample concentration was 1 mg / mL. The injection volume (sample loop volume) is 0.2175 mL. The data processing software ASTRA (version 4.73.04) attached to MALLS was used to calculate the absolute molecular weight (M) obtained from MALLS, the inertia squared radius (Rg), and the ultimate viscosity ([η]) obtained from Viscometer. , The calculation was performed with reference to the following documents.

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

[Calculation of branch index (g'm), etc.]
The branching index (g') is calculated as a ratio (ηbranch / ηlin) between the ultimate viscosity (ηbranch) obtained by measuring a sample with the above Viscometer and the ultimate viscosity (ηlin) obtained by separately measuring a linear polymer. do.
When a long chain branch is introduced into a polymer molecule, the radius of inertia 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 (ηbranch) of the branched polymer to the intrinsic viscosity (ηlin) of the linear polymer having the same molecular weight becomes smaller as the long-chain branching is introduced. It will become. Therefore, when the branch index (g'= ηbranch / ηlin) becomes a value smaller than 1, it means that a branch is introduced, and as the value becomes smaller, the introduced long-chain branch increases. Means that. In particular, in the present invention, as the absolute molecular weight obtained from MALLS, the above g'at a molecular weight of 100,000 is calculated as _g'm .
FIGS. 2 (a) and 2 (b) show an example of the analysis result by the above GPC-VIS. 2 (a) and 2 (b) represent the ramification 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. 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) represented by the following chemical formula 5-Tetramethylcyclopentadienyl) zirconium dichloride was synthesized according to the following method. 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 2 in a 100 ml flask -Bromobenzoic acid (5.30 g, 26.4 mmol) and 25 ml of thionyl chloride were added and refluxed for 2 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure, and 5.50 g of the obtained acid chloride was used in the next reaction without purification.
An acid chloride (5.00 g, 22.7 mmol) and 50 ml of dichloromethane were added to a 100 ml flask to make a solution, then aluminum chloride (3.02 g, 22.7 mmol) was further added, and ethylene was blown at 20 ° C. for 4 hours. After quenching the reaction with 4N hydrochloric acid to separate the organic phase and the aqueous phase, the aqueous phase was washed 3 times with 50 ml of methyl-t-butyl ether, the organic phase was collected, 3 times with 50 ml of water, and 100 ml of saturated sodium hydrogen carbonate water. , Then washed with 100 ml of saturated saline. After drying over sodium sulfate, the solvent was distilled off under reduced pressure to obtain 4.80 g (yield 85%) of compound 3. It was used for 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 the mixture was heated to 130 ° C. Then 2-bromophenyl-2-chloroethyl ketone (4.60 g, 18.5 mmol) was added slowly 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, the organic phase and the aqueous phase are separated, the aqueous phase is washed 3 times with 100 ml of dichloromethane, the organic phase is collected, washed with 100 ml of water and 100 ml of saturated saline, and dried over sodium sulfate. Then, the solvent was distilled off under reduced pressure to obtain a crude product. Further, the product was purified by a silica gel column (petroleum ether / ethyl acetate = 30/1) to obtain 1.60 g (yield 33%) of 7-bromo-1-indanone.
Synthesis of (1-1-c) 7- (2- (5-methyl) -frill) -1-indanone After adding 2-methylfuran (0.933 g, 11.4 mmol) and 10 ml of THF to a 100 ml flask to make a solution. , N-Butyllithium / Hexane solution (2.5M, 4.70ml, 11.4 mmol) 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, then the above reaction solution was added at 0 ° C., and the mixture was stirred at room temperature for 1 hour. Copper (I) iodide (90 mg, 0.473 mmol), Pd (dpppf) Cl ₂ (177 mg, 0.236 mmol), 7-bromo-1-indanone (2.00 g, 9.45 mmol) in a separately prepared 100 ml flask. ) And 10 ml of DMA were added to the suspension, and the above-mentioned reaction product was added, and reflux was carried out for 15 hours. After cooling to room temperature, 50 ml of water was added, and extraction was performed twice with 50 ml of ethyl acetate. The organic phase was collected, washed twice with 50 ml of water and with 50 ml of saturated brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. Further, the product was purified by a silica gel column (petroleum ether / ethyl acetate = 20/1) to obtain 0.70 g (yield 35%) of 7- (2- (5-methyl) -frill) -1-indanone.
Synthesis of (1-1-d) 1-Methyl-7- (2- (5-Methyl) -Frill) -Inden 7- (2- (5-Methyl) -Frill) -1-Indanone (1) in a 100 ml flask .40 g, 6.59 mmol) and 20 ml of THF were added to make a solution, then a 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 the volatile components were distilled off 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 the solvent was distilled off under reduced pressure to obtain a crude product. It was used for the next reaction without further purification.
The crude product and 30 ml of toluene were added to a 100 ml flask to prepare a solution, then p-toluenesulfonic acid (62.0 mg, 0.330 mmol) was added, and the mixture was stirred at 130 ° C. for 2 hours. During stirring, the water produced using the Dean-Stark trap was removed. The mixture was cooled to room temperature, 30 ml of saturated aqueous sodium hydrogen carbonate solution was added, and the organic phase was separated. The aqueous phase was extracted 3 times with 50 ml of ethyl acetate, the organic phase was collected, washed with 50 ml of saturated brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. Further, the product was purified by a silica gel column (petroleum ether) to obtain 0.850 g (yield 61%) of 1-methyl-7- (2- (5-methyl) -frill) -indene.

(1-2) Synthesis of (2,3,4,5-Tetramethylcyclopentadienyl) Dimethylchlorosilane Add 2.40 g (19.6 mmol) of tetramethylcyclopentadiene and 40 ml of THF to a 200 ml flask to make a solution, and then prepare a solution. The mixture was cooled to −78 ° C., 12.0 ml (30.0 mmol) of an 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 volatile substances by distillation under reduced pressure, 4.00 g of a yellow liquid was obtained. The obtained yellow liquid was used for 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, and then cool to -78 ° C to make an n-butyllithium / hexane solution. 5.2 ml (13.0 mmol) of (2.5 M) was added, and 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 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. Sodium sulfate was filtered, the solution was distilled off under reduced pressure, purified on a silica gel column (petroleum ether), and (3-methyl-4- (2- (5-methyl) -frill) -indenyl) (2,3). 4.40 g (yield 25%) of yellow oil of 4,5-tetramethylcyclopentadienyl) dimethylsilane was obtained.

(1-4) Synthesis of dimethylsilylene (3-methyl-4- (2- (5-methyl) -frill) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride 200 ml flask In addition, (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 an 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. The solvent was distilled off under reduced pressure from the filtrate obtained by filtering the reaction solution to obtain 3.0 g of a yellow powder. The 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. 0.75 g (yield 26%) of yellow powder was obtained.

^{1 1} H-NMR value (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 3.8 g of silica baked at 400 ° C. for 5 hours was placed in a 200 ml two-necked flask and dried under reduced pressure for 1 hour with a vacuum pump while heating in an oil bath at 150 ° C. 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. At room temperature, 11 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle Corporation was added to a toluene solution of metallocene compound A, and the mixture was 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 a total amount of a toluene solution of a reaction product of metallocene compound A and methylaluminoxane was added. 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 stirrer, 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 (2) above was press-fitted with nitrogen, and the 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, additional hydrogen was supplied at a supply rate proportional to the ethylene consumption rate. Polymerization was stopped by adding ethanol. The ethylene / 1-hexene copolymer thus obtained was 140 g. The polymerization results are summarized in the table.

[Example 1]
(1) Synthesis of catalyst for olefin polymerization Under a nitrogen atmosphere, 31.4 g of silica baked at 400 ° C. for 5 hours was placed in a 500 ml two-necked flask and dried under reduced pressure for 1 hour with a vacuum pump while heating in an oil bath at 150 ° C. 87 mg of the 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. At room temperature, 88 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle Corporation was added to a toluene solution of metallocene compound A, and the mixture was 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 toluene solution of the reaction product of metallocene compound A and methylaluminoxane was added. 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 Similar to Reference Example 1 (3), ethylene 1 was used, except that 25 mg of the solid catalyst obtained in (1) above was used to make triethylaluminum 0.30 mmol. -A hexene copolymer was produced. As a result, 30 g of an ethylene / 1-hexene copolymer was produced. The polymerization results are summarized in the table.

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

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

[Comparative Example 1]
(1) Cross-linked biscyclopentadienyl compound B; dimethylsilylene (3-methyl-4- (4-trimethylsilyl-phenyl) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride Synthetic

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

(2-3) Synthesis of 3-Methyl-4- (4-trimethylsilyl-phenyl) -Inden 2.50 g (12.0 mmol) of 3-methyl-4-bromoinden and 40 ml of dimethoxyethane were added to a 200 ml flask to prepare a solution. Then, at 15 ° C., 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. Was added, and reflux stirring was performed for 16 hours. It was cooled to room temperature and 50 ml of water was poured. After separating the organic phase, the aqueous phase was extracted 3 times with 50 ml of ethyl acetate, mixed with the above organic phase and dried over anhydrous sodium sulfate. The crude product was obtained by filtering sodium sulfate and distilling off the solvent under reduced pressure. Further, the product was purified by a silica gel column (petroleum ether) to obtain 3.10 g of 3-methyl-4- (4-trimethylsilyl-phenyl) -indene (yield 92.8%).

(2-4) Synthesis of (2,3,4,5-Tetramethylcyclopentadienyl) Dimethylchlorosilane 2,3,4,5-Tetramethyl in the same manner as in (1-2) of the metallocene compound A. 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) -(5-Methyl) -Frill) -Inden 3.10 g (11.1 mmol) of 3-methyl-4- (4-trimethylsilyl-phenyl) -Inden instead of 2.60 g (12.4 mmol) is used as a metallocene compound. The synthesis was carried out in the same procedure as in A (1-3), and (3-methyl-4- (4-trimethylsilyl-phenyl) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane. It was obtained as 1.00 g (yield 19.7%) of the yellow liquid of.

(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) -frill) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) dimethylsilane 2.20 g (5.70 mmol) instead of (3-methyl-4 -(4-Trimethylsilyl-phenyl) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) 3.24 g (7.09 mmol) of dimethylsilane is used, as in the metallocene compound A (1-4). 1.20 g of yellow powder of dimethylsilylene (3-methyl-4- (4-trimethylsilyl-phenyl) -indenyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride. It was obtained as (yield 27.4%).

^{1 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).

This compound is referred to as metallocene compound B (see the chemical formula below).

(2) Synthesis of catalyst for olefin polymerization 3.2 g of silica baked at 400 ° C. for 5 hours was placed in a 200 ml two-necked flask and dried under reduced pressure for 1 hour with a vacuum pump while heating in an oil bath at 150 ° C. 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. At room temperature, 9 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle Corporation was added to a toluene solution of metallocene compound B, and the mixture was 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 a total amount of a toluene solution of a reaction product of metallocene compound B and methylaluminoxane was added. 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 Same as in Reference Example 1 (3) except that 67 mg of the solid catalyst obtained in (2) above was used, and the hydrogen was 75 ml and the ethylene partial pressure was 1.4 MPa. In addition, an ethylene / 1-hexene copolymer was produced. As a result, 126 g of an 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 an ethylene / 1-hexene copolymer was produced. The polymerization results are summarized in the table. In Table 7, the C ₂ partial pressure means the ethylene partial pressure.

[Comparative Example 2]
(1) Synthesis of catalyst for olefin polymerization A mixed slurry liquid of 32.7 g of silica and 213 ml of dehydrated toluene was calcined in a 1 L flask at 480 ° C. for 6 hours 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. At room temperature, 90 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle Corporation was added to a toluene solution of metallocene compound A, and the mixture was stirred for 30 minutes. While heating and stirring the 1 L flask containing the previously prepared silica toluene slurry solution 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. After 1 hour, stirring was stopped, and the mixture was allowed to stand for 10 minutes while being heated to 40 ° C., and then the supernatant was removed. 600 ml of dehydrated hexane was added thereto, and the mixture was stirred for 5 minutes and then allowed to stand for 10 minutes to remove the supernatant. Similarly, the catalyst was washed again with 700 ml of dehydrated hexane, and then the hexane was distilled off under reduced pressure to obtain a powdery catalyst.
(2) Production of Ethylene / 1-Hexene Copolymer A continuous ethylene / 1-hexene vapor phase copolymerization was carried out using the powdery catalyst obtained in (1) above. That is, a gas phase continuous polymerization apparatus 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 (internal volume 100 L). , Flow bed diameter 10 cm, fluid bed type polymer (dispersant) 1.8 kg), the powdery catalyst was intermittently supplied at a rate of 56 mg / hour, and the gas composition and temperature were kept constant for polymerization. .. Further, 0.03 mol / L of a hexane-diluted solution of triethylaluminum (component D) was supplied to the gas circulation line at 16.7 ml / hr. As a result, the average production rate of the produced polyethylene was 274 g / hour. The MFR and density of the ethylene / 1-hexene copolymer obtained after producing a cumulative polyethylene of 5 kg or more 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;
Except for the conditions shown in the table below, ethylene / 1-hexene vapor phase continuous copolymerization was carried out in the same manner as in Comparative Example 2. However, in Examples 6 to 8, 0.15 mol / L of a hexane-diluted solution of triethylaluminum (component D) was used. The results are shown in the table below.

3. 3. As shown in the evaluation tables 5 to 8, in Examples 1, 2 and 3, the values of [Mw / Mn] / [Mw ₀ / Mn ₀ ] were lower than those in Reference Example 1. Similarly, in Example 4, the values of [Mw / Mn] / [Mw ₀ / Mn ₀ ] were lower than those of Comparative Example 1. Further, in Examples 5 to 9, the values of [Mw / Mn] / [Mw ₀ / Mn ₀ ] were lower than those in Comparative Example 2.
On the other hand, the ratio of the branch index ( _g'm / _g'm0 ) was the same in Examples 1, 2 and 3 and Reference Example 1, and was the same in Example 4 and Comparative Example 1. The ratio of the branch 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 structure characteristics of the produced olefin polymer. By controlling the long-chain branched structure and molecular weight distribution structure of the olefin polymer, it is possible to control the melt viscoelastic properties of the olefin polymer, and the moldability, mechanical properties, and transparency of the olefin polymer carried out 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 or modifications can be made within the scope of the claims of the present invention.

According to the present invention, there is provided an olefin polymer having a narrow molecular weight distribution without changing the long-chain branched structure characteristics. In this olefin polymer, it is possible to control the melt viscoelastic property of the olefin polymer by controlling the long chain branched structure and the molecular weight distribution structure, and the formability and mechanical properties of the olefin polymer carried out in the molten state, It is useful for improving transparency and has high industrial potential.

Claims (12)

In a vapor phase polymerization reaction, a catalyst for olefin polymerization 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 (1). A method for producing an olefin polymer having a long-chain branched structure, which is carried out by supplying to satisfy (3), wherein the supply amount ratio (mol / mol) of the component (D) to the component (A) is determined. A method for producing an olefin polymer having a narrow molecular weight distribution, which comprises 1.5 to 100 times the ratio (mol / mol) under the following condition (1).

Component (A): Cross-linked biscyclopentadienyl compound represented by the following general formula (1) containing the transition metal element M ¹ .

[In formula (1), M ¹ represents any transition metal of Ti, Zr or Hf. X ¹ and X ² independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, and 1 to 20 carbon atoms. A hydrogen group substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. ^Q1 and ^Q2 independently represent a carbon atom, a silicon atom, or a germanium atom. Each R ¹ 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 . You may. m is 0 or 1, and when m is 0, Q ¹ is directly attached to a conjugated 5-membered ring containing R ² and R ³ . ^{R2 ,} R3 and ^R4 are independently hydrogen atom, halogen atom, hydrogen group having 1 to 20 carbon atoms, and silicon-containing hydrocarbon group having 1 to 18 carbon atoms including silicon number 1 to 6. It shows a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrogen group having 1 to 40 carbon atoms including an oxygen atom or a sulfur atom, or a hydrogen group substituted silyl group having 1 to 40 carbon atoms, and has two ^R2 and 2. At least one of the ^four R3s is not a hydrogen atom and at least one of the ^four R4s is not a hydrogen atom. Of R ² , R ³ and R ⁴ , only one set of adjacent R ^3s or adjacent R ² and R ³ may form a ring together with the bonded carbon atom. ]

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

Component (D): Compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Group 1 Group 2 and Group 12 to 15 of the Periodic Table.
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group, and
n is a number corresponding to the valence of M ² )

Conditions (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
Conditions (3) The ratio of M ² to the polymerization medium (mmol / kg) is 0.01 to 100.
In a vapor phase polymerization reaction, a catalyst for olefin polymerization 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 (1a). A method for producing an olefin polymer having a long-chain branched structure, which is carried out by supplying to satisfy (3a).

Component (A): Cross-linked biscyclopentadienyl compound represented by the following general formula (1) containing the transition metal element M ¹ .

[In formula (1), M ¹ represents any transition metal of Ti, Zr or Hf. X ¹ and X ² independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, and 1 to 20 carbon atoms. A hydrogen group substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. ^Q1 and ^Q2 independently represent a carbon atom, a silicon atom, or a germanium atom. Each R ¹ 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 . You may. m is 0 or 1, and when m is 0, Q ¹ is directly attached to a conjugated 5-membered ring containing R ² and R ³ . ^{R2 ,} R3 and ^R4 are independently hydrogen atom, halogen atom, hydrogen group having 1 to 20 carbon atoms, and silicon-containing hydrocarbon group having 1 to 18 carbon atoms including silicon number 1 to 6. It shows a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrogen group having 1 to 40 carbon atoms including an oxygen atom or a sulfur atom, or a hydrogen group substituted silyl group having 1 to 40 carbon atoms, and has two ^R2 and 2. At least one of the ^four R3s is not a hydrogen atom and at least one of the ^four R4s is not a hydrogen atom. Of R ² , R ³ and R ⁴ , only one set of adjacent R ^3s or adjacent R ² and R ³ may form a ring together with the bonded carbon atom. ]

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

Component (D): Compound represented by the general formula M ² L ¹ _n (M ² represents a typical metal atom of Group 1 Group 2 and Group 12 to 15 of the Periodic Table.
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group, and
n is a number corresponding to the valence of M ² )

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 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) An olefin obtained when the value of the molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) and the supply amount ratio of the component (D) to the component (A) are not increased. The ratio ([Mw / Mn] / [Mw ₀ / Mn ₀ ]) to the value of 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 branch index g'measured by a GPC measuring device combined with a differential refractometer, a viscosity detector, and a light scattering detector at a molecular weight of 100,000, and the above component (A). ) To the ratio ( _g'm / _g'm0 ) of the branch index g'of the olefin polymer obtained when the supply amount ratio of the above component (D) is not increased to the value ( _g'm0 ) at a molecular weight of 100,000. Is 0.90 to 1.10.
The method for producing an olefin polymer according to any one of claims 1 to 3, wherein 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 characteristics (v) MFR is 0.001 to 1000 g / 10 minutes.
Physical properties (vi) The 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, wherein 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 gas phase polymerization reactor. The method for producing an olefin polymer according to any one of claims 1 to 8, wherein 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, wherein 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, wherein the component (D) is 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 catalyst for olefin polymerization further contains an inorganic compound carrier (component (C)).

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