JP7106971B2 - Method for producing olefin polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer and an olefin polymer. More particularly, the present invention relates to a method for producing an olefin polymer capable of narrowing the molecular weight distribution by adjusting the amount of specific components supplied during polymerization, and the olefin polymer obtained by this production method.

As a method to improve the molding processability of metallocene polyolefins, which generally have poor molding processability, there is a method of blending high-pressure low-density polyethylene with metallocene polyolefins, and a polymerization reaction using a specific metallocene to introduce long-chain branching into polyolefins. How to introduce is known. The former requires a blending process, resulting in high production costs. Moreover, although the obtained blend is excellent in moldability, the mechanical strength, which is an advantage of the metallocene polyolefin, is lowered.
On the other hand, a method using a bridged pentadienylindenyl compound as a specific metallocene catalyst for introducing the latter long-chain branching is known (see Patent Documents 1 to 3). By using these metallocene catalysts, it is possible to produce an olefinic polymer with a well-developed long-chain branched structure. However, this method tends to widen the molecular weight distribution of the polymer, resulting in problems such as rupture of the molten resin, poor appearance due to rough surface elasticity, and deterioration in mechanical strength due to melt orientation. However, it is still not sufficient to achieve both performance and product characteristics. Therefore, there is a demand for a production method capable of producing an olefin polymer with a narrow molecular weight distribution without changing the long-chain branching structural characteristics of the produced polymer.

JP 2013-227271 A JP 2017-020019 A JP 2016-017039 A

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 branching structural properties 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 branching structural properties.

In order to solve the above problems, the present inventors have made intensive studies and found that the molecular weight distribution can be narrowed by adjusting the amount of specific components supplied during polymerization. was completed.

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

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

［式（１）中、Ｍ^１は、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１およびＸ^２は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、酸素原子若しくは窒素原子を含む炭素数１～２０の炭化水素基、炭素数１～２０の炭化水素基置換アミノ基または炭素数１～２０のアルコキシ基を示す。Ｑ^１とＱ^２は、各々独立して、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１は、それぞれ独立して、水素原子または炭素数１～１０の炭化水素基を示し、４つのＲ^１のうち少なくとも２つが結合して、Ｑ^１およびＱ^２と一緒に環を形成していてもよい。ｍは、０または１であり、ｍが０の場合、Ｑ^１は、Ｒ^２およびＲ^３を含む共役５員環と直接結合している。Ｒ^２、およびＲ^３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す。Ｒ^２およびＲ^３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８５～１３０
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０．０１～２０

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. is a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. ^Q1 and ^Q2 each 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 may m is 0 or 1, and when m is 0, ^Q1 is directly bonded to the conjugated ^five -membered ring containing ^R2 and R3. R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, It represents a halogen-containing hydrocarbon group of 1 to 20, a hydrocarbon group of 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a hydrocarbon group-substituted silyl group of 1 to 40 carbon atoms. Among R ² and R ³ , adjacent R ³ or only one pair of adjacent R ² and R ³ may form a ring together with the bonding carbon atoms. ]

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

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

Condition ( ¹ ) The ratio of ^M2 to M1 (mol/mol) is 85-130
Condition (2) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12
Condition (3) The ratio of ^M2 to the polymerization medium (mmol/kg) is 0.01 to 20

In a second aspect of the present invention, an olefin polymerization catalyst containing the following essential components (A) and (B) and the following component (D) are added to a polymerization reactor in which an olefin monomer and a polymerization medium exist under the following conditions (1a): ) to (3a) are supplied to produce an olefin polymer having a long-chain branched structure.

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

［式（１）中、Ｍ^１は、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１およびＸ^２は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、酸素原子若しくは窒素原子を含む炭素数１～２０の炭化水素基、炭素数１～２０の炭化水素基置換アミノ基または炭素数１～２０のアルコキシ基を示す。Ｑ^１とＱ^２は、各々独立して、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１は、それぞれ独立して、水素原子または炭素数１～１０の炭化水素基を示し、４つのＲ^１のうち少なくとも２つが結合して、Ｑ^１およびＱ^２と一緒に環を形成していてもよい。ｍは、０または１であり、ｍが０の場合、Ｑ^１は、Ｒ^２およびＲ^３を含む共役５員環と直接結合している。Ｒ^２、およびＲ^３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す。Ｒ^２およびＲ^３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１３０～１００００
条件（２ａ）重合媒体に対するＭ^１の比（μｍｏｌ／ｋｇ）が０．００１～１０
条件（３ａ）重合媒体に対するＭ^２の比（ｍｍｏｌ／ｋｇ）が０．０５～２０

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. is a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. ^Q1 and ^Q2 each 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 may m is 0 or 1, and when m is 0, ^Q1 is directly bonded to the conjugated ^five -membered ring containing ^R2 and R3. R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, It represents a halogen-containing hydrocarbon group of 1 to 20, a hydrocarbon group of 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a hydrocarbon group-substituted silyl group of 1 to 40 carbon atoms. Among R ² and R ³ , adjacent R ³ or only one pair of adjacent R ² and R ³ may form a ring together with the bonding carbon atoms. ]

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

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

Condition (1a) ^The ratio of ^M2 to M1 (mol/mol) is 130 to 10000
Condition (2a) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 10
Condition (3a) The ratio of ^M2 to the polymerization medium (mmol/kg) is 0.05 to 20

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

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

Physical properties (ii) The value (g' _m ) of the branching index g' at a molecular weight of 100,000 measured by a GPC measurement device combining a differential refractometer, a viscosity detector, and a light scattering detector, and the component (A The ratio (g' _m /g' _m0 ) of the branching index g' of the olefin polymer obtained when the supply amount ratio of the component (D) to (D) is not increased to the value (g' _m0 ) at a molecular weight of 100,000 is between 0.90 and 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) and (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 invention of the present invention is a method for producing an olefin polymer according to any one of the first to fourth inventions, wherein the olefin monomer is ethylene.

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

A seventh 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 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 invention of the present invention is the process 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 invention 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 performed at an olefin partial pressure of 0.2 to 1.9 MPa. be.

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

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

A thirteenth aspect 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, it is possible to narrow the molecular weight distribution while maintaining the long-chain branching structural characteristics of the olefin polymer.
The olefin polymer of the present invention has a narrow molecular weight distribution while maintaining long-chain branching structural properties.

1 is a graph showing the baseline and intervals of a chromatogram used in a gel permeation chromatography (GPC) method; 2 is a graph showing the relationship between the branching index (g') calculated from GPC-VIS measurement (branching structure analysis) and the molecular weight (M).

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

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

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

［式（１）中、Ｍ^１は、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１およびＸ^２は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、酸素原子若しくは窒素原子を含む炭素数１～２０の炭化水素基、炭素数１～２０の炭化水素基置換アミノ基または炭素数１～２０のアルコキシ基を示す。Ｑ^１とＱ^２は、各々独立して、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１は、それぞれ独立して、水素原子または炭素数１～１０の炭化水素基を示し、４つのＲ^１のうち少なくとも２つが結合して、Ｑ^１およびＱ^２と一緒に環を形成していてもよい。ｍは、０または１であり、ｍが０の場合、Ｑ^１は、Ｒ^２およびＲ^３を含む共役５員環と直接結合している。Ｒ^２、およびＲ^３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す。Ｒ^２およびＲ^３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８５～１３０
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０．０１～２０

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. is a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. ^Q1 and ^Q2 each 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 may m is 0 or 1, and when m is 0, ^Q1 is directly bonded to the conjugated ^five -membered ring containing ^R2 and R3. R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, It represents a halogen-containing hydrocarbon group of 1 to 20, a hydrocarbon group of 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a hydrocarbon group-substituted silyl group of 1 to 40 carbon atoms. Among R ² and R ³ , adjacent R ³ or only one pair of adjacent R ² and R ³ may form a ring together with the bonding carbon atoms. ]

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

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

Condition ( ¹ ) The ratio of ^M2 to M1 (mol/mol) is 85-130
Condition (2) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12
Condition (3) The ratio of ^M2 to the polymerization medium (mmol/kg) is 0.01 to 20

(2) Olefin Monomer The olefin monomer is not particularly limited, and ethylene and other α-olefins can be mentioned. The method for producing an olefin polymer of the present invention can be suitably used for either homopolymerization of ethylene or copolymerization of ethylene and α-olefin.
α-Olefins as comonomers include those having 3 to 30 carbon atoms, preferably 3 to 8 carbon atoms, specifically propylene, 1-butene, 1-hexene, 1-octene, 4-methyl- 1-pentene and the like are exemplified. As for the α-olefins, it is also possible to copolymerize two or more α-olefins with ethylene. Copolymerization may be alternating copolymerization, random copolymerization, or block copolymerization. When ethylene and other α-olefin are copolymerized, the amount of the other α-olefin can be arbitrarily selected within the range of 90 mol% or less of the total monomers, but is generally 40 mol%. It is preferably selected in the range of 30 mol % or less, more preferably 10 mol % or less. Of course, it is also possible to use a small amount of comonomers other than ethylene and α-olefins. Dienes such as hexadiene, 1,4-hexadiene, and 1,7-octadiene; cyclic compounds such as norbornene and cyclopentene; oxygen-containing compounds such as hexenol, hexenoic acid and methyl octenate; compounds can be mentioned.

(3) Polymerization Medium Conventionally known polymerization mediums can be used and are not particularly limited, but hydrocarbon solvents or polyolefins (particles or pellets) are preferably used.
As the hydrocarbon solvent, conventionally known ones can be used. linear, branched or cyclic hydrocarbons, inert hydrocarbons such as benzene, toluene and xylene, and mixtures classified as liquid paraffins, isoparaffinic solvents and mixed aliphatic hydrocarbon solvents. , For example, commercially available products such as IP solvent, ISOPAR, kerosene, etc., alone or as a mixture, and 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. Among these, linear, branched or cyclic hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, heptane, octane, decane, dodecane, cyclopentane and cyclohexane; Liquid paraffins, isoparaffin solvents, mixtures classified as mixed aliphatic hydrocarbon solvents such as IP solvent, ISOPAR, and other commercially available products, liquefied ethylene, liquefied propylene, 1-butene, 1-hexene, 1-octene .alpha.-olefins such as .alpha.-olefins are preferably used alone or in mixture. Propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, IP solvent, ISOPAR, liquefied ethylene, liquefied propylene, 1-butene, 1- Hexene and 1-octene are more preferably used alone or as a mixture, and isobutane, isopentane, n-hexane, isohexane, heptane, cyclopentane, cyclohexane, IP solvent and ISOPAR are more preferably used alone or as a mixture.
As the polyolefin, it is possible to use conventionally known ones. Polyisobutene, polystyrene and the like are preferably used, but it is more preferable to use a polyolefin containing an olefin copolymer obtained by copolymerizing the same type of comonomer as the olefin polymer to be produced. Polymer particles (also referred to as polymer powder or polymer granules) or so-called pellets obtained through a melt kneader may be used. Particles are more preferred.

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

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

[In Formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. is a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ¹ and Q ² each independently represent a carbon atom, a silicon atom or a germanium atom. 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 may m is 0 or 1, and when m is 0, ^Q1 is directly bonded to the conjugated ^five -membered ring containing ^R2 and R3. R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, It represents a halogen-containing hydrocarbon group of 1 to 20, a hydrocarbon group of 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a hydrocarbon group-substituted silyl group of 1 to 40 carbon atoms. Among R ² and R ³ , adjacent R ³ or only one pair of adjacent R ² and R ³ may form a ring together with the bonding carbon atoms. ]

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

^Q1 and Q2 ^each represent a carbon atom, a silicon atom or a germanium atom. A carbon atom or a silicon atom is preferred. A silicon atom is more preferred.
Furthermore, each R ¹ independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, and an n-pentyl group. , neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group and the like. In addition, when 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. are mentioned.
Preferred specific examples of R ¹ include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an ethylene group and a cyclobutylidene group when Q ¹ and ^/ or Q ² are carbon atoms; and when ^Q2 is a silicon atom, it includes a methyl group, an ethyl group, a phenyl group and a silacyclobutyl group.

m is 0 or 1, and when m is 0, ^Q1 is directly bonded to the conjugated ^five -membered ring containing ^R2 and R3.

R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, It represents a halogen-containing hydrocarbon group of 1 to 20, a hydrocarbon group of 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a hydrocarbon group-substituted silyl group of 1 to 40 carbon atoms.
Preferred specific examples of R ² and R ³ 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 and trimethylsilyl group. Among these specific examples, hydrogen atom, methyl group, n-butyl group, t-butyl group, phenyl group and trimethylsilyl group are more preferred, and hydrogen atom, methyl group, t-butyl group, phenyl group and trimethylsilyl group are particularly preferred. preferable.
Among R ² and R ³ , adjacent R ³ or only one pair of adjacent R ² and R ³ may form a ring together with the bonding carbon atoms.

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

Here, M ¹ , X ¹ , X ² , Q ¹ , R ¹ , R ² , and R ³ follow the description of general formula (1) above. Adjacent R ³ groups preferably form a 5- to 7-membered ring structure together with the carbon atoms to which they are bonded. It is more preferable to form a 6-membered ring structure such as a cyclohexane ring, or a 7-membered ring structure such as a heptadiene ring. is more preferred.

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

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

Examples of the case where R ² and R ³ form a ring in general formula (2) include dimethylsilylene (4-methyl-5-phenyl-cyclopentathiophene)(cyclopentadienyl)zirconium dichloride, dimethylsilylene ( 3-methyl-5-(5-methyl-2-furyl)-cyclopentathiophene)(cyclopentadienyl)zirconium dichloride, dimethylsilylene(2-methyl-4-phenyl-4H-azulenyl)(cyclopentadienyl) zirconium dichloride, and the like.

Known bridged cyclopentadienyl/indenyl compounds included in general formula (3) include all exemplified compounds in JP-A-2011-137146, and [Chemical 1] general formula (1c) in JP-A-2013-227271. All exemplified compounds when R ^4c = H in JP 2014-70029 [Chemical 1] All exemplified compounds when R ⁴ = H in general formula (1), JP 2015-63515 [ Chemical Formula 1] All exemplified compounds in the case of R ⁵ =H in general formula (1), all exemplified compounds in the case of general formula (1) in which R ⁷ to R ¹⁰ are all H in JP-A-2015-172037 Compounds, [Chemical 1] General Formula (1) of JP-A-2012-25664, all exemplified compounds when R ¹¹ to R ¹⁴ are all H, [Chemical 1] General Formula (1) of JP-A-2016-141635 ), all exemplified compounds where R ⁸ to R ¹¹ are all H, all exemplified compounds where R ⁸ to R ¹¹ are all H in [Chemical 1] General Formula (1) of JP-A-2016-145190, etc. mentioned.

All exemplified compounds in JP-A-2011-137146 are specifically the compounds listed below. Dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride, Dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dimethyl, Dimethylsilylene (cyclopentadienyl) (indenyl) zirconium diphenyl, Isopropylidene (cyclopentadienyl) (indenyl)zirconium dichloride, silacyclobutyl(cyclopentadienyl)(indenyl)zirconium dichloride, silacyclopentyl(cyclopentadienyl)(indenyl)zirconium dichloride, silacyclohexyl(cyclopentadienyl)(indenyl)zirconium dichloride, cyclo butylidene (cyclopentadienyl) (indenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (indenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) enyl)(3-methylindenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dimethyl, isopropylidene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride, dimethylsilylene (Cyclopentadienyl)(3-ethylindenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(3-ethylindenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3-n-propylindenyl) ) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-n-propylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-i-propylindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) enyl)(3-i-propylindenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3-n-butylindenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(3-n-butylindenyl) ) zirconium dichloride, dimethylsilylene (cyclopentadienyl)(3-t-butylindenyl)zirconium dichloride, cyclobutylidenecyclopentadienyl)(3-t-butylindenyl)zirconium dichloride, dimethylsilylene (cyclopentadienyl) nyl)(3-t-butylindenyl)zirconium dimethyl, isopropylidene(cyclopentadienyl)(3-t-butylindenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3-n-pentylindenyl) ) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-hexylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-cyclohexylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenylindenyl)zirconium dichloride, dimethylsilylene (cyclopentadienyl)(3-benzylindenyl)zirconium dichloride, dimethylsilylene (cyclopentadienyl)(3-tolylindenyl)zirconium dichloride, dimethylsilylene (cyclo pentadienyl)(3-trimethylsilylindenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3-chlorophenylindenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3-fluorophenylindenyl)zirconium dichloride , dimethylsilylene (cyclopentadienyl) (4-methylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (5-methylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (6-methylindenyl) Nyl)zirconium dichloride, dimethylsilylene (cyclopentadienyl)(3,4-dimethylindenyl)zirconium dichloride, dimethylsilylene (cyclopentadienyl)(3-t-butyl-4-methylindenyl)zirconium dichloride, dimethyl silylene(cyclopentadienyl)(4-phenylindenyl)zirconium dichloride,

Dimethylgermylene (cyclopentadienyl) (indenyl) zirconium dichloride, Dimethylgermylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, Dimethylgermylene (cyclopentadienyl) (3-ethylindenyl) Zirconium dichloride, dimethylgermylene (cyclopentadienyl)(3-i-propylindenyl)zirconium dichloride, dimethylgermylene (cyclopentadienyl)(3-n-butylindenyl)zirconium dichloride, dimethylgermylene (cyclo pentadienyl)(3-t-butylindenyl)zirconium dichloride, diethylsilylene(cyclopentadienyl)(indenyl)zirconium dichloride, diethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride, diethylsilylene (Cyclopentadienyl)(3-ethylindenyl)zirconium dichloride, diethylsilylene(cyclopentadienyl)(3-i-propylindenyl)zirconium dichloride, diethylsilylene(cyclopentadienyl)(3-n-butyl) (indenyl) zirconium dichloride, diethylsilylene (cyclopentadienyl) (3-t-butylindenyl) zirconium dichloride, di-n-butylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride, di-n-butylsilylene (cyclo pentadienyl)(3-methylindenyl)zirconium dichloride, di-n-butylsilylene(cyclopentadienyl)(3-ethylindenyl)zirconium dichloride, di-n-butylsilylene(cyclopentadienyl)(3-i -propylindenyl)zirconium dichloride, di-n-butylsilylene (cyclopentadienyl)(3-n-butylindenyl)zirconium dichloride, di-n-butylsilylene (cyclopentadienyl)(3-t-butylindenyl) ) zirconium dichloride,

Diphenylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (indenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, diphenylsilylene (cyclo pentadienyl)(3-ethylindenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(3-i-propylindenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(3-n-butylindenyl) ) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (3-t-butylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (benzo[e]indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (Dibenzoindenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(azulenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(4-methylazulenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(4-phenyl) azulenyl)zirconium dichloride, dimethylsilylene (cyclopentadienyl)(5,6-dimethylindenyl)zirconium dichloride, dimethylsilylene (cyclopentadienyl)(benzo[f]indenyl)zirconium dichloride, dimethylsilylene (cyclopentadienyl) enyl) (6,7-dihydroindacenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (5,5,7,7-tetramethyl-6,7-dihydroindacenyl) zirconium dichloride, dimethylsilylene ( cyclopentadienyl)(5,6,7,8-tetrahydrobenzo[f]indenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(5,6,7,8-tetrahydro-5,5,8,8 - Tetramethylbenzo[f]indenyl)zirconium dichloride.

In addition, there are compounds in which zirconium in the above compounds is replaced with titanium or hafnium.
Furthermore, when using these metallocene compounds as the essential component (A), it is possible to use two or more of them.

Among the specific compounds exemplified above, preferred metallocene compounds as the essential component (A) are shown below.
dimethylsilylene(cyclopentadienyl)(indenyl)zirconium dimethyl, isopropylidene(cyclopentadienyl)(indenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride, dimethylsilylene (Cyclopentadienyl)(3-methylindenyl)zirconium dimethyl, isopropylidene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3-n-butylindenyl) ) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenylindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-n-butylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-t-butylindenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3-t-butylindenyl)zirconium dimethyl, dimethylsilylene(cyclopentadienyl)(4-phenylindenyl)zirconium dichloride, Dimethylsilylene(cyclopentadienyl)(benzo[e]indenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(3-t-butylindenyl)zirconium dichloride, cyclobutylidenecyclopentadienyl)(3-t -butylindenyl)zirconium dichloride, dimethylgermylene(cyclopentadienyl)(indenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(indenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(indenyl)zirconium dichloride , dimethylsilylene(cyclopentadienyl)(azulenyl)zirconium dichloride, and compounds obtained by replacing zirconium in the above compounds with titanium or hafnium, and the like.

Among the specific compounds exemplified above, particularly preferred metallocene compounds as the essential component (A) are shown below.
isopropylidene(cyclopentadienyl)(indenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3-phenylindenyl)zirconium dichloride, Dimethylsilylene(cyclopentadienyl)(4-phenylindenyl)zirconium dichloride, Dimethylsilylene(cyclopentadienyl)(benzo[e]indenyl)zirconium dichloride, Isopropylidene(cyclopentadienyl)(3-methylindenyl) ) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-t-butylindenyl) zirconium dichloride, dimethylgermylene (cyclopentadienyl) (indenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3 -t-butylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (indenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (3-methylindenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (3-t-butylindenyl)hafnium dichloride, and the like.

Specifically, the compounds of JP-A-2013-227271 are all exemplified compounds where R ^4c =H in the following general formula (1c).

Specifically, the compounds of JP-A-2014-70029 are all exemplified compounds where R ⁴ =H in the following general formula (1).

Specifically, the compounds of JP-A-2015-63515 are all exemplified compounds when R ⁵ =H in the following general formula (1).

Specifically, the compounds of JP-A-2015-172037 are all exemplified compounds where all of R ⁷ to R ¹⁰ are H in the following general formula (1).

Specifically, the compounds of JP-A-2012-25664 are all exemplified compounds when all of R ¹¹ to R ¹⁴ are H in the following general formula (1).

Specifically, the compounds of JP-A-2016-141635 are all exemplified compounds when all of R ⁸ to R ¹¹ are H in the following general formula (1).

Specifically, the compounds of JP-A-2016-145190 are all exemplified compounds when all of R ⁸ to R ¹¹ are H in the following general formula (1).

(5) Component (B)
The olefin polymerization catalyst contains, as an essential component, a cationic metallocene compound by reacting with the metallocene compound of component (A) (component (A), hereinafter simply referred to as A) in addition to component (A). Forming compound (component (B), hereinafter sometimes simply referred to as B).

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

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

The alkyl group of trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group and the like. is particularly preferred.
Two or more of the organoaluminum compounds may be used in combination.

The reaction ratio between water and the organoaluminum compound (water/Al molar ratio) is preferably 0.25/1 to 1.2/1, particularly preferably 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 water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate, etc., and components capable of producing water in the reaction system can be used. Among the organoaluminumoxy compounds described above, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, particularly methylaluminoxane (including those substantially composed of methylaluminoxane (MAO)). is suitable as the organoaluminum oxy compound.
Of course, as the organoaluminum oxy compound, two or more of the above organoaluminum oxy compounds can also be used in combination. It is also possible to use

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

Further, other specific examples of the compound (B) that reacts with the metallocene compound (A) to form a cationic metallocene compound include borane compounds and borate compounds. More specifically, the 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( perfluoroanthryl)borane, tris(perfluorobinaphthyl)borane, and the like.

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, and tris(perfluorobinaphthyl)borane are more preferred, and tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, and tris( Preferred compounds include perfluoronaphthyl)borane and tris(perfluorobiphenyl)borane.

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

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

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

Also, in formula (5), R ⁷ and R ⁸ are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms and are linked together by a bridging group. Preferred substituents of the substituted aromatic hydrocarbon group are alkyl groups typified by methyl, ethyl, propyl and isopropyl groups, and halogens such as fluorine, chlorine, bromine and iodine. Furthermore, X ⁴ and X ⁵ are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted hydrocarbon group containing 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by 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, tributylammonium tetra(3,5- ditrifluoromethylphenyl)borate, tributylammonium tetra(2,6-difluorophenyl)borate, tributylammonium tetra(perfluoronaphthyl)borate, dimethylaniliniumtetra(pentafluorophenyl)borate, dimethylaniliniumtetra(2,6- ditrifluoromethylphenyl)borate, dimethylanilinium tetra(3,5-ditrifluoromethylphenyl)borate, dimethylaniliniumtetra(2,6-difluorophenyl)borate, dimethylaniliniumtetra(perfluoronaphthyl)borate, triphenyl Phosphonium tetra(pentafluorophenyl)borate, Triphenylphosphoniumtetra(2,6-ditrifluoromethylphenyl)borate, Triphenylphosphoniumtetra(3,5-ditrifluoromethylphenyl)borate, Triphenylphosphoniumtetra(2,6- difluorophenyl)borate, 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, tripropylammoniumtetra(2,6-ditrifluoromethylphenyl)borate, tripropylammoniumtetra(perfluoro naphthyl)borate, di(1-propyl)ammonium tetra(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate and the like.

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

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

In formula ( ⁶ ), L2 is carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropynium cation, benzyl cation, trityl cation, sodium cations, protons, and the like. Also, R ⁷ , R ⁸ , X ⁴ and X ⁵ are the same as defined 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, Trityltetra(p-fluorophenyl)borate, Trityltetra(m-fluorophenyl)borate, Trityltetra(3,5-difluorophenyl)borate, Trityltetra(pentafluorophenyl)borate, Trityltetra(2,6-ditrifluoro methylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, tropinium tetraphenylborate, tropiniumtetra(o-tolyl)borate, tropiniumtetra(p- tolyl)borate, tropiniumtetra(m-tolyl)borate, tropiniumtetra(o-fluorophenyl)borate, tropiniumtetra(p-fluorophenyl)borate, tropiniumtetra(m-fluorophenyl)borate, tropiniumtetra (3,5-difluorophenyl)borate, tropinium tetra(pentafluorophenyl)borate, tropiniumtetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(3,5-ditrifluoromethylphenyl)borate, Tropinium tetra(perfluoronaphthyl)borate, NaBPh ₄ , NaB(o-CH ₃ -Ph) ₄ , NaB(p-CH ₃ -Ph) ₄ , NaB(m-CH ₃ -Ph) ₄ , NaB(o- F-Ph) ₄ , NaB(pF-Ph) ₄ , NaB(mF-Ph) ₄ , NaB(3,5-F ₂ -Ph) ₄ , NaB(C ₆ F ₅ ) ₄ , NaB( 2,6-(CF ₃ ) ₂ -Ph) ₄ , NaB(3,5-(CF ₃ ) ₂ -Ph) ₄ , NaB(C ₁₀ F ₇ ) ₄ , _HBPh 4.2 diethyl ether, HB(3, ₅ -F ₂ -Ph) 4.2 diethyl ether, HB(C ₆ F ₅ ) 4.2 diethyl ether, HB(2,6-(CF ₃ ) ₂ -Ph) 4.2 diethyl ether, HB( ₃ , 5- ₍ CF ₃ ) ₂ -Ph) 4.2 diethyl ether and 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, tropiniumtetra(3,5-ditrifluoromethylphenyl)borate, tropiniumtetra(perfluoronaphthyl)borate, NaB( _C6F5 ) ₄ , NaB(2,6-( _CF3 ) ₂ -Ph) ₄ , NaB(3,5-( _CF3 ) _{2 -} Ph) ₄ , NaB _{( C10F7} ) 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-ditrifluoro 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-( CF ₃ ) ₂ -Ph) 4.2 diethyl ether, HB(3,5- ₍ CF ₃ ) ₂ -Ph) _4.2 diethyl ether and HB(C ₁₀ H ₇ ) _4.2 diethyl ether.

When a borane compound or a borate compound is used as the component (B), the polymerization activity and copolymerizability are enhanced, thereby improving the productivity of the ethylene polymer having long chain branches. A mixture of the above organoaluminumoxy compound and the above borane compound or borate compound can also be used as the component (B). Furthermore, two or more of the above borane compounds and borate compounds can be mixed and used.

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

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

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

These inorganic supports are generally 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 use it after adjusting to . The properties of these inorganic carriers are not particularly limited, but usually the average particle diameter 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 gravity 0.20 to 0 It is preferred to use mineral supports having a weight of 0.50 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. It can be used after being brought into contact 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 olefin polymerization catalyst 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 groups 1, ² , and 12-15 of the periodic table,
L ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group,
n is the number corresponding to the valence of ^M2 )

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

Specific examples of component ₍ D) include LiH, LiF, LiCl, LiBr, LiI, _{CH3Li , C2H5Li} , _nC3H7Li , _{iC3H7Li , nC4H9Li} , _{iC 4H9Li} , _tC4H9Li , 1 _{- C5H11Li} , 2- _C5H11Li , _{3 - C5H11Li} , _{2 - CH3-2 - C4H8Li} , 2- CH ₃ -3-C ₄ H ₈ Li etc., 1-C ₆ H ₁₃ Li, 2-C ₆ H ₁₃ Li, 3-C ₆ H ₁₃ Li, 2-CH ₃ -1-C ₅ H ₁₀ Li, 2 —CH ₃ -2-C ₅ H ₁₀ Li, 2-CH ₃ -3-C ₅ H ₁₀ Li, 2,3-(CH ₃ ) ₂ -1-C ₄ H ₇ Li, etc., 1-C ₇ H ₁₅ Li etc., 1-C ₈ H ₁₇ Li etc., 1-C ₉ H ₁₉ Li etc., 1-C ₁₀ H ₂₁ Li etc., 1-C ₁₁ H ₂₃ Li etc., 1-C ₁₂ H ₂₅ Li etc., 1- _C13H27Li etc., BeH2, _BeF2 , _BeCl2 etc., _{( CH3} ) _2Be etc., BH3, _BF3 , _BCl3 etc., _{( CH3} ) _{3B ,} ( _CH3 ) _2BCl etc., NaH, NaF, NaCl, NaBr etc., CH ₃ Na, C ₂ H ₅ Na, nC ₃ H ₇ Na, iC ₃ H ₇ Na, nC ₄ H ₉ Na etc., 1-C ₅ H ₁₁ Na, 2-C ₅ H ₁₁ Na etc., MgH ₂ , MgF ₂ , MgCl ₂ etc., (CH ₃ ) ₂ Mg, (C ₂ H ₅ ) ₂ Mg, (nC ₃ H ₇ ) ₂ Mg, (iC ₃ H ₇ ) ₂ Mg etc. ( _nC4H9 ) _2Mg and the like, ( _CH3 )( _C2H5 )Mg and the like, _{( CH3} ) _{( nC3H7} )Mg and the like, _{( C2H5} ) _{( nC4H9} ) _Mg and the like, Mg compounds having a hydrocarbon group containing an unsaturated bond such as divinyl Mg, diallyl Mg, (hexenyl) ₂ Mg, (octenyl) ₂ Mg, diphenyl Mg, dibenzyl Mg, etc., AlH ₃ , AlF ₃ , AlCl ₃ , etc. ( _CH3 )3Al, _{( C2H5} )3Al, _{( nC3H7} )3Al, _{( iC3H7} ) _3Al , etc. _{, ( nC4H9} ) _3Al , etc., _{( CH3} ) _{2 (} C ₂ H ₅ ) Al, (CH ₃ ) ₂ (nC ₃ H ₇ ) Al, etc., (C ₂ H ₅ ) ₂ (nC ₄ H ₉ ) Al, etc., trivinyl Al, triallyl Al, (hexenyl) ₃ Al, ( Al compounds having a hydrocarbon group containing an unsaturated bond such as octenyl) ₃ Al, triphenyl Al, tribenzyl Al, etc., KH, KF, KCl, etc., CH ₃ K, C ₂ H ₅ K, nC ₃ H ₇ K, iC ₃ H ₇ K, nC ₄ H ₉ K, iC ₄ H ₉ K, tC ₄ H ₉ K, 1-C ₅ H ₁₁ K etc., CaH ₂ , CaF ₂ , CaCl ₂ etc., (CH ₃ ) ₂ Ca, ( _CH3 )CaCl etc., _ZnH2 , _ZnF2 , _ZnCl2 etc., ( _CH3 ) _2Zn , ( _CH3 )ZnCl etc., ( _C2H5 ) _2Zn , _{( CH3} ) _{( C2H5} ) Zn, _{( nC3H7} ) _2Zn , _{( iC3H7} ) _2Zn , _{( nC4H9} ) _2Zn , ( _iC4H9 ) _2Zn , _{( tC4H9} ) _2Zn , _{( nC5 H11} ) _2Zn , ( _nC6H13 ) _2Zn , _{( nC7H15} ) _2Zn , _{( nC8H17} ) _2Zn , _{( nC9H19} ) _2Zn , _{( nC10H21 ) 2Zn} Zn compounds having a hydrocarbon group containing an unsaturated bond such as divinyl Zn, diallyl Zn, (hexenyl) ₂ Zn, (octenyl) ₂ Zn, diphenyl Zn, dibenzyl Zn, etc., GaH ₃ , GaF ₃ , GaCl ₃ , etc. , (CH ₃ ) ₃ Ga, (C ₂ H ₅ ) ₃ Ga, (nC ₃ H ₇ ) ₃ Ga, (iC ₃ H ₇ ) ₃ Ga, etc., (nC ₄ H ₉ ) ₃ Ga, etc., (CH ₃ ) ₂ ( _C2H5 )Ga, ( _CH3 ) _{2 ( nC3H7} )Ga, etc., _{( C2H5} ) _{2 ( nC4H9} )Ga, etc., _GeH4 , _GeF4 , _GeCl4 , etc., _{( CH3} ) _4Ge , ( _C2H5 ) _4Ge , ( _nC3H7 ) _4Ge , _{( iC3H7} ) _4Ge , etc., _{( nC4H9} ) _4Ge , etc., _{( CH3} ) _{3 ( C2H5} )Ge, ( _CH3 ) _{3 ( nC3H7} )Ge, etc. _{, ( C2H5} ) ₃ (nC ₄ H ₉ ) Ge, etc., and MgX ¹ _m R ¹ _n (OR ² ) _2- mn in the general formula (a) described in paragraphs [0034] to [0038] of JP-A-2012-72229 and exemplified compounds for AlX ³ _q R ⁴ _r (OR ⁵ ) _3- qr in general formula (c) described in paragraphs [0044] to [0046] of the same publication. Furthermore, binuclear metal compounds having the structures of the above compounds, such as (1,2-ethylene)di(ZnCl), (1,2-ethylene)di(ZnCH ₃ ), (1,2-ethylene)di(MgC ₂ H ₅ ), (1,4-butylene)di[Al(CH ₃ ) ₂ ], (1,4-butylene)di[Al(CH ₃ )Cl] and the like.

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

(I) After component (A) and component (B) are brought into contact, component (C) is brought into contact, if necessary.
(II) Component (A) and, if necessary, component (C) are brought into contact, and then component (B) is brought into contact.
(III) After contacting component (B) and optionally component (C), component (A) is contacted.

Of these contacting methods, (I) and (III) are preferred, with (I) being the most preferred. In either contacting method, an aromatic hydrocarbon (generally having 6 to 12 carbon atoms), typically benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, dodecane, is usually reacted in an inert atmosphere such as nitrogen or argon. , cyclohexane, and other aliphatic or alicyclic hydrocarbons (usually having 5 to 12 carbon atoms) in the presence of a liquid inert hydrocarbon, with or without stirring, each component is brought into contact. 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, more preferably is preferably carried out for 30 minutes to 12 hours.

In addition, when the component (A), the component (B), and, if necessary, the component (C) are brought into contact with each other, as described above, an aromatic hydrocarbon solvent in which certain components are soluble or sparingly soluble, and a certain Any aliphatic or alicyclic hydrocarbon solvent in which the components are insoluble or sparingly soluble can be used.

When the contact reaction between each component is carried out in stages, the solvent used in the former step may be used as it is as the solvent for the contact reaction in the latter step without removing it. In addition, after the initial contact reaction using a soluble solvent, some components are insoluble or sparingly soluble in liquid inert hydrocarbons (e.g., aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, and xylene). after adding a hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon) and recovering the desired product as a solid matter, or once part or all of the soluble solvent is removed by drying or other means to obtain the desired product. After removing the product as a solid, subsequent catalytic reaction of the desired product can be carried out using any of the inert hydrocarbon solvents described above. In the present invention, the contact reaction of each component may be carried out multiple times.

In the present invention, the proportion of component (A) and component (B) used is not particularly limited, but the following ranges are preferred.

When an organoaluminumoxy compound is used as component (B) that reacts with component (A) to produce a cationic metallocene compound, the aluminum atom of the organoaluminumoxy compound relative to the transition metal (M ¹ ) in component (A) The ratio (Al/M ¹ ) is usually in the range of 1 to 100,000, preferably 5 to 1000, more preferably 50 to 500. When using a borane compound or borate compound, the transition in the metallocene compound The atomic ratio (B/M ¹ ) of boron to the metal (M ¹ ) is usually selected in the range of 0.01-100, preferably 0.1-50, more preferably 0.2-10. desirable. Furthermore, when a mixture of an organoaluminumoxy compound, a borane compound, and a borate compound is used as the compound (B) that produces a cationic metallocene compound, each compound in the mixture is added to the transition metal (M ¹ ). On the other hand, it is desirable to select the usage ratio similar to the above.

When component (C) is used, the amount of component (C) used is 1 g per 0.0001 to 5 millimoles of the transition metal in component (A), preferably 1 g per 0.001 to 0.5 millimoles, more preferably 1 g per 0.01-0.1 mmol.

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

The olefin polymerization catalyst can also be obtained by the following method.
(IV) contacting component (A) with component (C) to remove the solvent, using this as a solid catalyst component, and contacting it with an organoaluminumoxy compound, a borane compound, a borate compound, or a mixture thereof under polymerization conditions; .
(V) contacting an organoaluminumoxy compound, a borane compound, a borate compound, or a mixture thereof with component (C) to remove the solvent, and using this as a solid catalyst component, contacting component (A) under polymerization conditions; .
In the contact methods (IV) and (V), the same conditions as those described above can be used for the component ratio, contact conditions, and solvent removal conditions.

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

Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite, and other smectites, vermiculites, and micas are preferred.

In general, natural products are often non-ion-exchangeable (non-swelling). It is preferable to carry out a treatment for imparting. Particularly preferred among such treatments are the following chemical treatments. Here, the chemical treatment can be any of surface treatment for removing impurities adhering to the surface and treatment for influencing the crystal structure and chemical composition of the layered silicate. Specifically, (i) acid treatment using hydrochloric acid, sulfuric acid, or the like, (ii) alkali treatment using NaOH, KOH, _NH3 , or the like, (iii) selected from groups 2 to 14 of the periodic table. (iv) alcohol, hydrocarbon Compounds, formamide, organic matter treatment such as aniline, and the like. These treatments may be performed alone, or two or more treatments may be combined.

The particle properties of the layered silicate can be controlled by pulverization, granulation, sizing, fractionation, or the like before, during, or after all steps. The method can be anything sensible. In particular, granulation methods include spray granulation, tumbling granulation, compression granulation, stirring granulation, briquetting, compacting, extrusion granulation, and fluid bed granulation. method, emulsion granulation method and submerged granulation method. Particularly preferred granulation methods are spray granulation, tumbling granulation and compression granulation.

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

In order to support 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 contact with each other, or the component (A), an organic Aluminum compounds and layered silicates may be brought into contact with each other.
The method of contacting each component is not particularly limited, and for example, the following method can be optionally adopted.
(VI) After the component (A) and the organoaluminum compound are brought into contact, they are brought into contact with the layered silicate support.
(VII) After the component (A) and the layered silicate support are brought into contact, they are brought into contact with an organoaluminum compound.
(VIII) After contacting the organoaluminum compound with the layered silicate support, the component (A) is contacted.

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

The proportions of the component (A), the organoaluminum compound and the layered silicate support are not particularly limited, but are preferably within the following ranges. The amount of component (A) supported is 0.0001 to 5 millimoles, preferably 0.001 to 0.5 millimoles, more preferably 0.01 to 0.1 millimoles, per 1 g of the layered silicate support. In addition, when an organoaluminum compound is used, the amount of Al carried is desirably in the range of 0.01 to 100 mol, preferably 0.1 to 50 mol, more preferably 0.2 to 10 mol.

As for the method of supporting and solvent removal, the same conditions as those for the inorganic carrier can be used. When a layered silicate is used as a component that serves as component (B) and component (C), the obtained olefin polymer has a narrow molecular weight distribution. Furthermore, the productivity of the olefin polymer having high polymerization activity and long-chain branching is improved. The olefin polymerization catalyst thus obtained may be used after prepolymerizing 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 supported catalyst described above, preferably by slurry polymerization or gas phase polymerization. In the case of slurry polymerization, aliphatic hydrocarbons such as isobutane, hexane, and heptane; Ethylene or the like is polymerized in the presence or absence of an inert hydrocarbon solvent selected from group hydrocarbons and the like. It goes without saying that liquid monomers such as liquid ethylene and liquid propylene can also be used as solvents. In the case of gas phase polymerization, ethylene or the like is polymerized in a reactor in which a gas stream of ethylene or comonomer is introduced, distributed or circulated. In the present invention, more preferred polymerization is gas phase polymerization. The polymerization conditions are not particularly limited. It is preferably 0.2 to 1.8 MPa, particularly preferably 0.2 to 1.5 MPa, and the polymerization time is 5 minutes to 12 hours, preferably 20 minutes to 8 hours, more preferably 30 minutes to 5 hours. Time is commonly used.

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 more effectively adjusted by adding hydrogen to the polymerization reaction system. can be done. Also, a component for removing moisture, a so-called scavenger, may be added to the polymerization system without any problem. Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, the above organoaluminumoxy compounds, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethyl zinc and dibutyl zinc, diethyl Magnesium, organomagnesium compounds such as dibutylmagnesium and ethylbutylmagnesium, Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride, and the like are used. Among these, triethylaluminum, triisobutylaluminum and ethylbutylmagnesium are preferred, and triethylaluminum is particularly preferred. It can also be applied to a multi-stage polymerization system having two or more stages in which polymerization conditions such as hydrogen concentration, amount of monomers, polymerization pressure and polymerization temperature are different from each other.

(10) Conditions in First Production Method The first production method is a method for producing an olefin polymer having a long-chain branched structure by supplying so as to satisfy the following conditions (2) and (3). The supply amount ratio (mol/mol) of component (D) to component (A) is characterized by being 1.5 to 100 times the ratio (mol/mol) in the following condition (1).

Condition ( ¹ ) The ratio of ^M2 to M1 (mol/mol) is 85-130
Condition (2) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12
Condition (3) The ratio of ^M2 to the polymerization medium (mmol/kg) is 0.01 to 20

In condition (1), the ratio of M ² to M ¹ (mol/mol) is 85-130, preferably 90-130, more preferably 95-127.
Condition (2) is such that the ratio (μmol/kg) of M ¹ to the polymerization medium is 0.001-12, preferably 0.01-12, more preferably 0.1-11.
Condition (3) is such that the ratio (mmol/kg) of M ² to the polymerization medium is 0.01-20, preferably 0.02-10, more preferably 0.04-1.7.

In the first production method, the supply amount ratio (mol/mol) of component (D) to component (A) is 1.5 to 100 times the ratio (mol/mol) in the above condition (1), preferably 1.7 to 70 times, more preferably 1.8 to 50 times.
When the above conditions are met, the molecular weight distribution can be narrowed while maintaining the long-chain branching structural characteristics of the olefin polymer.

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

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

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. is a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. ^Q1 and ^Q2 each 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 may m is 0 or 1, and when m is 0, ^Q1 is directly bonded to the conjugated ^five -membered ring containing ^R2 and R3. R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, It represents a halogen-containing hydrocarbon group of 1 to 20, a hydrocarbon group of 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a hydrocarbon group-substituted silyl group of 1 to 40 carbon atoms. Among R ² and R ³ , adjacent R ³ or only one pair of adjacent R ² and R ³ may form a ring together with the bonding carbon atoms. ]

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

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

Condition (1a) ^The ratio of ^M2 to M1 (mol/mol) is 130 to 10000
Condition (2a) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 10
Condition (3a) The ratio of ^M2 to the polymerization medium (mmol/kg) is 0.05 to 20

In the second production method of the present invention, the characteristic requirements and various conditions (conditions (1), conditions (2), conditions (3)) in the first production method are the following conditions (1a) and conditions (2a) ) and condition (3a) are replaced, detailed description of the other conditions is omitted, and the description in the first manufacturing method is cited as it is.

Condition (1a) The ratio of M ² to M ¹ (mol/mol) is 130-10000, preferably 130-6000, more preferably 150-5000.
Condition (2a) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001-10, preferably 0.01-10, more preferably 0.1-10.
Condition (3a) The ratio (mmol/kg) of M ² to the polymerization medium is 0.05-20, preferably 0.05-18, more preferably 0.30-16.
When the above conditions are satisfied, the molecular weight distribution can be narrowed while maintaining the long-chain branching structural characteristics of the olefin polymer.

3. Properties of Olefin Polymer The properties of the olefin polymer obtained by the method for producing an olefin polymer of the present invention are not particularly limited, but from the viewpoint of moldability and mechanical properties, it preferably has the following properties.
(1) physical properties (i)
The value of the molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) and the molecular weight distribution of the olefin polymer obtained when the supply amount ratio of component (D) to component (A) is not increased ( Mw ₀ /Mn ₀ ) ratio ([Mw/Mn]/[Mw ₀ /Mn ₀ ]) is preferably 0.50 to 0.95, and is 0.55 to 0.93 is more preferred, and 0.60 to 0.91 is particularly preferred. Within this range, the olefin polymer has a narrow molecular weight distribution.
Here, "obtained when the supply amount ratio of component (D) to component (A) is not increased" means the following matters in the first manufacturing method. That is, it means that the ratio (mol/mol) of component (D) supplied to component (A) is 1.0 times the ratio of condition (1) below. Specifically, if the ratio (M ² /M ¹ ) of condition (1) is 30, it means that the supply ratio (D / A) is also 30 (hereinafter similarly defined ).


Condition ( ¹ ) The ratio of ^M2 to M1 (mol/mol) is 30 to 130

In the second manufacturing method, the phrase "obtained when the supply amount ratio of component (D) to component (A) is not increased" means the following. In condition (1a), it means that the ^ratio of ^M2 to M1 (mol/mol) is less than 130 (defined similarly below).

(2) physical properties (ii)
The value (g' _m ) at a molecular weight of 100,000 of the branching index g' measured by a GPC measurement device combining a differential refractometer, a viscosity detector, and a light scattering detector, and the component (D ) is not increased, the ratio ( _g'm / _g'm0 ) of the branching index g' of the olefin polymer obtained when the molecular weight is 100,000 ( _g'm0 ) is 0.90 to 1. 0.10 is preferred, 0.93 to 1.07 is more preferred, and 0.95 to 1.05 is particularly preferred. Within this range, the long-chain branched structure characteristic of the olefin polymer is maintained.

(3) Physical properties (iii)
The Mw/Mn of the olefin polymer is preferably 2.0 to 7.0, more preferably 2.4 to 6.7, particularly preferably 2.6 to 6.5. Within this range, the olefin polymer has a narrow molecular weight distribution.

(4) physical properties (iv)
The _g'm of the olefin polymer is preferably 0.50 to 0.95, more preferably 0.50 to 0.90, even more preferably 0.55 to 0.85. , 0.60 to 0.80 is particularly preferred. Within this range, the olefin polymer has a sufficiently high melt tension and excellent product properties such as moldability and mechanical strength.

(5) Physical properties (v)
The MFR (melt flow rate, 190° C., 2.16 kg load) of the olefin polymer is preferably 0.001 to 1000 g/10 min, more preferably 0.005 to 100 g/10 min, and 0 0.05 to 50 g/10 minutes is particularly preferred. Within this range, the olefin polymer has good melt fluidity and excellent product properties such as moldability and mechanical strength.

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

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

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. The evaluation methods used in the examples are as follows. The catalyst synthesis step and the polymerization step below were all performed in a purified nitrogen atmosphere, and the solvent used was dehydrated and purified with molecular sieve 4A. was used.

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

(2) Density: According to JIS K7112, the strand obtained during MFR measurement was heat-treated at 100°C for 1 hour, left at room temperature for 1 hour, and then measured by the density gradient tube method.

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

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

(4) Branching structure analysis by GPC-VIS Alliance GPCV2000 manufactured by Waters was used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). As a light scattering detector, a multi-angle laser light scattering detector (MALLS) DAWN-E manufactured by Wyatt Technology was used. The detectors were connected in the order MALLS, RI, Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (with the antioxidant Irganox 1076 added at a concentration of 0.5 mg/mL). The flow rate is 1 mL/min. Two columns of Tosoh GMHHR-H(S) HT were used. The temperature of the column, 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 determine the absolute molecular weight (M), the radius of inertia (Rg) obtained from MALLS, and the intrinsic viscosity ([η]) obtained from Viscometer. , was calculated with reference to the following literature.

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

[Calculation of branching index (g'm), etc.]
The branching index (g′) is calculated as the ratio (ηbranch/ηlin) between the intrinsic viscosity (ηbranch) obtained by measuring the sample with the Viscometer and the intrinsic viscosity (ηlin) obtained by separately measuring the linear polymer. do.
The introduction of long chain branches into a polymer molecule reduces the radius of gyration 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 of the same molecular weight decreases as long-chain branches are introduced. becoming. Therefore, when the branching index (g′=ηbranch/ηlin) is less than 1, it means that branching has been introduced, and as the value decreases, the number of long-chain branches introduced increases. means that In particular, in the present invention, the above g' at a molecular weight of 100,000 is calculated as _g'm as an absolute molecular weight obtained by MALLS.
FIG. 2 shows an example of the analysis results by the above GPC-VIS. FIG. 2 represents branching index (g′) at molecular weight (M) obtained from MALLS. Here, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) was used as the linear polymer.

2. Examples and Comparative Examples [Comparative Example 1]
(1) Synthesis of Bridged Biscyclopentadienyl Compound (Component A) Dimethylsilylene (4-(4-trimethylsilyl-phenyl)-indenyl)(cyclopentadienyl)zirconium dichloride represented by the following chemical formula was prepared in JP-A-2013-227271. Synthesized according to the method described in JP-A Nos. [0140] to [0143]. This compound is referred to as metallocene compound A.

(2) Synthesis of Olefin Polymerization Catalyst In a nitrogen atmosphere, 5 g of silica calcined at 600° C. for 5 hours was placed in a 200 mL two-necked flask and dried under reduced pressure with a vacuum pump for 1 hour while being heated in an oil bath at 150° C. 68 mg of metallocene compound A (component A) was placed in a separately prepared 100 ml two-necked flask under a nitrogen atmosphere and dissolved in 13.4 mL of dehydrated toluene. At room temperature, 8.6 mL of a 20% methylaluminoxane/toluene solution (component B solution) manufactured by Albemarle was added to the toluene solution of metallocene compound A, and the mixture was stirred for 30 minutes. While heating and stirring a 200 mL two-necked flask containing vacuum-dried silica in an oil bath at 40° C., the entire amount of the toluene solution of the reaction product of metallocene compound A and methylaluminoxane was added. 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 (2) Preparation of solid catalyst. That is, 30 mL of 1-hexene, 0.20 mmol of triethylaluminum (component D), 200 mL of hydrogen, and 441 g of isobutane were added to a 2 L autoclave equipped with an induction stirring device, the temperature was raised to 75° C., and ethylene was introduced to reduce the ethylene partial pressure to 1.1. It was kept at 4 MPa. Next, 226 mg of the solid catalyst obtained in the above (2) was injected with nitrogen, and the polymerization was continued for 60 minutes while maintaining the ethylene partial pressure of 1.4 MPa and the temperature of 75°C. During the polymerization reaction, hydrogen and 1-hexene were additionally supplied at a supply rate proportional to the ethylene consumption rate. The amount of 1-hexene additionally supplied was 16 mL. Polymerization was stopped by adding ethanol. The ethylene/1-hexene copolymer thus obtained was 130 g. The polymerization results are summarized in the table below.

[Example 1]
In the same manner as in Comparative Example 1, ethylene/1- A hexene copolymer was produced. As a result, 41 g of ethylene/1-hexene copolymer was produced. The polymerization results are summarized in the table below.

[Reference Example 1]
(1) Synthesis of a crosslinked biscyclopentadienyl compound (component A);
Dimethylsilylene (3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(cyclopentadienyl)zirconium dichloride, JP-A-2013-227271 [0159] ~ [0165] method described Synthesized according to This compound is referred to as metallocene compound B.

(2) Synthesis of Olefin Polymerization Catalyst A solid catalyst was prepared in the same manner as in Comparative Example 1, except that the calcination temperature of silica was 400° C. and 62 mg of metallocene compound B was used instead of 68 mg of metallocene compound A.
(3) Production of ethylene/1-butene copolymer An ethylene/1-butene copolymer was produced using the solid catalyst obtained in (2) above.
Specifically, 344 g of purified n-heptane, 0.50 mmol of triethylaluminum (component D), and 34 mL of hydrogen were added to a 1 L autoclave equipped with an induction stirring device, the temperature was raised to 75° C., and ethylene containing 5% by weight of 1-butene was introduced. to keep the ethylene partial pressure at 1.4 MPa. Then, 10 mL of a heptane slurry containing 99 mg of the solid catalyst obtained in (2) above was injected with argon gas, and the polymerization was continued for 60 minutes while maintaining the ethylene partial pressure of 1.4 MPa and the temperature of 75°C. During the polymerization reaction, hydrogen was additionally supplied at a supply rate proportional to the ethylene consumption rate. Polymerization was stopped by adding ethanol. The ethylene/1-butene copolymer thus obtained was 36 g. The polymerization results are summarized in the table below.

[Examples 2 and 3]
In Examples 2 and 3, the solid catalyst obtained in Reference Example 1 was used (see [Reference Example 1] (2)).
In Examples 2 and 3, this catalyst was used to produce ethylene/1-butene copolymers according to the conditions shown in the table below, and the other conditions were the same as in Comparative Example 1 ([Comparative Example 1] (3 )). The polymerization results are summarized in the table below. In addition, in Table 6, the _C2 partial pressure means the ethylene partial pressure.

[Comparative Example 2] Production of ethylene/1-hexene copolymer [Reference Example 1] Ethylene/1-hexene gas-phase continuous copolymerization was carried out using the solid catalyst (powdered catalyst) obtained in (2). . That is, a gas-phase continuous polymerization apparatus (internal volume: 100 L) was prepared at a temperature of 75°C, a hexene/ethylene molar ratio of 1.1%, a hydrogen/ethylene molar ratio of 0.20%, a nitrogen concentration of 33 mol%, and an ethylene partial pressure of 0.54 MPa. , fluidized bed diameter 10 cm, fluidized bed seed polymer (dispersant) 1.8 kg) was intermittently supplied with the powdery catalyst at a rate of 246 mg/hour, and polymerization was carried out at a constant gas composition and temperature. . Also, a 0.03 mol/L hexane diluted solution of triethylaluminum (component D) was supplied to the gas circulation line at 15.3 ml/hr. As a result, the average production rate of produced polyethylene was 413 g/hour. The MFR and density of the ethylene/1-hexene copolymer obtained after producing a cumulative 5 kg or more of polyethylene were 0.1 g/10 min and 0.916 g/cm ³ , respectively. The results are shown in the table below. In addition, in Table 7, the _C2 partial pressure means the ethylene partial pressure.

[Example 4] Production of ethylene/1-hexene copolymer Continuous gas-phase copolymerization of ethylene/1-hexene was carried out in the same manner as in Comparative Example 2 except for the conditions shown in the table below. The results are shown in the table below.

3. Evaluation As shown in Tables 4 to 7, in Example 1, the value of [Mw/Mn]/[Mw ₀ /Mn ₀ ] was lower than in Comparative Example 1. Similarly, in Examples 2 and 3, the value of [Mw/Mn]/[Mw ₀ /Mn ₀ ] was lower than in Reference Example 1. Similarly, in Example 4, the value of [Mw/Mn]/[Mw ₀ /Mn ₀ ] was lower than in Comparative Example 2.
On the other hand, the branching index ratio (g′ _m /g′ _m0 ) was equivalent between Example 1 and Comparative Example 1, and equivalent between Examples 2 and 3 and Reference Example 1. Similarly, the branching index ratio (g' _m /g' _m0 ) was comparable between Example 4 and Comparative Example 2.
From these results, it was found that the molecular weight distribution can be narrowed without changing the long-chain branching structure characteristics of the olefin polymer to be produced in the present invention. By controlling the long-chain branching structure and molecular weight distribution structure of the olefin polymer, it is possible to control the melt viscoelastic properties of the olefin polymer. It is considered useful for improving

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

The present invention provides an olefin polymer having a narrow molecular weight distribution without altering its long-chain branching structural properties. In this olefin polymer, it is possible to control the melt viscoelastic properties of the olefin polymer by controlling the long chain branch structure and the molecular weight distribution structure, and the moldability and mechanical properties of the olefin polymer performed in a molten state. It is useful for improving transparency and has high industrial applicability.

Claims (13)

An olefin polymerization catalyst containing the following essential components (A) and (B) and the following component (D) are added to a gas phase polymerization reactor in which an olefin monomer and a polymerization medium exist, under the following conditions (2) and A method for producing an olefin polymer having a long-chain branched structure, wherein the supply amount ratio (mol/mol) of the component (D) to the component (A) is as follows: A method for producing an olefin polymer having a narrow molecular weight distribution, characterized in that the ratio (mol/mol) in condition (1) is 1.5 to 100 times.

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

[In formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. is a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. ^Q1 and ^Q2 each 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 may m is 0 or 1, and when m is 0, ^Q1 is directly bonded to the conjugated ^five -membered ring containing ^R2 and R3. R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, It represents a halogen-containing hydrocarbon group of 1 to 20, a hydrocarbon group of 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a hydrocarbon group-substituted silyl group of 1 to 40 carbon atoms. Among R ² and R ³ , adjacent R ³ or only one pair of adjacent R ² and R ³ may form a ring together with the bonding carbon atoms. ]

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

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

Condition ( ¹ ) The ratio of ^M2 to M1 (mol/mol) is 90
Condition (2) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 12
Condition (3) The ratio of ^M2 to the polymerization medium (mmol/kg) is 0.01 to 20
An olefin polymerization catalyst containing the following essential components (A) and (B) and the following component (D) are added to a polymerization reactor, which is a gas phase polymerization reaction and in which an olefin monomer and a polymerization medium exist, under the following conditions (1a) to A method for producing an olefin polymer having a long-chain branched structure by supplying so as to satisfy (3a).

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

[In Formula (1), M ¹ represents a transition metal such as Ti, Zr or Hf. X ¹ and X ² each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. is a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ¹ and Q ² each independently represent a carbon atom, a silicon atom or a germanium atom. 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 may m is 0 or 1, and when m is 0, ^Q1 is directly bonded to the conjugated ^five -membered ring containing ^R2 and R3. R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, It represents a halogen-containing hydrocarbon group of 1 to 20, a hydrocarbon group of 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or a hydrocarbon group-substituted silyl group of 1 to 40 carbon atoms. Among R ² and R ³ , adjacent R ³ or only one pair of adjacent R ² and R ³ may form a ring together with the bonding carbon atoms. ]

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

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

Condition (1a) the ratio of ^M2 to M1 (mol/mol) is ¹³⁰ to 10000
Condition (2a) The ratio of M ¹ to the polymerization medium (μmol/kg) is 0.001 to 10
Condition (3a) The ratio of ^M2 to the polymerization medium (mmol/kg) is 0.05 to 20
2. The method for producing an olefin polymer according to claim 1, wherein the obtained olefin polymer satisfies the following physical properties (i) and (ii).

Physical properties (i) obtained when the value of molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) and the supply amount ratio of component (D) to component (A) is 30 to 130 The ratio ([Mw/Mn]/[Mw ₀ /Mn ₀ ]) to the value of the molecular weight distribution (Mw ₀ /Mn ₀ ) of the olefin polymer obtained is 0.50 to 0.95.

Physical properties (ii) The value (g' _m ) of the branching index g' at a molecular weight of 100,000 measured by a GPC measurement device combining a differential refractometer, a viscosity detector, and a light scattering detector, and the component (A ) to the value ( _g'm0 ) of the branching index g' of the olefin polymer obtained when the supply amount ratio of the component (D) to ) is 30 to 130 at a molecular weight of 100,000 ( _g'm /g' _m0 ) is between 0.90 and 1.10.
3. The method for producing an olefin polymer according to claim 2, wherein the obtained olefin polymer satisfies the following physical properties (i) and (ii).
Physical properties (i) are obtained when the value of molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) and the supply amount ratio of component (D) to component (A) are less than 130 The ratio ([Mw/Mn]/[Mw ₀ /Mn ₀ ]) to the molecular weight distribution (Mw ₀ /Mn ₀ ) of the olefin polymer is 0.50 to 0.95.
Physical properties (ii) The value (g' _m ) of the branching index g' at a molecular weight of 100,000 measured by a GPC measurement device combining a differential refractometer, a viscosity detector, and a light scattering detector, and the component (A ) to the value ( _g'm0 ) of the branching index g' of the olefin polymer obtained when the supply amount ratio of the component (D) to ) is less than 130 at a molecular weight of 100,000 ( _g'm / _g'm0 ) is between 0.90 and 1.10. 5. The method for producing an olefin polymer according to any one of claims 1 to 4, 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 5, wherein the olefin monomer is ethylene. 7. The method for producing an olefin polymer according to claim 6, wherein the obtained olefin polymer satisfies the following physical properties (v) and (vi).
Physical properties (v) MFR is 0.001 to 1000 g/10 minutes.
Physical Properties (vi) Density is 0.895 to 0.970 g/cm ³ . Process for producing olefin polymers according to any one of claims 1 to 7, characterized in that the polymerization medium is a hydrocarbon solvent or a polyolefin (particles or pellets). The method for producing an olefin polymer according to any one of claims 1 to 8, 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 9, wherein the polymerization reaction is carried out at a temperature of 60 to 110°C. 11. The method for producing an olefin polymer according to any one of claims 1 to 10, wherein the polymerization reaction is carried out at an olefin partial pressure of 0.2 to 1.9 MPa. Olefin polymer according to any one of claims 1 to 11, characterized in that component (D) has the general formula AlL ¹ ₃ (L ¹ is a hydrogen atom, a halogen atom or a hydrocarbon group). manufacturing method. The method for producing an olefin polymer according to any one of claims 1 to 12, wherein the olefin polymerization catalyst further contains an inorganic compound carrier (component (C)).

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