JP6036108B2 - Process for producing ethylene polymer - Google Patents

Description

  The present invention relates to a method for producing an ethylene polymer. More specifically, the present invention relates to an ethylene polymer having a sufficient number and length of long-chain branches introduced using an olefin polymerization catalyst containing a specific metallocene compound. It relates to a manufacturing method.

  In general, methods for improving the molding processability of metallocene polyethylene, which has poor molding processability, include blending high-density low-density polyethylene with metallocene polyethylene and polymerizing reaction using specific metallocenes to form long-chain branches in polyethylene. The method of introduction is known. The former requires a blending process and thus increases the manufacturing cost. Moreover, although the obtained blend is excellent in molding processability, the mechanical strength which is an advantage of the metallocene polyethylene is lowered. On the other hand, a method using a bridged bisindenyl compound (see, for example, Patent Document 1) or a geometrically constrained half metallocene (see, Patent Document 2) is known as a specific metallocene for introducing the latter long-chain branch. The number of terminal double bonds and long chain branches in the polymer is small, and the effect of improving molding processability is not yet sufficient.

Patent Document 3 discloses that branched polyethylene can be produced by homopolymerization of ethylene by solution polymerization using asymmetric metallocene and methylaluminoxane in which a cyclopentadienyl group and an indenyl group are carbon-bridged. However, the length of the branch is described as having 1 to 20 carbon atoms, and the length of the branch is too short to exhibit the effect of improving the molding processability as a long chain branch. Does not show cure.
Furthermore, Patent Document 4 discloses a macromonomer using a metallocene having a methyl group at positions 2, 4, and 7 of an indenyl group and a modified clay compound among asymmetric metallocenes in which a cyclopentadienyl group and an indenyl group are silicon-bridged. Although a catalyst system for producing an ethylene polymer and an ethylene / butene copolymer useful as the above has been reported, there is no description that the polymer has few terminal double bonds and long chain branching is generated by this catalyst alone.
Recently, the present inventors have disclosed in Patent Document 5 that there is no substituent other than the crosslinking group on the cyclopentadienyl group in the asymmetric metallocene obtained by crosslinking the cyclopentadienyl group and the indenyl group with a crosslinking group. Also reported is a method for producing an ethylene-based polymer with improved molding processability using a supported catalyst for olefin polymerization having a specific asymmetric metallocene as an essential component and having hydrogen or a specific substituent at the 3-position of the indenyl group. did.
However, according to the present invention, an ethylene polymer having a high strain hardening degree of elongational viscosity can be obtained. Thus, although improvement in molding processability is seen as compared with conventional long-chain branched polyethylene, branching of long-chain branching is achieved. Since the index still does not reach that of the high-pressure low-density polyethylene, further improvement of the long-chain branched structure has been demanded.
Under these circumstances, in order to further improve the moldability of metallocene polyethylene, it is required to develop a metallocene polyethylene production method in which a sufficient number and length of long chain branches are introduced at an early stage.

Japanese Patent Laid-Open No. 08-048711 Japanese Translation of National Publication No. 07-500622 JP 05-043619 A JP 2008-050278 A JP 2011-137146 A

  The object of the present invention is to provide a method for producing a metallocene polyethylene in which a sufficient number and length of long-chain branches are introduced in order to further improve the moldability of the metallocene polyethylene in view of the above-mentioned problems of the prior art. There is to do. In the present invention, polyethylene refers to a generic name of an ethylene homopolymer and a copolymer of ethylene and an olefin described later, and is also referred to as an ethylene polymer.

  As a result of intensive studies in order to achieve the above-mentioned problems, the present inventors have used a specific metallocene compound as a catalyst component for olefin polymerization and a compound that reacts with this to form a cationic metallocene compound, and a particulate carrier It was found that a metallocene polyethylene having a sufficient number and length of long-chain branching can be produced by using a catalyst composition comprising a combination of these, and based on these findings, the present invention has been completed.

That is, according to 1st invention of this invention, it is a manufacturing method for obtaining the ethylene-type polymer which satisfy | fills the following conditions (Bd-1 ')-(Bd-4'), Comprising: There is provided an ethylene-based polymer production method using an olefin polymerization catalyst comprising Ad), (B) and (C).
Component (Ad): Metallocene compound represented by the following general formula (1d)

［式（１ｄ）中、Ｍ^１ｄは、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１ｄおよびＸ^２ｄは、それぞれ独立して、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、酸素若しくは窒素を含む炭素数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^１ｄとＱ^２ｄは、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１ｄ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^１ｄは、結合しているＱ^１ｄおよびＱ^２ｄと一緒に環を形成していてもよい。ｍ^ｄは、０または１であり、ｍ^ｄが０の場合、Ｑ^１ｄは、Ｒ^３ｄを含む共役５員環と直接結合している。Ｒ^２ｄ は、水素原子、炭素数１〜２０の炭化水素基（但しメチル基を除く。）、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、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示し、Ｒ ^３ｄ は、水素原子、ハロゲン、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、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示し、４つのＲ^２ｄのうち少なくとも１つは水素ではない。Ｒ^４ｄは、結合する５員環に対して縮合環を形成する炭素数４または５の飽和または不飽和の２価の炭化水素基を示す。Ｒ^５ｄは、Ｒ^４ｄの炭素原子と結合する原子または基であり、それぞれ独立して、水素原子、ハロゲン、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のハロゲン化炭化水素基、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示す。ｎ^ｄは、０〜１０の整数を示し、ｎ^ｄが２以上の場合、Ｒ^５ｄ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（Ａｄ）のメタロセン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（Ｃ）：微粒子担体
（Ｂｄ−１’）：ＭＦＲＢ＝０．００１〜２００ｇ／１０分
（Ｂｄ−２”）：密度Ｂ＝０．８５〜０．９７ｇ／ｃｍ^３
（Ｂｄ−３）：［Ｍｗ／Ｍｎ］_Ｂ＝２．０〜１０．０
（Ｂｄ−４’）：次の要件（Ｂ−４’−ｉ）〜要件（Ｂ−４’−ｉｖ）の少なくともいずれか１つを充足すること。
（Ｂ−４’−ｉ）；温度１７０℃、伸長歪速度２（単位１／秒）で測定される伸長粘度η（ｔ）（単位：Ｐａ・秒）と伸長時間ｔ（単位：秒）の両対数プロットにおいて、歪硬化に起因する伸長粘度の変曲点が観測され、かつ、歪硬化後の最大伸長粘度をηＭａｘ（ｔ１）、硬化前の伸長粘度の近似直線をηＬｉｎｅａｒ（ｔ）としたとき、ηＭａｘ（ｔ１）／ηＬｉｎｅａｒ（ｔ１）で定義される歪硬化度［λｍａｘ（２．０）］_Ｂが１．２〜３０．０である。
（Ｂ−４’−ｉｉ）；上記（Ｂ−４’−ｉ）で定義された［λｍａｘ（２．０）］_Ｂと、伸長歪速度を０．１（単位１／秒）として同様に測定した場合の［λｍａｘ（０．１）］_Ｂの比［λｍａｘ（２．０）］_Ｂ／［λｍａｘ（０．１）］_Ｂが１．２〜１０．０である。
（Ｂ−４’−ｉｉｉ）；示差屈折計、粘度検出器、および光散乱検出器を組み合わせたＧＰＣ測定装置により測定される分子量１００万における分岐指数（ｇ_Ｃ’）が０．３０〜０．７０である。
（Ｂ−４’−ｉｖ）；示差屈折計、粘度検出器、および光散乱検出器を組み合わせたＧＰＣ測定装置により測定される分子量１００万以上の成分の含有量（Ｗ_Ｃ）が０．０１〜３０％である。

[In formula (1d), M ^1d represents a transition metal of Ti, Zr, or Hf. X ^1d and X ^2d each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ^1d and Q ^2d represent a carbon atom, a silicon atom, or a germanium atom. R ^1d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and four R ^{1d s} may form a ring together with Q ^1d and Q ^2d bonded ^thereto. . ^md is 0 or 1, and when ^md is 0, Q ^1d is directly bonded to a conjugated 5-membered ring containing R ^3d . R ^2d is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding a methyl group), a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 20 carbon atoms. A halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group, wherein R ^3d is a hydrogen atom, halogen, carbon atom having 1 to 20 carbon atoms A hydrogen group, a C1-C18 silicon-containing hydrocarbon group containing 1 to 6 silicon atoms, a C1-C20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen, or a carbon number 1 Represents a hydrocarbon group substituted silyl group of ˜20, and at least one of the four R ^2d is not hydrogen. R ^4d represents a saturated or unsaturated divalent hydrocarbon group having 4 or 5 carbon atoms that forms a condensed ring with respect to the 5-membered ring to be bonded. R ^5d is an atom or group bonded to the carbon atom of R ^4d , and each independently represents a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number 1 to 18 containing 1 to 6 silicon atoms. A silicon-containing hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. n ^d represents an integer of 0 to 10, and when n ^d is 2 or more, R ^5d may form a ring together with the carbon atoms to which R ^d is bonded. ]
Component (B): Compound that reacts with the metallocene compound of component (Ad) to form a cationic metallocene compound Component (C): Fine particle carrier (Bd-1 ′): MFRB = 0.001 to 200 g / 10 min (Bd −2 ″): density B = 0.85 to 0.97 g / cm ³
(Bd-3): [Mw / Mn] _B = 2.0 to 10.0
(Bd-4 ′): Satisfy at least one of the following requirements (B-4′-i) to requirements (B-4′-iv).
(B-4′-i); of elongation viscosity η (t) (unit: Pa · second) and elongation time t (unit: second) measured at a temperature of 170 ° C. and an elongation strain rate of 2 (unit: 1 / second) In the logarithmic plot, an inflection point of the extension viscosity due to strain hardening is observed, the maximum extension viscosity after strain hardening is ηMax (t1), and the approximate straight line of extension viscosity before hardening is ηLinear (t). In this case, the strain hardening degree [λmax (2.0)] _B defined by ηMax (t1) / ηLinear (t1) is 1.2 to 30.0.
(B-4′-ii); [λmax (2.0)] _B defined in (B-4′-i) above, and the elongation strain rate of 0.1 (unit: 1 / second), similarly measured In this case, the ratio [λmax (0.1)] _B [λmax (2.0)] _B /[λmax(0.1)] _B is 1.2 to 10.0.
(B-4′-iii); the branching index (g _C ′) at a molecular weight of 1 million as measured by a GPC measurement device in which a differential refractometer, a viscosity detector, and a light scattering detector are combined is 0.30 to 0.00. 70.
(B-4′-iv); the content (W _C ) of a component having a molecular weight of 1 million or more measured by a GPC measurement device in which a differential refractometer, a viscosity detector, and a light scattering detector are combined is 0.01 to 30%.

  According to the second invention of the present invention, in the first invention, the component (Ad) is a metallocene compound represented by the following general formula (2d): Is provided.

［式（２ｄ）中、Ｍ^１ｄは、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１ｄおよびＸ^２ｄは、それぞれ独立して、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、酸素若しくは窒素を含む炭素数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^１ｄは、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１ｄ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、２つのＲ^１ｄは、結合しているＱ^１ｄと一緒に環を形成していてもよい。Ｒ^２ｄ は、水素原子、炭素数１〜２０の炭化水素基（但しメチル基を除く。）、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、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示し、Ｒ ^３ｄ 、Ｒ ^５ｄ は、水素原子、ハロゲン、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、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示し、４つのＲ^２ｄのうち少なくとも１つは水素ではない。］

[In formula (2d), M ^1d represents a transition metal of Ti, Zr, or Hf. X ^1d and X ^2d each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ^1d represents a carbon atom, a silicon atom, or a germanium atom. R ^1d independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R ^{1d s} may form a ring together with Q ^1d bonded ^thereto . R ^2d is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding a methyl group), a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 20 carbon atoms. A halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group, wherein R ^3d and R ^5d are a hydrogen atom, halogen, C 1 -C 1 A hydrocarbon group having 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen, or A C1-C20 hydrocarbon group-substituted silyl group is shown, and at least one of the four R ^2d is not hydrogen. ]

According to a third aspect of the present invention, there is provided the production of an ethylene polymer according to the first or second aspect, wherein R ^5d is a hydrogen atom in the general formula (1d) or (2d). A method is provided.
According to a fourth invention of the present invention, in any one of the first to third inventions, in general formula (1d) or (2d), R ^3d and R ^5d are both hydrogen atoms. A method for producing an ethylene-based polymer is provided.

  According to a fifth aspect of the present invention, in the first aspect, the component (Ad) is a metallocene compound represented by the following general formula (3d), and the method for producing an ethylene polymer: Is provided.

［式（３ｄ）中、Ｍ^１ｄは、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１ｄおよびＸ^２ｄは、それぞれ独立して、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、酸素若しくは窒素を含む炭素数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^１ｄは、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１ｄ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、２つのＲ^１ｄは、結合しているＱ^１ｄと一緒に環を形成していてもよい。Ｒ^２ｄは、水素原子、炭素数１〜２０の炭化水素基（但しメチル基を除く。）、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、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示し、２つのＲ^２ｄのうち少なくとも１つは水素ではない。］

[In formula (3d), M ^1d represents a transition metal of Ti, Zr, or Hf. X ^1d and X ^2d each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ^1d represents a carbon atom, a silicon atom, or a germanium atom. R ^1d independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R ^{1d s} may form a ring together with Q ^1d bonded ^thereto . R ^2d is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding a methyl group), a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 20 carbon atoms. A halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group, wherein at least one of the two R ^2d is not hydrogen. ]

According to a sixth invention of the present invention, in the fifth invention, in the general formula (3d), one of two R ^2d is a hydrogen atom, and the method for producing an ethylene polymer Is provided.

According to a seventh invention of the present invention, in the fifth or sixth invention, in the general formula (3d), R ^2d is a t-butyl group, a trimethylsilyl group or a phenyl group. A method for producing a polymer is provided.

According to an eighth aspect of the present invention, in any one of the first to seventh aspects, M ^1d is Zr or Hf in the general formula (1d), (2d), or (3d). A method for producing an ethylene polymer is provided.

According to a ninth invention of the present invention, in any one of the first to seventh inventions, M ^1d is Zr in the general formula (1d), (2d) or (3d). A method for producing an ethylene polymer is provided.

  According to a tenth aspect of the present invention, there is provided the method for producing an ethylene polymer according to any one of the first to ninth aspects, wherein the component (B) is an aluminoxane.

  According to an eleventh aspect of the present invention, there is provided the method for producing an ethylene polymer, wherein in any one of the first to tenth aspects, the component (C) is silica.

  According to a twelfth aspect of the present invention, in any one of the first to eleventh aspects, the olefin polymerization catalyst carries a contact mixture of the component (Ad) and the component (B) on the component (C). A method for producing an ethylene-based polymer is provided, which is characterized by being obtained.

According to a thirteenth aspect of the present invention, in any one of the first to twelfth aspects, the strain hardening degree [λmax (2.0)] _B is 4.5 to 30.0. A method for producing an ethylene polymer is provided.

  According to the fourteenth aspect of the present invention, in any one of the first to thirteenth aspects, the number of double bonds present at the molecular end is 0.15 or more per 1000 carbon atoms. A method for producing an ethylene-based polymer is provided.

The present invention relates to a method for producing an ethylene polymer as described above, and preferred embodiments include the following.
(1) The method for producing an ethylene polymer according to any one of the first to ninth inventions, wherein the component (B) is a borane compound or a borate compound.
(2) In any one of the first to ninth inventions, as the component (B), an organoaluminum oxy compound (preferably an aluminoxane) and a borane compound or a borate compound are used in combination. .

  According to the method for producing an ethylene polymer of the present invention, a metallocene polyethylene having a long chain branch having a sufficient number and length can be obtained by polymerizing ethylene using a specific olefin polymerization catalyst. And the moldability of metallocene polyethylene can be improved.

It is a plot figure of the extensional viscosity of the ethylene-type polymer (Example 1) which concerns on this invention. 3 is a plot of elongational viscosity of the ethylene polymer of Comparative Example 2. FIG. It is a figure explaining the baseline and section of a chromatogram in GPC. It is a graph which shows the relationship between the molecular weight distribution curve computed from GPC-VIS measurement (branch structure analysis), and a branching index (g '), and molecular weight (M).

The method for producing an ethylene polymer of the present invention is an olefin comprising the following essential components (Ad), (B) and (C) in order to obtain a metallocene polyethylene having a sufficient number and length of long-chain branches. It is characterized by using a polymerization catalyst.
Component (Ad): Metallocene compound represented by the aforementioned general formula (1d) Component (B): Compound that reacts with the metallocene compound of component (A) to produce a cationic metallocene compound Component (C): Fine particle carrier The present invention will be specifically described for each item.

1. Ingredient (Ad)
The method for producing an ethylene polymer of the present invention is characterized in that it contains a metallocene compound represented by the following general formula (1d) as an essential component (Ad) as an olefin polymerization catalyst.

[In formula (1d), M ^1d represents a transition metal of Ti, Zr, or Hf. X ^1d and X ^2d each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ^1d and Q ^2d represent a carbon atom, a silicon atom, or a germanium atom. R ^1d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and four R ^{1d s} may form a ring together with Q ^1d and Q ^2d bonded ^thereto. . ^md is 0 or 1, and when ^md is 0, Q ^1d is directly bonded to a conjugated 5-membered ring containing R ^3d . R ^2d and R ^3d are a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, and a halogen-containing carbon atom having 1 to 20 carbon atoms. A hydrogen group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group is shown, and at least one of the four R ^2d is not hydrogen. R ^4d represents a saturated or unsaturated divalent hydrocarbon group having 4 or 5 carbon atoms that forms a condensed ring with respect to the 5-membered ring to be bonded. R ^5d is an atom or group bonded to the carbon atom of R ^4d , and each independently represents a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number 1 to 18 containing 1 to 6 silicon atoms. A silicon-containing hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. n ^d represents an integer of 0 to 10, and when n ^d is 2 or more, R ^5d may form a ring together with the carbon atoms to which R ^d is bonded. ]

In the general formula (1d), M ^1d of the metallocene compound represents Ti, Zr or Hf, M ^{1d of the} metallocene compound preferably represents Zr or Hf, and M ^{1d of the} metallocene compound more preferably represents Zr. Represent.
X ^1d and X ^2d are each independently a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i -Butyl group, t-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, benzyl group, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i- 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, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-furyl, 2-tetrahydrofuryl, dimethylaminomethyl, diethylaminomethyl, di-propylaminomethyl, bis (Dimethylamino) methyl group, bis (dii-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, dii-propylamino group, di-n-butyl A ruamino group, a di-i-butylamino group, a di-t-butylamino group, a diphenylamino group, and the like.
Specific examples of preferable X ^1d and X ^2d include chlorine atom, bromine atom, methyl group, n-butyl group, i-butyl group, methoxy group, ethoxy group, i-propoxy group, n-butoxy group, phenoxy group, Examples thereof include a dimethylamino group and a di i-propylamino group. Among these specific examples, a chlorine atom, a methyl group, and a dimethylamino group are particularly preferable.

Q ^1d and Q ^2d represent a carbon atom, a silicon atom, or a germanium atom. Preferably they are a carbon atom or a silicon atom. More preferably, it is a silicon atom.
Furthermore, as R ^1d , each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or an n-pentyl group. , Neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group and the like. Further, when R ^1d forms a ring together with Q ^1d and Q ^2d , a cyclobutylidene group, a cyclopentylidene group, a cyclohexylidene group, a silacyclobutyl group, a silacyclopentyl group, a silacyclohexyl group, etc. Is mentioned.
Specific examples of preferable R ^1d include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an ethylene group, and a cyclobutylidene group when Q ^1d and / or Q ^2d is a carbon atom, and Q ^1d or / When Q ^2d is a silicon atom, examples thereof include a methyl group, an ethyl group, a phenyl group, and a silacyclobutyl group.

R ^2d and R ^3d are hydrogen atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl. Group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethyl group Phenyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) methyl group, bromomethyl group, chloromethyl group, 2- Chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromocyclopentyl group, 2,3-dibromocyclo Nthyl group, 2-bromo-3-iodocyclopentyl group, 2,3-dibromocyclohexyl group, 2-chloro-3-iodocyclohexyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6 -Pentafluorophenyl group, 4-trifluoromethylphenyl group, furyl group, tetrahydrofuryl group, 2-methylfuryl group, trimethylsilyl group, tri-t-butylsilyl group, di-t-butylmethylsilyl group, t-butyldimethylsilyl group , Triphenylsilyl group, diphenylmethylsilyl group, phenyldimethylsilyl group and the like.
R ^2d and R ^3d are each a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, Since it is a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group substituted silyl group, since especially polymerization activity becomes high, it is preferable. Further, R ^2d is preferably a hydrocarbon group having 1 to 20 carbon atoms, particularly from the viewpoint of excellent moldability of polyethylene.
Preferred specific examples of R ^2d and R ^3d include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group. Cyclohexyl group, phenyl group, 2-methylfuryl group, and trimethylsilyl group. Among these specific examples, a hydrogen atom, a methyl group, an n-butyl group, a t-butyl group, a phenyl group, and a trimethylsilyl group are more preferable, and a hydrogen atom, a methyl group, a t-butyl group, a phenyl group, and a trimethylsilyl group are particularly preferable. preferable.

Specific examples of the condensed cyclopentadienyl structure formed from the cyclopentadienyl moiety to which R ^4d is bonded and R ^4d include the following partial structures (I) to (VI).
Among these specific examples, (I), (III), and (VI) are preferable. Further, R ^5d may be substituted on these partial structures (I) to (VI).

R ^5d of the substituent is a hydrogen atom, a chlorine atom, a bromine atom, an iodine 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. Group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-t-butyl Phenyl group, 3,5-dimethylphenyl group, 3,5-di-t-butylphenyl group, naphthyl group, anthracenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) methyl group, bromomethyl group, Chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromocyclopentyl Group, 2,3-dibromocyclopentyl group, 2-bromo-3-iodocyclopentyl group, 2,3-dibromocyclohexyl group, 2-chloro-3-iodocyclohexyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2 , 3,4,5,6-pentafluorophenyl group, 2,6-dichloro-4-trimethylsilylphenyl group, trimethylsilyl group, tri-t-butylsilyl group, di-t-butylmethylsilyl group, t-butyldimethylsilyl group, Examples thereof include a triphenylsilyl group, a diphenylmethylsilyl group, and a phenyldimethylsilyl group.
Examples of the case where R ^5d is 2 or more and form a ring together with bonded carbon atoms include benzo [e] indenyl group, benzo [f] indenyl group, 6,7-dihydroinda Senyl group, 5,5,7,7-tetramethyl-6,7-dihydroindacenyl group, 5,6,7,8-tetrahydro-benzo [f] indenyl group, 5,6,7,8- Examples thereof include a tetrahydro-5,5,8,8-tetramethyl-benzo [f] indenyl group.
Specific examples of preferable R ^5d include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, and a phenyl group. , A naphthyl group, and a trimethylsilyl group.

In general formula (1d), ^md is 0 or 1, and when ^md is 0, Q ^1d is directly bonded to a conjugated 5-membered ring containing R ^3d . Further, n ^d represents an integer of 0 to 10, and when n ^d is 2 or more, R ^5d may form a ring together with the carbon atoms to which it is bonded.

  As the olefin polymerization catalyst according to the present invention, the metallocene compound as the essential component (Ad) is preferably one represented by the following general formula (2d).

In the metallocene compound represented by the general formula (2d), M ^1d , X ^1d , X ^2d , Q ^1d , R ^1d , R ^2d , R ^3d , R ^4d and R ^5d are the same as those in the general formula (1d). Structures similar to the atoms and groups shown in the description of the metallocene compounds shown can be selected.
As the olefin polymerization catalyst according to the present invention, the metallocene compound of the essential component (Ad) is more preferably one represented by the following general formula (3d).

上記の一般式（３ｄ）で示されるメタロセン化合物において、Ｍ^１ｄ、Ｘ^１ｄ、Ｘ^２ｄ、Ｑ^１ｄ、Ｒ^１ｄおよびＲ^２ｄは、前述の一般式（１ｄ）で示されるメタロセン化合物の説明で示した原子および基と同様な構造を、選択することができる。

In the metallocene compound represented by the general formula (3d), M ^1d , X ^1d , X ^2d , Q ^1d , R ^1d, and R ^2d are the same as those in the description of the metallocene compound represented by the general formula (1d). Structures similar to atoms and groups can be selected.

  In the method for producing an ethylene-based polymer of the present invention, specific examples of the metallocene compound as an essential component (Ad) of the olefin polymerization catalyst are shown in the general formula (4d) and Tables 1-1 to 4, but are limited thereto. is not.

  In addition, the number which shows the position of the substituent on the cyclopentadienyl ring of the metallocene compound shown in these specific examples and an indenyl ring is as following Formula (5d).

Moreover, the compound which replaced the zirconium of the said compound with titanium or hafnium, etc. are mentioned.
Furthermore, when using these metallocene compounds as the essential component (Ad), two or more kinds can be used.

Among the specific compounds exemplified above, those preferable as the metallocene compound as the essential component (Ad) are shown below.
In Table 1, 1d-51d, 72d-77d, 84d-89d, 96d-101d, 114d-129d, 134d-149d etc. are mentioned.
Moreover, the compound etc. which replaced the zirconium of the said compound with titanium or hafnium are mentioned as a preferable thing.

Among the specific compounds exemplified above, particularly preferable examples of the metallocene compound which is an essential component (Ad) are shown below.
In Table 1, 1d to 6d, 17d, 18d, 46d to 49d, 115d, 117d, 118d, 121d, 123d, 125d, 127d, 129d, 135d, 137d, 139d, 141d, 143d, 145d, 147d, 149d, etc. Is mentioned.
Moreover, the compound etc. which replaced the zirconium of the said compound with titanium or hafnium are mentioned as a preferable thing.

Furthermore, among the specific compounds exemplified above, the metallocene compounds that are essential components (Ad) are particularly preferable in terms of high polymerization activity.
In Table 1, 1d-51, 114d-129d, 134d-149d, etc. are mentioned.

Further, among the specific compounds exemplified above, the metallocene compound which is an essential component (Ad) is particularly preferable in terms of excellent moldability.
In Table 1, 1d to 6d, 17d, 18d, 46d to 49d, 72d to 77d, 84d to 89d, 96d to 101d, 115d, 117d, 119d, 121d, 123d, 125d, 127d, 129d, 135d, 137d, 139d 141d, 143d, 145d, 147d, 149d, and the like.

Although the synthesis example of the metallocene compound which is an essential component (Ad) concerning this invention is shown below, it is not specifically limited to these synthesis methods.
For example, a ligand can be obtained by lithiation of an indene compound, reaction with a dichlorosilane compound, and subsequent reaction with a lithium salt of cyclopentadiene having a substituent. Examples thereof include a method of reacting the obtained ligand with tetrakis (alkylamido) zirconium and subsequently trimethylsilyl chloride, or a method of lithiating the obtained ligand and subsequently reacting with zirconium tetrachloride.

2. Ingredient (B)
In the method for producing an ethylene polymer of the present invention, as an essential component of an olefin polymerization catalyst, in addition to the above component (Ad), a metallocene compound (component (Ad) of component (Ad), hereinafter also simply referred to as Ad. A compound that forms a cationic metallocene compound (component (B), hereinafter may be simply referred to as B) and a fine particle carrier (component (C), hereinafter may be simply referred to as C). )) Is the biggest feature.

As one of the compounds (B) that react with the metallocene compound (Ad) to form a cationic metallocene compound, an organoaluminum oxy compound can be given.
The organoaluminum oxy compound has Al—O—Al bonds in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy 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 the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. Preference is given to using aromatic hydrocarbons.

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

  The alkyl group of the 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, etc. It is particularly preferred that In addition, the said organoaluminum compound can also be used in mixture of 2 or more types.

  The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably 0.25 / 1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1/1, and the reaction temperature is Usually, it is -70-100 degreeC, Preferably it exists in the range of -20-20 degreeC. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only mere water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like and components capable of generating water in the reaction system can be used. Of the organoaluminum oxy compounds described above, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, particularly methylaluminoxane (including those substantially consisting of methylaluminoxane (MAO)). Is suitable as an organoaluminum oxy compound. Of course, as the organoaluminum oxy compound, two or more of the above organoaluminum oxy compounds may be used in combination, and a solution obtained by dispersing or dispersing the organoaluminum oxy compound in the above-described inert hydrocarbon solvent. You may use.

  When an organoaluminum oxy compound is used as the component (B) for the olefin polymerization catalyst, the degree of strain hardening (λmax) of the resulting ethylene polymer increases, or Mz / Mw (which is a measure of the high molecular weight component content). Here, Mz represents a Z average molecular weight measured by GPC, and Mw represents the same weight average molecular weight. This is preferable because the moldability is further improved.

  Other specific examples of the compound (B) that reacts with the metallocene compound (Ad) to form a cationic metallocene compound include borane compounds and borate compounds. More specifically, the borane compound is represented by 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 (perfluorobi) Fuchiru) such as 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, tris ( Perfluoronaphthyl) borane and tris (perfluorobiphenyl) borane are exemplified as preferred compounds.

When the borate compound is specifically represented, the first example is a compound represented by the following general formula (7).
^{[L 1 -H] + [BR} 7 R 8 X 4 X 5] - ··· (7)

In Formula (7), 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 trialkylammonium 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, N, N-2,4,6-pentamethylanilinium. Furthermore, examples of the phosphonium include triarylphosphonium, tributylphosphonium, triarylphosphonium such as tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

In the formula (7), R ⁷ and R ⁸ are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and are connected to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, or a halogen such as fluorine, chlorine, bromine or iodine is preferable. Further, X ⁴ and X ⁵ are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted carbon atom 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 (7) 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, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6- Ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluoropheny) ) Borate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5- Ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (Pentafluorophenyl) borate, triethylammonium tetra (2,6
-Ditrifluoromethylphenyl) borate, triethylammonium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra ( Examples thereof include perfluoronaphthyl) borate, di (1-propyl) ammonium tetra (pentafluorophenyl) borate, and dicyclohexylammonium tetraphenylborate.

  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.

Moreover, the 2nd example of a borate compound is represented by following General formula (8).
^{[L 2] + [BR 7} R 8 X 4 X 5] - ··· formula (8)

In the formula (8), L ² represents carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium. A cation, a proton, etc. are mentioned. R ⁷ , R ⁸ , X ⁴ and X ⁵ are the same as defined in the general formula (7).

Specific examples of the compound include trityl tetraphenyl borate, trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoro) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) Rate, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m- Fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5 - ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) _{borate, NaBPh 4, NaB (o-} CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 - Ph) ₄ , Na B (o-F-Ph) 4, NaB (p-F-Ph) 4, NaB (m-F-Ph) 4, NaB (3,5-F2-Ph) 4, NaB (C6F5) 4, NaB ( _{2,6- (CF 3) 2 -Ph)} 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, HBPh 4 · 2 diethyl ether, HB (3, _{5-F 2 -Ph) 4 ·} 2 diethyl _{ether, HB (C 6 F 5)} 4 · 2 diethyl _{ether, HB (2,6- (CF 3)} 2 -Ph) 4 · 2 diethyl ether, HB (3, _{5- (CF 3) 2 -Ph)} 4 · 2 diethyl ether _can be exemplified _{HB (C 10 H 7) 4} · 2 diethyl ether.

Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, Tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, _{NaB (C 6 F 5) 4} , NaB (2,6- (CF 3) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, _{HB (C 6 F 5) 4} · 2 diethyl ether _{HB (2,6- (CF 3) 2} -Ph) 4 · 2 diethyl _{ether, HB (3,5- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (C 10 H 7)} 4 · 2 Diethyl ether is preferred.

More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-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, HB (C 10 H 7) 4} · 2 diethyl ether.

  When a borane compound or a borate compound is used as the catalyst component (B), the polymerization activity and copolymerizability are increased, so that the productivity of an ethylene polymer having a long chain branch is improved. Further, as the component (B) of the olefin polymerization catalyst, a mixture of the organoaluminum oxy compound and the borane compound or borate compound can be used. Further, two or more of the above borane compounds and borate compounds can be used in combination.

3. Ingredient (C)
Examples of the fine particle carrier that is an essential component (C) in the method for producing an ethylene polymer of the present invention include an inorganic carrier, a particulate polymer carrier, and a mixture thereof. As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof can be used.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.

Further, as the metal oxide, either alone oxide or composite oxide of the Periodic Table 1-14 Group elements include, for _{example, SiO 2, Al 2 O 3} , MgO, CaO, B 2 O 3, TiO 2, _{ZrO 2, Fe 2 O 3,} Al 2 O 3 · MgO, Al 2 O 3 · CaO, Al 2 O 3 · SiO 2, Al 2 O 3 · MgO · CaO, Al 2 O 3 · MgO · SiO 2, Al Examples include various natural or synthetic single oxides or composite oxides such as ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂ O ₃ .NiO, and SiO ₂ .MgO. Here, the above formula is not a molecular formula but represents only the composition, and the structure and component ratio of the composite oxide used in the present invention are not particularly limited. In addition, the metal oxide used in the present invention may absorb a small amount of moisture or may contain a small amount of impurities.

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

These inorganic carriers are usually calcined in air or an inert gas such as nitrogen or argon at 200 to 800 ° C., preferably 400 to 600 ° C., and the amount of surface hydroxyl groups is 0.8 to 1.5 mmol / g. It is preferable to adjust to use. The properties of these inorganic carriers are not particularly limited, but usually the average particle size is 5 to 200 μm, preferably 10 to 150 μm, the average pore size is 20 to 1000 mm, preferably 50 to 500 mm, and the specific surface area is 150 to 1000 m. ² / g, preferably 200-700 m ² / g, pore volume 0.3-2.5 cm ³ / g, preferably 0.5-2.0 cm ³ / g, apparent specific gravity 0.20-0 It is preferred to use an inorganic carrier having a density of .50 g / cm ³ , preferably 0.25 to 0.45 g / cm ³ .

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

4). Preparation of Olefin Polymerization Catalyst Metallocene Compound (Ad) which is an essential component of the method for producing an ethylene polymer of the present invention, Compound (B) which reacts with metallocene compound (Ad) to form a cationic metallocene compound, and The contact method of each component when obtaining the olefin polymerization catalyst comprising the fine particle carrier (C) is not particularly limited, and for example, the following methods can be arbitrarily adopted.

(I) After contacting the metallocene compound (Ad) with the compound (B) that reacts with the metallocene compound (Ad) to form a cationic metallocene compound, the fine particle carrier (C) is contacted.
(II) After contacting the metallocene compound (Ad) with the fine particle carrier (C), the compound (B) that reacts with the metallocene compound (Ad) to form a cationic metallocene compound is contacted.
(III) The compound (B) that reacts with the metallocene compound (Ad) to form a cationic metallocene compound and the fine particle carrier (C) are contacted, and then the metallocene compound (Ad) is contacted.

  Of these contact methods, (I) and (III) are preferred, and (I) is most preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually 6 to 12 carbon atoms), heptane, hexane, decane and dodecane. In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane, a method of bringing each component into contact with stirring or non-stirring is employed. This contact is usually −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. It is desirable to carry out in 30 minutes to 12 hours.

  In addition, as described above, certain components are soluble when the metallocene compound (Ad), the compound (B) that reacts with the metallocene compound (Ad) to form a cationic metallocene compound and the fine particle carrier (C) are contacted. Either an aromatic hydrocarbon solvent that is hardly soluble or an aliphatic or alicyclic hydrocarbon solvent in which a certain component is insoluble or hardly soluble can be used.

  In the case where the contact reaction between the components is performed stepwise, this may be used as it is as the solvent for the subsequent contact reaction without removing the solvent used in the previous step. In addition, after the previous catalytic reaction using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.) Hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons) and the desired product is recovered as a solid or once or part of the soluble solvent is removed by means such as drying. After removing the product as a solid, the subsequent catalytic reaction of the desired product can also be carried out using any of the inert hydrocarbon solvents described above. In this invention, it does not prevent performing contact reaction of each component in multiple times.

  In the present invention, the ratio of use of the metallocene compound (Ad), the compound (B) that reacts with the metallocene compound (Ad) to form a cationic metallocene compound, and the fine particle carrier (C) is not particularly limited. A range is preferred.

When an organoaluminum oxy compound is used as the compound (B) that reacts with the metallocene compound (Ad) to form a cationic metallocene compound, aluminum of the organoaluminum oxy compound with respect to the transition metal (M ^1d ) in the metallocene compound (Ad) The atomic ratio (Al / M ^1d ) is usually in the range of 1 to 100,000, preferably 5 to 1000, more preferably 50 to 200, and when a borane compound or a borate compound is used, in the metallocene compound The atomic ratio of boron to transition metal (M ^1d ) (B / M ^1d ) is usually selected in the range of 0.01 to 100, preferably 0.1 to 50, more preferably 0.2 to 10. It is desirable. Further, when a mixture of an organoaluminum oxy compound, a borane compound, and a borate compound is used as the compound (B) for generating a cationic metallocene compound, the transition metal (M ^1d ) is used for each compound in the mixture. On the other hand, it is desirable to select at the same usage ratio as above.

  The amount of the fine particle carrier (C) used is preferably 0.0001 to 5 mmol, more preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, per 0.0001 to 5 mmol of the transition metal in the metallocene compound (Ad). Per gram.

  The metallocene compound (Ad), the compound (B) that reacts with the metallocene compound (Ad) to form a cationic metallocene compound, and the fine particle carrier (C) are any of the contact methods (I) to (III). The catalyst for olefin polymerization can be obtained as a solid catalyst by bringing them into contact with each other and then removing the solvent. The removal of the solvent is desirably performed 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) The metallocene compound (Ad) and the fine particle carrier (C) are contacted to remove the solvent, which is used as a solid catalyst component, and an organoaluminum oxy compound, borane compound, borate compound or a mixture thereof under polymerization conditions Make contact.
(V) The organoaluminum oxy compound, borane compound, borate compound or a mixture thereof and the fine particle carrier (C) are contacted to remove the solvent, which is used as a solid catalyst component, and the metallocene compound (Ad) under polymerization conditions. Make contact.
In the case of the contact methods (IV) and (V), the same conditions as described above can be used for the component ratio, contact conditions, and solvent removal conditions.

  In addition, as a component that serves as both the compound (B) that reacts with the metallocene compound (Ad) that is an essential component of the method for producing an ethylene polymer of the present invention to form a cationic metallocene compound and the fine particle carrier (C), Silicates can also be used. The 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 each other with a weak binding force. Most layered silicates are naturally produced mainly as the main component of clay minerals, but these layered silicates are not limited to natural ones and may be artificially synthesized.

  Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite and the like, smectite group, vermiculite group and mica group are preferable.

  In general, natural products are often non-ion-exchangeable (non-swellable). In that case, in order to have preferable ion-exchange (or swellable), ion exchange (or swellable) is provided. It is preferable to perform the process for providing. Among such treatments, particularly preferred are the following chemical treatments. Here, as the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the crystal structure and chemical composition of the layered silicate can be used. Specifically, (a) acid treatment performed using hydrochloric acid, sulfuric acid, etc., (b) alkali treatment performed using NaOH, KOH, NH3, etc., (c) selected from Group 2 to Group 14 of the periodic table. Salt treatment with a salt comprising at least one anion selected from the group consisting of a cation containing at least one atom and a halogen atom or an anion derived from an inorganic acid, (d) an alcohol, a hydrocarbon compound , Organic matter treatment such as formamide and aniline. These processes may be performed independently or two or more processes may be combined.

  The layered silicate can be controlled in particle properties by pulverization, granulation, sizing, fractionation, etc. at any time before, during, or after all the steps. The method can be any purposeful. In particular, for granulation methods, for example, spray granulation method, rolling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation Method, emulsion granulation method and submerged granulation method. Particularly preferable granulation methods are the spray granulation method, the rolling granulation method and the compression granulation method.

  Of course, the above-mentioned layered silicate can be used as it is, but these layered silicates are 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 carry the metallocene compound (Ad), which is an essential component of the method for producing an ethylene polymer of the present invention, on the layered silicate, the metallocene compound (Ad) and the layered silicate are brought into contact with each other, or the metallocene compound ( Ad), an organoaluminum compound, and a layered silicate may be brought into contact with each other.
The contact method of each component is not specifically limited, For example, the following methods are arbitrarily employable.
(VI) The metallocene compound (Ad) and the organoaluminum compound are contacted and then contacted with the layered silicate support.
(VII) The metallocene compound (Ad) and the layered silicate support are contacted and then contacted with the organoaluminum compound.
(VIII) The organoaluminum compound and the layered silicate support are contacted and then contacted with the metallocene compound (Ad).

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

  The use ratio of the metallocene compound (Ad), the organoaluminum compound, and the layered silicate carrier is not particularly limited, but the following ranges are preferable. The supported amount of the metallocene compound (Ad) is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, per 1 g of the layered silicate support. In the case of using an organoaluminum compound, the amount of Al supported is preferably in the range of 0.01 to 100 mol, preferably 0.1 to 50 mol, more preferably 0.2 to 10 mol.

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

5. Ethylene polymer production method (polymerization method)
The above-mentioned catalyst for olefin polymerization can be used for homopolymerization of ethylene or copolymerization of ethylene and α-olefin.

  The α-olefins which are 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- Examples include 1-pentene and the like. As for the α-olefins, two or more types of α-olefins can be copolymerized with ethylene. The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. When ethylene and another α-olefin are copolymerized, the amount of the other α-olefin can be arbitrarily selected within a range of 90 mol% or less of the total monomers, but generally 40 mol%. In the following, it is preferably selected in the range of 30 mol% or less, more preferably 10 mol% or less. Of course, a small amount of a comonomer other than ethylene or α-olefin can be used. In this case, styrenes such as styrene, 4-methylstyrene, 4-dimethylaminostyrene, 1,4-butadiene, 1,5- It has polymerizable double bonds such as 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 octenoate. A compound can be mentioned.

  In the present invention, the polymerization reaction can be carried out in the presence of the above-mentioned supported catalyst, preferably by slurry polymerization or gas phase polymerization. In the case of slurry polymerization, with substantially no oxygen, water, etc., aliphatic hydrocarbons such as isobutane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic rings such as cyclohexane and methylcyclohexane Ethylene or the like is polymerized in the presence or absence of an inert hydrocarbon solvent selected from group hydrocarbons and the like. Needless to say, liquid monomers such as liquid ethylene and liquid propylene can also be used as the solvent. In the case of gas phase polymerization, ethylene or the like is polymerized in a reactor in which a gas flow of ethylene or comonomer is introduced, distributed, or circulated. In the present invention, more preferred polymerization is gas phase polymerization. The polymerization conditions are such that the temperature is 0 to 250 ° C., preferably 20 to 110 ° C., more preferably 60 to 100 ° C., and the pressure is normal pressure to 10 MPa, preferably normal pressure to 4 MPa, more preferably 0.5 to 2 MPa. The polymerization time is usually 5 minutes to 10 hours, preferably 5 minutes to 5 hours.

  The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system. Can do. Moreover, even if a component for the purpose of removing moisture, a so-called scavenger, is added to the polymerization system, the polymerization can be carried out without any trouble. Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, the organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethyl zinc and dibutyl zinc, diethyl Organic magnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and grinier compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Of these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable. The present invention can also be applied to a multistage polymerization system having two or more stages having different polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature without any trouble.

6). Physical properties of ethylene polymers (characteristics)
The ethylene polymer produced by the present invention is characterized by having the following properties (Bd-1 ′), (Bd-2 ″), (Bd-3) and (Bd-4 ′).
(Bd-1 ′): MFR _B = 0.001 to 200 g / 10 min (Bd-2 ″): Density _B = 0.85 to 0.97 g / cm ³
(Bd-3): [Mw / Mn] _B = 2.0 to 10.0
(Bd-4 ′): Satisfy at least one of the following requirements (B-4′-i) to requirements (B-4′-iv).
(B-4′-i); of elongation viscosity η (t) (unit: Pa · second) and elongation time t (unit: second) measured at a temperature of 170 ° C. and an elongation strain rate of 2 (unit: 1 / second) In the logarithmic plot, an inflection point of the extension viscosity due to strain hardening is observed, the maximum extension viscosity after strain hardening is ηMax (t1), and the approximate straight line of extension viscosity before hardening is ηLinear (t). In this case, the strain hardening degree [λmax (2.0)] _B defined by ηMax (t1) / ηLinear (t1) is 1.2 to 30.0. Here, the approximate straight line of the extension viscosity before curing is a tangent line having the smallest inclination among the tangent lines of the logarithmic graph curve within the range of t corresponding to the strain amount of 0.2 to 1.0. (However, the slope is 0 or a positive value).
(B-4′-ii); [λmax (2.0)] _B defined in (B-4′-i) above, and the elongation strain rate of 0.1 (unit: 1 / second), similarly measured In this case, the ratio [λmax (0.1)] _B [λmax (2.0)] _B /[λmax(0.1)] _B is 1.2 to 10.0.
(B-4′-iii); the branching index (g _C ′) at a molecular weight of 1 million as measured by a GPC measurement device in which a differential refractometer, a viscosity detector, and a light scattering detector are combined is 0.30 to 0.00. 70.
(B-4′-iv); the content (W _C ) of a component having a molecular weight of 1 million or more measured by a GPC measurement device in which a differential refractometer, a viscosity detector, and a light scattering detector are combined is 0.01 to 30%.

Hereinafter, each characteristic will be specifically described.
The density of the ethylene polymer of the present invention is 0.85 to 0.97 g / cm ³ , preferably 0.88 to 0.97 g / cm ³ , more preferably 0.90 to 0.97 g / cm ^3. It is.
The MFR (melt flow rate, 190 ° C., 2.16 kg load) is 0.001 to 200 g / 10 min, preferably 0.01 to 100 g / 10 min, more preferably 0.05 to 50 g / 10. Min, more preferably 0.1 to 50 g / 10 min.
On the other hand, the molecular weight distribution [Mw / Mn] _B of the ethylene polymer of the present invention is 2.0 to 10.0, preferably 2.0 to 6.0, more preferably 2.5 to 6.0. More preferably, it is 2.5-4.5.

And the ethylene polymer manufactured by this invention is the big characteristic that melt property is improved with respect to a normal ethylene polymer, and has the outstanding moldability.
In general, polyethylene is processed into an industrial product by a molding method that passes through a molten state such as film molding, blow molding, foam molding, etc., but at this time, the elongation flow characteristic has a great influence on the ease of moldability. Giving is well known. That is, polyethylene having a narrow molecular weight distribution and no long chain branching has poor moldability due to its low melt strength, whereas polyethylene having an ultrahigh molecular weight component or a long chain branching component is strain-hardened (strain Hardening), that is, polyethylene having a characteristic that the extensional viscosity rapidly increases on the high strain side, and polyethylene that exhibits this characteristic remarkably is said to be excellent in moldability.

  As a method for quantitatively expressing this extensional viscosity characteristic, there is a method for calculating the ratio of the extensional viscosity before strain hardening and the extensional viscosity after strain hardening as the strain hardening degree (λmax), which is an index representing the nonlinearity of extensional viscosity. Useful as. When this λmax value is large, for example, there is an effect of preventing uneven thickness and blow-through of the product in film molding and blow molding, enabling high-speed molding, and increasing the closed cell ratio during foam molding. Advantages such as improved product strength, improved design, lighter weight, improved molding cycle, and improved heat insulation can be obtained.

Further, in recent years, it has been found that the strain rate dependence of the elongational viscosity characteristic of polyethylene has a great influence on the ease of moldability. That is, when it is deformed at a low strain rate, it does not show a large extensional viscosity, and it can be deformed with a smaller force, while when a large strain rate is applied, it develops a large extensional viscosity to cause the above-mentioned blow-through. Polyethylenes having properties that can prevent the above are useful, and this property tends to be more prominent as long-chain branched structures develop more highly.
That is, it has been found that the characteristics of these preferable polyethylenes are realized by satisfying at least one of the requirements (B-4′-i) to (B-4′-iv). Furthermore, an ethylene polymer satisfying these characteristics can be produced by a method for producing an ethylene polymer using an olefin polymerization catalyst containing the component (Ad) which is a specific metallocene compound of the present invention. It came to find out.

The ethylene-based polymer according to the present invention is at least one of the requirements (B-4′-i), (B-4′-ii), (B-4′-iii), and (B-4′-iv). Satisfy one. If none of these requirements is satisfied, the ethylene polymer does not have satisfactory moldability.
[Λmax (2.0)] of requirement (B-4′-i) When _B is 1.2 to 30.0, preferably 2.0 to 20.0, more preferably 5.0 to 10.0 As described above, strain hardening (strain / hardening) at the time of melt elongation, that is, the property that the elongational viscosity rapidly increases on the high strain side is excellent in moldability. If λmax is smaller than 1.2, sufficient melt strength cannot be obtained, and the above-described effects may not be obtained. On the other hand, if λmax is larger than 30.0, the strength of the product is reduced with an increase in the branched structure, which is not preferable.

In addition, [λmax (2.0)] _B / [λmax (0.1)] _B in the requirement (B-4′-ii) is 1.2 to 10.0, preferably 1.3 to 5.0, More preferably 1.4 to 4.0, and even more preferably 1.5 to 3.0, as described above, when it is easily deformed at a low strain rate, but is rapidly stretched at a large strain rate. Blowing breakage and the like can be prevented by expressing a large elongation viscosity, so that polyethylene having characteristics excellent in moldability, particularly uniform stretchability can be obtained. If λmax (2.0) / λmax (0.1) is less than 1.2, the ethylene polymer may not be homogeneously melted, may have a thermally unstable structure, In some cases, the impact strength is lowered due to the strength anisotropy of the molded product due to the presence of the long long-chain branched structure, and the transparency is deteriorated. If λmax (2.0) / λmax (0.1) is greater than 10.0, the melt tension and fluidity during molding are excellent, but the impact strength of the ethylene-based polymer is reduced or the transparency is deteriorated. May not be preferable.

Further, g _C ′ of requirement (B-4′-iii) is 0.30 to 0.70, preferably 0.30 to 0.59, more preferably 0.35 to 0.55, and still more preferably. In the case of 0.35 to 0.50, and particularly preferably 0.35 to 0.45, an ethylene polymer excellent in the balance between elongation viscosity behavior and melt fluidity can be obtained. If the g _C ′ value is greater than 0.70, the ethylene polymer may be unsatisfactory due to insufficient molding processability or insufficient transparency. If the g _C ′ value is less than 0.30, the molding processability of the ethylene polymer is improved, but the impact strength of the molded body is lowered or the transparency is deteriorated, which may not be preferable.

Further, _{W C} 0.01 to 30% of the requirement (B-4'-iv), preferably 0.01 to 10.0%, more preferably from 0.02 to 8.0%, more preferably 0. In the case of 1 to 6.0%, most preferably 0.2 to 4.0%, an ethylene polymer excellent in elongational viscosity behavior, impact strength, transparency and the like can be obtained. W _C value is sometimes not preferable or insufficient transparency such is insufficient or moldability of lower than 0.01% and the ethylene-based polymer, said ethylene polymer. W and _C value is greater than 30.0%, of the moldability such as the ethylene-based polymer, is improved in melt tension, too low melt flowability, Ya Manufacture of the ethylene-based polymer This is not preferable because it hinders the molding process, and further, it is not preferable because the impact strength of the molded body is lowered or the transparency is deteriorated.

As described above, the ethylene polymer produced in the present invention has extremely characteristic elongational viscosity characteristics, molecular weight distribution, and intrinsic viscosity characteristics based on its characteristic long-chain branched structure. The ethylene polymer produced by the method for producing an ethylene polymer comprises the above requirements (B-4′-i), (B-4′-ii), (B-4′-iii), (B-4). '-Iv) satisfying at least one of them, preferably at least any two or more, more preferably three or more, still more preferably all satisfying all of the ethylene produced in the present invention The polymer has a particularly improved melt property as compared with a normal ethylene polymer, has excellent moldability, and is excellent in mechanical properties such as rigidity, impact strength, and transparency.
Furthermore, in the ethylene polymer according to the present invention, it is desirable that the number of double bonds present at the molecular ends measured by infrared absorption spectrum (IR) is 0.15 or more per 1000 carbon atoms.

  Regarding the method for measuring the strain hardening degree, as long as the uniaxial extensional viscosity can be measured, the same value can be obtained in principle by any method. For example, the measurement method and the measuring instrument are disclosed in the known document: Polymer 42 (2001) 8663 Details are described. In the measurement of the ethylene-based polymer according to the present invention, preferred measurement methods and measuring instruments include the following.

Measuring method:
・ Device: Ales manufactured by Rheometrics
-Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
・ Measurement temperature: 170 ℃
-Strain rate: 2 / sec-Preparation of test piece: Press-molded to produce a sheet of 18 mm x 10 mm and a thickness of 0.7 mm.

Calculation method:
The elongational viscosity at 170 ° C. and a strain rate of 2 / second is plotted as a log-log graph of time t (second) on the horizontal axis and elongation viscosity η (Pa · second) on the vertical axis. On the logarithmic graph, the maximum elongation viscosity until strain is 4.0 after strain hardening is ηMax (t1) (t1 is the time when the maximum elongation viscosity is shown), and the elongation viscosity before strain hardening is When the approximate straight line is ηLinear (t), a value calculated as ηMax (t1) / ηLinear (t1) is defined as strain hardening degree (λmax). The presence / absence of strain hardening is determined by whether or not there is an inflection point at which the extensional viscosity changes from an upward convex curve to a downward convex curve over time.
1 and 2 are plots of elongational viscosity of Example 1 and Comparative Example 2 described in the following examples.

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

(I) Various evaluation (measurement) methods (i) MFR:
Based on JIS K6760, it measured by 190 degreeC and 2.16kg load. The FR (flow rate ratio) was calculated from the ratio of MFR 10 kg and MFR (= MFR 10 kg / MFR), which was MFR measured in the same manner under the conditions of 190 ° C. and 10 kg load.

(Ii) Density:
The density was measured by a density gradient tube method after the strand obtained at the time of MFR measurement was heat-treated at 100 ° C. for 1 hour and further left at room temperature for 1 hour in accordance with JIS K7112.

(Iii) Elongation viscosity strain hardening degree (λmax):
Using a rheometer, measurement was performed by the method described in the present specification. Prior to the preparation of the test piece, the polymer was dissolved and reprecipitated according to the following procedure. 300 ml of xylene was introduced into a 500 ml two-necked flask equipped with a cooling tube, and nitrogen bubbling was performed at room temperature for 30 minutes. 6.0 grams of polymer and 1.0 gram of 2,6-di-t-butylhydroxytoluene (BTH) were introduced. The mixture was stirred at 125 ° C. for 30 minutes under a nitrogen atmosphere to completely dissolve the polymer in xylene. The xylene solution in which the polymer was dissolved was poured into 2.5 L of ethanol to precipitate the polymer. The polymer recovered by filtration was dried with a vacuum dryer at 80 ° C.

(Iv) Measurement of the number of terminal double bonds:
The terminal double bond was quantified by preparing a press film and using an apparatus of FTIR-8300 manufactured by Shimadzu Corporation for an infrared absorption spectrum (IR), which is absorption of out-of-plane bending vibration of monosubstituted alkene at 910 cm −1. From the absorbance of the peak of
Number of terminal double bonds (per piece / 1000 carbons) = 1.14 × ΔA / d / t
Here, ΔA is the absorbance at the peak of 910 cm −1, d is the film density (g / cm 3), and t is the film thickness (mm).

(V) Measurement of molecular weight distribution:
In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those measured by gel permeation chromatography (GPC). Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000. A calibration curve is generated by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. In addition, the following numerical value is used for the viscosity formula [η] = K × Mα 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

The measurement conditions for GPC are as follows.
Apparatus: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour. The baseline and section of the obtained chromatogram are performed as illustrated in FIG.

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

References:
1. Developments in polymer characterization, vol. 4). Essex: Applied Science; 1984. Chapter 1.
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4). Macromolecules, 33, 6945-6925 (2000).

[Calculation of branching index (g _C '), etc.]
The branching index (g ′) is a ratio (η _branch / η) between the intrinsic viscosity (η _branch ) obtained by measuring a sample with the above Viscometer and the intrinsic viscosity (η _lin ) obtained separately by measuring a linear polymer. _lin ).
When long chain branching is introduced into a polymer molecule, the radius of inertia is reduced compared to a linear polymer molecule of the same molecular weight. Since the intrinsic viscosity becomes smaller as the radius of inertia becomes smaller, the ratio (η _branch / η) of the intrinsic viscosity (η _branch ) of the branched polymer to the intrinsic viscosity (η _lin ) of the linear polymer having the same molecular weight as long chain branching is introduced. _lin ) becomes smaller. Therefore, when the branch index (g ′ = η _branch / η _lin ) is a value smaller than 1, it means that a branch is introduced, and as the value decreases, the introduced long chain branch increases. It means to go. In particular, in the present invention, the absolute molecular weight obtained from MALLS is the content ratio (%) of the component having a molecular weight of 1 million or more to the total component amount measured by RI, and the content (W _C ) of the component having a molecular weight of 1 million or more. As the absolute molecular weight obtained from MALLS, the above g ′ at a molecular weight of 1,000,000 is calculated as g _C ′.
FIG. 4 shows an example of the analysis result by the GPC-VIS. The left side of FIG. 4 shows the molecular weight distribution curve measured based on the molecular weight (M) obtained from MALLS and the concentration obtained from RI, and the right side of FIG. 4 shows the branching index (g ′) at the molecular weight (M). . Here, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) was used as the linear polymer.

(II) Synthesis of Metallocene Compound After the following metallocene compound was synthesized, it was used as a catalyst component.
[Metalocene Compound Synthesis Example 1] (hereinafter sometimes simply referred to as “metallocene compound A”)
Synthesis of dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) zirconium dichloride was carried out according to the procedure described in Example 1 of JP-A-09-87314.

[Metalocene Compound Synthesis Example 2] (hereinafter sometimes simply referred to as “metallocene compound E”)
The synthesis of dimethylsilylene (3-t-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride is described in J. Am. AM. CHEM. SOC. 2004, 126, 2089-2104.

[Metalocene Compound Synthesis Example 3] (hereinafter sometimes simply referred to as “metallocene compound F”)
Synthesis of dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride was carried out according to the procedure described in Macromolecules 1995, 28, 3771-3778.

[Metalocene Compound Synthesis Example 4] (hereinafter sometimes simply referred to as “metallocene compound B”)
Dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) hafnium dichloride was synthesized by the same method as in [Synthesis Example 1] using hafnium tetrachloride.

[Metalocene Compound Synthesis Example 5] (hereinafter sometimes simply referred to as “metallocene compound C”)
Synthesis of dimethylsilylene (3-trimethylsilylcyclopentadienyl) (indenyl) zirconium dichloride was performed using (3-trimethylsilylcyclopentadienyl) (indenyl) dimethylsilane in the same manner as in [Synthesis Example 1]. Metallocene was obtained as a mixture of isomers.

[Metalocene Compound Synthesis Example 6] (hereinafter sometimes simply referred to as “metallocene compound D”)
The synthesis of isopropylidene (4-t-butylcyclopentadienyl) (indenyl) zirconium dichloride was carried out in the same manner as in [Synthesis Example 1] using (4-t-butylcyclopentadienyl) (indenyl) dimethylmethane. The target metallocene was obtained as a mixture of isomers.

[Metalocene Compound Synthesis Example 7] (hereinafter sometimes simply referred to as “metallocene compound H”)
The synthesis of isopropylidene (3-t-butylcyclopentadienyl) (3-t-butylindenyl) zirconium dichloride was carried out according to the procedure described in Macromolecules 1995, 28, 3074-3079.

[Metalocene Compound Synthesis Example 8] (hereinafter sometimes simply referred to as “metallocene compound I”)
Synthesis of dimethylsilylene (3-tert-butylcyclopentadienyl) (3-tert-butylindenyl) zirconium dichloride was carried out according to the procedure described in Macromolecules 1995, 28, 3074-3079.

Example 1
(1) Preparation of Solid Catalyst Under a nitrogen atmosphere, 5 grams of silica baked 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 heating in a 150 ° C. oil bath. In a separately prepared 100 ml two-necked flask, 57 mg of the metallocene compound A was placed 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 manufactured by Albemarle was added to a toluene solution of the metallocene compound A and stirred for 30 minutes. While heating and stirring the 200 ml two-necked flask containing the vacuum-dried silica in a 40 ° C. oil bath, the whole amount of the toluene solution of the reaction product of the 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 to 40 ° C. to obtain a solid catalyst.

(2) Production of ethylene / 1-butene copolymer An ethylene / 1-butene copolymer was produced using the solid catalyst obtained in the preparation of the solid catalyst of (1) above.
That is, 80 g of polyethylene pellets sufficiently dehydrated and deoxygenated and 33 mg of triethylaluminum were introduced into a 1 liter stainless steel autoclave having a stirring and temperature control device, and the temperature was raised to 90 ° C. while stirring. . Ethylene containing 10% by weight of 1-butene was introduced until the partial pressure reached 2.0 MPa, and then 50 mg of the solid catalyst was injected with argon gas for polymerization for 60 minutes.
As a result, 20.3 grams of ethylene / 1-butene copolymer was produced. The polymerization results are summarized in Table 2. Incidentally, H2 / C2 in Table 2 shows the average value of the hydrogen / ethylene _(H 2 / _{C 2)} molar ratio.

(Comparative Example 1)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 51 mg of the metallocene compound E obtained in Synthesis Example 2 was used instead of 57 mg of the metallocene compound A.
(2) Production of ethylene / 1-butene copolymer Instead of 50 mg of the solid catalyst obtained in Example 1, 56 mg of the solid catalyst obtained in the preparation of the solid catalyst was used, and the polymerization temperature was set to 80 ° C. An ethylene / 1-butene copolymer was produced in the same manner as in Example 1 except that the polymerization was performed for 51 minutes.
As a result, 25.8 grams of ethylene / 1-butene copolymer was produced. The polymerization results are summarized in Table 2.

(Example 2)
(2) Production of ethylene / 1-hexene copolymer Using the solid catalyst obtained in Example 1, an ethylene / 1-hexene copolymer was produced.
That is, 50 grams of 0.20 mmol of triethylaluminum pellets that had been sufficiently dehydrated and deoxygenated were introduced into a 2 liter stainless steel autoclave having a stirring and temperature control device, and the temperature was raised to 75 ° C. while stirring. . After introducing 1.5 ml of 1-hexene and ethylene until the partial pressure became 1.4 MPa, 64 mg of the solid catalyst was injected with nitrogen gas and polymerization was carried out for 90 minutes. During the polymerization reaction, 1-hexene was additionally supplied at a supply rate proportional to the ethylene consumption rate. As a result, the H ₂ / C ₂ (hydrogen / ethylene) molar ratios of the autoclave gas phase portion at 10 minutes after the start of polymerization and immediately before the termination of the polymerization were 0.093% and 0.104%, respectively. The amount of hexene was 9.5 mL. As a result, 49.5 grams of ethylene / 1-hexene copolymer was produced. The polymerization results are summarized in Table 2.

(Comparative Example 2)
In the same manner as in Example 2, except that 64 mg of the solid catalyst obtained in the preparation of the solid catalyst of Comparative Example 1 was used instead of 64 mg of the solid catalyst obtained in Example 1, ethylene / 1-hexene copolymer was used. A coalescence was produced. However, the amount of 1-hexene additionally supplied was 7.5 mL. The H ₂ / C ₂ (hydrogen / ethylene) molar ratio of the autoclave gas phase portion 10 minutes after the start of polymerization and immediately before the termination of the polymerization was 0.122% and 0.137%, respectively. As a result, 42.0 grams of ethylene / 1-hexene copolymer was produced. The polymerization results are summarized in Table 2.

(Comparative Example 3)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 50 mg of the metallocene compound F obtained in Synthesis Example 3 was used instead of 57 mg of the metallocene compound A.
(2) Production of ethylene / 1-hexene copolymer Using 194 milligrams of the solid catalyst obtained in the preparation of the solid catalyst of (1) above, 1-hexene 10 weight instead of ethylene containing 1-butene 10 wt% An ethylene / 1-hexene copolymer was produced in the same manner as in Example 1 except that ethylene containing 1% was used and the polymerization temperature was set to 70 ° C.
As a result, 13.7 grams of ethylene / 1-hexene copolymer was produced. The polymerization results are summarized in Table 2.

(Reference Example 1)
(2) Production of ethylene / 1-hexene copolymer Using 52 mg of the solid catalyst obtained in Example 1, ethylene containing 10% by weight of 1-hexene was used instead of ethylene containing 10% by weight of 1-butene. Except that, an ethylene / 1-hexene copolymer was produced in the same manner as in Example 1.
As a result, 17.5 grams of ethylene / 1-hexene copolymer was produced. The polymerization results are summarized in Table 2.

(Comparative Example 4)
(1) Preparation of solid catalyst The same procedure as in Example 1 except that 44 mg of metallocene compound G (dimethylsilylenebis (cyclopentadienyl) zirconium dichloride) manufactured by Wako Pure Chemical Industries, Ltd. was used instead of 57 mg of metallocene compound A. A solid catalyst was prepared.
(2) Production of ethylene / 1-hexene copolymer Using 49 mg of the solid catalyst obtained in the preparation of the above solid catalyst, ethylene containing 5% by weight of 1-hexene instead of ethylene containing 10% by weight of 1-butene An ethylene / 1-hexene copolymer was produced in the same manner as in Example 1 except that was used.
As a result, 4.5 grams of ethylene / 1-hexene copolymer was produced. The polymerization results are summarized in Table 2.

(Comparative Example 5)
(1) Production of ethylene polymer An ethylene polymer was produced using the solid catalyst obtained in the preparation of the solid catalyst of Comparative Example 4.
That is, 800 mL of isobutane and 0.20 mmol of triethylaluminum were added to a 2 L autoclave equipped with an induction stirrer, the temperature was raised to 75 ° C., and ethylene was introduced to keep the ethylene partial pressure at 1.4 MPa. Next, 525 mg of the solid catalyst of Comparative Example 4 was injected with nitrogen, polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 1.4 MPa and a temperature of 75 ° C., and then ethanol was added to stop the polymerization. The H ₂ / C ₂ (hydrogen / ethylene) molar ratio in the gas phase part of the autoclave immediately before the termination of the polymerization was 0.088%. The ethylene polymer thus obtained was 60.0 g. The polymerization results are summarized in Table 2.

Example 3
(2) Production of ethylene / 1-butene copolymer As in Example 1, except that 55 mg of the solid catalyst obtained in Example 1 was used, the polymerization temperature was set to 70 ° C., and polymerization was performed for 31 minutes. An ethylene / 1-butene copolymer was produced.
As a result, 25.6 grams of ethylene / 1-butene copolymer was produced. The polymerization results are summarized in Table 2.

(Reference Example 2)
(1) Preparation of triethylaluminum-treated montmorillonite Under a nitrogen atmosphere, 3.0 g of commercially available montmorillonite was placed in a 200 ml two-necked flask and dried under reduced pressure with a vacuum pump for 1 hour while heating in a 200 ° C. oil bath. After cooling to room temperature, 75 mL of heptane was added to form a slurry, and 14.4 mL of triethylaluminum (concentration 70 g / L heptane solution) was added with stirring. After stirring at room temperature for 1 hour, the solid was washed by decantation to a dilution ratio of 1/100. Finally, heptane was added until the liquid volume reached 150 ml to obtain a slurry of triethylaluminum-treated montmorillonite.
2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the triethylaluminum-treated montmorillonite of (1) above.
That is, 500 ml of fully dehydrated heptane, 55 mg of triethylaluminum, and 10 ml of 1-hexene were introduced into a 1 liter stainless steel autoclave having a stirring and temperature control device and heated to 80 ° C. while stirring. Warm up. After introducing ethylene to a partial pressure of 1.5 MPa, 50 mg of the above triethylaluminum-treated montmorillonite (2.5 ml of heptane slurry) and 2.5 micromol of metallocene compound A were injected with argon gas for polymerization for 60 minutes. It was. During the polymerization reaction, ethylene containing 10% by weight of 1-hexene was introduced according to the amount of ethylene consumed in the system, and the pressure was kept at 1.5 MPa.
As a result, 3.0 grams of ethylene / 1-hexene copolymer was produced. The polymerization results are summarized in Table 2.

Example 4
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 68 mg of the metallocene compound B obtained in Synthesis Example 4 was used instead of 57 mg of the metallocene compound A.
(2) Production of ethylene / 1-butene copolymer Instead of 50 milligrams of the solid catalyst obtained in Example 1, 210 milligrams of the solid catalyst obtained in the preparation of the solid catalyst was used, and 34 milliliters of hydrogen was added. Except for the above, an ethylene / 1-butene copolymer was produced in the same manner as in Example 1.
As a result, 10.0 grams of ethylene / 1-butene copolymer was produced. The polymerization results are summarized in Table 2.

(Example 5)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 59 mg of the metallocene compound C obtained in Synthesis Example 5 was used instead of 57 mg of the metallocene compound A.
(2) Production of ethylene / 1-butene copolymer Example 1 except that 54 mg of the solid catalyst obtained in the preparation of the above solid catalyst was used instead of 50 mg of the solid catalyst obtained in Example 1. In the same manner as above, an ethylene / 1-butene copolymer was produced.
As a result, 16.5 grams of ethylene / 1-butene copolymer was produced. The polymerization results are summarized in Table 2.

(Example 6)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 55 mg of the metallocene compound D obtained in Synthesis Example 6 was used instead of 57 mg of the metallocene compound A.
(2) Production of ethylene / 1-hexene copolymer An ethylene / 1-hexene copolymer was produced using the solid catalyst obtained in the preparation of the solid catalyst of (1) above.
That is, 800 mL of isobutane, 40 mL of 1-hexene, and 0.20 mmol of triethylaluminum were added to a 2 L autoclave with an induction stirrer, the temperature was raised to 75 ° C., and ethylene was introduced to keep the ethylene partial pressure at 1.4 MPa.
Next, 180 mg of the solid catalyst obtained in the above (1) was injected with nitrogen, polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 1.4 MPa and a temperature of 75 ° C., and then ethanol was added to stop the polymerization. During the polymerization reaction, 1-hexene was additionally supplied at a supply rate proportional to the ethylene consumption rate. As a result, the average value of the H ₂ / C ₂ (hydrogen / ethylene) molar ratio in the autoclave gas phase part 10 minutes after the start of polymerization and immediately before the termination of the polymerization was 0.098%, and the amount of 1-hexene supplied additionally was 12 mL. The ethylene polymer thus obtained was 48.5 g. The polymerization results are summarized in Table 2.

(Example 7)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 62 mg of the metallocene compound H obtained in Synthesis Example 7 was used instead of 57 mg of the metallocene compound A.
(2) Production of ethylene / 1-butene copolymer Instead of 50 milligrams of the solid catalyst obtained in Example 1, 53 milligrams of the solid catalyst obtained in the preparation of the solid catalyst was used. An ethylene / 1-butene copolymer was produced in the same manner as in Example 1 except that milliliter was added and the polymerization temperature was set to 70 ° C.
As a result, 13.7 grams of ethylene / 1-butene copolymer was produced. The polymerization results are summarized in Table 3.

(Example 8)
(2) Production of ethylene / 1-butene copolymer Example 1 except that 51 milligrams of the solid catalyst obtained in the preparation of the solid catalyst of Example 7 (1) and 170 ml of hydrogen were added before the start of polymerization. In the same manner as in Example 7, an ethylene / 1-butene copolymer was produced.
As a result, 18.0 grams of ethylene / 1-butene copolymer was produced. The polymerization results are summarized in Table 3.

Example 9
(2) Production of ethylene / 1-butene copolymer Example 1 except that 50 milligrams of the solid catalyst obtained in (1) Preparation of solid catalyst in Example 7 was used and 68 milliliters of hydrogen was added before the start of polymerization. As in Example 1, an ethylene / 1-butene copolymer was produced.
As a result, 8.5 grams of ethylene / 1-butene copolymer was produced. The polymerization results are summarized in Table 3.

(Example 10)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 64 mg of the metallocene compound I obtained in Synthesis Example 8 was used instead of 57 mg of the metallocene compound A.
(2) Production of ethylene / 1-butene copolymer Instead of 50 mg of the solid catalyst obtained in Example 1, 57 mg of the solid catalyst obtained in the preparation of the solid catalyst was used, and the polymerization temperature was set to 70 ° C. Except that, an ethylene / 1-butene copolymer was produced in the same manner as in Example 1.
As a result, 21.1 grams of ethylene / 1-butene copolymer was produced. The polymerization results are summarized in Table 3.

(Example 11)
(2) Production of ethylene / 1-butene copolymer Example 1 except that 57 milligrams of the solid catalyst obtained in (1) preparation of solid catalyst in Example 10 was used and 34 milliliters of hydrogen was added before the start of polymerization. In the same manner as in Example 10, an ethylene / 1-butene copolymer was produced.
As a result, 22.5 grams of ethylene / 1-butene copolymer was produced. The polymerization results are summarized in Table 3.

(Example 12)
(2) Production of ethylene / 1-butene copolymer Using 54 mg of the solid catalyst obtained in Example 10 (1) Preparation of the solid catalyst, 17 ml of hydrogen was added before the polymerization was started, and the polymerization temperature was 90 ° C. Except that, an ethylene / 1-butene copolymer was produced in the same manner as in Example 10.
As a result, 17.1 grams of ethylene / 1-butene copolymer was produced. The polymerization results are summarized in Table 3.

As described above, from the results shown in Table 2, when Example 1 and Comparative Example 1 were compared and Example 2 and Comparative Example 2 were compared, a catalyst that did not satisfy the requirements of the metallocene compound of the present invention was obtained. The ethylene-based polymers shown in Comparative Example 1 and Comparative Example 2 are [λmax (2.0)] _{B of} requirement (B-4′-i) and [λmax (2. 0)] _{B / [} λmax (0.1)] _B is inferior, g _C ′ of requirement (B-4′-iii) is not sufficiently small, or of requirement (B-4′-iv) W _C is or inferior. From these, it is clear that the ethylene-based polymer produced in the examples according to the present invention is excellent in moldability.
Moreover, since the polymerization activity of the ethylene polymerization by the catalyst which does not satisfy | fill the requirements of the metallocene compound of this invention like Comparative Example 3-Comparative Example 5 compared with the polymerization activity of Example 1 and Example 2 of Table 2 is very low. It is clear that there is a problem in economic efficiency as a method for producing an ethylene polymer. Furthermore, since the [lambda] max (2.0)] _B is too large, the ethylene polymer obtained in Comparative Example 3 can only provide an ethylene polymer having inferior strength. Further, the ethylene polymer obtained in Comparative Example 4 or Comparative Example 5 has [λmax (2.0)] _B /[λmax(0.1)] _B of the requirement (B-4′-ii). Inferior. From these facts, it is clear that the ethylene-based polymer produced in the examples according to the present invention is excellent in moldability and also in economic efficiency.

In addition, Examples 4 to 6 in Table 2 are examples using a metallocene compound having a structure different from that of the catalyst satisfying the requirements of the metallocene compound of the present invention used in Examples 1 to 3.
The metallocene compound of Example 4 is different from the metallocene compound of Example 1 only in the central metal species of Hf and Zr, and the ligand has the same structure. W _C of the invention requirements (B-4'-iv) have a relatively large value, the ethylene polymer is expected to be excellent moderately moldability.
The metallocene compound of Example 5 has the same structure as that of Example 1 except that the substituent on the cyclopentadienyl ring is different from that of the trimethylsilyl group and the t-butyl group. Since it has the same high activity and sufficiently satisfies the requirements (B-4′-i), (B-4′-ii) and (B-4′-iv) of the present invention, The coalescence has excellent moldability.
The metallocene compound of Example 6 has the same structure except that the metallocene compound of Example 1 and the bridging group connecting the cyclopentadienyl ring and the indenyl ring are different from the i-propyl group and the dimethylsilylene group. Since it has the same high activity as that of Example 1 and satisfies the requirement (B-4′-iv) of the present invention, the ethylene polymer is excellent in moldability.
From the above, it was shown that any ethylene polymer produced with a catalyst using a metallocene compound belonging to the present invention would exhibit sufficiently improved moldability.

Examples 7 to 12 in Table 3 are examples using a metallocene compound having a structure different from that of the catalyst satisfying the requirements of the metallocene compound of the present invention used in Examples 1 to 6 of Table 2. .
The metallocene compound H and the metallocene compound I of Examples 7 to 12 are different in structure from the metallocene compounds of the present invention used in Examples 1 to 6 of Table 2 in that they have a substituent at the 3-position of indene. The obtained ethylene / 1-butene copolymer sufficiently satisfies any of the requirements (B-4′-i), (B-4′-ii) and (B-4′-iv) of the present invention. Therefore, it is expected that the ethylene polymer is excellent in moldability. Moreover, compared with the Example and comparative example of Table 2, Example 7-Example 9 of Table 3 showed MFR equivalent or low value in spite of performing superposition | polymerization by higher hydrogen concentration. It was confirmed that a higher molecular weight ethylene / 1-butene copolymer can be produced.
Note that inflection points were observed in all examples in which the extensional viscosity was measured.

  By using the metallocene compound of the present invention as a catalyst component for olefin polymerization, a metallocene polyethylene having a long chain branch having a sufficient number and length can be obtained as compared with conventional metallocene compounds. And the moldability of metallocene polyethylene can be improved. Therefore, the method for producing an ethylene-based polymer using the olefin polymerization catalyst containing the metallocene compound of the present invention is very useful industrially.

Claims (14)

It is a manufacturing method for obtaining the ethylene polymer which satisfy | fills the following conditions (Bd-1 ')-(Bd-4'), Comprising: Olefin polymerization which consists of the following essential components (Ad), (B), and (C) A method for producing an ethylene-based polymer, characterized by using a catalyst for use.
Component (Ad): Metallocene compound represented by the following general formula (1d)

[In formula (1d), M ^1d represents a transition metal of Ti, Zr, or Hf. X ^1d and X ^2d each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ^1d and Q ^2d represent a carbon atom, a silicon atom, or a germanium atom. R ^1d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and four R ^{1d s} may form a ring together with Q ^1d and Q ^2d bonded ^thereto. . ^md is 0 or 1, and when ^md is 0, Q ^1d is directly bonded to a conjugated 5-membered ring containing R ^3d . R ^2d is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding a methyl group), a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 20 carbon atoms. A halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group, wherein R ^3d is a hydrogen atom, halogen, carbon atom having 1 to 20 carbon atoms A hydrogen group, a C1-C18 silicon-containing hydrocarbon group containing 1 to 6 silicon atoms, a C1-C20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen, or a carbon number 1 Represents a hydrocarbon group substituted silyl group of ˜20, and at least one of the four R ^2d is not hydrogen. R ^4d represents a saturated or unsaturated divalent hydrocarbon group having 4 or 5 carbon atoms that forms a condensed ring with respect to the 5-membered ring to be bonded. R ^5d is an atom or group bonded to the carbon atom of R ^4d , and each independently represents a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number 1 to 18 containing 1 to 6 silicon atoms. A silicon-containing hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. n ^d represents an integer of 0 to 10, and when n ^d is 2 or more, R ^5d may form a ring together with the carbon atoms to which R ^d is bonded. ]
Component (B): Compound that reacts with the metallocene compound of component (Ad) to form a cationic metallocene compound Component (C): Fine particle carrier (Bd-1 ′): MFR _B = 0.001 to 200 g / 10 min ( Bd-2 ″): density _B = 0.85 to 0.97 g / cm ³
(Bd-3): [Mw / Mn] _B = 2.0 to 10.0
(Bd-4 ′): Satisfy at least one of the following requirements (B-4′-i) to requirements (B-4′-iv).
(B-4′-i); of elongation viscosity η (t) (unit: Pa · second) and elongation time t (unit: second) measured at a temperature of 170 ° C. and an elongation strain rate of 2 (unit: 1 / second) In the logarithmic plot, an inflection point of the extension viscosity due to strain hardening is observed, the maximum extension viscosity after strain hardening is ηMax (t1), and the approximate straight line of extension viscosity before hardening is ηLinear (t). In this case, the strain hardening degree [λmax (2.0)] _B defined by ηMax (t1) / ηLinear (t1) is 1.2 to 30.0.
(B-4′-ii); [λmax (2.0)] _B defined in (B-4′-i) above, and the elongation strain rate of 0.1 (unit: 1 / second), similarly measured In this case, the ratio [λmax (0.1)] _B [λmax (2.0)] _B /[λmax(0.1)] _B is 1.2 to 10.0.
(B-4′-iii); the branching index (g _C ′) at a molecular weight of 1 million as measured by a GPC measurement device in which a differential refractometer, a viscosity detector, and a light scattering detector are combined is 0.30 to 0.00. 70.
(B-4′-iv); the content (W _C ) of a component having a molecular weight of 1 million or more measured by a GPC measurement device in which a differential refractometer, a viscosity detector, and a light scattering detector are combined is 0.01 to 30%. The method for producing an ethylene polymer according to claim 1, wherein the component (Ad) is a metallocene compound represented by the following general formula (2d).

[In formula (2d), M ^1d represents a transition metal of Ti, Zr, or Hf. X ^1d and X ^2d each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ^1d represents a carbon atom, a silicon atom, or a germanium atom. R ^1d independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R ^{1d s} may form a ring together with Q ^1d bonded ^thereto . R ^2d is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding a methyl group), a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 20 carbon atoms. A halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group, wherein R ^3d and R ^5d are a hydrogen atom, halogen, C 1 -C 1 A hydrocarbon group having 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen, or A C1-C20 hydrocarbon group-substituted silyl group is shown, and at least one of the four R ^2d is not hydrogen. ] In the general formula (1d) or (2d), R ^5d is a hydrogen atom, The method for producing an ethylene polymer according to claim 1 or 2. The method for producing an ethylene polymer according to any one of claims 1 to 3, wherein in the general formula (1d) or (2d), R ^3d and R ^5d are both hydrogen atoms. The method for producing an ethylene polymer according to claim 1, wherein the component (Ad) is a metallocene compound represented by the following general formula (3d).

[In formula (3d), M ^1d represents a transition metal of Ti, Zr, or Hf. X ^1d and X ^2d each independently represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ^1d represents a carbon atom, a silicon atom, or a germanium atom. R ^1d independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R ^{1d s} may form a ring together with Q ^1d bonded ^thereto . R ^2d is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding a methyl group), a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 20 carbon atoms. A halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group, wherein at least one of the two R ^2d is not hydrogen. ] ^6. The method for producing an ethylene-based polymer according to claim 5, wherein one of two R ^<2d > s in the general formula (3d) is a hydrogen atom. In the general formula (3d), R ^2d is a t-butyl group, a trimethylsilyl group or a phenyl group, The method for producing an ethylene polymer according to claim 5 or 6. In the general formula (1d), (2d), or (3d), M ^1d is Zr or Hf, The method for producing an ethylene-based polymer according to any one of claims 1 to 7. In the general formula (1d), (2d) or (3d), M ^1d is Zr, The method for producing an ethylene-based polymer according to any one of claims 1 to 7.   Component (B) is aluminoxane, The manufacturing method of the ethylene-type polymer as described in any one of Claims 1-9 characterized by the above-mentioned.   Component (C) is a silica, The manufacturing method of the ethylene polymer as described in any one of Claims 1-10 characterized by the above-mentioned.   The said catalyst for olefin polymerization is a thing obtained by carrying | supporting the contact mixture of a component (Ad) and a component (B) on a component (C), It is any one of Claims 1-11 characterized by the above-mentioned. The manufacturing method of ethylene polymer of description. The method for producing an ethylene polymer according to any one of claims 1 to 12, wherein the strain hardening degree [λmax (2.0)] _B is 4.5 to 30.0.   Furthermore, the number of double bonds which exist in a molecular terminal is 0.15 or more per 1000 carbon atoms, The manufacturing method of the ethylene-type polymer as described in any one of Claims 1-13 characterized by the above-mentioned. .

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