JP2009185259A - METHOD FOR PRODUCING PROPYLENE/ETHYLENE-alpha-OLEFIN BLOCK COPOLYMER - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for stably and efficiently producing a propylene/ethylene-α-olefin block copolymer having a high-molecular weight ethylene-α-olefin copolymer component (CP) by using a metallocene catalyst including a novel transition metal compound. <P>SOLUTION: The method for producing a propylene/ethylene-α-olefin block copolymer comprises: a pre-process of producing a crystalline propylene polymer component by using the metallocene catalyst carried by a carrier; and a post-process performed following the pre-process for producing a copolymer component of ethylene and at least one comonomer selected from the group consisting of 4-20C α-olefin by carrying out gas-phase polymerization in the presence of the crystalline propylene polymer component. The metallocene catalyst includes a transition metal compound having a specific structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a propylene / ethylene-α-olefin block copolymer, and more particularly, by using a metallocene catalyst containing a novel transition metal compound, a high molecular weight ethylene-α-olefin copolymer component. The present invention relates to a method for stably and efficiently producing a propylene / ethylene-α-olefin block copolymer having (hereinafter also referred to as “CP”).

Crystalline polypropylene is widely used in various molding fields because of its excellent mechanical properties and chemical resistance. However, crystalline polypropylene has high rigidity but lacks impact resistance.
Therefore, in order to improve the impact resistance of polypropylene, a rubber-like substance having a narrow composition distribution such as ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-diene copolymer rubber (EPDM) has been conventionally applied to polypropylene. Blending has been done.
In recent years, these rubber-like substances are produced by homogeneous catalysts represented by metallocene catalysts, and these ethylene-higher α-olefin copolymer rubbers (α-olefins having 4 to 8 carbon atoms) are blended. Improvement of impact resistance is also disclosed (see, for example, Patent Documents 1 and 2).
However, such a rubbery copolymer is generally difficult to handle depending on the composition, and can not be used after being pelletized like a crystalline resin. In the case of a so-called polymer blend in which a rubber-like copolymer is added to polypropylene, the rubber-like copolymer is not sufficiently dispersed, and in terms of physical properties, both sufficiently high rigidity and impact resistance must be achieved. It was difficult.

On the other hand, it is already known that ethylene and propylene are subsequently copolymerized after polymerization of propylene to produce a block copolymer containing ethylene-propylene copolymer rubber (EPR) as CP (for example, (See Patent Documents 3 to 5).
Such a so-called polymer blend is known to improve physical properties because the dispersion of the rubbery copolymer is improved. Furthermore, when using a metallocene catalyst, by optimizing the design of the transition metal compound to be used, higher rigidity and impact resistance can be exhibited, and blocks using transition metal compounds having various specific structures A method for producing a copolymer is disclosed.

Further, ethylene-higher α-olefins such as ethylene-butene copolymer rubber (EBR) or ethylene-octene copolymer rubber (EOR) instead of EPR for the purpose of further improving the impact resistance of the block copolymer. A method for producing a copolymer rubber by multistage polymerization is also known.
For example, a method for producing a propylene / ethylene-α-olefin block copolymer having high rigidity and excellent impact resistance by performing multistage polymerization using a metallocene catalyst is disclosed (for example, Patent Documents 6 to 6). 8).
However, in the liquid phase polymerization using a solvent, the produced CP is dissolved in the solvent, and in order to isolate the polymer, it is necessary to distill off the solvent. It was.

It is also disclosed that CP is produced by gas phase polymerization using a specific transition metal compound (see, for example, Patent Documents 9 to 12).
However, when these transition metal compounds are used, in addition to the problem that CP having a sufficiently high molecular weight cannot be produced in an industrially feasible temperature / pressure range, rigidity and impact resistance are improved to some extent. However, there is still room for improvement in terms of the molecular weight and comonomer composition of the ethylene-α-olefin copolymer that imparts impact resistance.

  Under such circumstances, a method for stably and efficiently producing a propylene / ethylene-α-olefin block copolymer having an ethylene-α-olefin copolymer at an improved level in terms of the molecular weight and comonomer composition. Development was desired.

Japanese Patent Laid-Open No. 6-192500 JP-A-6-192506 JP-A-4-337308 JP-A-6-287257 Japanese Patent Laid-Open No. 11-228648 JP-A-9-316145 JP 9-316147 A JP-A-10-158351 International Publication (WO) pamphlet No. 95/27740 International Publication (WO) Pamphlet No. 2005/23890 International Publication (WO) Pamphlet No. 2005/23891 International Publication (WO) Pamphlet No. 2005/23892 Organometallics, 1994, 13, 954 Macromo. Chem. Phys. 2005, 206, 1043 Organometallics, 2001, 20, 1918

  An object of the present invention is to provide a propylene / ethylene-ethylene compound having a high molecular weight ethylene-α-olefin copolymer component (CP) by using a metallocene catalyst containing a novel transition metal compound in view of the above-mentioned problems of the prior art. An object of the present invention is to provide a method for producing an α-olefin block copolymer stably and efficiently.

  As a result of various studies to solve the above problems, the present inventors have used a metallocene catalyst supported on a support to produce a crystalline propylene polymer component (hereinafter also referred to as “PP”). And a copolymer component (hereinafter referred to as “CP”) of at least one comonomer selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of the crystalline propylene polymer component. A metallocene containing a novel transition metal compound having a specific structure as the polymerization catalyst in a method for producing a propylene / ethylene-α-olefin block copolymer comprising a subsequent step of producing by vapor phase polymerization. By using a catalyst, a propylene / ethylene-α-olefin block having a high molecular weight ethylene-α-olefin copolymer component (CP) is obtained. It found that click copolymer can be produced and stably and efficiently, and have completed the present invention.

  In particular, in view of the prior art, the inventors of the present invention are concerned with the ligand structure of the transition metal compound in the metallocene catalyst, the symmetry of the transition metal compound resulting from its basic skeleton, and the mechanism of polymer formation at the catalytic active point. In addition, in consideration of empirical rules from the viewpoint of the steric effect of the substituent of the transition metal compound and the influence of the resulting polymer on the coordination monomer, in propylene polymerization, high stereoregular polymerization is performed, and A search for a molecular weight improvement in the copolymerization of ethylene and an α-olefin having 4 to 20 carbon atoms was conducted, and a multifaceted investigation and experimental search were conducted. In the process, a specific three-dimensional structure was obtained. When a transition metal compound is formed, the propylene polymerization keeps a high stereoregular polymerization, while co-polymerizing ethylene and an α-olefin having 4 to 20 carbon atoms. It was possible to recognize the fact that the elimination reaction of the polymer was effectively suppressed. Furthermore, in the results of consideration of model compounds and experimental demonstrations, by using a metallocene catalyst composed of a transition metal compound having a specific structure, propylene / having a high molecular weight ethylene-α-olefin copolymerization component (CP) / It has been found that an ethylene-α-olefin block copolymer can be produced.

  In addition, by using a transition metal compound having a specific structure described above and a catalyst consisting of a specific promoter, it has been found that high activity is expressed. As a result, the present propylene / ethylene-α-olefin block The present inventors have found that a copolymer can be produced stably and efficiently, and have led to the present invention.

That is, according to the first invention of the present invention, the first step of producing the crystalline propylene polymer component using the metallocene catalyst supported on the carrier, and subsequently in the presence of the crystalline propylene polymer component. A propylene / ethylene-α-olefin block copolymer comprising a subsequent step of producing a copolymer component of ethylene and at least one comonomer selected from the group consisting of α-olefins having 4 to 20 carbon atoms by gas phase polymerization. A method for producing a polymer, comprising:
The metallocene catalyst includes a transition metal compound represented by the following general formula (I), and a method for producing a propylene / ethylene-α-olefin block copolymer is provided.

［式中、Ｒ^１は、次の一般式（ＩＩ）

[Wherein R ¹ represents the following general formula (II)

（式中、Ａ^１は炭素原子、珪素原子、ゲルマニウム原子またはスズ原子を表わし、Ｒ^１１は水素原子、ハロゲン原子、または、珪素原子及び／またはハロゲン原子を含んでもよい炭素原子数１〜７の炭化水素基を表わす。）で示される基を表わし、
Ｒ^２は、次の一般式（ＩＩＩ）

(In the formula, A ¹ represents a carbon atom, a silicon atom, a germanium atom, or a tin atom, and R ¹¹ is a hydrogen atom, a halogen atom, or a C 1-7 carbon atom that may contain a silicon atom and / or a halogen atom. Represents a hydrocarbon group).
R ² represents the following general formula (III)

（式中、Ａ^２は、炭素原子、珪素原子、ゲルマニウム原子またはスズ原子を表わし、Ｒ^１２、Ｒ^１３は互いに同じでも異なっていてもよく、ハロゲン原子、または珪素原子あるいはハロゲン原子を含んでもよい炭素原子数１〜７の炭化水素基を表わすか、またはＲ^１２とＲ^１３はは互いに結合して環を形成してもよい。）で示される基を表わし、
Ｒ^３及びＲ^４は、同じでも異なってもよく、炭素数６〜２０のアリール基、ハロゲン含有置換基を有する炭素数６〜２０のアリール基、またはケイ素含有置換基を有する炭素数６〜２０のアリール基を表す。
Ｒ^５〜Ｒ^１０は、互いに同じでも異なっていてもよく、各々水素原子または珪素原子或いはハロゲン原子を含んでもよい炭素原子数１〜２０の炭化水素基を表わし、
Ｑは、二つのシクロペンタジエニル環を連結する架橋基を表す。
Ｘ及びＹはそれぞれ独立して、Ｍとσ結合を形成する配位子を表す。また、Ｍは周期律表第４族の遷移金属を表す。］

(In the formula, A ² represents a carbon atom, a silicon atom, a germanium atom or a tin atom, and R ¹² and R ¹³ may be the same as or different from each other, and may contain a halogen atom, a silicon atom or a halogen atom. Represents a hydrocarbon group having 1 to 7 carbon atoms, or R ¹² and R ¹³ may combine with each other to form a ring,
R ³ and R ⁴ may be the same or different, and the aryl group having 6 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms having a halogen-containing substituent, or the carbon number having 6 to 20 having a silicon-containing substituent. Represents an aryl group.
R ^{5 to} R ¹⁰ may be the same or different from each other, and each represents a hydrogen atom, a silicon atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom,
Q represents a bridging group that connects two cyclopentadienyl rings.
X and Y each independently represent a ligand that forms a σ bond with M. M represents a transition metal of Group 4 of the periodic table. ]

According to a second aspect of the present invention, in the first aspect, the metallocene catalyst includes a component (B) and optionally a component (C) in addition to the following component (A). A process for producing a propylene / ethylene-α-olefin block copolymer is provided.
Component (A): Transition metal compound represented by general formula (I) Component (B): Compound selected from the group consisting of ion-exchangeable layered compounds or inorganic silicates Component (C): Organoaluminum compound

According to a third invention of the present invention, in the first or second invention, the propylene / ethylene-α-olefin system is characterized in that, in the general formula (I), R ² is an isopropyl group. A method for producing a block copolymer is provided.

According to a fourth invention of the present invention, in the first or second invention, in the general formula (I), R ¹ is a methyl group, and R ² is an isopropyl group. A method for producing a propylene / ethylene-α-olefin block copolymer is provided.

  According to a fifth invention of the present invention, in any one of the second to fourth inventions, the ion-exchange layered compound of the component (B) is a smectite silicate. A method for producing a propylene / ethylene-α-olefin block copolymer is provided.

  According to a sixth invention of the present invention, in any one of the second to fourth inventions, the ion-exchange layered compound of the component (B) is montmorillonite, propylene / ethylene- A method for producing an α-olefin block copolymer is provided.

  According to the seventh invention of the present invention, in any one of the first to sixth inventions, the comonomer used in the subsequent step is selected from 1-butene, 1-hexene or 1-octene. A process for producing a propylene / ethylene-α-olefin block copolymer is provided.

  According to the method for producing a propylene / ethylene-α-olefin block copolymer of the present invention, the molecular weight of the ethylene-α-olefin copolymer component (CP) is higher than before, the content of low molecular weight components is small, and A propylene / ethylene-α-olefin block copolymer excellent in impact resistance can be produced stably and efficiently.

  The method for producing a propylene-based block copolymer of the present invention is a multistage polymerization reaction using a metallocene catalyst containing a novel transition compound having a specific structure, wherein a crystalline propylene component is produced in the preceding step, and the latter step In this process, a copolymer component (CP) of at least one comonomer selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms is produced by gas phase polymerization.

  Hereinafter, the transition metal compound, the metallocene catalyst, the polymerization method, the resulting propylene / ethylene-α-olefin block copolymer used in the present invention will be described in detail.

I. Metallocene catalyst (olefin polymerization catalyst)
1. Transition Metal Compound (1) Structure of Transition Metal Compound The transition metal compound forming the metallocene complex in the metallocene catalyst of the present invention is a transition metal compound having a specific structure represented by the following general formula (I).

上記の一般式（Ｉ）において、
Ｒ^１は、次の一般式（ＩＩ）

In the above general formula (I),
R ¹ represents the following general formula (II)

（式中、Ａ^１は炭素原子、珪素原子、ゲルマニウム原子またはスズ原子を表わし、Ｒ^１１は水素原子、ハロゲン原子、または、珪素原子及び／またはハロゲン原子を含んでもよい炭素原子数１〜７の炭化水素基を表わす。）で示される基を表わし、
Ｒ^２は、次の一般式（ＩＩＩ）

(In the formula, A ¹ represents a carbon atom, a silicon atom, a germanium atom, or a tin atom, and R ¹¹ is a hydrogen atom, a halogen atom, or a C 1-7 carbon atom that may contain a silicon atom and / or a halogen atom. Represents a hydrocarbon group).
R ² represents the following general formula (III)

（式中、Ａ^２は炭素原子、珪素原子、ゲルマニウム原子またはスズ原子を表わし、Ｒ^１２、Ｒ^１３は互いに同じでも異なっていてもよく、ハロゲン原子、または珪素原子あるいはハロゲン原子を含んでもよい炭素原子数１〜７の炭化水素基を表わすか、またはＲ^１２とＲ^１３は互いに結合して環を形成してもよい。）で示される基を表わし、
Ｒ^３及びＲ^４は、同じでも異なってもよく、炭素数６〜２０のアリール基、ハロゲン含有置換基を有する炭素数６〜２０のアリール基、ケイ素含有置換基を有する炭素数６〜２０のアリール基を表す。
また、Ｒ^５〜Ｒ^１０は互いに同じでも異なっていてもよく、各々水素原子または珪素原子或いはハロゲン原子を含んでもよい炭素原子数１〜２０の炭化水素基を表わし、
Ｑは、二つのシクロペンタジエニル環を連結する架橋基を表わし、
Ｘ及びＹは、それぞれ独立して、Ｍとσ結合を形成する配位子を表わし、
Ｍは周期律表第４族の遷移金属を表す。

(In the formula, A ² represents a carbon atom, a silicon atom, a germanium atom, or a tin atom, and R ¹² and R ¹³ may be the same or different from each other, and may be a halogen atom, or a carbon atom that may contain a silicon atom or a halogen atom. Represents a hydrocarbon group having 1 to 7 atoms, or R ¹² and R ¹³ may be bonded to each other to form a ring.
R ³ and R ⁴ may be the same or different, and are an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms having a halogen-containing substituent, and a 6 to 20 carbon atom having a silicon-containing substituent. Represents an aryl group.
R ^{5 to} R ¹⁰ may be the same as or different from each other, and each represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom, a silicon atom or a halogen atom,
Q represents a bridging group connecting two cyclopentadienyl rings;
X and Y each independently represent a ligand that forms a σ bond with M;
M represents a transition metal of Group 4 of the periodic table.

(2) Features of the transition metal compound The feature of the transition metal compound of the present invention as a complex ligand is that it has a basic feature in chemical structure, and has a bridged indenyl skeleton as a basic skeleton and is located at the 2-position on the indenyl group. In particular. That is, one of the 2-position substituents on the indenyl group has a hydrogen atom (ie, a methyl group, a silyl group, etc.) at the α-position of the position substituted with the indenyl ring, or one substituent other than hydrogen. (That is, an ethyl group, n-butyl group, etc.). The other of the 2-position substituents on the indenyl group is characterized by having two substituents other than hydrogen at the α-position of the position substituted with the indenyl ring (ie, i-propyl group and the like).
Further, the transition metal compound of the present invention is naturally a compound in which two indenyl skeletons are different in symmetry with respect to a plane including M, X and Y in terms of relative positions via the bonding group Q [(a) Stereoisomers (usually referred to as pseudo-rac isomers) and (b) isomers (usually referred to as pseudo-meso isomers)].
However, in order to produce a high molecular weight α-olefin polymer, the compound (a) is used from the viewpoint of the action of regulating the growth direction of the polymer chain and the coordination direction of the monomer. Is preferred.

In addition, it is thought that the reason (mechanism) that the transition metal compound of the present invention exhibits a unique catalytic function in olefin polymerization is as follows.
The transition metal compound represented by the general formula (I) in the present invention has substituents having different sterically different bulky structures at the 2-position on the indenyl group, using a bridged indenyl skeleton as a basic skeleton. It has the basic characteristic of having a unique structure in terms of steric, steric and electronic environment, and the reason can be presumed as follows.

In the transition metal compounds having such a representatively shown as such C ₂ symmetry Non-Patent Documents 1 and 2 (symmetry with Dyad) (so-called racemic), very high molecular weight in the propylene polymer While it is known to give polypropylene, it is known that the copolymerization of ethylene and propylene reduces the molecular weight. The cause is considered to be due to the following two mechanisms.

  First, in the polypropylene produced by propylene polymerization, a methyl group is arranged in the polymer chain. This is due to steric repulsion of the coordination field by the methyl group and the transition metal compound, and by β-hydrogen elimination from the polymer chain. The polymerization termination reaction is effectively suppressed. On the other hand, in the copolymerization of ethylene and propylene, a polymer main chain (methylene chain) in which a methyl group derived from an ethylene unit is not present exists in a part of the obtained polymer chain. It is considered that the β-hydrogen elimination of the compound tends to occur, resulting in a decrease in molecular weight.

Secondly, as shown in Non-Patent Document 3 and the like, it is known that a portion having a double bond is generated in a polymer chain generated by polymerization, and molecular hydrogen is generated accordingly. It is widely known that the hydrogen produced by this mechanism acts as an effective chain transfer agent for the polymerization reaction, resulting in a decrease in the molecular weight of the resulting polymer.
However, depending on the transition metal compound used, the steric and electronic environment of the coordination field also changes. In a specific transition metal compound, it is considered that the arrangement of the polymer chain that generates the molecular hydrogen described above is effectively suppressed, molecular hydrogen is hardly generated, and as a result, a decrease in molecular weight is suppressed.
The reaction based on the above two mechanisms is greatly influenced by the steric and electronic environment of the coordination field formed by the transition metal compound used.

  This is because β-hydrogen elimination in the coordination field formed by arbitrarily changing the basic skeleton, symmetry of the transition metal compound, and the steric and electronic effects of the substituent to be arranged. It shows that it is possible to effectively suppress reactions and reactions that generate molecular hydrogen. As a result, a propylene / ethylene-α olefin block copolymer having a higher molecular weight than that of the conventional ethylene-α olefin copolymer component (CP), a low content of low molecular weight components, and excellent impact resistance is obtained. It will be possible to manufacture stably.

(3) Substituent of transition metal compound (i) R ¹ and R ²
R ¹ represents the following general formula (II)

（式中、Ａ^１は炭素原子、珪素原子、ゲルマニウム原子またはスズ原子を表わし、Ｒ１１は水素原子、ハロゲン原子、または、珪素原子及び／またはハロゲン原子を含んでもよい炭素原子数１〜７の炭化水素基を表わす。）で示される基である。
Ｒ^１の具体例としては、メチル、エチル、ｎ−プロピル、ｎ−ブチル、ｎ−ペンチル、ｎ−ヘキシル、フルオロメチル、クロロメチル、シリル基、ゲルミル基、メチルシリル基などが挙げられ。
Ａ^１は炭素原子が特に好ましく、Ｒ^１の特に好ましい具体例としては、メチル、エチル、ｎ−プロピルである。

(In the formula, A ¹ represents a carbon atom, a silicon atom, a germanium atom or a tin atom, and R 11 represents a hydrogen atom, a halogen atom, or a carbon atom having 1 to 7 carbon atoms which may contain a silicon atom and / or a halogen atom. Represents a hydrogen group).
Specific examples of R ¹ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, fluoromethyl, chloromethyl, silyl group, germyl group, methylsilyl group and the like.
A ¹ is particularly preferably a carbon atom, and particularly preferred specific examples of R ¹ are methyl, ethyl, and n-propyl.

On the other hand, R ² represents the following general formula (III)

（式中、Ａ^２は炭素原子、珪素原子、ゲルマニウム原子またはスズ原子を表わし、Ｒ^１２、Ｒ^１３は互いに同じでも異なっていてもよく、ハロゲン原子、または珪素原子あるいはハロゲン原子を含んでもよい炭素原子数１〜７の炭化水素基を表わすか、またはＲ^１２とＲ^１３は互いに結合して環を形成してもよい。）で示される基である。
Ｒ^２の具体例としては、ｉ−プロピル、ｓｅｃ−ブチル、ジフルオロメチル、ジクロロメチル、ジメチルシリル基、ジメチルゲルミル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基などが挙げられ。
Ａ^２は炭素原子が特に好ましく、Ｒ^２の特に好ましい具体例としては、ｉ−プロピル、ｓｅｃ−ブチル、シクロペンチル基、シクロヘキシル基である。

(In the formula, A ² represents a carbon atom, a silicon atom, a germanium atom, or a tin atom, and R ¹² and R ¹³ may be the same or different from each other, and may be a halogen atom, or a carbon atom that may contain a silicon atom or a halogen atom. Represents a hydrocarbon group having 1 to 7 atoms, or R ¹² and R ¹³ may combine with each other to form a ring.
Specific examples of R ² include i-propyl, sec-butyl, difluoromethyl, dichloromethyl, dimethylsilyl group, dimethylgermyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like.
A ² is particularly preferably a carbon atom, and specific examples of R ² are i-propyl, sec-butyl, cyclopentyl group, and cyclohexyl group.

(Ii) R ³ and R ⁴
R ³ and R ⁴ may be the same or different, and (a) an aryl group having 6 to 20 carbon atoms, (b) an aryl group having 6 to 20 carbon atoms having a halogen-containing substituent, and (c) silicon-containing It represents an aryl group having 6 to 20 carbon atoms having a substituent.

(A) A C6-C20 aryl group As a specific example of a C6-C20 hydrocarbon group, a phenyl group, a tolyl group, a dimethylphenyl group, a mesityl group, an ethylphenyl group, a diethylphenyl group, a triethylphenyl group I-propylphenyl group, di-i-propylphenyl group, tri-i-propylphenyl group, n-butylphenyl group, di-n-butylphenyl group, tri-n-butylphenyl group, t-butylphenyl group, di-t- Examples thereof include aryl groups such as butylphenyl group, tri-t-butylphenyl group, biphenylyl group, p-terphenyl group, m-terphenyl group, naphthyl group, anthryl group, and phenanthryl group.

(B) Halogen-containing aryl group having 6 to 20 carbon atoms In the halogenated hydrocarbon substituent having 6 to 20 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated hydrocarbon substituent is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group.
Specifically, fluorodimethylphenyl group, (fluoromethyl) methylphenyl group, ethylfluorophenyl group, diethylfluorophenyl group, triethylfluorophenyl group, fluoro i-propylphenyl group, fluorodi i-propylphenyl group, (fluoro i -Propyl) i-propylphenyl group, fluorotri-i-propylphenyl group, n-butylfluorophenyl group, di-n-butylfluorophenyl group, (fluorobutyl) butylphenyl group, tri-n-butylfluorophenyl group, t- Butylfluorophenyl group, di-t-butylfluorophenyl group, tri-t-butylfluorophenyl group, fluorobiphenylyl group, fluoro p-terphenyl group, fluoro m-terphenyl group, fluoronaphthyl group, fluoroanthryl group, fluoro And phenanthryl groups.

(C) Silicon-containing aryl group having 6 to 20 carbon atoms Specific examples of the above-described silicon hydrocarbon substituent having 6 to 20 carbon atoms include trimethylsilylphenyl, triethylsilylphenyl, isopropyldimethylsilylphenyl, and t-butyldimethylsilylphenyl. And silyl group-substituted aryl groups such as phenyldimethylsilylphenyl.

(Iii) R ^{5 to} R ¹⁰
R ^{5 to} R ¹⁰ may be the same or different from each other, and each represents a hydrogen atom, a silicon atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom.
Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n -Hexyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.
Examples of the halogen-containing alkyl group having 1 to 20 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as the halogen atom in the halogenated hydrocarbon group.
The halogenated hydrocarbon group is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group.

Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2,1 , 1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl and the like.
Examples of the silicon-containing alkyl group having 1 to 20 carbon atoms include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl, and alkylsilylalkyl groups such as bis (trimethylsilyl) methyl.
Particularly preferable specific examples of R ^{5 to} R ¹⁰ include a hydrogen atom, a methyl group, an ethyl group, and an i-propyl group, and a hydrogen atom is particularly preferable.

(Iv) Q
In general formula (I), Q is a bridging group that connects two cyclopentadienyl rings.
Specific examples of Q include methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene and the like. An arylalkylene group such as (methyl) (phenyl) methylene and diphenylmethylene; a silylene group; a methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di ( (Cyclohexyl) silylene and other alkylsilylene groups, methylphenylsilylene and (alkyl) (aryl) silylene groups such as methyl (tolyl) silylene; arylsilylene groups such as diphenylsilylene; alkyl oligosilylene groups such as tetramethyldisilylene; germylene group Above divalent carbon number 1-20 Alkylgermylene alkylene group silicon silylene group having a hydrocarbon group is replaced with germanium; (alkyl) (aryl) germylene group; an aryl gel Mi alkylene group can be exemplified.

  In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, an alkylsilylene group, an (alkyl) (aryl) silylene group or Arylsilylene groups are particularly preferred.

(V) X and Y
X and Y are ligands that form a σ bond with M, and are not particularly limited, but preferred X and Y are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substitution having 1 to 20 carbon atoms. Examples thereof include an amino group and a nitrogen-containing hydrocarbon group. Among these, a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a benzyl group, a dimethylamino group or a diethylamino group is particularly preferable.

(V) M
M represents a transition metal of Group 4 of the periodic table, preferably zirconium or hafnium, and more preferably zirconium.

(4) Specific examples of transition metal compounds Preferred specific examples of the transition metal compounds of the present invention are shown below. Zirconium dichloride is selected as a representative, and examples of the names are given in the compounds of the structural formula shown in the following chemical formula (IV).
The compound of this structural formula is referred to as dichlorodimethylsilylene (2-methyl-4-phenylindenyl) (2-i-propyl-4-phenylindenyl) zirconium.

By the way, since the present invention mainly comprises a novel transition metal compound, it is basically necessary to exemplify a large number of transition metal compounds. However, in order to make the specification concise and concise, the transition metal compound is required. The illustration of the compound avoids a complicated description, and has left it as the main representative example.
Accordingly, transition metal compounds other than the transition metal compounds listed below are also included in the scope described in the claims of the present application. For example, in the following specific examples, it can be said that titanium, hafnium, and other compounds of X and Y instead of zirconium are exemplified.

(1) dichlorodimethylsilylene (2-methyl-4-phenylindenyl) (2-i-propyl-4-phenylindenyl) zirconium (2) dichlorodimethylsilylene (2-methyl-4- (2-methylphenyl) Indenyl) (2-i-propyl-4- (2-methylphenyl) indenyl) zirconium (3) dichlorodimethylsilylene (2-methyl-4- (3-methylphenyl) indenyl) (2-i-propyl-4- (3-methylphenyl) indenyl) zirconium (4) dichlorodimethylsilylene (2-methyl-4- (4-methylphenyl) indenyl) (2-i-propyl-4- (4-methylphenyl) indenyl) zirconium (5 ) Dichlorodimethylsilylene (2-methyl-4- (2,3-dimethylphenyl) indenyl (2-i-propyl-4- (2,3-dimethylphenyl) indenyl) zirconium (6) dichlorodimethylsilylene (2-methyl-4- (2,4-dimethylphenyl) indenyl) (2-i-propyl- 4- (2,4-dimethylphenyl) indenyl) zirconium (7) dichlorodimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2-i-propyl-4- (4-t- Butylphenyl) indenyl) zirconium (8) dichlorodimethylsilylene (2-methyl-4- (3,5-di-t-butylphenyl) indenyl) (2-i-propyl-4- (3,5-di-t-butyl) Phenyl) indenyl) zirconium (9) dichlorodimethylsilylene (2-methyl-4- (2-methyl-4-tert-butylphenyl) indene ) (2-i-propyl-4- (2-methyl-4-t-butylphenyl) indenyl) zirconium (10) dichlorodimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (2-i -Propyl-4- (1-naphthyl) indenyl) zirconium

(11) dichlorodimethylsilylene (2-methyl-4- (2-naphthyl) indenyl) (2-i-propyl-4- (2-naphthyl) indenyl) zirconium (12) dichlorodimethylsilylene (2-methyl-4- (4-Fluorophenyl) indenyl) (2-i-propyl-4- (4-fluorophenyl) indenyl) zirconium (13) dichlorodimethylsilylene (2-methyl-4- (4-chlorophenyl) indenyl) (2-i -Propyl-4- (4-chlorophenyl) indenyl) zirconium (14) dichlorodimethylsilylene (2-methyl-4- (4-trimethylsilylphenyl) indenyl) (2-i-propyl-4- (4-trimethylsilylphenyl) indenyl ) Zirconium (15) Dichlorodimethylsilylene (2- Tyl-4-phenylindenyl) (2-i-propyl-4- (4-t-butylphenyl) indenyl) zirconium (16) dichlorodimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl ) (2-i-propyl-4-phenylindenyl) zirconium (17) dichlorodimethylsilylene (2-ethyl-4-phenylindenyl) (2-i-propyl-4-phenylindenyl) zirconium (18) dichloro Dimethylsilylene (2-ethyl-4- (4-t-butylphenyl) indenyl) (2-i-propyl-4- (4-t-butylphenyl) indenyl) zirconium (19) dichlorodimethylsilylene (2-ethyl- 4- (4-Chlorophenyl) indenyl) (2-i-propyl-4- (4-chlorophenyl) Indenyl) zirconium (20) Dichloro dimethylsilylene (2-methyl-4-phenyl-indenyl) (2-sec-butyl-4-phenyl indenyl) zirconium

(21) dichlorodimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2-sec-butyl-4- (4-t-butylphenyl) indenyl) zirconium (22) dichlorodimethylsilylene ( 2-methyl-4- (4-chlorophenyl) indenyl) (2-sec-butyl-4- (4-chlorophenyl) indenyl) zirconium (23) dichlorodimethylsilylene (2-n-furopyl-4-phenylindenyl) ( 2-i-propyl-4-phenylindenyl) zirconium (24) dichlorodimethylsilylene (2-n-furopyl-4- (4-t-butylphenyl) indenyl) (2-i-propyl-4- (4- t-butylphenyl) indenyl) zirconium (25) dichlorodimethylsilylene (2-n-furo) 4- (4-chlorophenyl) indenyl) (2-i-propyl-4- (4-chlorophenyl) indenyl) zirconium (26) dichlorodimethylsilylene (2-methyl-4-phenylindenyl) (2-cyclohexyl- 4-Phenylindenyl) zirconium (27) dichlorodimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2-cyclohexyl-4- (4-t-butylphenyl) indenyl) zirconium (28 ) Dichlorodimethylsilylene (2-methyl-4- (4-chlorophenyl) indenyl) (2-cyclohexyl-4- (4-chlorophenyl) indenyl) zirconium (29) dichlorodimethylsilylene (2,5-dimethyl-4-phenylindene) Nyl) (2-i-propyl-4-fe Ru-5-methylindenyl) zirconium (30) dichlorodimethylsilylene (2,5-di-methyl-4- (4-tert-butylphenyl) -7-methylindenyl) (2-i-propyl-4- (4-t-Butylphenyl) -5-methylindenyl) zirconium

(31) dichlorodimethylsilylene (2,5-dimethyl-4- (4-chlorophenyl) indenyl) (2-i-propyl-4- (4-chlorophenyl) -5-methylindenyl) zirconium (32) dichlorodimethylsilylene (2,6-Dimethyl-4-phenylindenyl) (2-i-propyl-4-phenyl-6-methylindenyl) zirconium (33) dichlorodimethylsilylene (2,6-di-methyl-4- (4 -T-butylphenyl) -6-methylindenyl) (2-i-propyl-4- (4-t-butylphenyl) -5-methylindenyl) zirconium (34) dichlorodimethylsilylene (2,6-dimethyl) -4- (4-Chlorophenyl) indenyl) (2-i-propyl-4- (4-chlorophenyl) -6-methylindenyl ) Zirconium (35) dichlorodimethylsilylene (2,7-dimethyl-4-phenylindenyl) (2-i-propyl-4-phenyl-7-methylindenyl) zirconium (36) dichlorodimethylsilylene (2,7- Di-methyl-4- (4-t-butylphenyl) -6-methylindenyl) (2-i-propyl-4- (4-t-butylphenyl) -7-methylindenyl) zirconium (37) dichloro Dimethylsilylene (2,7-dimethyl-4- (4-chlorophenyl) indenyl) (2-i-propyl-4- (4-chlorophenyl) -7-methylindenyl) zirconium (38) dichlorodimethylgermylene (2- Methyl-4-phenylindenyl) (2-i-propyl-4-phenylindenyl) zirconium (39) Rodimethylgermylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2-i-propyl-4- (4-t-butylphenyl) indenyl) zirconium (40) dichlorodimethylgermylene (2 -Methyl-4- (4-chlorophenyl) indenyl) (2-i-propyl-4- (4-chlorophenyl) indenyl) zirconium

(41) dichloromethylphenylsilylene (2-methyl-4-phenylindenyl) (2-i-propyl-4-phenylindenyl) zirconium (42) dichloromethylphenylsilylene (2-methyl-4- (4-t -Butylphenyl) indenyl) (2-i-propyl-4- (4-t-butylphenyl) indenyl) zirconium (43) dichloromethylphenylsilylene (2-methyl-4- (4-chlorophenyl) indenyl) (2- i-propyl-4- (4-chlorophenyl) indenyl) zirconium (44) dichloro1,2-ethylene (2-methyl-4-phenylindenyl) (2-i-propyl-4-phenylindenyl) zirconium (45 ) Dichloro 1,2-ethylene (2-methyl-4- (4-t-butylphenyl) in Nyl) (2-i-propyl-4- (4-t-butylphenyl) indenyl) zirconium (46) dichloro1,2-ethylene (2-methyl-4- (4-chlorophenyl) indenyl) (2-i- Propyl-4- (4-chlorophenyl) indenyl) zirconium

  As described above, in the above series of compounds, one or both of the two chlorine atoms corresponding to the X and Y portions of the general formula (I) are fluorine atom, bromine atom, iodine atom, methyl group, phenyl group. Further, compounds substituted for benzyl group, dimethylamino group, diethylamino group and the like can also be exemplified. In addition, the compounds exemplified above are equivalent to compounds in which the central metal (M) is replaced by titanium or hafnium instead of zirconium.

By the way, in general, in the technical field of olefin polymerization catalysts, it is known that the catalytic action is greatly influenced by the metal species of the transition metal compound as the catalyst component, and only the metal species of certain transition metal catalysts are used. There is no theoretical guarantee that other different catalysts have equivalent catalysis. However, it has been confirmed through experiments that when Group 4 zirconium, titanium, and hafnium are used as the metallocene catalyst component, it has been confirmed by experiments and is well known to those skilled in the art. No. 60-130604, JP-A-4-100808).
Therefore, it can be said that the above examples of the transition metal compounds in the present specification are rational and are not merely enumerated.

2. Other Components In the present invention, the transition metal compound described above forms an essential component of an olefin polymerization catalyst (metallocene catalyst) (hereinafter, sometimes simply abbreviated as “component (A)”), which will be described next. It is used as an olefin polymerization catalyst together with other components.
In the metallocene catalyst in the present invention, the component contained in addition to the transition metal compound is not particularly limited, and examples thereof include those described in detail below, and the following metallocene catalyst ( Olefin polymerization catalyst).

(1) Specific examples of olefin polymerization catalysts

(1a) Olefin polymerization catalyst (i) containing component (B)
The olefin polymerization catalyst (i) is a catalyst comprising the component (A) and the component (B), and the component (C) used as necessary. “Consisting of” is not intended to exclude the case of containing other components in addition to these components, and may be a system that further includes (C), for example.
Component (B) is selected from the group consisting of ion-exchangeable layered compounds or inorganic silicates, and component (C) is an organoaluminum compound.
Of the component (B), the ion-exchange layered compound occupies most of the clay mineral, and is preferably an ion-exchange layered silicate.
An ion-exchange layered silicate (hereinafter sometimes simply referred to as “silicate”) has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other and have a binding force. Refers to a silicate compound in which the ions to be exchanged are exchangeable. Most silicates are naturally produced mainly as clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. You may go out.
Various known silicates can be used. Specifically, the following layered silicates described in “Clay Mineralogy”, Asakura Shoten (1995), by Haruo Shiramizu, can be mentioned as typical examples.

(I) 2: 1 type minerals Smectite group such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, etc .; vermiculite group such as vermiculite; mica such as mica, illite, sericite, marine Pyrophyllites such as pyrophyllite and talc-talc; chlorite such as magnesium chlorite.

(B) 2: 1 ribbon type minerals Sepiolite, palygorskite and the like.

The silicate used as a raw material in the present invention may be a layered silicate in which the above mixed layer is formed. In the present invention, the main component silicate is preferably a silicate having a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite.
As the silicate used in the present invention, those obtained as natural products or industrial raw materials can be used as they are without any particular treatment, but chemical treatment is preferred. Specific examples include acid treatment, alkali treatment, salt treatment, and organic matter treatment. These processes may be used in combination with each other. In the present invention, these treatment conditions are not particularly limited, and known conditions can be used.
Moreover, since these ion-exchange layered silicates usually contain adsorbed water and interlayer water, it is preferable to use them after removing moisture by heat dehydration under an inert gas flow.

In the olefin polymerization catalyst (i) of the present invention, an example of the organoaluminum compound as the optional component (C) is represented by the following general formula (V).
AlR _a X _3-a (V)

In general formula (V), R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents hydrogen, halogen, an alkoxy group, or a siloxy group, and a represents a number greater than 0 and 3 or less.
Specific examples of the organoaluminum compound represented by the general formula (V) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, halogen such as diethylaluminum monochloride and diethylaluminum monomethoxide. Or the alkoxy-containing alkylaluminum is mentioned. Of these, trialkylaluminum is preferred.

  In the olefin polymerization catalyst (i) of the present invention, an aluminoxane such as methylaluminoxane can be used as the component (C) in addition to the organoaluminum compound represented by the above general formula. Moreover, said organoaluminum compound and aluminoxane can also be used together.

Although the contact method of a component (A) and a component (B) and arbitrary components (C) is not specifically limited, The following methods can be illustrated.
(1) Method of contacting component (A) and component (B) (2) Method of adding optional component (C) after contacting component (A) and component (B) (3) Component (A ) And the optional component (C) are contacted and then the component (B) is added (4) The component (B) and the optional component (C) are contacted and then the component (A) is added (5) ) Each component (A), (B), (C) is contacted simultaneously.

  The above-mentioned contact of each component may be performed in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene in an inert gas such as nitrogen. The contact temperature is preferably in the range of −20 ° C. to the boiling point of the solvent, particularly in the range of room temperature to the boiling point of the solvent. The catalyst thus prepared may be used without washing after preparation, or may be used after washing. Furthermore, you may use it combining a component newly as needed after preparation.

This contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin. During or after the contact of each of the above components, a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may coexist or contact.
Moreover, you may perform contact of said each component in inert hydrocarbon solvents, such as pentane, hexane, heptane, toluene, and xylene, in inert gas, such as nitrogen. The contact is preferably performed at a temperature between −20 ° C. and the boiling point of the solvent, particularly at a temperature between room temperature and the boiling point of the solvent.

(1b) Olefin polymerization catalyst containing a promoter component other than ion-exchangeable layered compound or inorganic silicate (ii)
In order to activate the transition metal compound (A) instead of the component (B), the following components can also be used. Specific examples include (D-1) to (D-3) below.
(D-1) Aluminum Oxy Compound (D-2) An ionic compound or Lewis acid capable of reacting with component (A) to convert component (A) into a cation (D-3) solid acid

  (D-1) In aluminum oxy compounds, it is well known that aluminum oxy compounds can activate metallocene complexes. Specific examples of such compounds include the following general formulas (VI) to (VIII): And the compounds represented.

In the above general formulas (VI) to (VII), ^Ra represents a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. Moreover, several ^Ra may be same or different, respectively. P represents an integer of 0 to 40, preferably 2 to 30.
Among the general formulas, the compounds represented by the general formulas (VI) and (VIII) are also referred to as aluminoxanes. Among these, methylaluminoxane or methylisobutylaluminoxane is preferable. The above aluminoxanes can be used in combination within a group and between groups. And said aluminoxane can be prepared on well-known various conditions.
The compound represented by the general formula (VIII) is a compound of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula R ^b B (OH) _2. : 1 to 1: 1 (molar ratio). In the general formula (VIII), R ^b represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

The compound (D-2) is an ionic compound or a Lewis acid capable of reacting with the component (A) to convert the component (A) into a cation. Examples of such an ionic compound include carbonium. Examples thereof include complexes of cations such as cations and ammonium cations with organic boron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron, and tris (pentafluorophenyl) boron.
Examples of the Lewis acid as described above include various organic boron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halide compounds such as aluminum chloride and magnesium chloride are exemplified.
In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with a component (A) and can convert a component (A) into a cation.
Examples of the metallocene catalyst using the non-coordinating boron compound described above are disclosed in JP-A-3-234709 and JP-A-5-247128.

  Examples of the solid acid (D-3) include alumina, silica-alumina, and silica-magnesia.

In the olefin polymerization catalyst (ii) of the present invention, a carrier (E) as an optional component can also be used. The carrier (E) is composed of an inorganic or organic compound, and is usually a fine particle carrier having a particle size of 5 μm to 5 mm, preferably 10 μm to 2 mm.
Examples of inorganic carriers include oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , ZnO, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO. ₂ , composite oxides such as SiO ₂ —Cr ₂ O ₃ and SiO ₂ —Al ₂ O ₃ —MgO.
Examples of organic carriers include (co) polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturation such as styrene and divinylbenzene. Examples thereof include porous polymer fine particle carriers made of hydrocarbon (co) polymers.
The specific surface area of these particles is usually 20~1,000m ² / g, preferably 50~700m ² / g, pore volume is usually 0.1 cm ³ / g or more, preferably 0.3 cm ³ / g or more, more preferably 0.8 cm ³ / g or more.

Further, as an optional component, for example, an active hydrogen-containing compound such as H ₂ O, methanol, ethanol, butanol, an electron donating compound such as ether, ester, amine, phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, or Alkoxy-containing compounds such as tetraethoxysilane and diphenyldimethoxysilane can be included.

  Examples of optional components other than the above include tri-lower alkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum, halogen-containing alkylaluminums such as diethylaluminum chloride, diisobutylaluminum chloride and methylaluminum sesquichloride, and diethylaluminum hydride. Alkyl-containing alkylaluminums such as alkylaluminum hydride, diethylaluminum ethoxide, dimethylaluminum butoxide, and aryloxy-containing alkylaluminums such as diethylaluminum phenoxide.

(2) Use amount of catalyst component The use amount of component (A) and component (B) is used in an optimal amount ratio in each combination.
When an ion-exchange layered compound or the like is used as the component (B), the transition metal complex is in the range of 0.001 to 10 mmol, preferably 0.001 to 1 mmol, per 1 g of the component.
These use ratios are examples of normal ratios, and the present invention is limited by the range of use ratios described above as long as the catalyst meets the purpose of the invention. It is natural that it must not be.

(3) Prepolymerization In this invention, before using the catalyst for polyolefin manufacture which consists of a transition metal complex and a co-catalyst as a catalyst for olefin polymerization (main polymerization), after carrying | supporting to a support | carrier as needed, particle property In order to improve the above, it is preferable to subject to a prepolymerization treatment consisting of preliminarily contacting an olefin and polymerizing a small amount.
The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like can be used. It is possible to use it, and it is particularly preferable to use propylene. The olefin can be supplied by any method such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change. The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. Further, the amount of prepolymerization is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass with respect to 1 part by mass of the prepolymerized polymer. After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst, but may be dried if necessary.

  The prepolymerization temperature is not particularly limited, but is usually 0 ° C to 100 ° C, preferably 10 to 70 ° C, more preferably 20 to 60 ° C, and particularly preferably 30 to 50 ° C. Below this range, the reaction rate may decrease or the activation reaction may not proceed, and if it exceeds this range, the prepolymerized polymer may be dissolved, or the prepolymerization rate may be too high and the particle properties may deteriorate. There is a possibility that the active point may be deactivated due to a side reaction.

  The preliminary polymerization can be carried out in a liquid such as an organic solvent, but it is preferable to do so. The concentration of the solid catalyst during the prepolymerization is not particularly limited, but is preferably 50 g / L or more, more preferably 60 g / L or more, and particularly preferably 70 g / L or more. The higher the concentration, the more active the metallocene and the higher the activity of the catalyst.

II. 1. Propylene / ethylene-α olefin block copolymer Propylene / Ethylene-α-Olefin Block Copolymer Production Method The propylene block copolymer production method of the present invention is a pre-stage process for producing a crystalline propylene polymer component (PP), followed by ethylene and 4 carbon atoms. It is comprised from the back | latter stage process which manufactures the copolymer component (CP) with the at least 1 sort (s) comonomer chosen from the group which consists of -20 alpha olefins.
In the preceding step, either a bulk polymerization method or a gas phase polymerization method can be employed. In the subsequent step, the ethylene-α-olefin copolymer component to be produced is a rubber component, and it is desirable that the ethylene-α-olefin copolymer component does not elute in the solvent, so a gas phase polymerization method is employed.
As the polymerization method, both the batch method and the continuous method can be adopted for the former step and the latter step, respectively. In the present invention, two-stage polymerization consisting of a front stage and a rear stage is performed, but in some cases, each stage can be further divided. In particular, a method of making many kinds of rubber components by dividing the subsequent process into two or more stages is one of the physical property improving methods.

(1) Production of crystalline propylene polymer component (PP) In the preceding polymerization step, a metallocene catalyst, preferably a catalyst comprising the above-described components (A) and (B), optionally (C), or the above-mentioned A crystalline propylene polymer component (PP) is produced using a catalyst comprising components (A), (D) and, if necessary, (E). That is, a propylene homopolymer or a copolymer of propylene and α-olefin in one or more stages, 20 to 99% by weight, preferably 30%, based on the total polymerization amount (total of propylene / ethylene-α-olefin block copolymer). It is a step of forming so as to correspond to ˜90% by weight.
Here, the α-olefin is an α-olefin having 4 to 20 carbon atoms other than propylene including ethylene, such as 1-butene, 1-hexene, 4-methyl-pentene-1, 1-octene, 1-octene, Examples include decene. Of these, ethylene is most preferred. When α-olefin is used, the amount used is 10% by weight or less, preferably 5% by weight or less, based on the total monomers (total of propylene and α-olefin).

  The polymerization temperature in the preceding polymerization step is about 30 to 120 ° C, preferably about 50 to 90 ° C. The polymerization pressure is 0.1 to 6 MPa, preferably 0.1 to 4 MPa. Moreover, it is preferable to use a molecular weight (MFR) adjusting agent so that the fluidity of the polymer is appropriate, and hydrogen is preferable as the adjusting agent. Although MFR depends on the use of the final polymer, the preferred range is 0.1 to 3000 g / 10 minutes, preferably 0.5 to 2000 g / 10 minutes, and more preferably 0.5 to 1000 g / 10 minutes.

(2) Production of propylene-α-olefin copolymer component (CP) In the subsequent polymerization step of the present invention, the ethylene-α-olefin copolymer component produced in this step is a rubber component and does not elute into the solvent. Therefore, it is necessary to carry out by gas phase polymerization. A known gas phase polymerization process can be used as the gas phase polymerization process, but a vertical or horizontal gas phase polymerization process that is mechanically stirred is preferable.
In the subsequent step of the present invention, an ethylene-α olefin copolymer having a polymerization ratio (molar ratio) of ethylene and α-olefin of 95/5 to 50/50, preferably 90/10 to 70/30, is produced. Let
Here, the α-olefin is an α-olefin having 4 to 20 carbon atoms, and examples thereof include 1-butene, 1-hexene, 4-methyl-pentene-1, 1-octene-1, 1-decene and the like. . Of these, 1-butene and 1-hexene are most preferable. This copolymer can further contain, for example, propylene, a diene monomer or the like as the third component. In that case, the content of these third components is preferably 20% by weight or less.

In the subsequent step, an amount corresponding to 1 to 80% by weight, preferably 10 to 70% by weight, of the total polymerization amount (total of the propylene / ethylene-α-olefin block copolymer) is formed.
The polymerization temperature in the subsequent polymerization step is about 30 to 120 ° C, preferably about 50 to 80 ° C. The polymerization pressure is 0.1 to 5 MPa, preferably 0.5 to 4 MPa. Although it is known that when the polymerization pressure becomes too high, the supercritical state is known, but the gas phase polymerization in the present invention does not include such a supercritical state.

At the time of polymerization, it is preferable to use a molecular weight regulator in the polymerization system so that the molecular weight and fluidity of the resulting polymer are appropriate, and hydrogen is preferred as the molecular weight regulator.
Thereby, a desired polymer can be obtained by controlling the molecular weight (or MFR). When a conventional metallocene catalyst is used, the molecular weight decreases as the 1-butene content in the copolymer increases, particularly in the subsequent step. Therefore, in order to obtain a practical molecular weight (MFR) for molding processing, the molecular weight is adjusted. Hydrogen as an agent could not be used (molecular weight / MFR could not be controlled), or the control range was very narrow. In the present invention, even if hydrogen is present, the average weight molecular weight (MFR) can be adjusted, and the molecular weight (MFR) suitable for resin processing moldability can be controlled. At this time, the control range of the hydrogen concentration can be set to an arbitrary value of 0 to 10,000 ppm.

  Thus, the range of the weight average molecular weight of the ethylene-alpha olefin copolymer obtained is 10,000-5 million, Preferably it is 50,000-3 million, More preferably, it is 100,000-1 million. Although it depends on the use of the final polymer, in order to suppress the generation of gel at the time of molding and lower the linear expansion coefficient, the weight average molecular weight of the polymer polymerized in the previous stage is used as the weight average molecular weight of the ethylene-α-olefin copolymer. It is effective to make it as close as possible.

In consideration of the properties of the polymer, it is desirable that the generation of low molecular weight components of rubber, which is a cause of stickiness, be as small as possible. Specifically, the component having a molecular weight of 5000 or less in the rubber is preferably 0.8% by weight or less with respect to the whole rubber. For this purpose, polymerization is performed under conditions different from those in the subsequent polymerization step, such as by taking polymerization conditions that do not lower the average molecular weight of the rubber, or by releasing residual monomers or deactivating the catalyst immediately after completion of the polymerization. It is necessary to avoid the reaction from occurring.
In the present invention, the low molecular weight component amount in the rubber means a component amount having a molecular weight of 5000 or less in an eluted component at 40 ° C. or lower as measured by a CFC analyzer described later.

2. Characteristics of Propylene / Ethylene-α-Olefin Block Copolymer According to the above production method, the propylene-α-olefin copolymer component (CP) is converted into a total polymerization amount (total of propylene / ethylene-α-olefin block copolymer). 1) to 80% by weight, and a preferred range is 10 to 70% by weight. Moreover, it can manufacture so that ethylene content in rubber | gum (CP) may be 99 to 50 weight%, Among these, a preferable range is 95 to 60 weight%. Further, the intrinsic viscosity of the rubber (CP) part can be produced such that [η] cp is 1-10.
The Tm of the crystalline propylene polymer component (PP) (melting point by differential scanning calorimeter (DSC)) can be produced so as to be 120 to 165 ° C, and the preferred range is 150 to 165 ° C.
And the propylene / ethylene-alpha olefin type block copolymer by the manufacturing method of this invention can be used suitably especially for an injection molded product, a film, etc. taking advantage of the characteristic.

  The following examples and comparative examples are provided to further illustrate the present invention. The present invention is not limited by these examples without departing from the gist thereof.

In addition, the measuring method used by the Example and the comparative example is as follows.
(1) Measurement of MFR 6 g of an acetone solution (0.6 wt%) of a heat stabilizer (BHT) was added to 6 g of the polymer. Subsequently, after drying said polymer, it filled with the melt indexer (230 degreeC), and was left to stand on the conditions of a 2.16kg load for 5 minutes. Thereafter, the extrusion amount of the polymer was measured, converted into an amount per 10 minutes, and used as the MFR value (unit: g / 10 minutes).
(2) Measurement of Melting Point (Tm) Using DSC (DSC6200, manufactured by Seiko Instruments Inc.), after raising and lowering temperature from 20 to 200 ° C. once at 10 ° C./min, 2 at 10 ° C./min. It calculated | required from the measured value at the time of temperature rising of the 2nd time.

(3) Cross fractionation (abbreviated as “CFC”)
Content of copolymer component (rubber-like component, hereinafter referred to as “CP”) in the propylene / ethylene-α-olefin block copolymer obtained using the catalyst of the present invention, α in CP -The olefin polymerization ratio is determined by the following method.
In addition, although the following examples are the cases where propylene is used as the α-olefin in CP (that is, assuming ethylene-propylene copolymerization), α-olefins such as 1-butene are also included in the following examples. It shall be obtained using a similar method.

(3-1) Analytical device to be used (i) Cross fractionation device CFC T-100 manufactured by Dia Instruments Co., Ltd.
(Ii) Fourier transform infrared absorption spectrum analysis FT-IR, Perkin Elmer 1760X
A fixed wavelength infrared spectrophotometer attached as a CFC detector is removed and an FT-IR is connected instead, and this FT-IR is used as a detector. The transfer line from the outlet of the solution eluted from the CFC to the FT-IR is 1 m long, and the temperature is maintained at 140 ° C. throughout the measurement. The flow cell attached to the FT-IR has an optical path length of 1 mm and an optical path width of 5 mmφ, and the temperature is maintained at 140 ° C. throughout the measurement.
(Iii) Gel permeation chromatography (GPC)
Three GPC columns (AD806MS manufactured by Showa Denko KK) are connected in series to the subsequent stage of the CFC. The GPC column in the latter part of the CFC is used by connecting three AD806MS manufactured by Showa Denko KK in series.

(3-2) CFC measurement conditions (i) Solvent: orthodichlorobenzene (ODCB)
(Ii) Sample concentration: 4 mg / mL
(Iii) Injection volume: 0.4 mL
(Iv) Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 40 minutes.
(V) Fractionation method: Fractionation temperature at the time of temperature-raising elution fractionation is 40, 100, 140 ° C., and fractionation is performed in all three fractions. In addition, the elution ratio (unit:% by weight) of the component eluting at 40 ° C. or lower (fraction 1), the component eluting at 40 to 100 ° C. (fraction 2), and the component eluting at 100 to 140 ° C. (fraction 3), respectively It is defined as W40, W100, and W140. W40 + W100 + W140 = 100. Moreover, each fractionated fraction is automatically transported to the FT-IR analyzer as it is.
(Vi) Elution solvent flow rate: 1 mL / min

(3-3) Measurement conditions of FT-IR After elution of the sample solution started from GPC at the latter stage of CFC, FT-IR measurement was performed under the following conditions, and GPC-IR data was obtained for each of the above-described fractions 1 to 3. Collect.
(I) Detector: MCT
(Ii) Resolution: 8 cm ⁻¹
(Iii) Measurement interval: 0.2 minutes (12 seconds)
(Iv) Number of integrations per measurement: 15 times

(3-4) Post-processing and analysis of measurement results The elution amount and molecular weight distribution of the components eluted at each temperature are determined using the absorbance at 2945 cm ⁻¹ obtained by FT-IR as a chromatogram. The elution amount is normalized so that the total elution amount of each elution component is 100%. Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
Standard polystyrenes used are the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is created by injecting 0.4 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. Conversion to molecular weight uses a general-purpose calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical values are used for the viscosity equation ([η] = K × M ^α ) used at that time.
(I) When creating a calibration curve using standard polystyrene K = 0.000138, α = 0.70
(Ii) Sample measurement of propylene-based block copolymer K = 0.000103, α = 0.78
Ethylene content distribution of each eluted component (ethylene content distribution along the molecular weight axis), using the ratio between the absorbance of the absorbance and 2927cm ^-1 of 2956Cm ^-1 obtained by GPC-IR, polyethylene and polypropylene, and ¹³ By using a calibration curve prepared in advance using an ethylene-propylene copolymer (EPR) whose ethylene content is known by C-NMR measurement or the like and a mixture thereof, the ethylene polymerization ratio (mol%) is obtained. Calculate by conversion.

(3-5) CP content CP content of the block copolymer in this invention is defined by following formula (I), and is calculated | required in the following procedures.
CP content (% by weight) = W40 × A40 / B40 + W100 × A100 / B100 (I)
In the formula (I), W40 and W100 are the elution ratios (unit:% by weight) in each of the above-mentioned fractions, and A40 and A100 are the average ethylene content of actual measurement in each fraction corresponding to W40 and W100. (Unit: wt%), and B40 and B100 are the ethylene content (unit: wt%) of CP contained in each fraction. A method for obtaining A40, A100, B40, and B100 will be described later.

The meaning of the formula (I) is as follows. That is, the first term on the right side of the formula (I) is a term for calculating the amount of CP contained in fraction 1 (portion soluble at 40 ° C.). When fraction 1 contains only CP and no PP, W40 contributes to the CP content derived from fraction 1 as a whole, but fraction 1 contains a small amount of PP in addition to the components derived from CP. Since components derived from the components (extremely low molecular weight components and atactic polypropylene) are also included, it is necessary to correct the portion. Therefore, by multiplying W40 by A40 / B40, the amount derived from the CP component in fraction 1 is calculated. For example, when the average ethylene content (A40) of fraction 1 is 30% by weight and the ethylene content (B40) of CP contained in fraction 1 is 40% by weight, 30/40 = 3/4 of fraction 1 (Ie, 75% by weight) is derived from CP, and 1/4 is derived from PP. Thus, the operation of multiplying A40 / B40 in the first term on the right side means that the contribution of CP is calculated from the weight% (W40) of fraction 1.
The same applies to the second term on the right side, and for each fraction, the CP content is calculated by adding and calculating the contribution of CP.

The average ethylene content A40 of fractions 1 to 3, A100, A140, the ethylene content of the weight ratio and each data point for each data point in the chromatogram absorbance 2945cm ^-1 (absorbance 2956Cm ^-1 and 2927cm ^{- (} Obtained from the ratio to the absorbance of ¹ ).

The ethylene content corresponding to the peak position in the differential molecular weight distribution curve of fraction 1 is defined as B40 (unit is% by weight). Fraction 2 is considered to be completely eluted at 40 ° C. and cannot be defined with the same definition, so in the present invention, it is defined as B100 = 100. B40 and B100 are ethylene contents of CP contained in each fraction, but it is practically impossible to obtain this value analytically. This is because there is no means for completely separating and separating PP and CP mixed in the fraction. As a result of examination using various model samples, it was found that B40 can explain the effect of improving the material properties well by using the ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1. It was. Further, B100 has crystallinity derived from ethylene chain, and the amount of CP contained in these fractions is relatively small compared to the amount of CP contained in fraction 1; The approximation is closer to the actual situation, and there is almost no error in calculation. Therefore, the analysis is performed with B100 = 100.
Therefore, the CP content can be determined according to the following formula (II).
CP content (% by weight) = W40 × A40 / B40 + W100 × A100 / 100 (II)
That is, W40 × A40 / B40, which is the first term on the right side of the formula (II), indicates the CP content (% by weight) having no crystallinity, and W100 × A100 / 100, which is the second term, is a CP having crystallinity. Content (% by weight) is indicated.

The ethylene content in the copolymer component is determined by the following formula (III) using the content of the copolymer component determined by the formula (II).
Ethylene content (% by weight) in copolymer component = (W40 × A40 + W100 × A100 + W140 × A140) / [copolymer component content (% by weight)] (III)

  The significance of setting the three types of fractionation temperatures is as follows. In the CFC analysis of the present invention, only polymers having no crystallinity from 40 ° C. (for example, most of CP, or extremely low molecular weight components and atactic components among propylene polymer components (PP)) are separated. It has the meaning that it is a necessary and sufficient temperature condition. 100 ° C. means only components that are insoluble at 40 ° C. but become soluble at 100 ° C. (eg, components having crystallinity due to the chain of ethylene and / or propylene and PP having low crystallinity in CP) The temperature is necessary and sufficient to elute. 140 ° C. is a component that is insoluble at 100 ° C. but becomes soluble at 140 ° C. (for example, a component having particularly high crystallinity in PP and a component having extremely high molecular weight and extremely high ethylene crystallinity in CP ) Only and the temperature is necessary and sufficient to recover the entire amount of the block copolymer used in the analysis. It should be noted that W140 does not contain any CP component, or even if it is present, it is extremely small and can be substantially ignored, so it is excluded from the calculation of the CP content and the ethylene content.

(3-6) Ethylene polymerization ratio The ethylene content in CP is determined by the following formula.
Ethylene content (% by weight) in CP = (W40 × A40 + W100 × A100) / [CP] where [CP] is the CP content (% by weight) determined previously.

(4) Polymerization activity (first stage activity, second stage activity)
In the present invention, the polymerization activity is defined by the following formula and is determined by the following procedure.
The first stage activity is the polymerization activity of the process for producing the crystalline propylene polymer component (PP), and the second stage activity is the polymerization of the process for producing the ethylene-α olefin copolymer component (CP). Active.
Block copolymer yield (g): [WT]
First stage extraction polymer amount (g): [WT ']
CP content (% by weight): [CP]
Amount of catalyst used (g): [cat]
First stage polymerization time (hr): T1, Second stage polymerization time (hr): T2,
Then, the first-stage activity and the second-stage activity are as follows.
First stage activity = (([WT] × (100− [CP]) / 100) + [WT ′]) / ([cat] × T1)
Second stage activity = ([WT] × [CP] / 100) / ([cat] × T2)

(Example 1)
(1) Metallocene complex Synthesis of dichlorodimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2-i-propyl-4- (4-t-butylphenyl) indenyl) zirconium Synthesized according to the method described in Table 2003-533550 (Example 18).

(2) Catalyst preparation Into a 5 L separable flask equipped with a stirring blade and a reflux apparatus, 1,698 g of pure water was added, and 501 g of 98% sulfuric acid was added dropwise. Further, 300 g of commercially available granulated montmorillonite (Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 19.5 μm) was added and stirred. Thereafter, the mixture was reacted at 90 ° C. for 2 hours. This slurry was washed with an apparatus in which an aspirator was connected to Nutsche and a suction bottle. A 900 mL aqueous solution of 324 g of lithium sulfate monohydrate was added to the recovered cake and reacted at 90 ° C. for 2 hours. This slurry was washed to pH> 4 with an apparatus in which an aspirator was connected to Nutsche and a suction bottle. The collected cake was dried at 120 ° C. overnight. As a result, 275 g of a chemically treated product was obtained.
10.0 g of the chemically treated montmorillonite obtained above was weighed into a flask having an internal volume of 1 L, 65 mL of heptane and 35.4 mL (25 mmol) of a heptane solution of triisobutylaluminum were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the remaining liquid was washed to 1/100 with heptane, and finally the amount of slurry was adjusted to 100 mL.

(3) Prepolymerization with propylene 0.85 mL of a triisobutylaluminum heptane solution was added to the montmorillonite heptane slurry prepared above and treated with triisobutylaluminum and stirred at room temperature for 10 minutes. Further, dichlorodimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2-i-propyl-4- (4-t-butylphenyl) indenyl)} zirconium synthesized in (1) ( (300 μmol) in toluene (60 mL) was added to the 1 L flask and stirred at room temperature for 60 minutes.
Next, 340 mL of heptane was further added to the above montmorillonite heptane slurry, and the mixture was introduced into a 1 L stirred autoclave. Supplied. After completion of the propylene supply, the temperature was raised to 50 ° C. and maintained for 2 hours, after which the remaining gas was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and the supernatant liquid was extracted. To the remaining solid, 8.5 mL (6.0 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover a solid catalyst. The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.88.

(4) Block polymerization After the inside of the stirred autoclave with an internal volume of 3 L was sufficiently substituted with propylene, 2.76 ml (2.02 mmol) of triisobutylaluminum / n-heptane solution was added, and 200 ml of hydrogen and then 750 g of liquid propylene were introduced. The temperature was raised to 65 ° C. and the temperature was maintained. The prepolymerized catalyst prepared in the above (3) was slurried in normal heptane, and 30 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The temperature in the tank was maintained at 65 ° C., and after 1 hour from the catalyst addition, the remaining monomer was purged, and the inside of the tank was replaced with argon five times. Stirring was stopped, and while flowing argon, a Teflon (registered trademark) tube was inserted into the tank, and a small amount of polypropylene was extracted. As a result of measurement after drying for 30 minutes under a nitrogen stream at 90 ° C., the extraction amount was 24 g.
On the other hand, the internal temperature of a stirring autoclave having an internal volume of 14 L was adjusted to 90 ° C., and 1-butene (150 mL) was introduced. Further, ethylene was press-fitted to 3.5 MPa to prepare a mixed gas of 1-butene and ethylene.
The 3 L autoclave subjected to propylene polymerization was heated to 80 ° C., and a previously prepared mixed gas of 1-butene and ethylene was introduced. The polymerization reaction was controlled for 30 minutes while supplying a mixed gas so that the internal pressure was 2.0 MPa and the pressure did not change during the polymerization. As a result, 332 g of a propylene / ethylene-butene block copolymer having good particle properties was obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 17.5% by weight based on the entire block copolymer (hereinafter the same). The ethylene content in the rubber (CP) is 85.7% by weight based on the whole rubber component (hereinafter the same), the MFR is 3.87 (dg / min), and the weight average molecular weight of the CP part. Was 420,000. Moreover, Tm of the propylene homopolymer collected separately was 156 ° C., and MFR was 10.05. The first-stage activity was 9900 (g-polymer / g-catalyst · time), and the second-stage activity was 3900 (g-polymer / g-catalyst · time).
The results are shown in Table 1.

(Example 2)
(1) Block polymerization The same procedure as in Example 1 (4) except that the prepolymerized catalyst prepared in Example 1 (3) was used and 300 mL of 1-butene introduced when preparing the mixed gas was used. did. As a result, a first-stage extraction amount of 29 g and 234 g of a propylene / ethylene-butene block copolymer having good particle properties were obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 6.0% by weight, and the ethylene content in rubber (CP) is 78.5% by weight. , MFR was 5.7 (dg / min), and the weight average molecular weight of the CP part was 420,000. The MFR of the separately collected propylene homopolymer was 8.1. The first-stage activity was 8300 (g-polymer / g-catalyst · hour), and the second-stage activity was 940 (g-polymer / g-catalyst · hour).
The results are shown in Table 1.

(Example 3)
(1) Catalyst preparation As a methylalumoxane-supported silica, a commercially available product manufactured by Witco, code number: TA02794, (aluminum content = 23 wt%) was used.

(2) Prepolymerization with propylene The dichlorodimethylsilylene (2-methyl-4- (4-methyl-4-silylene) synthesized in Example 1 (1) was added to the slurry solution of methylalumoxane-supported silica (3 g) in heptane (30 mL) prepared above. A solution of t-butylphenyl) indenyl) (2-i-propyl-4- (4-t-butylphenyl) indenyl)} zirconium (300 μmol) in heptane (30 mL) was added and stirred at room temperature for 60 minutes.
Next, 190 mL of heptane was further added to the above heptane slurry and introduced into a stirring autoclave having an internal volume of 1 L, and propylene was supplied at a constant rate of 119 mmol / hr (5 g / hr) at 40 ° C. over 120 minutes. After completion of the propylene supply, the temperature was raised to 50 ° C. and maintained for 2 hours, after which the remaining gas was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and the supernatant liquid was extracted. To the remaining solid, 2.5 mL (1.7 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover a solid catalyst. The prepolymerization ratio (a value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 2.72.

(3) Block polymerization The same operation as in Example 1 (4) was performed except that 50 mg of the prepolymerized catalyst prepared in Example 3 (2) was used. As a result, a first-stage extraction amount of 12 g and 98 g of propylene / ethylene-butene block copolymer having good particle properties were obtained.
From the result of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 2.7% by weight, and the ethylene content in rubber (CP) is 88% by weight. Was 11.6 (dg / min), and the weight average molecular weight of the CP part was 570,000. Moreover, Tm of propylene homopolymer collected separately was 154.7 ° C. and MFR was 16. The first-stage activity was 2100 (g-polymer / g-catalyst · hour), and the second-stage activity was 110 (g-polymer / g-catalyst · hour).
The results are shown in Table 1.

Example 4
(1) Block polymerization The same operation as in Example 2 was performed except that 50 mg of the prepolymerized catalyst prepared in Example 3 (2) was used.
As a result, a first-stage extraction amount of 12 g and 100 g of propylene / ethylene-butene block copolymer having good particle properties were obtained. From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 0.9% by weight and an ethylene content in rubber (CP) of 77.5% by weight. , MFR was 20.2 (dg / min), and the weight average molecular weight of the CP part was 480,000. The MFR of the propylene homopolymer collected separately was 22.9. The first-stage activity was 2200 (g-polymer / g-catalyst · time), and the second-stage activity was 40 (g-polymer / g-catalyst · time).
The results are shown in Table 1.

(Comparative Example 1)
(1) Metallocene Complex The synthesis of dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenylindenyl)} zirconium was synthesized according to the method described in Organometallics 1994, Vol.

(2) Prepolymerization with propylene A prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) is 2.07 in the same manner as in Example 1 (3) except that the above complex is used. A polymerization catalyst was prepared.

(3) Block polymerization The same operation as in Example 1 (4) was carried out except that 30 mg of the prepolymerized catalyst prepared in (2) was used and 180 mL of hydrogen used in the pre-stage polymerization was used.
As a result, a first-stage extraction amount of 18 g and 203 g of propylene / ethylene-butene block copolymer with good particle properties were obtained. From the result of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 29% by weight, an ethylene content in rubber (CP) of 90.1% by weight, and MFR 0.38 (dg / min), and the weight average molecular weight of the CP part was 137,000. Moreover, Tm of the propylene homopolymer collected separately was 149.2 ° C. and MFR was 0.18. The first-stage activity was 5400 (g-polymer / g-catalyst · time), and the second-stage activity was 3900 (g-polymer / g-catalyst · time).
The results are shown in Table 1.

(Comparative Example 2)
(1) Block polymerization The same operation as in Example 2 was performed using 30 mg of the prepolymerized catalyst prepared in Comparative Example 1 (2).
As a result, a first-stage extraction amount of 34 g and 345 g of propylene / ethylene-butene block copolymer having good particle properties were obtained. From the result of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 24.4% by weight and an ethylene content in rubber (CP) of 77.9% by weight. , MFR was 1.36 (dg / min), and the weight average molecular weight of the CP part was 120,000. Moreover, Tm of the propylene homopolymer collected separately was 149.4 ° C. and MFR was 0.65. The first stage activity was 9800 (g-polymer / g-catalyst · hour), and the second stage activity was 5600 (g-polymer / g-catalyst · hour).
The results are shown in Table 1.

(Consideration by comparison of results of Examples and Comparative Examples)
From the results of Table 1, when Examples 1-4 and Comparative Examples 1 and 2 are compared, the requirement of using a metallocene catalyst containing a transition metal compound having a specific general formula, which is a feature of the present invention, is not satisfied. In the comparative example, a propylene / ethylene-α-olefin block copolymer having a low molecular weight copolymer part (CP) is produced, and in the examples according to the production method of the present invention, the conventional production method is used. It can be seen that a propylene / ethylene-α-olefin block copolymer having a much higher molecular weight copolymer portion (CP) is produced.
Furthermore, in Examples 1 and 2 using an ion-exchange layered compound as a cocatalyst, in addition to obtaining a copolymer part (CP) having a high molecular weight, it was revealed that the polymerization activity was also high. ing.
From the above, the rationality and significance of the configuration requirements in the present invention, and the superiority of the present invention over the prior art are clear.

According to the method for producing a propylene / ethylene-α-olefin block copolymer of the present invention, the molecular weight of the ethylene-α-olefin copolymer component is higher than before, the content of the low molecular weight component is small, and the impact resistance is high. Propylene / ethylene-α-olefin block copolymer excellent in water resistance can be produced stably and efficiently. And the propylene / ethylene-alpha olefin type block copolymer by the manufacturing method of this invention can be used especially suitably for an injection molded product and a film.
Therefore, the industrial value of the production method of the present invention for producing such a block copolymer stably and efficiently is extremely large.

Claims (7)

Using a metallocene catalyst supported on a carrier, a pre-stage process for producing a crystalline propylene polymer component, and subsequently, in the presence of the crystalline propylene polymer component, from ethylene and an α-olefin having 4 to 20 carbon atoms. A process for producing a propylene / ethylene-α-olefin block copolymer comprising a subsequent step of producing a copolymer component with at least one comonomer selected from the group consisting of gas phase polymerization,
The said metallocene catalyst contains the transition metal compound represented by the following general formula (I), The manufacturing method of the propylene / ethylene-alpha olefin type block copolymer characterized by the above-mentioned.

[Wherein R ¹ represents the following general formula (II)

(In the formula, A ¹ represents a carbon atom, a silicon atom, a germanium atom, or a tin atom, and R ¹¹ is a hydrogen atom, a halogen atom, or a C 1-7 carbon atom that may contain a silicon atom and / or a halogen atom. Represents a hydrocarbon group).
R ² represents the following general formula (III)

(In the formula, A ² represents a carbon atom, a silicon atom, a germanium atom or a tin atom, and R ¹² and R ¹³ may be the same as or different from each other, and may contain a halogen atom, a silicon atom or a halogen atom. Represents a hydrocarbon group having 1 to 7 carbon atoms, or R ¹² and R ¹³ may combine with each other to form a ring,
R ³ and R ⁴ may be the same or different, and the aryl group having 6 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms having a halogen-containing substituent, or the carbon number having 6 to 20 having a silicon-containing substituent. Represents an aryl group.
R ^{5 to} R ¹⁰ may be the same or different from each other, and each represents a hydrogen atom, a silicon atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom,
Q represents a bridging group that connects two cyclopentadienyl rings.
X and Y each independently represent a ligand that forms a σ bond with M. M represents a transition metal of Group 4 of the periodic table. ] The propylene / ethylene-α-olefin block copolymer according to claim 1, wherein the metallocene catalyst contains a component (B) and optionally a component (C) in addition to the following component (A). Manufacturing method.
Component (A): Transition metal compound represented by general formula (I) Component (B): Compound selected from the group consisting of ion-exchangeable layered compounds or inorganic silicates Component (C): Organoaluminum compound In the above formula (I), wherein R ² is an isopropyl group, The process according to claim 1 or 2, wherein the propylene / ethylene -α-olefin-based block copolymer. In the above general formula (I), R ¹ is a methyl group, wherein R ² is an isopropyl group, prepared according to claim 1 or 2, wherein the propylene / ethylene -α-olefin-based block copolymer Method.   The method for producing a propylene / ethylene-α-olefin block copolymer according to any one of claims 2 to 4, wherein the ion-exchangeable layered compound of component (B) is a smectite group silicate. .   The method for producing a propylene / ethylene-α-olefin block copolymer according to any one of claims 2 to 4, wherein the ion-exchangeable layered compound of the component (B) is montmorillonite.   The propylene / ethylene-α-olefin block copolymer according to any one of claims 1 to 6, wherein the comonomer used in the subsequent step is selected from 1-butene, 1-hexene or 1-octene. Manufacturing method.