JP2021152155A - Support catalyst for olefin polymerization, and method for producing propylene polymer with support catalyst for olefin polymerization - Google Patents

Abstract

To provide a catalyst for olefin polymerization that can efficiently polymerize a propylene polymer of a branched structure, and a method for producing a propylene polymer of a branched structure with the catalyst for olefin polymerization.SOLUTION: A support catalyst for olefin polymerization has the following component (A) supported on an inorganic carrier. Component (A): a metallocene complex represented by the following general formula [I] (where Q is a carbon atom, silicon atom or germanium atom, X1 and X2 independently represent a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a halogen atom-substituted C1-6 alkyl group or the like).SELECTED DRAWING: None

Description

The present invention relates to a carrier-based catalyst for olefin polymerization and a method for producing a propylene-based polymer having a branched structure using the carrier-based catalyst for olefin polymerization.

In recent years, many studies have been conducted to improve the suitability for sheet molding, blow molding, thermoforming, foam molding, etc., which require a material having a relatively high melt tension, by introducing a branched structure into polypropylene.

Recently, a macromer copolymerization method mainly using a metallocene catalyst has been proposed. The branched polypropylene obtained by the macromer copolymerization method has an advantage that less gel is generated due to a cross-linking reaction than polypropylene in which a branched structure is introduced by irradiating an electron beam or the like.

As such a macromer copolymerization method, for example, in the first stage of polymerization (macromer synthesis step), propylene macromer having a vinyl structure at the terminal is produced by a specific catalyst and specific polymerization conditions, and the second stage of polymerization (macromer). In the copolymerization step), a method of copolymerizing propylene and propylene macromer under a specific polymerization condition with a specific catalyst has been proposed, and it has been shown that the obtained branched polypropylene has high melt strength and melt tension. (See, for example, Patent Documents 1 and 2).

In addition, a single-stage polymerization method in which a macromer synthesis step and a macromer copolymerization step are simultaneously performed using a specific metallocene catalyst has also been proposed, and it has been shown that the obtained branched polypropylene exhibits improved melt strength. (See, for example, Patent Document 3).

Furthermore, catalysts containing two specific metallocene compounds, specifically rac-SiMe ₂ [2-Me-4-Ph-lnd] _{2 ZrC1 2} and rac-SiMe ₂ [2-Me-4-Ph-]. Ind] and ₂ HFC1 metallocene compounds such _2, using a catalyst of a combination of a silica supported methyl aluminoxane (MAO), have a method of multi-stage polymerization is proposed, the resulting propylene polymer has a relatively high It has been reported that it exhibits melt tension (see Patent Document 4).

Further, a method using a catalyst containing a specific metallocene compound and an ion-exchangeable layered silicate has been devised, and the obtained propylene-based polymer has a wide molecular weight distribution and a large amount of branching, and has a good melt tension. It has been reported (see Patent Document 5).
Further, a method using a catalyst containing a plurality of specific metallocene compounds has been devised, and it has been reported that the obtained propylene-based polymer has a good melt tension (see Patent Document 6).
On the other hand, polymerization of a propylene-based polymer using a metallocene complex having cyclopenta [b] thienyl is known (Patent Document 7). However, Patent Document 7 only shows a polymerization example using a zirconium complex, and there is no polymerization example using a hafnium complex.

Special Table 2001-525460 Japanese Unexamined Patent Publication No. 10-338717 Special Table 2002-523575 Japanese Unexamined Patent Publication No. 2001-64314 Japanese Unexamined Patent Publication No. 2007-154121 JP-A-2009-57542 Special Table 2003-517010

As described above, it is desired to produce a propylene-based polymer having a branched structure as one method for improving the melting characteristics. Conventionally, a method using two types of metallocene complexes has been known, but using two types of complexes is not efficient and has a problem.
An object of the present application is to provide a catalyst for olefin polymerization capable of efficiently polymerizing a propylene-based polymer having a branched structure, and a method for producing a propylene-based polymer having a branched structure using the catalyst.

As a result of diligent studies to solve the above problems, the present inventors have performed propylene polymerization using a catalyst in which a hafnium complex having a cyclopenta [b] thienyl structure is supported on an inorganic carrier, and the branched structure is efficiently branched. It has been found that a propylene-based polymer having the above can be obtained, and the present invention has been completed.

That is, the catalyst for olefin polymerization of the present invention is a supported catalyst for olefin polymerization, characterized in that the following component (A) is supported on an inorganic carrier.
Component (A): Metallocene complex represented by the following general formula [I]

（Ｑは、炭素原子、珪素原子又はゲルマニウム原子であり、
Ｘ^１とＸ^２は、それぞれ独立して、ハロゲン原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、ハロゲン原子で置換された炭素数１〜６のアルキル基、炭素数１〜６のアルキル基で置換されたアミノ基、炭素数１〜６の炭化水素基で置換されていてもよい炭素数６〜１８のアリール基、又は、ハロゲン原子で置換された炭素数６〜１８のアリール基である。
Ｒ^１とＲ^１１は、それぞれ独立して、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、置換されていてもよいフリル基、又は、置換されていてもよいチエニル基である。
Ｒ^２、Ｒ^３、Ｒ^１２、及びＲ^１３は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、ハロゲン原子で置換された炭素数１〜６のアルキル基、トリアルキルシリル基で置換された炭素数１〜６のアルキル基、炭素数１〜６の炭化水素基で置換されたシリル基、炭素数１〜６の炭化水素基で置換されていてもよい炭素数６〜１８のアリール基、ハロゲン原子で置換された炭素数６〜１８のアリール基、置換されていてもよいフリル基、又は、置換されていてもよいチエニル基である。
Ｒ^４とＲ^１４は、それぞれ独立して、炭素数１〜６のアルキル基、ハロゲン原子で置換された炭素数１〜６のアルキル基、トリアルキルシリル基で置換された炭素数１〜６のアルキル基、炭素数１〜６の炭化水素基で置換されていてもよい炭素数６〜１８のアリール基、又は、ハロゲン原子で置換された炭素数６〜１８のアリール基である。
また、Ｒ^４とＲ^１４双方でＱを含む４〜７員環を構成してもよい。）

(Q is a carbon atom, a silicon atom or a germanium atom,
X ¹ and X ² are independently halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, alkyl groups having 1 to 6 carbon atoms substituted with halogen atoms, and carbon atoms. An amino group substituted with an alkyl group of 1 to 6, an aryl group having 6 to 18 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 6 carbon atoms substituted with a halogen atom. It is an aryl group of 18.
R ¹ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a frill group which may be substituted, or may be substituted. It is a thienyl group.
^{R 2, R 3, R 12} , and ^{R 13} are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon substituted with a halogen atom Alkyl groups of numbers 1 to 6, alkyl groups having 1 to 6 carbon atoms substituted with trialkylsilyl groups, silyl groups substituted with hydrocarbon groups of 1 to 6 carbon atoms, hydrocarbon groups having 1 to 6 carbon atoms Aryl group having 6 to 18 carbon atoms substituted with, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, a frill group optionally substituted, or a thienyl group optionally substituted with Is.
R ⁴ and R ¹⁴ independently have an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, and an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group. It is an alkyl group, an aryl group having 6 to 18 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms substituted with a halogen atom.
Further, ^{both R 4} and R ¹⁴ may form a 4- to 7-membered ring including Q. )

In the support catalyst for olefin polymerization of the present invention, in the general formula [I], the R ¹ and R ¹¹ are independently alkyl groups having 1 to 6 carbon atoms and optionally substituted frill groups. , Or a thienyl group which may be substituted is preferable from the viewpoint of catalytic activity and the obtained polymer molecular weight.

In the support catalyst for olefin polymerization of the present invention, in the general formula [I], the R ² and R ¹² each independently have an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. The catalytic activity and the melting point of the obtained polymer are that it is an aryl group having 6 to 18 carbon atoms which may be substituted with a hydrocarbon group or an aryl group having 6 to 18 carbon atoms substituted with a halogen atom. Is preferable.
Further, in the carrying catalyst for olefin polymerization of the present invention, in the general formula [I], the R ² , R ³ , R ¹² and R ¹³ are independently alkyl groups having 1 to 6 carbon atoms. The catalytic activity is that an aryl group having 6 to 18 carbon atoms substituted with a hydrocarbon group having 1 to 6 carbon atoms or an aryl group having 6 to 18 carbon atoms substituted with a halogen atom is used. It is preferable from the viewpoint of the melting point of the obtained polymer.

In the carrier-based catalyst for olefin polymerization of the present invention, the inorganic carrier is the following component (B) and further contains (C) to produce a propylene-based polymer having a branched structure with high activity and high production efficiency. It is preferable from the possible point.
Component (B): A compound that reacts with a solid component (b-1) component (A) containing at least one selected from the group consisting of the following (b-1) and (b-2) to form an ion pair. Fine particle carrier (b-2) ion-exchangeable layered compound component (C): alkylaluminum compound

In the support catalyst for olefin polymerization of the present invention, the component (B) containing an almoxane compound or an ion-exchangeable layered silicate is a propylene-based polymer having a highly active and highly efficient branched structure. Is preferable from the viewpoint of being able to manufacture.

In the carrier-based catalyst for olefin polymerization of the present invention, the component (B) is (b-1) and the inclusion of an almoxane compound produces a propylene-based polymer having a branched structure with high activity and high production efficiency. It is preferable from the possible point.
Further, in the carrier-based catalyst for olefin polymerization of the present invention, the component (B) is (b-1), the alumoxane compound is contained, and the fine particle carrier is silica, which is particularly highly active. It is preferable from the viewpoint that a propylene-based polymer having a branched structure can be produced with high production efficiency.

In the carrier-based catalyst for olefin polymerization of the present invention, the component (B) being (b-2) ion-exchangeable layered silicate is a propylene-based polymer having a branched structure with high activity and high production efficiency. It is preferable because it can be manufactured.
Further, in the supported catalyst for olefin polymerization of the present invention, the fact that the ion-exchangeable layered silicate (b-2) is montmorillonite produces a propylene-based polymer having a branched structure with high activity and high production efficiency. It is preferable from the possible point.

The method for producing a propylene-based polymer having a branched structure of the present invention is characterized in that propylene is polymerized or copolymerized using the olefin polymerization supporting catalyst of the present invention.

According to the present invention, it is possible to provide a catalyst for olefin polymerization capable of efficiently polymerizing a propylene-based polymer having a branched structure, and a method for producing a propylene-based polymer having a branched structure using the catalyst.

FIG. 1 is a diagram illustrating a chromatogram baseline and an interval in GPC.

I. Supporting catalyst for olefin polymerization The supporting catalyst for olefin polymerization of the present invention is characterized in that the following component (A) is supported on an inorganic carrier.
Component (A): Metallocene complex represented by the following general formula [I]

（Ｑは、炭素原子、珪素原子又はゲルマニウム原子であり、
Ｘ^１とＸ^２は、それぞれ独立して、ハロゲン原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、ハロゲン原子で置換された炭素数１〜６のアルキル基、炭素数１〜６のアルキル基で置換されたアミノ基、炭素数１〜６の炭化水素基で置換されていてもよい炭素数６〜１８のアリール基、又は、ハロゲン原子で置換された炭素数６〜１８のアリール基である。
Ｒ^１とＲ^１１は、それぞれ独立して、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、置換されていてもよいフリル基、又は、置換されていてもよいチエニル基である。
Ｒ^２、Ｒ^３、Ｒ^１２、及びＲ^１３は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、ハロゲン原子で置換された炭素数１〜６のアルキル基、トリアルキルシリル基で置換された炭素数１〜６のアルキル基、炭素数１〜６の炭化水素基で置換されたシリル基、炭素数１〜６の炭化水素基で置換されていてもよい炭素数６〜１８のアリール基、ハロゲン原子で置換された炭素数６〜１８のアリール基、置換されていてもよいフリル基、又は、置換されていてもよいチエニル基である。
Ｒ^４とＲ^１４は、それぞれ独立して、炭素数１〜６のアルキル基、ハロゲン原子で置換された炭素数１〜６のアルキル基、トリアルキルシリル基で置換された炭素数１〜６のアルキル基、炭素数１〜６の炭化水素基で置換されていてもよい炭素数６〜１８のアリール基、又は、ハロゲン原子で置換された炭素数６〜１８のアリール基である。
また、Ｒ^４とＲ^１４双方でＱを含む４〜７員環を構成してもよい。）

(Q is a carbon atom, a silicon atom or a germanium atom,
X ¹ and X ² are independently halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, alkyl groups having 1 to 6 carbon atoms substituted with halogen atoms, and carbon atoms. An amino group substituted with an alkyl group of 1 to 6, an aryl group having 6 to 18 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 6 carbon atoms substituted with a halogen atom. It is an aryl group of 18.
R ¹ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a frill group which may be substituted, or may be substituted. It is a thienyl group.
^{R 2, R 3, R 12} , and ^{R 13} are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon substituted with a halogen atom Alkyl groups of numbers 1 to 6, alkyl groups having 1 to 6 carbon atoms substituted with trialkylsilyl groups, silyl groups substituted with hydrocarbon groups of 1 to 6 carbon atoms, hydrocarbon groups having 1 to 6 carbon atoms Aryl group having 6 to 18 carbon atoms substituted with, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, a frill group optionally substituted, or a thienyl group optionally substituted with Is.
R ⁴ and R ¹⁴ independently have an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, and an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group. It is an alkyl group, an aryl group having 6 to 18 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms substituted with a halogen atom.
Further, ^{both R 4} and R ¹⁴ may form a 4- to 7-membered ring including Q. )

In the case of a zirconium complex even if it has a cyclopenta [b] thienyl group as in the technique of Patent Document 7, even if propylene polymerization is performed using a catalyst supported on an inorganic carrier, in the comparative example described later, As shown, a propylene-based polymer having a branched structure cannot be obtained.
Further, even if a hafnium complex having two cyclopenta [b] thienyl groups represented by the general formula [I] in the molecule is used, it is uniformly combined with, for example, methylaluminoxane (MAO) without being supported on an inorganic carrier. Even if propylene polymerization is carried out using it as a system catalyst, a propylene polymer having a branched structure cannot be obtained as shown in a comparative example described later.
On the other hand, as in the present invention, propylene polymerization is carried out using a catalyst in which a hafnium complex having two cyclopenta [b] thienyl groups represented by the general formula [I] in the molecule is supported on an inorganic carrier. By performing the above, a propylene-based polymer having a branched structure can be efficiently produced.
The propylene-based polymer having a branched structure has a high melt tension, and by using the propylene-based polymer having the branched structure, the melt tension of the polymer material can be improved, and the moldability can be improved. can.
When a hafnium complex having two cyclopenta [b] thienyl groups represented by the general formula [I] in the molecule is used, a propylene-based polymer having a high terminal vinyl ratio (propylene-based polymer containing a terminal vinyl macromer) can be obtained. When the hafnium complex is supported on an inorganic carrier, the terminal vinyl macromer can be copolymerized with propylene by the hafnium complex itself to produce a branched polymer.

In the present invention, "polymerization" is a general term for homopolymerization of one type of monomer and copolymerization of a plurality of types of monomers, and when it is not necessary to distinguish between the two, the generic term is simply "polymerization". ".
Further, in the present specification, "~" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

1. 1. Ingredient (A)
The component (A) used in the present invention is a metallocene complex represented by the general formula [I].

Specific examples of the halogen atom in the formula [I] include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.
Specific examples of the alkyl group having 1 to 6 carbon atoms in the formula [I] include, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and s-. Butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned.
Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a t-butoxy group and a phenoxy group. Can be mentioned.

Specific examples of the alkyl group having 1 to 6 carbon atoms substituted with a halogen atom in the formula [I] include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group and a trichloromethyl group. , Bromomethyl group, dibromomethyl group, tribromomethyl group, iodomethyl group, 2,2,2-trifluoroethyl group, 2,2,1,1-tetrafluoroethyl group, pentafluoroethyl group, pentachloroethyl group, Pentafluoropropyl group, nonafluorobutyl group, 5-chloropentyl group, 5,5,5-trichloropentyl group, 5-fluoropentyl group, 5,5,5-trifluoropentyl group, 6-chlorohexyl group, 6 , 6,6-trichlorohexyl group, 6-fluorohexyl group, 6,6,6-trifluorohexyl group.
Specific examples of the substituted amino group substituted with an alkyl group having 1 to 6 carbon atoms in the formula [I] include a dimethylamino group, a diethylamino group, a di-n-propylamino group, and a di-i-propylamino group. Examples thereof include a methyl ethyl amino group.

In the formula [I], specific examples of the aryl group having 6 to 18 carbon atoms which may be substituted with the hydrocarbon group having 1 to 6 carbon atoms are phenyl group, 2-, 3- and 4-substituted, respectively. Methylphenyl groups, 2,4-, 2,5-, 2,6- and 3,5-substituted dimethylphenyl groups, 2-, 3- and 4-substituted ethylphenyl groups, 2,4,6 -, 2,3,4-, 2,4,5- and 3,4,5-substituted trimethylphenyl groups, 2-, 3- and 4-substituted t-butylphenyl groups, 2,4- , 2,5-, 2,6- and 3,5-substituted dit-butylphenyl groups, biphenylyl groups, 1-naphthyl groups, 2-naphthyl groups, acenaphthyl groups, phenanthryl groups, anthryl groups and the like. Can be done.
Specific examples of the aryl group having 6 to 18 carbon atoms substituted with a halogen atom include 2-, 3- and 4-substituted fluorophenyl groups and 2-, 3- and 4-substituted chlorophenyl groups. , 2-, 3- and 4-substituted bromophenyl groups, 2,4-, 2,5-, 2,6- and 3,5-substituted difluorophenyl groups, 2,4-, 2,5 -, 2,6- and 3,5-substituted dichlorophenyl groups, 2,4,6-, 2,3,4-, 2,4,5- and 3,4,5-substituted trifluorophenyls Group, 2,4,6-, 2,3,4-, 2,4,5- and 3,4,5-substituted trichlorophenyl groups, pentafluorophenyl groups, pentachlorophenyl groups, 3,5-dimethyl Examples thereof include a -4-chlorophenyl group and a 3,5-dichloro-4-biphenylyl group.

Specific examples of the alkyl group having 1 to 6 carbon atoms substituted with the trialkylsilyl group in the formula [I] include a (trimethylsilyl) methyl group, a (triethylsilyl) methyl group, and a (t-butyldimethylsilyl) methyl group. , (Trimethylsilyl) ethyl group and the like.
In the formula [I], the silyl group substituted with the hydrocarbon group having 1 to 6 carbon atoms is a substituent in which three hydrocarbon groups having 1 to 6 carbon atoms are substituted on the silicon atom independently of each other. The hydrocarbon group having 1 to 6 carbon atoms includes an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and a phenyl group, and the phenyl group is substituted with an alkyl group or the like. May be good. Specific examples thereof include a trimethylsilyl group, a triethylsilyl group, a tri-n-butylsilyl group, a t-butyldimethylsilyl group, a trivinylsilyl group, a triallylsilyl group and a triphenylsilyl group.

In the formula [I], the optionally substituted frill group or the optionally substituted thienyl group is a substituted or unsubstituted frill group or a substituted or unsubstituted thienyl group.
In the formula [I], examples of the substituent of the frill group or the thienyl group include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 1 carbon number substituted with a halogen atom. With an alkyl group of ~ 6, an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group, an aryl group having 6 to 18 carbon atoms optionally substituted with an alkyl group having 1 to 6 carbon atoms, and a halogen atom. Examples thereof include a substituted aryl group having 6 to 18 carbon atoms and a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms. Specific examples of these may be the same as described above.

Specific examples of the frill group which may be substituted include a 2-furyl group, a 2- (5-methylfuryl) group, a 2- (5-ethylfuryl) group, and a 2- (5-n-propylfuryl) group. , 2- (5-i-propylfuryl) group, 2- (5-t-butylfuryl) group, 2- (5-trimethylsilylfuryl) group, 2- (5-triethylsilylfuryl) group, 2- (5-) Phenylfuryl) group, 2- (5-tolylfuryl) group, 2- (5-fluorophenylfuryl) group, 2- (5-chlorophenylfuryl) group, 2- (4,5-dimethylfuryl) group, 2- ( 3,5-Dimethylfuryl) group, 2-benzofuryl group, 3-furyl group, 3- (5-methylfuryl) group, 3- (5-ethylfuryl) group, 3- (5-n-propylfuryl) group , 3- (5-i-propylfuryl) group, 3- (5-t-butylfuryl) group, 3- (5-trimethylsilylfuryl) group, 3- (5-triethylsilylfuryl) group, 3- (5-) Phenylfuryl) group, 3- (5-tolylfuryl) group, 3- (5-fluorophenylfuryl) group, 3- (5-chlorophenylfuryl) group, 3- (4,5-dimethylfuryl) group, 3-benzofuryl The group and the like can be mentioned.

Specific examples of the optionally substituted thienyl group include a 2-thienyl group, a 2- (5-methylthienyl) group, a 2- (5-ethylthienyl) group, and a 2- (5-n-propylthienyl) group. , 2- (5-i-propylthienyl) group, 2- (5-t-butylthienyl) group, 2- (5-trimethylsilylthienyl) group, 2- (5-triethylsilylthienyl) group, 2- (5) -Phenylthienyl) group, 2- (5-trilthienyl) group, 2- (5-fluorophenylthienyl) group, 2- (5-chlorophenylthienyl) group, 2- (4,5-dimethylthienyl) group, 2 -(3,5-dimethylthienyl) group, 2-benzothienyl group, 3-thienyl group, 3- (5-methylthienyl) group, 3- (5-ethylthienyl) group, 3- (5-n-propyl) Thienyl) group, 3- (5-i-propylthienyl) group, 3- (5-t-butylthienyl) group, 3- (5-trimethylsilylthienyl) group, 3- (5-triethylsilylthienyl) group, 3 -(5-phenylthienyl) group, 3- (5-trilthienyl) group, 3- (5-fluorophenylthienyl) group, 3- (5-chlorophenylthienyl) group, 3- (4,5-dimethylthienyl) Groups, 3-benzothienyl groups, etc. can be mentioned.

Q is a carbon atom, a silicon atom or a germanium atom, and is preferably a silicon atom or a germanium atom.

X ¹ and X ² are independently halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, alkyl groups having 1 to 6 carbon atoms substituted with halogen atoms, and carbon atoms. An amino group substituted with an alkyl group of 1 to 6, an aryl group having 6 to 18 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 6 carbon atoms substituted with a halogen atom. It is an aryl group of 18. Above all, from the viewpoint of the stability of the complex, X ¹ and X ² may be independently substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms. It is preferably an aryl group having 6 to 18 carbon atoms, more preferably a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and specifically, a chlorine atom, a bromine atom, an iodine atom or a methyl group. , Ethyl group, i-butyl group, or phenyl group is particularly preferable.

R ¹ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a frill group which may be substituted, or may be substituted. It is a thienyl group. Among them, from the viewpoint of catalytic activity and the obtained polymer molecular weight, R ¹ and R ¹¹ may be independently substituted with an alkyl group having 1 to 6 carbon atoms, a frill group which may be substituted, or a substituent. It is preferably a thienyl group, more preferably an alkyl group having 1 to 6 carbon atoms.

^{R 2, R 3, R 12} , and ^{R 13} are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon substituted with a halogen atom Alkyl groups of numbers 1 to 6, alkyl groups having 1 to 6 carbon atoms substituted with trialkylsilyl groups, silyl groups substituted with hydrocarbon groups of 1 to 6 carbon atoms, hydrocarbon groups having 1 to 6 carbon atoms Aryl group having 6 to 18 carbon atoms substituted with, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, a frill group optionally substituted, or a thienyl group optionally substituted with Is. Among them, from the viewpoint of catalytic activity, R ² and R ¹² may be independently substituted with an alkyl group having 1 to 6 carbon atoms and a hydrocarbon group having 1 to 6 carbon atoms, respectively. It is preferably an aryl group of 18 or an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, and particularly preferably independently, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms. It is an aryl group having 6 to 18 carbon atoms which may be substituted with a hydrocarbon group, or an aryl group having 6 to 18 carbon atoms substituted with a halogen atom. Further, from the viewpoint of the terminal vinyl ratio and the amount of LCB of the obtained polymer, the R ³ and R ¹³ are hydrogen atoms, and from the viewpoint of the molecular weight, an alkyl group having 1 to 6 carbon atoms is preferable.
^{Among them, R 2} , R ³ , R ¹² and R ¹³ are independently substituted with an alkyl group having 1 to 6 carbon atoms and a hydrocarbon group having 1 to 6 carbon atoms in terms of catalytic activity and the melting point of the obtained polymer. It is preferably an aryl group having 6 to 18 carbon atoms which may be used, or an aryl group having 6 to 18 carbon atoms substituted with a halogen atom. Further, ^{it is more preferable that R 3} and R ¹³ are independently alkyl groups having 1 to 6 carbon atoms, and R ² and R ¹² are independently substituted with hydrocarbon groups having 1 to 6 carbon atoms, respectively. More preferably, it may be an aryl group having 6 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms substituted with a halogen atom.

R ⁴ and R ¹⁴ independently have an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, and an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group. It is an alkyl group, an aryl group having 6 to 18 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms substituted with a halogen atom.
Further, ^{both R 4} and R ¹⁴ may form a 4- to 7-membered ring including Q. In this case, R ⁴ and R ¹⁴ are divalent hydrocarbon groups having 3 to 6 carbon atoms forming a ring together with Q, and may contain an unsaturated bond. When ^{both R 4} and R ¹⁴ form a 4- to 7-membered ring containing Q, it is more preferable to form a 4- or 5-membered ring.
R ⁴ and R ¹⁴ have an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, or 1 to 6 carbon atoms in terms of catalytic activity and the melting point of the obtained polymer. It is preferably an aryl group having 6 to 18 carbon atoms which may be substituted with a hydrocarbon group of 6, or ^{both R 4} and R ¹⁴ preferably form a 4- to 7-membered ring containing Q, preferably having a carbon number of 6. It is more preferable that the alkyl group is 1 to 6 or a phenyl group, or that ^{both R 4} and R ^{14 form} a 4- or 5-membered ring containing Q.

The divalent groups of −Q (R ⁴ ) (R ¹⁴ ) − include a dimethylmethylene group, a phenylmethylmethylene group, a diphenylmethylene group, a dimethylsilylene group, a silacyclobutylene group, a silacyclopentylene group, and a silacyclohexylene. Examples thereof include a group, a dimethyl silylene group, a phenylmethyl silylene group, a diphenyl silylene group, a dimethyl gel millene group, a diphenyl gel millene group and the like.

Specific examples of the metallocene complex represented by the general formula [I] are shown below, but the present invention is not limited thereto.
Dimethylsilylenebis (cyclopenta [b] thienyl) phenylnium dichloride dimethylsilylenebis (5-methyl-cyclopenta [b] thienyl) hafnium dichloride dimethylsilylenebis (2,5-dimethyl-cyclopenta [b] thienyl) phenyldichromide dimethylsilylenebis (5-methyl-cyclopenta [b] thienyl) 2,3,5-trimethyl-Cyclopenta [b] thienyl) Hafnium dichloride dimethyl silylenebis (2,5-dimethyl-3-phenyl-cyclopenta [b] thienyl) Hafnium dichloride dimethylsilylenebis (2,5-dimethyl-3-3) (4-t-Butylphenyl) -Cyclopenta [b] thienyl) Hafnium dichloride dimethylsilylenebis (2,5-dimethyl-3- (2,5-dimethylphenyl) -cyclopenta [b] thienyl) Hafnium dichloridedimethylsilylenebis (2,5-dimethyl-3- (2,5-dimethylphenyl) -cyclopenta [b] thienyl) 2,5-dimethyl-3- (3,5-dimethylphenyl) -cyclopenta [b] thienyl) hafnium dichloride dimethylsilylenebis (2,5-dimethyl-3- (3,5-di-t-butylphenyl)- cyclopenta [b] thienyl) hafnium dichloride in addition to this, instead of X ^1, X ² are exemplified chlorine atoms of the compounds illustrated above, one or both bromine atom, an iodine atom, a methyl group, a phenyl group, Compounds that replace dimethylamino groups, diethylamino groups, and the like can also be exemplified. When asymmetric carbon is generated in these metallocene complexes, one of the stereoisomers or a mixture thereof (including a racemic mixture) is shown unless otherwise specified.

As a method for synthesizing the metallocene complex represented by the general formula [I], a conventionally known synthesis method can be appropriately selected and used, and for example, it can be synthesized with reference to Japanese Patent Application Laid-Open No. 2003-517010. ..

2. Inorganic Carrier As the inorganic carrier for supporting the component (A) of the present invention, an inorganic carrier used for supporting a transition metal complex can be appropriately selected and used.
As the inorganic carrier in the present invention, the following component (B), which not only functions as a carrier carrying the component (A) but also acts as a co-catalyst in the polymerization reaction, has a branched structure with high production efficiency. It is preferable from the viewpoint that a propylene-based polymer can be produced.
When the component (A) is supported on the inorganic carrier alone, if the polymerizable ability is insufficient, it is preferable to further contain a compound that reacts with the component (A) to form an ion pair.

Component (B): A compound that reacts with a solid component (b-1) component (A) containing at least one selected from the group consisting of the following (b-1) and (b-2) to form an ion pair. (B-2) Ion-exchangeable layered compound containing

(B-1) is a fine particle carrier containing a compound that reacts with the component (A) to form an ion pair.
Examples of the compound that reacts with the component (A) to form an ion pair include an aluminum oxy compound and a boron compound. Specific examples of the aluminum oxy compound include the following general formulas [II] to [IV]. Examples thereof include compounds represented by.

In the general formula [II] ~ [IV], R a each independently represent a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms Represents a hydrocarbon group. Further, a plurality of R ^a may each be the same or different.
Further, p represents an integer of 0 to 40, preferably 2 to 30.
The compounds represented by the general formulas [II] and [III] are compounds also referred to as aluminoxane, and among these, methylaluminoxane or methylisobutylaluminoxane is preferable. It is also possible to use a plurality of types of the above-mentioned aluminoxane in combination within each group and between each group. The above aluminoxane can be prepared under various known conditions.
In the general formula [IV], R ^b represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. The compound represented by the general formula [IV] is 10: 1 to 10: 1 of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and ^{an alkylboronic acid represented by the general formula RBB} (OH) _2. It can be obtained by a 1: 1 (molar ratio) reaction.

As the boron compound, a complex of cations such as carbonium cation and ammonium cation with an organic boron compound such as triphenylboron, tris (3,5-difluorophenyl) boron and tris (pentafluorophenyl) boron, or a complex. Various organoboron compounds such as tris (pentafluorophenyl) boron can be mentioned.

Here, the fine particle carrier in (b-1) described above will be described. The fine particle carrier used in the present invention is not particularly limited in its elemental composition and compound composition as long as it contains an inorganic compound, and a fine particle carrier containing an inorganic compound can be exemplified. Examples of the inorganic compound constituting the fine particle carrier include oxides such as silica, alumina, magnesium oxide, zirconium oxide, titanium oxide, boron oxide and zinc oxide, silica-magnesium oxide, silica-alumina, silica-titanium oxide and silica-. Examples thereof include chromium (III) oxide, silica-alumina-magnesium oxide, activated carbon, inorganic silicate, or a mixture thereof. The fine particle carrier may be a fine particle inorganic carrier made of an inorganic compound.
These particulate carriers usually have an average particle size of 1 μm to 5 mm, preferably 5 μm to 1 mm, more preferably 10 μm to 200 μm.
The specific surface area of these fine particles generally ^{20m 2} / ^g~1,000m 2 / g, preferably ^{50m 2} / ^g~700m 2 / g, pore volume is usually 0.1 cm ³ / g or more , Preferably 0.3 cm ³ / g or more, and more preferably 0.8 cm ³ / g or more.

Among (b-1), using aluminoxane as the compound that reacts with the component (A) to form an ion pair enables the production of a propylene-based polymer having a highly active and highly efficient production efficiency. Is preferable.
Further, using aluminoxane as a compound that reacts with the component (A) to form an ion pair and further using silica as a fine particle carrier produces a propylene-based polymer having a branched structure with high activity and high production efficiency. It is preferable because it can be manufactured.

(B-2) In the ion-exchangeable layered compound, it occupies most of the clay mineral, and is preferably an ion-exchangeable layered silicate.
The layered silicate is a silicate compound having a crystal structure in which surfaces formed by ionic bonds or the like are stacked in parallel with each other with a weak bonding force.
Most layered silicates are naturally produced mainly as the main component of clay minerals, but these layered silicates are not limited to those naturally produced, and may be artificial compounds.

Specific examples of layered silicates include known layered silicates described in Haruo Shiramizu's "Clay Minerals" Asakura Shoten (1995), such as dikite, nallite, kaolinite, and anoxite. , Metahalosite, Kaolinite such as Halloysite, Serpentine such as Chrysotile, Rizardite, Antigolite, Montmorillonite, Zauconite, Bidelite, Nontronite, Saponite, Teniolite, Hectrite, Smectite such as Stevensite, Vermiculite, etc. Examples include vermiculite, mica, illite, serpentine, mica such as sea green stone, attapargit, sepiolite, parigol silicate, bentonite, pyrophyllite, talc, and green mudstone. These may form a mixed layer.

Among these, montmorillonite, saponite, byderite, nontronite, saponite, hectorite, stepnsite, bentonite, teniolite and other smectites, vermiculite and mica are preferred.
Typical smectites are generally montmorillonite, biderite, saponite, nontrite, hectorite, saponite and the like. "Benclay SL" (manufactured by Mizusawa Industrial Chemicals), "Kunipia", "Smecton" (all manufactured by Kunimine Kogyo), "Montmorillonite K10" (manufactured by Aldrich, Jutehemy), "K-Catalysts series" (Jutehemy) Commercial products such as (manufactured by the company) can also be used. Typical mica tribes include muscovite, palatinite, phlogopite, biotite, and lepidrite. Commercially available products such as "Synthetic Mica Somasif" (manufactured by CO-OP CHEMICAL), "Fluorine Phlogopite", "Fluorine Four Silicon Mica", and "Teniolite" (all manufactured by Topy Industries, Ltd.) can also be used. More preferred are smectites such as "Benclay SL".
Among these, more preferably, the main component is a smectite group silicate, and even more preferably, the main component is montmorillonite.

In general, natural products are often non-ion exchangeable (non-swellable), and in that case, in order to have preferable ion exchange property (or swelling property), the ion exchange property (or swelling property) is set. It is preferable to carry out a process for imparting. Among such treatments, the following chemical treatments are particularly preferable, and these silicates are preferably those that have been chemically treated.
Here, as the chemical treatment, either a surface treatment for removing impurities adhering to the surface or a treatment for affecting the crystal structure and chemical composition of the layered silicate can be used. Specific examples thereof include (a) acid treatment, (b) alkali treatment, (c) salt treatment, and (d) organic substance treatment.

These treatments have actions such as removing impurities on the surface, exchanging cations between layers, and eluting cations such as Al, Fe, and Mg in the crystal structure, and as a result, an ion complex and a molecular composite. It can form bodies, organic derivatives, etc., and can change the surface area, interlayer distance, solid acidity, and the like. These processes may be performed alone or in combination of two or more processes.
The (a) acid used in the chemical treatment may be either an inorganic acid or an organic acid, preferably, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and the like, and the (b) alkali includes NaOH and KOH. , NH _{3 and the} like. (C) As the salts, at least selected from the group consisting of a cation containing at least one atom selected from the group consisting of groups 2 to 14 atoms and a halogen atom or an anion derived from an inorganic acid or an organic acid. A compound consisting of one type of anion is preferred.
More preferred are Li, Mg, Ca, Al, Ti, Zr, Hf, V, Nb, Ta, Cr, Mn, W, Mn, Fe, Co, Ni, Cu, Zn, B, Al, Ge or Sn. Ions derived from cations are cations, and ions derived from Cl, SO ₄ , NO ₃ , OH, C ₂ H ₄ and PO ₄ are anions. (D) Examples of organic substances include alcohols (aliphatic alcohols having 1 to 4 carbon atoms, preferably, for example, methanol, ethanol, propanol, ethylene glycol, glycerin, aromatic alcohols having 6 to 8 carbon atoms, preferably phenols), higher grades. Hydrocarbons (with 5 to 10 carbon atoms, preferably 5 to 8 carbon atoms, preferably, for example, hexane, heptane, etc.) can be mentioned. Further, formamide, hydrazine, dimethyl sulfoxide, N-methylformamide, N, N-dimethylaniline and the like are preferably mentioned. The number of salts and acids may be two or more.

When the salt treatment and the acid treatment are combined, there are a method of performing the acid treatment after the salt treatment, a method of performing the salt treatment after the acid treatment, and a method of performing the salt treatment and the acid treatment at the same time. The treatment conditions with salts and acids are not particularly limited, but usually, the salt and acid concentrations are 0.1% by weight to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to select the above and carry out under the condition that at least a part of the substance constituting the layered silicate is eluted. Further, the salts and acids can be used in an organic solvent such as toluene, n-heptane or ethanol, or if the salts and acids are liquid at the treatment temperature, they can be used without a solvent, but are preferably used as an aqueous solution. ..

The particle properties of the component (B) of the present invention can be controlled by pulverization, granulation, granulation, separation and the like. The method can be arbitrary as long as it does not interfere with catalytic performance.
In particular, regarding the granulation method, for example, spray granulation method, rolling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized layer granulation method, etc. Examples thereof include an emulsified granulation method and an in-liquid granulation method. Of the above, particularly preferable granulation methods are the spray granulation method, the rolling granulation method, and the compression granulation method.
Among the above (b-1) and (b-2), the ion-exchange layered compound of (b-2) is particularly selected from the viewpoint of being able to produce a propylene-based polymer having a highly active and highly efficient production efficiency. preferable.

3. 3. Ingredient (C)
The component (C) is an alkylaluminum compound, and preferably an organoaluminum compound represented by the following general formula (V) is used.
(AlR _n X _3-n ) _m ... General formula (V)
[In the above general formula (V), R represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen atom, a hydrogen atom, an alkoxy group or an amino group, n is 1-3, and m is 1. Represents an integer of ~ 2. ] X is preferably a chlorine atom when it is a halogen atom, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and an amino group having 1 to 8 carbon atoms when it is an amino group.
The organoaluminum compound can be used alone or in combination of two or more.
Specific examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like. Of these, trialkylaluminum and alkylaluminum hydride with m = 1 and n = 3 are preferred. More preferably, it is trialkylaluminum in which R has 1 to 8 carbon atoms.

4. Preparation of catalyst The supported catalyst for olefin polymerization according to the present invention contains the above component (A) and an inorganic carrier as essential components, and the inorganic carrier may be the above component (B), and may further contain the component (C). good.
These may be brought into contact with each other in the polymerization tank or outside the polymerization tank to perform prepolymerization in the presence of an olefin.
Contact of each catalyst component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. The contact temperature is not particularly limited, but is preferably between −20 ° C. and 150 ° C.
The contact order can be any combination for the purpose of purpose, and particularly preferable ones are as follows for each catalyst component.
When the component (C) is used, before the component (A) and the component (B) are brought into contact with each other, the component (A) or the component (B), or both the component (A) and the component (B) The component (C) is brought into contact with the component (C), or the component (A) and the component (B) are brought into contact with each other at the same time, or the component (C) is brought into contact with the component (C), or the component (A) and the component (B) are brought into contact with each other. Although it is possible to bring the component (C) into contact with the component (C) later, it is preferably a method in which the component (A) and the component (B) are brought into contact with any of the components (C) before being brought into contact with each other.
When an inorganic carrier different from the component (B) is used, an inorganic carrier may be used instead of the component (B), and a co-catalyst may be added if necessary.
Further, in the fine particle carrier containing the compound that reacts with the component (b-1) component (A) to form an ion pair, the method for containing the compound forming the ion pair in the fine particle carrier is to use the ion pair. In addition to contacting the compound to be formed with the fine particle carrier in a solvent, the fine particle carrier may be brought into contact with a mixture of the compound forming the ion pair and the component (A) first.
Further, after contacting each catalyst component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of the component (A) and the inorganic carrier used in the present invention and the amount of the components (A), (B) and (C) used are arbitrary, but the amount of the component (A) used with respect to the inorganic carrier is inorganic. It is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol with respect to 1 g of the carrier. Similarly, the amount of the component (A) used with respect to the component (B) is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol with respect to 1 g of the component (B).
The amount of the component (C) used with respect to the component (A) is preferably 0.01 to 5 × 10 ⁶ and more preferably 0.1 to 1 × 10 ^{4 in terms of the molar ratio of the transition metal of the component (A).} Is the range of.

The carrier catalyst for olefin polymerization is preferably subjected to prepolymerization consisting of contacting olefins and polymerizing in a small amount. By performing the prepolymerization treatment, it is possible to prevent the formation of a gel when the main polymerization is performed. It is considered that the reason is that the long-chain branches can be uniformly distributed among the polymer particles when the main polymerization is performed.
The olefin used during the prepolymerization is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, etc. Examples thereof include styrene, and propylene is preferable.
The olefin feeding method can be any method such as a feeding method for maintaining the olefin in the prepolymerization tank at a constant speed or a constant pressure state, a combination thereof, and a stepwise change.

The prepolymerization temperature and the prepolymerization time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C., 5 minutes to 24 hours, respectively.
As for the amount of prepolymerization, the mass ratio of the prepolymerized polymer to the component (B) is preferably 0.01 to 100, more preferably 0.1 to 50.
In addition, the component (C) can be added at the time of prepolymerization, and it is also possible to wash at the end of prepolymerization.
Further, a method such as coexistence of a polymer such as polyethylene or polypropylene or a solid of an inorganic oxide such as silica or titania is also possible at the time of or after the contact of each of the above catalyst components.
The catalyst may be dried after the prepolymerization. The drying method is not particularly limited, and examples thereof include vacuum drying, heat drying, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. good. The catalyst may be agitated, vibrated and flowed in the drying step.

II. Method for Producing Propylene-based Polymer with Branched Structure In the method for producing a propylene-based polymer having a branched structure of the present invention, propylene is polymerized or copolymerized using the olefin polymerization supporting catalyst of the present invention. It is characterized by that.
The present invention is a method for producing propylene alone or a propylene-based polymer that polymerizes propylene with ethylene and / or α-olefin, and the α-olefin referred to here is preferably an olefin having 2 to 20 carbon atoms. Yes, specifically 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene, styrene, vinylcyclohexane. , Diene, triene, cyclic olefin, etc., and may be a mixture of two or more of these.

As the polymerization mode, any mode can be adopted as long as the olefin polymerization supporting catalyst and the monomer are in efficient contact with each other.
Specifically, a slurry polymerization method using an inert solvent, a bulk polymerization method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or a gaseous state of each monomer substantially without using a liquid solvent. A vapor phase polymerization method for maintaining can be adopted.
Further, a method of performing continuous polymerization or batch polymerization is also applied.
In addition to single-stage polymerization, it is also possible to carry out multi-stage polymerization of two or more stages.

In the case of the slurry polymerization method, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene and toluene is used as the inert solvent.
The polymerization temperature is preferably 0 ° C. or higher and 150 ° C. or lower. In particular, in the case of the bulk polymerization method, 40 ° C. or higher is more preferable, and 50 ° C. or higher is more preferable. The upper limit is preferably 80 ° C. or lower, more preferably 75 ° C. or lower.
In the case of the vapor phase polymerization method, the temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher.
The upper limit is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.

The polymerization pressure is preferably 1.0 MPa or more and 5.0 MPa or less. In particular, in the case of the bulk polymerization method, 1.5 MPa or more is more preferable, and 2.0 MPa or more is more preferable. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.
In the case of the vapor phase polymerization method, 1.5 MPa or more is preferable, and 1.7 MPa or more is more preferable. The upper limit is preferably 2.5 MPa or less, more preferably 2.3 MPa or less.

Further, hydrogen can be used as an auxiliary as a molecular weight regulator. Normally, hydrogen functions as a chain transfer agent to produce saturated terminals, but in the method for producing a propylene-based polymer of the present invention, the vinyl terminal ratio is maintained high even when hydrogen is added.
Hydrogen is preferably used in a molar ratio of 1.0 × ^10-6 or more and 1.0 × ^{10-2 or less with respect to propylene, preferably 1.0 × 10-5} or more, and more preferably 1.0 × 10-5 or more. It is recommended to ^{use 1.0 × 10 -4} or more. The upper limit is preferably 0.9 × ^10-2 or less, and more preferably 0.8 × ^10-2 or less.

<Characteristics of propylene-based polymer having a branched structure>
(1) Mass average molecular weight (Mw)
The mass average molecular weight (Mw) of the propylene-based polymer produced by the production method of the present invention preferably has a lower limit of 1 × 10 ³ or more, preferably 1 × 10 ⁴ or more, from the viewpoint of melt tension. It is more preferable that the upper limit value is 1 × ¹⁰⁷ or less, and ^{more preferably 1 × 10 6} or less.
Here, the mass average molecular weight (Mw) and the number average molecular weight (Mn) are obtained by gel permeation chromatography (GPC), and the details of the measuring method and the measuring device are as follows.

Equipment: Waters GPC (ALC / GPC, 150C)
Detector: FOXBORO MIRAN, 1A, IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M / S (3)
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml

The sample is prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolving the sample at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are as shown in FIG.
Further, the conversion from the holding capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve using standard polystyrene prepared in advance. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
Brands: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximating with the least squares method.
Viscosity formula used for conversion to molecular weight: [η] = K × Mα uses the following numerical values.
PS: K = 1.38 × 10-4, α = 0.7
PP: K = 1.03 × 10-4, α = 0.78

(2) Mw / Mn
In the production method of the present invention, a propylene-based polymer produced having a ratio Mw / Mn of 2 or more of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC can be produced. When an ion-exchangeable layered silicate is used, one having a large Mw / Mn tends to be produced, which is preferable in terms of moldability. As the amount of branching increases, the high molecular weight component increases and Mw / Mn increases.

(3) Amount of long-chain branched (LCB) The propylene-based polymer produced by the production method of the present invention has a long-chain branched (LCB) structural portion represented by the following structural formula (1a).

［但し、構造式（１ａ）中、Ｐ^１、Ｐ^２、Ｐ^３はプロピレン重合体残基であり、それぞれ１つ以上のプロピレンユニットを有し、Ｃ_ｂｒは、炭素数７以上の分岐鎖の根元のメチン炭素を示し、Ｃ_ａ、Ｃ_ｂ、Ｃ_ｃは、該メチン炭素（Ｃ_ｂｒ）に隣接するメチレン炭素を示す。］

[However, in the structural formula (1a), P ¹ , P ² , and P ³ are propylene polymer residues, each having one or more propylene units, and C _br is a branched chain having 7 or more carbon atoms. The methine carbon at the root is shown, and C _a , C _b , and C _c indicate the methylene carbon adjacent to the methine carbon (C _br). ]

It is considered that the propylene-based polymer produced by the production method of the present invention has a characteristic of having a long-chain branch, and thus the melt property is remarkably improved.
In the production method of the present invention, the terminal (vinyl structure: structural formula (vinyl structure: structural formula)) is subjected to a special chain transfer reaction generally called β-methyl elimination from the component (A) of the carrier catalyst for olefin polymerization of the present invention. 2a)) macromer is generated.

In the supported catalyst for olefin polymerization of the present invention, it is presumed that this macromer is further incorporated into the component (A) in the system, and the macromer copolymerization is proceeding. Therefore, the propylene-based polymer produced by the production method of the present invention has a specific branched structure as shown in the structural formula (1a).

In formula (1a), propylene main chain of the ^polymer, P _{1 -C} br -P ^{2 lines,} 3 types of P _{1 -C} br of -P ³ lines or ^P 2 _-C br -P ³ lines Exists. Therefore, correspondingly, the C _{br −} P ³ line, the C _{br −} P ² line, or the C _{br −} P ¹ line can be the above-mentioned branched chain. P ¹ , P ² , and P ³ may contain a branched carbon (C _{br ) different from that of C br} described in the structural formula (1a) in itself.
Here, the attribution of the LCB structure is determined ^{by 13} _{C-NMR of the propylene polymer to 3 methylene carbons (C a} , 44.1 to 43.9 ppm, 44.7 to 44.5 ppm and 44.9 to 44.7 ppm). C _b , C _c ) is observed, and it is observed as methine carbon (C _br ) at 31.7 to 31.5 ppm. It is characterized in that three methylene carbons close to C _{br are observed in three non-equivalent diastereotopics.}
^{The measurement of 13} C-NMR can be carried out in the same manner as the method described for the terminal vinyl ratio described later.

The number of LCBs is the number _{of methine carbons (C br} ) at the root of a branched chain having 7 or more carbon atoms per 1000 monomer units calculated by ^{13 C-NMR.}
A branched chain having more than 6 carbon atoms and a branched chain having 6 or less carbon atoms can be distinguished by the difference in the peak position of the methine carbon at the root of the branch (Macromol.chem. Phys. 2003, Vol. 204, 1738). See page.).
In the propylene-based polymer produced by the production method of the present invention, the number of LCBs is not particularly limited, but the lower limit is 0.03 or more / 1000 monomers, preferably 0.1 from the viewpoint of improving melt properties. If the number of monomers is 1000 or more and the amount of branching is too large, gel may be formed and the appearance of the molded product may be spoiled. Therefore, the number of monomers is preferably 0.5 / 1000 or less, preferably 0.4 / More preferably, it is 1000 monomers or less.

(4) Terminal vinyl ratio The propylene-based polymer produced by the production method of the present invention has a high terminal vinyl ratio (the ratio of chains having a vinyl group at the end to the total polymer chains) represented by the following formula. The polymer can be polymerized. The terminal vinyl ratio is not particularly limited as long as a propylene-based polymer containing LCB can be produced, but the higher the terminal vinyl ratio, the higher the LCB amount tends to be. According to the carrier-based catalyst for olefin polymerization of the present invention, a propylene-based polymer having a terminal vinyl ratio of 60% or more can be produced.
(Terminal vinyl ratio) = Mn / 21000 × [Vi] × 100 (%)
(However, Mn is the number average molecular weight determined by GPC, and [Vi] is the number of terminal vinyl groups per 1000 C calculated by ^{13 C-NMR.}
Here, 1000C means 1000 total skeleton-forming carbons, and the total skeleton-forming carbon means all carbon atoms other than methyl carbon. That is, [Vi] is the number of terminal vinyl groups per 1000 total skeleton-forming carbons. )

As described above, when the complex of the component (A) in the supported catalyst for olefin polymerization of the present invention is used, a special chain transfer reaction generally called β-methyl elimination occurs, and the structural formula (2a) is described. ), It is presumed that a polymer having a propenyl structure (vinyl structure) at the end is produced.

For the terminal vinyl ratio, the following formula is used as the ratio of the 1-propenyl (vinyl) terminal concentration [Vi] obtained from ^{13 C-NMR to the total number of polymer chains obtained from the number average molecular weight (Mn) obtained from GPC.} To calculate.
(Terminal vinyl ratio) = (Mn / 42) × 2 × [Vi] / 1000 × 100 (%)
(However, Mn is a number average molecular weight determined by GPC.)

Here, the details of the method for measuring the 1-propenyl (vinyl) terminal concentration [Vi] by ^{13 C-NMR are as follows.}
After 390 mg of the sample was completely dissolved in 2.5 ml of deuterated 1,1,2,2-tetrachloroethane in an NMR sample tube (10φ), the measurement was carried out at 125 ° C. by the proton complete decoupling method. The chemical shift set the central peak of the three peaks of deuterated 1,1,2,2-tetrachloroethane to 74.2 ppm. Chemical shifts of other carbon peaks are based on this.
Flip angle: 90 degrees Pulse interval: 15 seconds Resonance frequency: 400 MHz or more Integration frequency: 2048 times or more Observation range: -20 ppm to 179 ppm
The terminal vinyl ratio of the propylene-based polymer produced by the production method of the present invention can be controlled by appropriately selecting the complex of the component (A). This selectivity can also be controlled by changing the polymerization temperature.

[Vi] is calculated as the following formula as the number of carbon 1 and carbon 2 in the structural formula (2a) for 1000 total skeleton-forming carbons by utilizing the fact that carbon 1 and carbon 2 are detected at 115.5 ppm and 137.6 ppm. do.
[Vi] = [Peak intensity of carbon 1] / [Total peak intensity of total skeleton-forming carbon] × 1000

<Use of propylene-based polymer with branched structure>
The propylene-based polymer having a branched structure produced in the present invention can be used as a molding material as pellets cut into granules after heat-melt-kneading using a melt-kneader. Then, the propylene-based polymer having a branched structure produced in the present invention includes, if necessary, known antioxidants, ultraviolet absorbers, antistatic agents, nucleating agents, lubricants, flame retardants, and antiblocking agents. , Colorants, various additives such as inorganic or organic fillers, and various synthetic resins can be blended.
These pellet-shaped molding materials are molded by various known molding methods of polypropylene, for example, injection molding, extrusion molding, foam molding, hollow molding, and industrial injection molding parts, containers, non-stretched films, and uniaxial moldings. Various molded products such as stretched films, biaxially stretched films, sheets, pipes and fibers can be manufactured.
Further, since the propylene-based polymer having a branched structure produced in the present invention has a high melt tension, the thickness is uniform in sheet molding, blow molding, etc., and the foam cell diameter is uniform in foam molding, etc. In melt spinning and the like, it can be suitably used in fields where finer fiber diameters are required.
Further, the propylene-based polymer having a branched structure produced in the present invention can also be blended with another resin and used as a modifier.

The present invention will be described in more detail in the following Examples and Comparative Examples, but the present invention is not limited thereto.
The physical property measurement, analysis, etc. in the following examples follow the following methods.

(1) Molecular weight and molecular weight distribution (Mw, Mn, Mw / Mn):
It was measured by gel permeation chromatography (GPC) by the method described herein above.
(2) LCB amount
¹³ Measured by the method described in the present specification using C-NMR.
(3) Terminal vinyl ratio
^{13 The} 1-propenyl (vinyl) terminal concentration [Vi] obtained from C-NMR is calculated by the method described in the above specification as a ratio to the total number of polymer chains obtained from the number average molecular weight (Mn) obtained from GPC. bottom.

(Example 1)
(1) Synthesis of rac-dimethylsilylenebis (2,5-dimethyl-3-phenyl-cyclopentane [b] thienyl) hafnium dichloride (complex A):
(1-a) Synthesis of 2,5-dimethyl-3-phenyl-hydrocyclopenta [b] thiophene Synthesis was carried out with reference to the method described in Example 1 of JP-A-2003-517010.
(1-b) Synthesis of dimethylbis (2,5-dimethyl-3-phenyl-hydrocyclopenta [b] thiophene) silane:
2,5-Dimethyl-3-phenyl-hydrocyclopenta [b] thiophene (8.8 g, 39 mmol) and THF (200 ml) were added to a 500 ml glass reaction vessel, and the mixture was cooled to −70 ° C. A n-butyllithium-n-hexane solution (1.55 mol / L, 25 ml, 39 mmol) was added dropwise thereto. After the dropping, the mixture was stirred for 2 hours while gradually returning to room temperature. The mixture was cooled to −70 ° C. again, 1-methylimidazole (0.15 ml, 1.9 mmol) was added, and a THF solution (30 ml) containing dimethyldichlorosilane (2.5 g, 19 mmol) was added dropwise. After the dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, and the mixture was transferred to a separating funnel and washed with saline solution until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered, the solvent was evaporated under reduced pressure, and the residue was purified on a silica gel column. White powder (9.8 g) of dimethylbis (2,5-dimethyl-3-phenyl-hydrocyclopenta [b] thiophene) silane. , Yield 99%) was obtained.

(1-c) Synthesis of rac-dimethylsilylenebis (2,5-dimethyl-3-phenyl-cyclopentane [b] thienyl) hafnium dichloride (complex A):
To a 500 ml glass reaction vessel, add dimethylbis (2,5-dimethyl-3-phenyl-hydrocyclopenta [b] thiophene) silane (6.1 g, 12 mmol) and 200 ml of diethyl ether, and in a dry ice-methanol bath. It was cooled to −70 ° C. A n-butyllithium-n-hexane solution (1.55 mol / L, 16 ml, 24 mmol) was added dropwise thereto. After the dropping, the temperature was returned to room temperature and the mixture was stirred for 2 hours. The solvent of the reaction solution was concentrated under reduced pressure to about 20 ml, 250 ml of toluene and 10 ml of THF were added, and the mixture was cooled to −70 ° C. in a dry ice-methanol bath. To that, 3.8 g (12 mmol) of hafnium tetrachloride was added.
Then, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was evaporated under reduced pressure, recrystallized from toluene / hexane, and the racemate of dimethylsilylenebis (2,5-dimethyl-3-phenyl-cyclopenta [b] thienyl) hafnium dichloride (purity 97%) represented by the following chemical formula. ) Was obtained as yellow crystals in an amount of 0.87 g (yield 10%).

The identification values of the obtained racemic mixture by proton nuclear magnetic resonance ( ¹ H-NMR) are described below.
^{1 1} H-NMR (CDCl ₃ ) identification result Racemic: δ1.06 (s, 6H), δ2.42 (s, 6H), δ2.59 (s, 6H), δ8.51 (s, 2H), δ7 .28 to δ7.33 (m, 2H), δ7.39 to δ7.43 (m, 4H), δ7.46 to δ7.50 (m, 4H)

(2) Preparation of catalyst (2-a) Chemical treatment of ion-exchangeable layered silicate (clay carrier) 96% sulfuric acid (1044 g) was added to 3456 g of distilled water in a separable flask. Granulated montmorillonite (600 g, Benclay SL manufactured by Mizusawa Industrial Chemicals, Inc .: average particle size 19 μm) was added thereto as an ion-exchangeable layered silicate. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./min and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, 2400 g of distilled water was added, and the mixture was filtered to obtain 1230 g of a cake-like solid.
Next, 648 g of lithium sulfate and 1800 g of distilled water were added to a separable flask to prepare an aqueous solution, and the entire amount of the solid on the cake was added, and 522 g of distilled water was further added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./min and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, 1980 g of distilled water was added, and the mixture was filtered. The mixture was washed with distilled water to pH 3 and filtered to obtain 1150 g of a cake-like solid.
The obtained solid was pre-dried at 130 ° C. under a nitrogen stream for 2 days, then coarse particles of 53 μm or more were removed, and then rotary kiln-dried at 215 ° C. under a nitrogen stream for a residence time of 10 minutes to chemically treat montmorillonite. 340 g was obtained.

(2-b) Preparation of clay-supported catalyst 1 g of the chemically treated montmorillonite obtained above was placed in a 100 ml glass flask, and 6.5 ml of heptane was added to prepare a slurry, to which a triisobutylaluminum-n-heptane solution (140 mg / ml) was prepared. , 3.5 ml) was added and stirred for 1 hour. Then, it was washed with heptane to 1/1000 to make the total volume 5 ml. To this, a tri-n-octyl aluminum-n-heptane solution (140 mg / ml, 0.6 ml) was added, and the mixture was contacted at room temperature for 15 minutes. Then, a solution of complex A (12 mg, 15 μmol) and 3 ml of toluene was added, and the mixture was contacted at room temperature for 1 hour. Then, heptane was added to adjust the concentration to 40 mg-clay / ml to prepare a clay-supported catalyst slurry.

(3) Polymerization A 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 1000 mL of heptane was introduced. A triisobutylaluminum-n-heptane solution (140 mg / ml, 5.6 ml) was added thereto, and the temperature was raised to 70 ° C. Propylene was pressurized to 0.5 MPa, and the clay-supported catalyst slurry (2 ml, 80 mg-clay) prepared above was press-fitted. The propylene pressure was maintained at 0.5 MPa and polymerization was carried out for 1 hour. Then, ethanol was press-fitted and then depressurized, and the polymer was filtered, decalcified, dried and recovered. 29.3 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

(Example 2)
(1-a) Preparation of MAO / Silica Carrier Add silica fine particles (6.8 g, average particle size 45 μm, surface area 315 m ² / g, pore volume 1.5 cm ³ / g) to a 1 L glass three-necked flask. , 150 ° C., dried under reduced pressure for 1 hour. Toluene (45 ml) and a methylalmoxane (MAO) -toluene solution (39 ml, manufactured by Albemarle Corporation, 3 mol-Al / L) were sequentially added thereto, and the mixture was contacted at 40 ° C. for 1 hour. Then, it was dried under reduced pressure at 40 ° C. for 1 hour to obtain 14 g of MAO / silica carrier.

(1-b) Preparation of MAO / Silica-Supported Catalyst 1 g of the MAO / silica carrier obtained above and 6.5 ml of heptane were added to a 100 ml glass flask to prepare a slurry. A triisobutylaluminum-n-heptane solution (140 mg / ml, 0.3 ml) was added thereto, and the mixture was contacted at room temperature for 5 minutes. Then, a solution of complex A (12 mg, 15 μmol) and 3 ml of toluene was added, and the mixture was contacted at room temperature for 1 hour.
Then, heptane was added to adjust the concentration to 40 mg-clay / ml to prepare a MAO / silica-supported catalyst slurry.

(2) Polymerization A 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 1000 mL of heptane was introduced. A triisobutylaluminum-n-heptane solution (140 mg / ml, 5.6 ml) was added thereto, and the temperature was raised to 70 ° C. Propylene was pressurized to 0.5 MPa and the previously prepared MAO / silica-supported catalyst slurry (15 mL, 600 mg-carrier) was press-fitted. The propylene pressure was maintained at 0.5 MPa and polymerization was carried out for 30 minutes. Then, ethanol was press-fitted and then depressurized, and the polymer was filtered, decalcified, dried and recovered. 17.3 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

(Comparative Example 1)
(1) Preparation of MAO homogeneous catalyst solution Complex A (21 mg, 30 μmol) and 20 ml of toluene were added to a 100 ml glass flask to prepare a solution. A MAO-n-hexane solution (10 mL, manufactured by Tosoh Finechem Co., Ltd., MMAO3A, 5.9 wt% -Al) was added thereto, and the mixture was stirred for 30 minutes to prepare a MAO homogeneous catalyst solution.

(2) Polymerization A 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 1000 mL of heptane was introduced. A triisobutylaluminum-n-heptane solution (140 mg / ml, 5.6 ml) was added thereto, and the temperature was raised to 70 ° C. Propylene was pressurized to 0.5 MPa, and the previously prepared MAO homogeneous catalyst solution (20 mL, 18 μmol) was press-fitted. The propylene pressure was maintained at 0.5 MPa and polymerization was carried out for 20 minutes. Then, ethanol was press-fitted and then depressurized, and the polymer was filtered, decalcified, dried and recovered. 82 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

(Comparative Example 2)
(1) Synthesis of rac-dimethylsilylenebis (2,5-dimethyl-3-phenyl-cyclopentane [b] thienyl) zirconium dichloride (complex B):
To a 500 ml glass reaction vessel, add dimethylbis (2,5-dimethyl-3-phenyl-hydrocyclopenta [b] thiophene) silane (9.8 g, 19 mmol) and 300 ml of diethyl ether, and in a dry ice-methanol bath. It was cooled to −70 ° C. A n-butyllithium-n-hexane solution (1.55 mol / L, 25 ml, 39 mmol) was added dropwise thereto. After the dropping, the temperature was returned to room temperature and the mixture was stirred for 2 hours. The solvent of the reaction solution was distilled off under reduced pressure, 300 ml of toluene and 15 ml of diethyl ether were added, and the mixture was cooled to −70 ° C. in a dry ice-methanol bath. To that, 4.5 g (19 mmol) of zirconium tetrachloride was added. Then, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallization was performed with toluene / hexane, and a racemate of dimethylsilylenebis (2,5-dimethyl-3-phenyl-cyclopenta [b] thienyl) hafnium dichloride represented by the following chemical formula (purity 98%). ) Was obtained as yellow crystals in an amount of 4.6 g (yield 36%).

The identification values of the obtained racemic mixture by proton nuclear magnetic resonance ( ¹ H-NMR) are described below.
^{1 1} H-NMR (CDCl ₃ ) identification result Racemic: δ1.07 (s, 6H), δ2.33 (s, 6H), δ2.54 (s, 6H), δ6.60 (s, 2H), δ7 .29 to δ7.33 (m, 2H), δ7.40 to δ7.44 (m, 4H), δ7.48 to δ7.51 (m, 4H)

(2) Preparation of clay-supported catalyst 1 g of the chemically treated montmorillonite obtained in Example 1 was placed in a 100 ml glass flask, and 6.5 ml of heptane was added to prepare a slurry, which was prepared with a triisobutylaluminum-n-heptane solution (140 mg / ml). , 3.5 ml) was added and stirred for 1 hour. Then, it was washed with heptane to 1/1000 to make the total volume 5 ml. To this, a tri-n-octyl aluminum-n-heptane solution (140 mg / ml, 0.6 ml) was added, and the mixture was contacted at room temperature for 15 minutes. Then, a solution of complex B (10 mg, 15 μmol) and 3 ml of toluene was added, and the mixture was contacted at room temperature for 1 hour. Then, heptane was added to adjust the concentration to 40 mg-clay / ml to prepare a clay-supported catalyst slurry.

(3) Polymerization A 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 1000 mL of heptane was introduced. A triisobutylaluminum-n-heptane solution (140 mg / ml, 5.6 ml) was added thereto, and the temperature was raised to 70 ° C. Propylene was pressurized to 0.5 MPa, and the clay-supported catalyst slurry (3 ml, 120 mg-clay) prepared above was press-fitted. The propylene pressure was maintained at 0.5 MPa and polymerization was carried out for 1 hour. Then, ethanol was press-fitted and then depressurized, and the polymer was filtered, decalcified, dried and recovered. 24.5 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

(Comparative Example 3)
(1) Preparation of MAO / silica-supported catalyst 1 g of the MAO / silica carrier obtained in Example 2 and 6.5 ml of heptane were added to a 100 ml glass flask to prepare a slurry. A triisobutylaluminum-n-heptane solution (140 mg / ml, 0.3 ml) was added thereto, and the mixture was contacted at room temperature for 5 minutes. Then, a solution of complex B (10 mg, 15 μmol) and 3 ml of toluene was added, and the mixture was contacted at room temperature for 1 hour. Then, heptane was added to adjust the concentration to 20 mg-clay / ml to prepare a MAO / silica-supported catalyst slurry.

(2) Polymerization A 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 1000 mL of heptane was introduced. A triisobutylaluminum-n-heptane solution (140 mg / ml, 5.6 ml) was added thereto, and the temperature was raised to 70 ° C. Propylene was pressurized to 0.5 MPa and the previously prepared MAO / silica-supported catalyst slurry (3 mL, 60 mg-carrier) was press-fitted. The propylene pressure was maintained at 0.5 MPa and polymerization was carried out for 30 minutes. Then, ethanol was press-fitted and then depressurized, and the polymer was filtered, decalcified, dried and recovered. 3.4 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

(Example 3)
(1) Synthesis of rac-dimethylsilylenebis (5-methyl-3-phenyl-cyclopentane [b] thienyl) hafnium dichloride (complex C):
(1-a) Synthesis of 5-methyl-3-phenyl-hydrocyclopenta [b] thiophene Synthesis was carried out with reference to the method described in Example 1 of JP-A-2003-517010.
(1-b) Synthesis of dimethylbis (5-methyl-3-phenyl-hydrocyclopenta [b] thiophene) silane:
5-Methyl-3-phenyl-hydrocyclopenta [b] thiophene (5.0 g, 24 mmol) and THF (100 ml) were added to a 500 ml glass reaction vessel, and the mixture was cooled to −70 ° C. A n-butyllithium-n-hexane solution (1.57 mol / L, 15 ml, 24 mmol) was added dropwise thereto. After the dropping, the mixture was stirred for 2 hours while gradually returning to room temperature. The mixture was cooled to −70 ° C. again, 1-methylimidazole (0.15 ml, 1.9 mmol) was added, and dimethyldichlorosilane (1.4 ml) was added dropwise. After the dropping, the mixture was stirred for 1.5 hours while gradually returning to room temperature. Distilled water was added to the reaction solution, and the mixture was transferred to a separating funnel and washed with saline solution until neutral. Magnesium sulfate was added thereto, and the reaction solution was dried. After filtering anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product (5.6 g) of dimethylbis (5-methyl-3-phenyl-hydrocyclopenta [b] thiophene) silane.

(1-c) Synthesis of rac-dimethylsilylenebis (5-methyl-3-phenyl-cyclopentane [b] thienyl) hafnium dichloride (complex C):
Crude product of dimethylbis (5-dimethyl-3-phenyl-hydrocyclopenta [b] thiophene) silane (5.6 g, 12 mmol), diethyl ether (40 ml) and toluene (40 ml) in a 500 ml glass reaction vessel. Was added, the mixture was cooled in an ice bath, and an n-butyllithium-n-hexane solution (1.57 mol / L, 15 ml) was added dropwise thereto. After the dropping, the temperature was returned to room temperature and the mixture was stirred for 1 hour. Toluene (160 ml) was added to the reaction mixture, and the mixture was cooled to −70 ° C. in a dry ice-acetone bath. Hafnium tetrachloride (3.8 g, 12 mmol) was added thereto, the temperature was raised to room temperature, and the mixture was stirred for 2 hours.
The solvent was distilled off under reduced pressure, toluene was extracted, and then methylene chloride-hexane mixed solution extraction was performed. 0.4 g of a mixture of racemates was obtained as yellow crystals.

The identification values of the obtained mixture of racemate and meso by proton nuclear magnetic resonance ( ¹ H-NMR) are described below.
^{1 1} H-NMR (CDCl ₃ ) identification result Racemic: δ1.11 (s, r-body 6H), δ1.16 (s, m-body 3H), δ1.22 (s, m-body 3H), δ2 .44 (s, r-body 6H), δ2.54 (s, m-body 6H), δ6.70 (s, m-body 2H), δ6.81 (s, r-body 2H) δ7.2 δ7.6 (m, r-body 6H, m-body 6H)

(2) Preparation of clay-supported catalyst 1 g of the chemically treated montmorillonite obtained in Example 1 was placed in a 100 ml glass flask, and 6.5 ml of heptane was added to prepare a slurry, which was prepared with a triisobutylaluminum-n-heptane solution (140 mg / ml). , 3.5 ml) was added and stirred for 1 hour. Then, it was washed with heptane to 1/1000 to make the total volume 5 ml. To this, a tri-n-octyl aluminum-n-heptane solution (140 mg / ml, 0.6 ml) was added, and the mixture was contacted at room temperature for 15 minutes. Then, a solution of complex C (11 mg, 15 μmol) and 3 ml of toluene was added, and the mixture was contacted at room temperature for 1 hour. Then, heptane was added to adjust the concentration to 40 mg-clay / ml to prepare a clay-supported catalyst slurry.

(3) Polymerization A 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 1000 mL of heptane was introduced. A triisobutylaluminum-n-heptane solution (140 mg / ml, 5.6 ml) was added thereto, and the temperature was raised to 70 ° C. Propylene was pressurized to 0.5 MPa, and the clay-supported catalyst slurry (4 ml, 160 mg-clay) prepared above was press-fitted. The propylene pressure was maintained at 0.5 MPa and polymerization was carried out for 1 hour. Then, ethanol was press-fitted and then depressurized, and the polymer was filtered, decalcified, dried and recovered. 50.7 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

(Example 4)
(1) Synthesis of rac-dimethylsilylenebis (2,5-dimethyl-3- (3,5-dimethyl-phenyl) -cyclopentane [b] thienyl) hafnium dichloride (complex D):
(1-a) Synthesis of 2,5-dimethyl-3- (3,5-dimethylphenyl) -hydrocyclopenta [b] thiophene Synthesized with reference to the method described in Example 1 of JP-A-2003-517010. Was done.
(1-b) Synthesis of dimethylbis (2,5-dimethyl-3- (3,5-dimethylphenyl) -hydrocyclopenta [b] thiophene) silane:
To a 500 ml glass reaction vessel, 2,5-dimethyl-3- (3,5-dimethylphenyl) -hydrocyclopenta [b] thiophene (6.6 g, 26 mmol) and THF (100 ml) were added, and the temperature was −70 ° C. Cooled to. A n-butyllithium-n-hexane solution (1.57 mol / L, 16.6 ml) was added dropwise thereto. After the dropping, the mixture was stirred for 2 hours while gradually returning to room temperature. The mixture was cooled to −70 ° C. again, 1-methylimidazole (0.15 ml, 1.9 mmol) was added, and dimethyldichlorosilane (1.1 ml, 13 mmol) was added dropwise. After the dropping, the mixture was stirred for 2 hours while gradually returning to room temperature.
Distilled water was added to the reaction solution, and the mixture was transferred to a separating funnel and washed with saline solution until neutral. Magnesium sulfate was added thereto, and the reaction solution was dried. Anhydrous magnesium sulfate was filtered, the solvent was evaporated under reduced pressure, and a crude product of dimethylbis (2,5-dimethyl-3- (3,5-dimethylphenyl) -hydrocyclopenta [b] thiophene) silane (7 g). Got

(1-c) Synthesis of rac-dimethylsilylenebis (2,5-dimethyl-3- (3,5-dimethylphenyl) -cyclopentane [b] thienyl) hafnium dichloride (complex D):
Crude product of dimethylbis (2,5-dimethyl-3- (3,5-dimethylphenyl) -hydrocyclopenta [b] thiophene) silane (7 g), diethyl ether (150 ml) in a 500 ml glass reaction vessel. Was added, and the mixture was cooled to −70 ° C. in a dry ice-acetone bath. A n-butyllithium-n-hexane solution (1.57 mol / L, 16.6 ml, 26 mmol) was added dropwise thereto. After the dropping, the temperature was returned to room temperature and the mixture was stirred for 2 hours. The solvent was distilled off under reduced pressure, methylene chloride (150 ml) was added, and the mixture was cooled to −50 ° C. in a dry ice-acetone bath. 4.2 g (13 mmol) of hafnium tetrachloride was added thereto, the temperature was raised to room temperature, and the mixture was stirred for 2 hours.
The solvent was distilled off under reduced pressure, washed with toluene, extracted with methylene chloride, and dimethylsilylenebis (2,5-dimethyl-3- (3,5-dimethylphenyl) -cyclopenta [b] thienyl) hafnium dichloride represented by the following chemical formula. 1.0 g (yield 9%) of the racemic mixture was obtained as yellow crystals.

The identification values of the obtained racemic mixture by proton nuclear magnetic resonance ( ¹ H-NMR) are described below.
^{1 1} H-NMR (CDCl ₃ ) identification result Racemic: δ1.03 (s, 6H), δ2.32 (s, 12H), δ2.41 (s, 6H), δ2.56 (s, 6H), δ6 .49 (s, 2H), δ6.93 (s, 2H), δ7.08 (s, 4H)

(2) Preparation of clay-supported catalyst 1 g of the chemically treated montmorillonite obtained in Example 1 was placed in a 100 ml glass flask, and 6.5 ml of heptane was added to prepare a slurry, which was prepared with a triisobutylaluminum-n-heptane solution (140 mg / ml). , 3.5 ml) was added and stirred for 1 hour. Then, it was washed with heptane to 1/1000 to make the total volume 5 ml. To this, a tri-n-octyl aluminum-n-heptane solution (140 mg / ml, 0.6 ml) was added, and the mixture was contacted at room temperature for 15 minutes. Then, a solution of complex D (12 mg, 15 μmol) and 3 ml of toluene was added, and the mixture was contacted at room temperature for 1 hour. Then, heptane was added to adjust the concentration to 40 mg-clay / ml to prepare a clay-supported catalyst slurry.

(3) Polymerization A 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 1000 mL of heptane was introduced. A triisobutylaluminum-n-heptane solution (140 mg / ml, 5.6 ml) was added thereto, and the temperature was raised to 70 ° C. Propylene was pressurized to 0.5 MPa, and the clay-supported catalyst slurry (2 ml, 80 mg-clay) prepared above was press-fitted. The propylene pressure was maintained at 0.5 MPa and polymerization was carried out for 1 hour. Then, ethanol was press-fitted and then depressurized, and the polymer was filtered, decalcified, dried and recovered. 8.4 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

(Comparative Example 4)
(1) Preparation of MAO homogeneous catalyst solution Complex C (10 mg, 14 μmol) and 10 ml of toluene were added to a 100 ml glass flask to prepare a solution. A MAO-n-hexane solution (10 mL, manufactured by Tosoh Finechem, MMAO3A, 5.9 wt% -Al) was added thereto, and the mixture was stirred for 30 minutes, and toluene was added thereto to obtain 0.3 μmol-Hf / ml. To prepare a MAO homogeneous catalyst solution.

(2) Polymerization A 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 1000 mL of heptane was introduced. A triisobutylaluminum-n-heptane solution (140 mg / ml, 5.6 ml) was added thereto, and the temperature was raised to 70 ° C. Propylene was pressurized to 0.5 MPa, and the MAO homogeneous catalyst solution (4 mL, 1.2 μmol) prepared above was press-fitted. The propylene pressure was maintained at 0.5 MPa and polymerization was carried out for 1 hour. Then, ethanol was press-fitted and then depressurized, and the polymer was filtered, decalcified, dried and recovered. 0.6 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

(Comparative Example 5)
(1) Preparation of MAO homogeneous catalyst solution Complex D (11 mg, 14 μmol) and 10 ml of toluene were added to a 100 ml glass flask to prepare a solution. A MAO-n-hexane solution (10 mL, manufactured by Tosoh Finechem, MMAO3A, 5.9 wt% -Al) was added thereto, and the mixture was stirred for 30 minutes, and toluene was added thereto to obtain 0.3 μmol-Hf / ml. To prepare a MAO homogeneous catalyst solution.

(2) Polymerization A 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 1000 mL of heptane was introduced. A triisobutylaluminum-n-heptane solution (140 mg / ml, 5.6 ml) was added thereto, and the temperature was raised to 70 ° C. Propylene was pressurized to 0.5 MPa, and the MAO homogeneous catalyst solution (4 mL, 1.2 μmol) prepared above was press-fitted. The propylene pressure was maintained at 0.5 MPa and polymerization was carried out for 1 hour. Then, ethanol was press-fitted and then depressurized, and the polymer was filtered, decalcified, dried and recovered. 1.1 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

表中、「n.d.」とは、検出限界未満を意味する。

In the table, "nd" means below the detection limit.

[Discussion]
As is clear from Table 1, the propylene-based polymers of Examples 1 and 2 produced using the carrying catalyst for olefin polymerization of the present invention have terminal vinyl ratios of 64% and 71%, and the polymer ends. Is a polymer controlled to have a vinyl structure, and the amount of long-chain branched (LCB) is 0.2 / 1000 monomer and 0.3 / 1000 monomer. In Examples 1 and 2, propylene having a branched structure is used. It is shown that the system polymer is produced.
On the other hand, in Comparative Example 1, the complex A having the same component (A) as in Example was used, but propylene polymerization was carried out by using it as a homogeneous catalyst combined with methylaluminoxane (MAO) without supporting it on an inorganic carrier. As a result, the terminal vinyl ratio was 70%, but the amount of long-chain branched (LCB) was less than the detection limit, and the production of a propylene-based polymer having a branched structure was not shown.
Further, in Comparative Examples 2 and 3, since a zirconium complex having a cyclopenta [b] thienyl group was used as in the technique of Patent Document 7, propylene polymerization was carried out using a catalyst supported on an inorganic carrier as in the examples. However, the terminal vinyl ratio was as low as 21% and 25%, the amount of long-chain branched (LCB) was below the detection limit, and the production of a propylene-based polymer having a branched structure was not shown.
Further, the propylene-based polymers of Examples 3 to 4 produced by using the carrying catalyst for olefin polymerization of the present invention have terminal vinyl ratios of 84% and 53%, and the polymer terminals are controlled to have a vinyl structure. The polymer has a long-chain branched (LCB) amount of 0.3 / 1000 monomers and 0.1 / 1000 monomers, and in Examples 3 to 4, propylene-based polymers having a branched structure are produced. It is shown that
On the other hand, in Comparative Examples 4 and 5, the complex C or complex D of the same component (A) as in Examples 3 and 4 was used, but it was used as a homogeneous catalyst in combination with MAO without being supported on an inorganic carrier. Since the propylene polymerization was carried out, the terminal vinyl ratio was as low as 63% or 44%, the amount of long-chain branched (LCB) was less than the detection limit, and the production of a propylene-based polymer having a branched structure was not shown.

By using the supported catalyst for olefin polymerization of the present invention, it is possible to produce a propylene-based polymer in which the terminal structure is highly controlled so as to contain a vinyl terminal structure in a high proportion, and the branched structure can be efficiently formed. A propylene-based polymer having a propylene polymer can be produced. The propylene-based polymer having a branched structure produced in the present invention has an improved melt tension, and can be used for sheet molding, blow molding, thermoforming, foam molding, etc., which require a material having a relatively high melt tension. Expected to be applied.

Claims (11)

A carrier-based catalyst for olefin polymerization, wherein the following component (A) is supported on an inorganic carrier.
Component (A): Metallocene complex represented by the following general formula [I]

(Q is a carbon atom, a silicon atom or a germanium atom,
X ¹ and X ² are independently halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, alkyl groups having 1 to 6 carbon atoms substituted with halogen atoms, and carbon atoms. An amino group substituted with an alkyl group of 1 to 6, an aryl group having 6 to 18 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 6 carbon atoms substituted with a halogen atom. It is an aryl group of 18.
R ¹ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a frill group which may be substituted, or may be substituted. It is a thienyl group.
^{R 2, R 3, R 12} , and ^{R 13} are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon substituted with a halogen atom Alkyl groups of numbers 1 to 6, alkyl groups having 1 to 6 carbon atoms substituted with trialkylsilyl groups, silyl groups substituted with hydrocarbon groups of 1 to 6 carbon atoms, hydrocarbon groups having 1 to 6 carbon atoms Aryl group having 6 to 18 carbon atoms substituted with, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, a frill group optionally substituted, or a thienyl group optionally substituted with Is.
R ⁴ and R ¹⁴ independently have an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, and an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group. It is an alkyl group, an aryl group having 6 to 18 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms substituted with a halogen atom.
Further, ^{both R 4} and R ¹⁴ may form a 4- to 7-membered ring including Q. ) In the general formula [I], the R ¹ and R ¹¹ are independently an alkyl group having 1 to 6 carbon atoms, a frill group which may be substituted, or a thienyl group which may be substituted. The supported catalyst for olefin polymerization according to claim 1, wherein the catalyst is provided. In the general formula [I], the R ² and R ¹² are independently substituted with an alkyl group having 1 to 6 carbon atoms and a hydrocarbon group having 1 to 6 carbon atoms, respectively. The carrying catalyst for olefin polymerization according to claim 1 or 2, wherein the aryl group has 6 to 18 or an aryl group having 6 to 18 carbon atoms substituted with a halogen atom. In the general formula [I], the R ² , R ³ , R ¹² and R ¹³ are independently substituted with an alkyl group having 1 to 6 carbon atoms and a hydrocarbon group having 1 to 6 carbon atoms, respectively. The olefin polymerization according to any one of claims 1 to 3, wherein the aryl group may have 6 to 18 carbon atoms, or the aryl group has 6 to 18 carbon atoms substituted with a halogen atom. Support system catalyst for. The carrier catalyst for olefin polymerization according to any one of claims 1 to 4, wherein the inorganic carrier is the following component (B) and further contains (C).
Component (B): A compound that reacts with a solid component (b-1) component (A) containing at least one selected from the group consisting of the following (b-1) and (b-2) to form an ion pair. Fine particle carrier (b-2) ion-exchangeable layered compound component (C): alkylaluminum compound The carrier-based catalyst for olefin polymerization according to claim 5, wherein the component (B) contains an almoxane compound or an ion-exchangeable layered silicate. The carrier catalyst for olefin polymerization according to claim 5 or 6, wherein the component (B) is (b-1) and contains an alkoxane compound. The carrier catalyst for olefin polymerization according to claim 7, wherein the component (B) is (b-1) and the fine particle carrier is silica. The carrier catalyst for olefin polymerization according to claim 5 or 6, wherein the component (B) is (b-2) an ion-exchangeable layered silicate. The carrier-based catalyst for olefin polymerization according to claim 9, wherein the ion-exchangeable layered silicate (b-2) is montmorillonite. A method for producing a propylene-based polymer having a branched structure, which comprises polymerizing or copolymerizing propylene using the carrier-based catalyst for olefin polymerization according to any one of claims 1 to 10.

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