Metallocene complex, olefin polymerization catalyst, and method for producing propylene-based polymer using olefin polymerization catalyst

Abstract

To provide a metallocene complex and an olefin polymerization catalyst enabling production of a macromer with a high vinyl selectivity (number of terminal vinyl groups / (number of terminal vinyl groups+number of terminal vinylidene groups)) in an unsaturated structure in a terminal structure of a polymer, a suitable low molecular weight, and a broad melting point range, and also to provide a method for producing a propylene-based polymer using the same.SOLUTION: A metallocene complex represented by following General Formula [I] (where M is zirconium or hafnium, Y is a carbon atom or a silicon atom, and X1 and X2 are each independently a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, or a C6-10 aryl group which may be substituted).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a metallocene complex, an olefin polymerization catalyst, and a method for producing a propylene polymer using the olefin polymerization catalyst. [Background technology]

[0002] Polypropylene has high chemical stability, excellent mechanical properties, and is inexpensive, making it widely used in everyday life and industrial materials. Furthermore, attempts to improve the functionality of polypropylene, which contains unsaturated bonds, are being investigated by taking advantage of the reactivity resulting from the unsaturated bonds.

[0003] Introducing a branched structure into polypropylene can impart a relatively high melt tension, and various methods for introducing branched structures are being investigated to improve its suitability for sheet molding, blow molding, thermoforming, foam molding, and other processes.

[0004] A macromer copolymerization method using a metallocene catalyst has been proposed as a method for introducing branched structures. Branched polypropylene obtained by this macromer copolymerization method has advantages over polypropylene in which branched structures are introduced by electron beam irradiation, such as less gel generation due to crosslinking reactions.

[0005] As such a macromer copolymerization method, for example, a method has been proposed in which a propylene macromer having a vinyl structure at its terminal is produced using a specific catalyst and specific polymerization conditions in the first polymerization stage (macromer synthesis step), and then propylene and the propylene macromer are copolymerized using a specific catalyst and specific polymerization conditions in the second polymerization stage (macromer copolymerization step). It has been shown that the resulting branched polypropylene has high melt strength and melt tension (see, for example, Patent Document 1).

[0006] Patent Document 2 discloses a method for producing a vinyl-terminated propylene polymer with high activity, which has a low molecular weight, high stereoregularity, a high vinyl-terminated ratio, and good particle properties, by homopolymerizing or copolymerizing propylene using an olefin polymerization catalyst containing a specific metallocene catalyst to produce a propylene polymer with a number-average molecular weight measured by GPC of less than 50,000 and a vinyl-terminated ratio of 0.7 or more.

[0007] Patent Document 3 discloses a method for using, as a catalyst component, a metallocene compound having a specific substitution pattern at the 2-, 3-, and 4-positions of at least one indenyl group or at a sterically corresponding position of a cyclopentadienyl derivative, in ethylene / propylene copolymerization, with the aim of improving ethylene copolymerizability and increasing the molecular weight.

[0008] Patent Document 4 discloses polypropylene with a weight-average molecular weight of 20,000 to 70,000 g / mol, a stereoregularity (mmmm) of less than 30%, and a terminal vinyl group content of 0.6 mol% or more, with the aim of providing a polypropylene having a high vinyl end group content, a low vinylidene end group content, and good melt strength properties. It also discloses a method for producing the polypropylene, which comprises polymerizing propylene monomer in the presence of a catalyst composition containing a transition metal compound having two indenyl ligands. It also discloses that the number of terminal vinyl groups is increased by adjusting the carbon number of the substituent at the 3-position of one of the indenyl ligands in the transition metal compound having two indenyl ligands to 3 or more.

[0009] Patent Document 5 discloses a metallocene complex in which at least one of two indenyl ligands is substituted with a cyclopropyl substituent, and the indenyl ligand substituted with the cyclopropyl substituent is further substituted with at least one substituent, for the purpose of increasing the melting point and molecular weight of the polymer, as well as the activity and comonomer content. One preferred embodiment of the metallocene complex is a metallocene complex having a cyclopropyl group at at least one of the 2-, 4-, and 6-positions of the indenyl ligand. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Special Publication No. 2001-525460 [Patent Document 2] Japanese Patent Application Laid-Open No. 2018-193476 [Patent Document 3] Special Publication No. 2005-529185 [Patent Document 4] Korean Publication No. 2022-0017201 [Patent Document 5] International Publication No. 2015 / 009473 Summary of the Invention [Problem to be solved by the invention]

[0011] As described above, vinyl-terminated propylene polymers are expected to be used as macromers and as raw materials for functionalization such as maleation. The above-mentioned compounds obtained by functionalizing the vinyl-terminated propylene polymer are considered to be suitable for applications such as paints and primers. In such applications, it is preferable that the compounds obtained by functionalizing the vinyl-terminated propylene polymer be soluble in solvents and have high affinity with other substrates. In order to improve solubility in solvents and affinity with other substrates, it is desirable that the compounds obtained by functionalizing the vinyl-terminated propylene polymer and the vinyl-terminated propylene polymer used as the raw material have low molecular weights. Furthermore, it is desirable that the vinyl-terminated propylene polymer also has a low molecular weight as a macromer. This is because a high molecular weight macromer is not suitable for use because the macromer becomes a side chain moiety. Furthermore, for applications requiring transparency and flexibility, propylene-based polymers with low melting points are required. Since the desired melting points vary depending on the application, there is a demand for metallocene complexes that can be used as catalysts to produce propylene-based polymers with a wide range of melting points.

[0012] The specific metallocene complex disclosed in Patent Document 2 has a high stereoregularity (high melting point), as shown in the comparative example described later, and the vinyl selectivity (number of terminal vinyl groups / (number of terminal vinyl groups+number of terminal vinylidene groups)) in the unsaturated structure in the terminal structure of the polymer is still insufficient, making it difficult to obtain a propylene polymer with a low melting point. Therefore, the propylene polymer obtained therefrom cannot be used in applications requiring a low melting point. Furthermore, Patent Document 3 discloses a metallocene complex (Example 5) in which one of the two indenyl ligands has a methyl group at both the 2- and 3-positions, and the other has a methyl group at the 2-position and is unsubstituted at the 3-position, and a metallocene complex (Example 7) in which one of the two indenyl ligands has a methyl group at both the 2- and 3-positions, and the other has an isopropyl group at the 2-position and is unsubstituted at the 3-position. However, in propylene polymerization using these metallocene complexes (Examples 11 and 12), high molecular weight polymers with weight-average molecular weights Mw exceeding 200,000 were obtained. Although the terminal structure of the polymers is not described, and the terminal vinyl ratio, etc., are unknown, the high molecular weight polymers suggest that β-hydrogen elimination is suppressed in propylene polymerization using these metallocene complexes. However, due to their high molecular weights, such polymers are unsuitable as macromers.

[0013] Furthermore, Patent Document 4 discloses a metallocene complex in a comparative example (Comparative Example 8) in which one of the two indenyl ligands has methyl groups at the 2- and 3-positions and the other has an isopropyl group at the 2-position, but it is shown that the vinyl selectivity is low. Thus, it is described that substitution of a methyl group at the 3-position of one of the indenyl ligands reduces vinyl terminals and predominantly increases vinylidene terminals. Furthermore, Patent Document 4 adjusts the molecular weight to be low by hydrogenation, but this is inappropriate because it is expected to increase saturated terminals and reduce the amount of vinyl terminals. There is a demand for metallocene complexes that can produce low molecular weight compounds without using hydrogen. Furthermore, Patent Document 5 discloses a metallocene complex in which both 2-positions of two indenyl ligands are cyclopropyl groups and both 3-positions are unsubstituted, and a metallocene complex in which one of two indenyl ligands is methyl group at the 2-position and the other is cyclopropyl group at the 2-position and both 3-positions are unsubstituted. However, Patent Document 5 aims to increase the melting point and molecular weight of the polymer, as well as the activity and comonomer content, and suggests that introducing a cyclopropyl group at the 2-position is also for that purpose.

[0014] The metallocene complexes of the prior art described above are still insufficient for producing propylene polymers with high vinyl selectivity, a moderately low molecular weight, and a wide melting point range. The present invention aims to provide a metallocene complex capable of producing a propylene polymer having a high vinyl selectivity in unsaturated structures in the terminal structures of the polymer, a moderately low molecular weight, and a wide melting point range; an olefin polymerization catalyst containing the metallocene complex; and a method for producing a propylene polymer using the same. [Means for solving the problem]

[0015] As a result of extensive research to solve the above problems, the present inventors have found that in a metallocene complex having a bridged bisindene skeleton, one indenyl ligand is bonded to the second position (R 11 ) has a cyclic substituent with moderate bulkiness, the 3-position is unsubstituted, and the other indenyl ligand is at the 3-position (R 2 ) and has a specific substituent at the 2-position (R 1 ) have found that when propylene is polymerized using a catalyst containing a metallocene complex that is unsubstituted or has a specific substituent, it is possible to produce a propylene-based polymer that has a high vinyl selectivity in the unsaturated structure at the terminal structure of the polymer, a moderately low molecular weight, a low melting point, and a wide melting point range, and has completed the present invention. That is, the present invention includes the following aspects.

[0016] <1> A metallocene complex represented by the following general formula [I]:

[0017] [ka] (In formula [I], M is zirconium or hafnium; Y is a carbon atom or a silicon atom; X 1 and X 2 each independently represents an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms; R1 is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, R 11 represents a saturated or unsaturated alicyclic hydrocarbon group having 3 to 5 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a 4- or 5-membered saturated or unsaturated heterocyclic group which contains one heteroatom selected from an oxygen atom and a sulfur atom and which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, R 2 represents an aryl group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 6 carbon atoms, R 3 , R 4 , R 5 , R 13 , R 14 , and R 15 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 silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms substituted with a halogen atom, a furyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, a thienyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, a benzofuryl group, or a benzothienyl group, or adjacent substituents may be joined together to form a 5- or 6-membered cyclic structure, which cyclic structure may contain an unsaturated bond, R 6 and R 16 are each independently an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group, an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms substituted with a halogen atom; R 6 and R 16 Both may form a 4- or 5-membered ring containing Y.) <2> In the general formula [I], R 3 , R 4 , R5 , R 13 , R 14 , and R 15 are each independently a hydrogen atom, an aryl group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 6 carbon atoms, or adjacent substituents may be joined together to form a 5- or 6-membered cyclic structure, and the cyclic structure may contain an unsaturated bond; <1> The metallocene complex according to claim 1. <3> In the general formula [I], R 11 is a cycloalkyl group having 3 to 5 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, a furyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a thienyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, <1> or <2> The metallocene complex according to claim 1. <4> In the general formula [I], R 2 is an alkyl group having 1 to 6 carbon atoms, <1> ~ <3> 10. The metallocene complex according to claim 1 , <5> In the general formula [I], R 1 is a hydrogen atom, a methyl group, or an ethyl group, and R 2 is a methyl group or an ethyl group, <1> ~ <4> 10. The metallocene complex according to claim 1 , <6> A catalyst for olefin polymerization comprising the following components (A), (B) and (C): Component (A): <1> ~ <5> The metallocene complex according to any one of the preceding claims Component (B): A component containing at least one selected from the group consisting of the following (b-1) and (b-2): (b-1) A component containing a compound that reacts with component (A) to form an ion pair. (b-2) Ion-exchange layered compound Component (C): Alkyl aluminum compound <7> The component (B) contains an aluminoxane compound or an ion-exchange layered silicate. <6> The olefin polymerization catalyst according to claim 1. <8> The ion-exchange layered silicate contains montmorillonite as a main component. <6> or <7> The olefin polymerization catalyst according to claim 1. <9> The aforementioned <6> ~ <8> 1. A method for producing a propylene-based polymer, comprising polymerizing or copolymerizing propylene in the presence of the olefin polymerization catalyst according to any one of claims 1 to 9. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a metallocene complex capable of producing a propylene polymer having a high vinyl selectivity in an unsaturated structure in the terminal structure of the polymer, a moderately low molecular weight, and a wide melting point range; an olefin polymerization catalyst containing the metallocene complex; and a method for producing a propylene polymer using the same. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 is a diagram illustrating the baseline and intervals of a chromatogram in GPC. DETAILED DESCRIPTION OF THE INVENTION

[0020] The polar group-containing olefin copolymer of the present invention will be described in detail below for each item. In the present invention, "polymerization" refers collectively to homopolymerization of one type of monomer and copolymerization of multiple types of monomers, and when there is no particular need to distinguish between the two, they are collectively referred to simply as "polymerization." In addition, in this specification, the use of "to" to indicate a range of values ​​means that the values ​​before and after it are included as the lower limit and upper limit.

[0021] I. Metallocene Complexes The metallocene complex of the present invention is a metallocene complex represented by the following general formula [I].

[0022] [ka] (In formula [I], M is zirconium or hafnium; Y is a carbon atom or a silicon atom; X1 and X 2 each independently represents an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms; R 1 is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, R 11 represents a saturated or unsaturated alicyclic hydrocarbon group having 3 to 5 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a 4- or 5-membered saturated or unsaturated heterocyclic group which contains one heteroatom selected from an oxygen atom and a sulfur atom and which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, R 2 represents an aryl group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 6 carbon atoms, R 3 , R 4 , R 5 , R 13 , R 14 , and R 15 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 silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms substituted with a halogen atom, a furyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, a thienyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, a benzofuryl group, or a benzothienyl group, or adjacent substituents may be joined together to form a 5- or 6-membered cyclic structure, which cyclic structure may contain an unsaturated bond, R 6 and R 16are each independently an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group, an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms substituted with a halogen atom; R 6 and R 16 Both may form a 4- or 5-membered ring containing Y.)

[0023] The metallocene complex of the present invention is a bridged bisindene skeleton metallocene complex, in which one indenyl ligand is at the 2-position (R 11 ) has a cyclic substituent with moderate bulkiness, the 3-position is unsubstituted, and the other indenyl ligand is at the 3-position (R 2 ) and has a specific substituent at the 2-position (R 1 ) is unsubstituted or has a specific substituent, which is thought to balance the frequency of monomer coordination insertion and β-methyl elimination in the stereocontrol at the active site during polymerization. As a result, the resulting polymer has a high vinyl selectivity in the unsaturated structure at the terminal structure (number of terminal vinyl groups / (number of terminal vinyl groups + number of terminal vinylidene groups)), and is thought to have a moderate molecular weight even under hydrogen-free conditions. In addition, the 3-position substituent (R 2 ) and the 4-position substituent (R 13 ) can control the regularity of the resulting propylene polymer and adjust the melting point, and it is believed that a propylene polymer having a wide melting point range can be obtained.

[0024] In the present invention, the racemic and meso isomers are defined as follows: a racemic isomer is one in which the six-membered rings of two indenyl ligands face in different directions relative to a five-membered ring of the same indenyl ligand, as shown in the following formula [Ia], and a meso isomer is one in which they face in the same direction. Similarly, the respective enantiomers are also referred to as racemic and meso isomers.

[0025] [ka]

[0026] In the formula [I], specific examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. In formula [I], the alkyl group having 1 to 6 carbon atoms may be a linear, branched, or cyclic alkyl group, and specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. 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, and a t-butoxy group.

[0027] In formula [I], the optionally substituted hydrocarbon group having 1 to 6 carbon atoms includes a saturated or unsaturated hydrocarbon group, and may be an alkyl group, an alkenyl group, or an aryl group, and may be the aforementioned alkyl group or a phenyl group. The optionally substituted hydrocarbon group having 1 to 6 carbon atoms may be an alkyl group having 1 to 4 carbon atoms or a phenyl group. In formula [I], specific examples of the aryl group having 6 to 10 carbon atoms which may be substituted by a hydrocarbon group having 1 to 6 carbon atoms include a phenyl group, 2-, 3-, and 4-substituted 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 di-t-butylphenyl groups, a biphenylyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0028] In formula [I], the silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms refers to a substituent in which three hydrocarbon groups, each independently having 1 to 6 carbon atoms, are substituted on the silicon atom, and 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 may be substituted with an alkyl group, etc. Specific examples 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.

[0029] Specific examples of the aryl group having 6 to 10 carbon atoms and substituted with a halogen atom include 2-, 3-, and 4-substituted fluorophenyl groups, 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 trifluorophenyl groups, 2,4,6-, 2,3,4-, 2,4,5-, and 3,4,5-substituted trichlorophenyl groups, pentafluorophenyl group, pentachlorophenyl group, 3,5-dimethyl-4-chlorophenyl group, 1-naphthyl groups or 2-naphthyl groups substituted with one or two or more fluorine atoms, chlorine atoms, or bromine atoms at substitutable positions, and the like.

[0030] In formula [I], the furyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, or the thienyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, is a substituted or unsubstituted furyl group or a substituted or unsubstituted thienyl group. The substituent of the furyl group or thienyl group is at least one selected from the group consisting of hydrocarbon groups having 1 to 6 carbon atoms and silyl groups substituted with a hydrocarbon group having 1 to 6 carbon atoms. In addition, in formula [I], R 3 , R 4 , R 5 , R13 , R 14 , and R 15 may be a benzofuryl group or a benzothienyl group.

[0031] Specific examples of the furyl group and benzofuryl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms include a 2-furyl group, a 2-(5-methylfuryl) group, a 2-(5-ethylfuryl) group, a 2-(5-n-propylfuryl) group, a 2-(5-i-propylfuryl) group, a 2-(5-t-butylfuryl) group, a 2-(5-phenylfuryl) group, a 2-(4,5-dimethylfuryl) group, a 2-(3,5-dimethylfuryl) group, a 2-(5-trimethylfuryl) ...methylfuryl) group, a 2-(5-methylfuryl) group, a 2-(5-methylfuryl) group, a 2-(5-methylfuryl) group, a 2-(5-methylfuryl) group, a 2-(5-methylfuryl) group, a 2-(5-methylfuryl) group, a 2-(5-methylfuryl) group, a 2-(5-methylfuryl) group, a 2-(5-methylfuryl) group, a 2-(5-methylfuryl) group, a 2-(5 Examples of such an alkyl group include a 2-(5-phenylfuryl) group, a 2-(5-triethylsilylfuryl) group, a 2-benzofuryl group, a 3-furyl group, a 3-(5-methylfuryl) group, a 3-(5-ethylfuryl) group, a 3-(5-n-propylfuryl) group, a 3-(5-i-propylfuryl) group, a 3-(5-t-butylfuryl) group, a 3-(5-phenylfuryl) group, a 3-(4,5-dimethylfuryl) group, a 3-(5-trimethylsilylfuryl) group, a 3-(5-triethylsilylfuryl) group, and a 3-benzofuryl group.

[0032] Specific examples of the thienyl group and benzothienyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms include a 2-thienyl group, a 2-(5-methylthienyl) group, a 2-(5-ethylthienyl) group, a 2-(5-n-propylthienyl) group, a 2-(5-i-propylthienyl) group, a 2-(5-t-butylthienyl) group, a 2-(5-phenylthienyl) group, a 2-(4,5-dimethylthienyl) group, a 2-(3,5-dimethylthienyl) group, a 2-(5-trimethylsilyl) ...methylthienyl) group, a 2-(5-methylthienyl) group, a 2-(5-methylthienyl) group, a 2-(5-methylthienyl) group, a 2-(5-methylthienyl) group, a 2-(5-methylthienyl) group, a 2-(5-methylthienyl) group, a 2-(5-methylthienyl) group, a 2-(5-methylthienyl) group, a 2-(5-methylthienyl) group, a 2-(5-methylthienyl) group, a 2-(5- Examples of the thienyl group include a 2-(5-triethylsilylthienyl) group, a 2-benzothienyl group, a 3-thienyl group, a 3-(5-methylthienyl) group, a 3-(5-ethylthienyl) group, a 3-(5-n-propylthienyl) group, a 3-(5-i-propylthienyl) group, a 3-(5-t-butylthienyl) group, a 3-(5-phenylthienyl) group, a 3-(4,5-dimethylthienyl) group, a 3-(5-trimethylsilylthienyl) group, a 3-(5-triethylsilylthienyl) group, and a 3-benzothienyl group.

[0033] In formula [I], specific examples of the alkyl group having 1 to 6 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, an iodomethyl group, a 2,2,2-trifluoroethyl group, a 2,2,1,1-tetrafluoroethyl group, a pentafluoroethyl group, a pentachloroethyl group, a pentafluoropropyl group, a nonafluorobutyl group, a 5-chloropentyl group, a 5,5,5-trichloropentyl group, a 5-fluoropentyl group, a 5,5,5-trifluoropentyl group, a 6-chlorohexyl group, a 6,6,6-trichlorohexyl group, a 6-fluorohexyl group, and a 6,6,6-trifluorohexyl group.

[0034] In formula [I], specific examples of the alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group include a (trimethylsilyl)methyl group, a (triethylsilyl)methyl group, a (t-butyldimethylsilyl)methyl group, and a (trimethylsilyl)ethyl group.

[0035] M is zirconium or hafnium, preferably hafnium.

[0036] Y is a carbon atom or a silicon atom, but is preferably a silicon atom in order to maintain high vinyl selectivity.

[0037] X 1 and X 2 are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. 1 and X 2 are each preferably independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, more preferably a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and specifically, a chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, i-butyl group, or phenyl group is particularly preferred.

[0038] R 1 is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms. 1 From the viewpoint of catalytic activity, is preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom, a methyl group, or an ethyl group.

[0039] R 11 is a saturated or unsaturated alicyclic hydrocarbon group having 3 to 5 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a 4- or 5-membered saturated or unsaturated heterocyclic group which contains one heteroatom selected from an oxygen atom and a sulfur atom and which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms.

[0040] Examples of the saturated or unsaturated alicyclic hydrocarbon group having 3 to 5 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopropenyl group, a cyclobutenyl group, and a cyclopentenyl group. Specific examples of the saturated or unsaturated alicyclic hydrocarbon group having 3 to 5 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a 2-methylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 2,2,3,3-tetramethylcyclopropyl group, a 3-methylcyclobutyl group, a 3,3-dimethylcyclobutyl group, a 3-phenylcyclobutyl group, a 3,4-dimethylcyclopentyl group, and a 3,3,4,4-tetramethylcyclopentyl group.

[0041] Examples of the 4- or 5-membered saturated or unsaturated heterocyclic group containing one heteroatom selected from an oxygen atom and a sulfur atom include an oxetane group, a thietane group, a tetrahydrofuryl group, a tetrahydrothienyl group, a furyl group, and a thienyl group. Specific examples of the 4- or 5-membered saturated or unsaturated heterocyclic group containing one heteroatom selected from an oxygen atom and a sulfur atom, which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, include an oxetane group, a thietane group, a tetrahydrofuryl group, a tetrahydrothienyl group, a furyl group, a thienyl group, a 3-methyl-2-oxetane group, a 3-methyl-2-thietane group, a tetrahydro-4,5-dimethyl-2-furyl group, and a tetrahydro-5-methyl -2-furyl group, tetrahydro-4,5-dimethyl-2-thienyl group, tetrahydro-5-methyl-2-thienyl group, 2-furyl group, 2-(5-methylfuryl) group, 2-(5-ethylfuryl) group, 2-(5-n-propylfuryl) group, 2-(5-i-propylfuryl) group, 2-(5-t-butylfuryl) group, 2-(5-phenylfuryl) group, 2-(4,5-dimethylfuryl) group, 2-(3,5-dimethylfuryl) group, 3-furyl group, 3 -(5-methylfuryl), 3-(5-ethylfuryl), 3-(5-n-propylfuryl), 3-(5-i-propylfuryl), 3-(5-t-butylfuryl), 3-(5-phenylfuryl), 3-(4,5-dimethylfuryl), 2-thienyl, 2-(5-methylthienyl), 2-(5-ethylthienyl), 2-(5-n-propylthienyl), 2-(5-i-propylthienyl), 2-(5-t-butylthienyl), Examples of the thienyl group include a 2-(5-phenylthienyl) group, a 2-(4,5-dimethylthienyl) group, a 2-(3,5-dimethylthienyl) group, a 3-thienyl group, a 3-(5-methylthienyl) group, a 3-(5-ethylthienyl) group, a 3-(5-n-propylthienyl) group, a 3-(5-i-propylthienyl) group, a 3-(5-t-butylthienyl) group, a 3-(5-phenylthienyl) group, and a 3-(4,5-dimethylthienyl) group.

[0042] R 11is preferably a cycloalkyl group having 3 to 5 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, a furyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a thienyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, from the viewpoint of catalytic activity, and is more preferably a cyclopropyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. From the viewpoint of reducing the molecular weight, a furyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a thienyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms is preferred. R 11 may be a cycloalkyl group having 3 to 5 carbon atoms which may be substituted with a hydrocarbon group having 1 to 3 carbon atoms, a furyl group which may be substituted with a hydrocarbon group having 1 to 3 carbon atoms, or a thienyl group which may be substituted with a hydrocarbon group having 1 to 3 carbon atoms, and may further be a cycloalkyl group having 3 to 5 carbon atoms which may be substituted with a hydrocarbon group having 1 to 2 carbon atoms, a furyl group which may be substituted with a hydrocarbon group having 1 to 2 carbon atoms, or a thienyl group which may be substituted with a hydrocarbon group having 1 to 2 carbon atoms.

[0043] R 2 represents an aryl group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 6 carbon atoms. R 2 From the viewpoint of catalytic activity, is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a linear alkyl group having 1 to 6 carbon atoms, and even more preferably an ethyl group or a methyl group.

[0044] R 3 , R 4 , R 5 , R 13 , R 14 , and R 15are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms substituted with a halogen atom, a furyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, a thienyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, a benzofuryl group, or a benzothienyl group, or adjacent substituents may be joined together to form a 5- or 6-membered cyclic structure, and the cyclic structure may contain an unsaturated bond.

[0045] R 3 , R 4 , R 5 , R 13 , R 14 , and R 15 In the formula (I), adjacent substituents may be linked to each other to form a 5- to 6-membered alicyclic ring or aromatic ring. In this case, the ring may or may not have a substituent. Examples of the substituent include R 3 , R 4 , R 5 , R 13 , R 14 , and R 15 The substituents in the above formula (I) are at least one of the substituents in the above formula (I). R 3 , R 4 , R 5 , R 13 , R 14 , and R 15 Specific examples of adjacent substituents forming a 5- or 6-membered ring structure include a 1,2,3,6-tetrahydro-as-indacene ring, a 1,2,3,5-tetrahydro-s-indacene ring, and a benzoindene ring formed by condensing benzene rings.

[0046] R 3 , R 4 , R 5 , R 13 , R 14 , and R 15are each independently a hydrogen atom, an aryl group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms, or adjacent substituents may be joined together to form a 5- or 6-membered cyclic structure, and the cyclic structure may preferably contain an unsaturated bond.

[0047] R 3 and R 13 In view of catalytic activity, at least one of R is independently an aryl group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 6 carbon atoms, or 3 , R 4 , R 14 , and R 15 Preferably, adjacent substituents R form a 5- or 6-membered cyclic structure, and the cyclic structure may contain an unsaturated bond. 13 is an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or R 13 and R 14 It is more preferable that the rings form a 5- or 6-membered ring structure, and the cyclic structure may contain an unsaturated bond.

[0048] R 6 and R 16 are each independently an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group, an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms substituted with a halogen atom; R 6 and R 16 Both may form a 4- or 5-membered ring containing Y. R 6 and R 16 R when both form a 4- to 5-membered ring containing Y 6 and R 16 is a divalent hydrocarbon group having 3 to 4 carbon atoms which forms a ring together with Y and may contain an unsaturated bond. R 6 and R 16is, from the viewpoint of catalytic activity, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms substituted with a halogen atom, or R 6 and R 16 Preferably, both of them form a 4- to 5-membered ring containing Y, and R 6 and R 16 It is more preferable that both of them form a 4- to 5-membered ring containing Y.

[0049] -Y(R 6 )(R 16 Examples of the divalent group of - include a dimethylmethylene group, a phenylmethylmethylene group, a diphenylmethylene group, a silacyclobutylene group, a silacyclopentylene group, a dimethylsilylene group, a phenylmethylsilylene group, and a diphenylsilylene group.

[0050] Specific examples of the metallocene complex represented by the general formula [I] are shown below, but the invention is not limited to these. Dimethylsilylene(2,3-dimethyl-4-phenylindenyl)(2-(5'-methyl-2'-furyl)-4-phenylindenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4,5-benzoindenyl)hafnium dichloride

[0051] Dimethylsilylene(2,3-dimethyl-4-phenylindenyl)(2-cyclopropyl-4-phenylindenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4,5-benzoindenyl)hafnium dichloride

[0052] Dimethylsilylene(2,3-dimethyl-4-phenylindenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(3',5'-di-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(3',5'-dimethylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-naphthylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride

[0053] Dimethylsilylene(2,3-dimethyl-4-phenylindenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(3',5'-di-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(3',5'-dimethylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-naphthylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)hafnium dichloride

[0054] Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(3',5'-dimethylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-iso-propylindenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-t-butyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-phenyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(4',5'-dimethyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride

[0055] Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-thienyl)-4-(3',5'-dimethylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-thienyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-t-butyl-2'-thienyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-phenyl-2'-thienyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride Dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(4',5'-dimethyl-2'-thienyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride

[0056] Dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6,7-dimethyl-s-indacenyl)hafnium dichloride Dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6-methyl-7-phenyl-s-indacenyl)hafnium dichloride Dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6-methyl-7-(4'-t-butylphenyl)-s-indacenyl)hafnium dichloride Dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6-methyl-7-(2'-naphthyl)-s-indacenyl)hafnium dichloride Dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6-methyl-7-(3',5'-di-t-butylphenyl)-s-indacenyl)hafnium dichloride Dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6-methyl-7-(4'-t-butylphenyl)-8-methyl-s-indacenyl)hafnium dichloride

[0057] In addition, compounds in which hafnium is replaced with zirconium in the compounds exemplified above can also be exemplified. 1 , X 2 Examples of compounds in which one or both of the chlorine atoms exemplified above are replaced with a bromine atom, an iodine atom, a methyl group, a phenyl group, a dimethylamino group, a diethylamino group, or the like can also be mentioned. Unless otherwise specified, these metallocene complexes represent one of the stereoisomers (meso or racemic) or a mixture thereof (including meso and racemic).

[0058] The metallocene complex represented by the general formula [I] can be synthesized by appropriately selecting from conventionally known synthesis methods, for example, by referring to JP-A-2003-517010.

[0059] II. Olefin polymerization catalysts The olefin polymerization catalyst of the present invention is characterized by comprising the following components (A), (B) and (C): Component (A): the metallocene complex according to the present invention Component (B): A component containing at least one selected from the group consisting of the following (b-1) and (b-2): (b-1) A component containing a compound that reacts with component (A) to form an ion pair. (b-2) Ion-exchange layered compound Component (C): Alkyl aluminum compound

[0060] Each component of the olefin polymerization catalyst of the present invention will be described in detail below. However, component (A) is the metallocene complex of the present invention, which has been described above, and therefore further description will be omitted here. 1. Ingredient (B) Component (B) is a component containing at least one selected from the group consisting of (b-1) and (b-2).

[0061] 1-1. (b-1) A component containing a compound that reacts with component (A) to form an ion pair (b-1) is a component containing a compound that reacts with component (A) to form an ion pair. Examples of compounds that react with component (A) to form an ion pair include aluminum oxy compounds and boron compounds. Specific examples of aluminum oxy compounds include compounds represented by the following general formulas [II] to [IV].

[0062] [ka]

[0063] In the general formulae [II] to [IV], R a each independently represents a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. a may be the same or different. Furthermore, p represents an integer of 0 to 40, preferably 2 to 30. The compounds represented by the general formulas [II] and [III] are also called aluminoxanes, and among them, methylaluminoxane or methylisobutylaluminoxane is preferred. The above aluminoxanes can be used in combination with one another within each group or between groups. The above aluminoxanes can be prepared under various known conditions. In 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 a compound comprising one kind of trialkylaluminum or two or more kinds of trialkylaluminum and a group represented by the general formula R b It can be obtained by reacting with an alkylboronic acid represented by B(OH)2 in a molar ratio of 10:1 to 1:1.

[0064] Examples of boron compounds include complexes of cations such as carbonium cations and ammonium cations with organic boron compounds such as triphenylboron, tris(3,5-difluorophenyl)boron and tris(pentafluorophenyl)boron, as well as various organic boron compounds such as tris(pentafluorophenyl)boron.

[0065] Here, the component (b-1) containing a compound that reacts with the component (A) to form an ion pair may be a particulate carrier. The particulate carrier used in the present invention is not particularly limited in terms of elemental composition and compound composition, as long as it contains an inorganic compound, and examples thereof include particulate carriers containing inorganic compounds. Examples of inorganic compounds that constitute particulate carriers 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, silica-chromium (III) oxide, silica-alumina-magnesium oxide, activated carbon, inorganic silicates, and mixtures thereof. The particulate carrier may be a particulate inorganic carrier made of an inorganic compound. These fine particle carriers usually have an average particle size of 1 μm to 5 mm, preferably 5 μm to 1 mm, and more preferably 10 μm to 200 μm. The specific surface area of ​​these particles is usually 20 m 2 / g~1,000m 2 / g, preferably 50m 2 / g~700m 2 / g, and the pore volume is typically 0.1 cm 3 / g or more, preferably 0.3 cm 3 / g or more, more preferably 0.8 cm 3 / g or more is suitable.

[0066] Among (b-1), it is preferable to use an aluminoxane compound as the compound that reacts with component (A) to form an ion pair, since this allows for the production of a propylene-based polymer having a branched structure with high activity and production efficiency. Alternatively, aluminoxane may be used as the compound that reacts with component (A) to form an ion pair, and silica may be used as the fine particle carrier.

[0067] 1-2.(b-2) Ion-exchange layered compounds (b-2) The ion-exchangeable layered compound accounts for the majority of the clay mineral, and is preferably an ion-exchangeable layered silicate (hereinafter sometimes simply abbreviated as layered silicate). Layered silicate refers to a silicate compound that has a crystalline structure in which layers formed by ionic bonds or the like are stacked in parallel with each other through bonding forces, has interlayer ions between the layers, and the contained interlayer ions are exchangeable. Most layered silicates occur naturally as the main component of clay minerals, but these layered silicates are not limited to those that are naturally occurring, and may also be artificially synthesized products.

[0068] Specific examples of layered silicates include known layered silicates described in, for example, Shiramizu Haruo's "Clay Mineralogy" (Asakura Shoten, 1995), such as kaolin group such as dickite, nacrite, kaolinite, anoxite, metahalloysite, and halloysite, serpentine group such as chrysotile, lisardite, and antigorite, smectite group such as montmorillonite, sauconite, beidellite, nontronite, saponite, taeniolite, hectorite, and stevensite, vermiculite group such as vermiculite, mica group such as mica, illite, sericite, and glauconite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, and chlorite. These may form mixed layers.

[0069] Among these, smectites, vermiculites, and micas, such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, and taeniolite, are preferred. Representative smectites include montmorillonite, beidellite, saponite, nontrite, hectorite, and sauconite. Commercially available products include "Benclay SL" (manufactured by Mizusawa Chemical Industry Co., Ltd.), "Kunipia," and "Sumecton" (both manufactured by Kunimine Industries Co., Ltd.), "Montmorillonite K10" (manufactured by Aldrich Chemical Co., Ltd. and Jut Chemie), and "K-Catalysts Series" (manufactured by Jut Chemie). Representative mica products include muscovite, paragonite, phlogopite, biotite, and lepidolite. Commercially available products include "Synthetic Mica Somasif" (manufactured by Co-op Chemical Co., Ltd.), "Fluorophlogopite," "Fluorotetrasilicic Mica," and "Taeniolite" (all manufactured by Topy Industries Co., Ltd.). Smectites such as "Benclay SL" are particularly preferred. Among these, the main component is more preferably a smectite silicate, and even more preferably, the main component is montmorillonite.

[0070] Generally, natural silicates are often non-ion-exchangeable (non-swellable), and in such cases, it is preferable to subject them to a treatment to impart ion-exchangeability (or swelling ability) to give them the desired ion-exchangeability (or swelling ability). Among such treatments, the following chemical treatments are particularly preferable, and it is preferable that these silicates have been subjected to a chemical treatment. Here, chemical treatment can be either a surface treatment to remove impurities adhering to the surface or a treatment that affects the crystal structure and chemical composition of the layered silicate.Specific examples include (a) acid treatment, (b) alkali treatment, (c) salt treatment, and (d) organic treatment.

[0071] These treatments have the effect of removing surface impurities, exchanging cations between layers, and eluting cations such as Al, Fe, and Mg in the crystal structure, thereby forming ionic complexes, molecular complexes, organic derivatives, etc., and changing the surface area, interlayer distance, solid acidity, etc. These treatments may be performed alone or in combination of two or more. The (a) acid used in the chemical treatment may be either an inorganic acid or an organic acid, and preferred examples include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and oxalic acid, while the (b) alkali includes NaOH, KOH, and NH3. The (c) salt is preferably a compound comprising a cation containing at least one atom selected from the group consisting of atoms of Groups 2 to 14 and at least one anion selected from the group consisting of halogen atoms or anions derived from inorganic or organic acids. More preferred are those with ions derived from Li, Mg, Ca, Al, Ti, Zr, Hf, V, Nb, Ta, Cr, Mn, W, Mn, Fe, Co, Ni, Cu, Zn, B, Al, Ge, or Sn as cations, and those with ions derived from Cl, SO, NO, OH, CH, and PO as anions. (iv) Examples of organic substances include alcohols (aliphatic alcohols having 1 to 4 carbon atoms, preferably methanol, ethanol, propanol, ethylene glycol, glycerin, and aromatic alcohols having 6 to 8 carbon atoms, preferably phenol), and higher hydrocarbons (those having 5 to 10 carbon atoms, preferably 5 to 8 carbon atoms, preferably hexane and heptane). Other preferred examples include formamide, hydrazine, dimethyl sulfoxide, N-methylformamide, and N,N-dimethylaniline. Two or more types of salts and acids may be used.

[0072] When salt treatment and acid treatment are combined, there are methods in which salt treatment is performed followed by acid treatment, methods in which acid treatment is performed followed by salt treatment, and methods in which salt treatment and acid treatment are performed simultaneously. The conditions for the salt and acid treatment are not particularly limited, but typically, salt and acid concentrations of 0.1 wt% to 50 wt%, treatment temperatures between room temperature and boiling point, and treatment times of 5 minutes to 24 hours are selected to elute at least a portion of the substances constituting the layered silicate. Furthermore, the salt and acid can be used in an organic solvent such as toluene, n-heptane, or ethanol, or without a solvent if the salt and acid are liquid at the treatment temperature, but are preferably used as an aqueous solution.

[0073] The particle properties of component (B) of the present invention may be controlled by pulverization, granulation, sizing, fractionation, etc. Any method may be used as long as it does not impair catalytic performance. Particularly, examples of granulation methods include spray granulation, tumbling granulation, compression granulation, stirring granulation, briquetting, compaction, extrusion granulation, fluidized bed granulation, emulsion granulation, and submerged granulation. Of the above, particularly preferred granulation methods are spray granulation, tumbling granulation, and compression granulation.

[0074] From the viewpoint of productivity of the propylene-based polymer, the component (B) preferably contains an aluminoxane compound or an ion-exchangeable layered silicate, more preferably contains an ion-exchangeable layered silicate, and further preferably contains montmorillonite.

[0075] 2.Component (C) 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 represents an integer of 1 to 3, and m represents an integer of 1 or 2.] When X is a halogen atom, it is preferably a chlorine atom; when X is an alkoxy group, it is preferably an alkoxy group having 1 to 8 carbon atoms; and when X is an amino group, it is preferably an amino group having 1 to 8 carbon atoms. The organoaluminum compounds can be used alone or in combination of two or more. Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-normal propylaluminum, tri-normal butylaluminum, triisobutylaluminum, tri-normal hexylaluminum, tri-normal octylaluminum, tri-normal decylaluminum, diethylaluminum chloride, diethylaluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Among these, preferred are trialkylaluminums and alkylaluminum hydrides in which m=1 and n=3. More preferred are trialkylaluminums in which R has 1 to 8 carbon atoms.

[0076] 3. Catalyst Preparation The olefin polymerization catalyst according to the present invention contains the above-mentioned components (A), (B), and (C). These can be obtained by contacting them in a polymerization vessel or outside the polymerization vessel. The olefin polymerization catalyst may be prepolymerized in the presence of an olefin. The catalyst components are usually contacted in an aliphatic or aromatic hydrocarbon solvent. The contact temperature is not particularly limited, but is preferably between -20°C and 150°C. The order of contact may be any combination suitable for the purpose, but the particularly preferred orders for each catalyst component are as follows: When component (C) is used, it is possible to contact component (C) with component (A), or with component (B), or with both components (A) and (B) before contacting components (A) and (B), or to contact component (C) with component (A) and component (B) simultaneously, or to contact component (C) after contacting components (A) and (B). Preferably, component (C) is contacted with either component (A) or component (B) before contacting components (A) and (B). Furthermore, if necessary, an inorganic carrier different from component (B) or a co-catalyst may be added. In addition, in the case of a component (b-1) containing a compound that reacts with component (A) to form an ion pair, the method of incorporating the compound that forms the ion pair into a particulate carrier may involve contacting the compound that forms the ion pair with the particulate carrier in a solvent, or may involve contacting the particulate carrier with a mixture of the compound that forms the ion pair and component (A). After contacting the catalyst components, they can be washed with an aliphatic hydrocarbon or aromatic hydrocarbon solvent.

[0077] The amounts of component (A) and the inorganic carrier used in the present invention, and the amounts of components (A), (B) and (C) used are optional. For example, the amount of component (A) used is preferably in the range of 0.1 μmol to 1000 μmol, more preferably 0.5 μmol to 500 μmol, per 1 g of component (B). The amount of component (C) used relative to component (A) is preferably 0.01 to 5×10 in terms of the molar ratio of the transition metal in component (A). 6 , more preferably 0.1 to 1 × 10 4 The range is.

[0078] The olefin polymerization catalyst is preferably subjected to prepolymerization, which involves contacting an olefin with the catalyst and polymerizing a small amount of the olefin. By carrying out the prepolymerization treatment, gel formation can be prevented during main polymerization. This is thought to be because long chain branches can be uniformly distributed among the polymer particles during main polymerization. The olefin used in the prepolymerization is not particularly limited, but examples thereof include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, and styrene, with propylene being preferred. The olefin may be fed to the prepolymerization reactor at a constant rate or at a constant pressure, or any combination thereof, or by stepwise change.

[0079] The prepolymerization temperature and prepolymerization time are not particularly limited, but are preferably in the range of −20° C. to 100° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50, in terms of the mass ratio of the prepolymerized polymer to the component (B). Furthermore, component (C) can be added during the prepolymerization, and washing can also be carried out at the end of the prepolymerization. It is also possible to use a method in which a polymer such as polyethylene or polypropylene or a solid inorganic oxide such as silica or titania is made to coexist during or after the contact of the above catalyst components. After the prepolymerization, the catalyst may be dried. The drying method is not particularly limited, and examples thereof include drying under reduced pressure, drying by heating, and drying by passing a dry gas through the catalyst. These methods may be used alone or in combination of two or more. In the drying step, the catalyst may be stirred, vibrated, or fluidized.

[0080] III. Method for producing propylene polymer The method for producing a propylene polymer of the present invention is characterized by polymerizing or copolymerizing propylene in the presence of the above-mentioned catalyst for olefin polymerization of the present invention. The present invention is a method for producing a propylene-based polymer by polymerizing propylene alone or propylene with ethylene and / or an α-olefin. The α-olefin referred to here is suitably an olefin having 2 to 20 carbon atoms, and specific examples thereof include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene, styrene, vinylcyclohexane, dienes, trienes, and cyclic olefins, and may also be a mixture of two or more of these.

[0081] Any polymerization mode can be adopted as long as the olefin polymerization catalyst and the monomer are brought into contact with each other efficiently. 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 gas phase polymerization method in which each monomer is kept in a gaseous state without substantially using a liquid solvent can be used. Furthermore, continuous polymerization and batch polymerization may also be used. In addition to single-stage polymerization, multi-stage polymerization of two or more stages is also possible.

[0082] In the case of the slurry polymerization method, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene, either alone or in mixture, are 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 bulk polymerization, the polymerization temperature is more preferably 40° C. or higher, and even more preferably 50° C. or higher. The upper limit is preferably 80° C. or lower, and even more preferably 75° C. or lower. In the case of gas phase polymerization, the temperature is preferably 40°C or higher, more preferably 50°C or higher. The upper limit is preferably 100°C or lower, and more preferably 90°C or lower.

[0083] The polymerization pressure is preferably 1.0 MPa or more and 5.0 MPa or less. In particular, in the case of bulk polymerization, it is more preferably 1.5 MPa or more, and even more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, and even more preferably 3.5 MPa or less. In the case of gas phase polymerization, the pressure is preferably 1.5 MPa or more, more preferably 1.7 MPa or more, and the upper limit is preferably 2.5 MPa or less, more preferably 2.3 MPa or less.

[0084] <Properties of propylene polymers> (1) Mass average molecular weight (Mw) The mass average molecular weight (Mw) of the propylene polymer produced by the production method of the present invention has a lower limit of 1 × 10 3 May be greater than or equal to 5 x 10 3 or more, with an upper limit of 1.5 × 105 may be less than or equal to 1.2 x 10 5 It may be the following: Here, the mass average molecular weight (Mw) and number average molecular weight (Mn) are obtained by gel permeation chromatography (GPC), and the details of the measuring method and measuring equipment are as follows.

[0085] Apparatus: Agilent Technology PLGPC 220 Detector: R-4 (Polymer Char) Column: Showa Denko AD806M / S (3 columns) Mobile phase solvent: o-dichlorobenzene (ODCB) Measurement temperature: 140℃ Flow rate: 1.0ml / min Injection amount: 0.3ml

[0086] The sample is prepared by preparing a 1 mg / mL solution of the sample using ODCB (containing 0.5 mg / mL of BHT) and dissolving the sample at 140° C. for about 1 hour. The baseline and intervals of the obtained chromatogram are as shown in Figure 1. The conversion from the retention volume obtained by GPC measurement to molecular weight is performed using a calibration curve prepared in advance using standard polystyrenes. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. Brand Name: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000 A 0.2 mL solution of each compound dissolved in ODCB (containing 0.5 mg / mL BHT) was injected to prepare a calibration curve. The calibration curve was calculated using a cubic equation obtained by approximating the curve using the least squares method. Viscosity formula used to convert to molecular weight: [η] = K × M α The following values ​​are used: PS:K = 1.38 × 10 -4 , α=0.7 PP:K = 1.03 × 10 -4 , α=0.78

[0087] (2) Mw / Mn In the production method of the present invention, it is possible to produce a propylene-based polymer having a ratio Mw / Mn of Mw to Mn measured by GPC of at least 2. When an ion-exchange layered silicate is used, a polymer with a large Mw / Mn tends to be produced, which is preferable in terms of moldability.

[0088] (3) Melting point In the production method of the present invention, the melting point (Tm) of the produced propylene polymer measured by differential scanning calorimetry (DSC) is in the range of 100°C to 155°C, and a propylene polymer having a wide melting point range can be produced. The melting point (Tm) of the produced propylene polymer depends on the isomer species and R 13 It can be controlled by controlling the structure of In the present invention, Tm can be determined using a differential scanning calorimeter (DSC) (DSC6200, manufactured by Seiko Instruments Inc.) by placing 5 mg of a sheet-like sample piece in an aluminum pan, heating it from room temperature to 200°C at a heating rate of 100°C / min, holding it for 5 minutes, and then cooling it to 40°C at a heating rate of 10°C / min, and determining the maximum crystallization peak temperature (°C) when crystallizing it as the crystallization temperature (Tc), and then heating it to 200°C at a heating rate of 10°C / min, and determining the maximum melting peak temperature (°C) when melting it as the melting point (Tm). The sheet-like sample can be obtained by sandwiching the propylene polymer powder between press plates, preheating at 190°C for 2 minutes, pressing at 5 MPa for 2 minutes, and then cooling at 0°C and 10 MPa for 2 minutes.

[0089] (4) Vinyl selectivity In the production method of the present invention, a propylene polymer having a terminal propenyl structure (vinyl structure: structural formula (1a)) is produced from the component (A) of the olefin polymerization catalyst of the present invention by a special chain transfer reaction generally called β-methyl elimination. On the other hand, in the polymerization of propylene, a chain transfer reaction generally known as β-hydrogen elimination occurs as a termination reaction, resulting in the production of a polymer with a propyl-vinylidene structure (vinylidene structure) as the termination end, as shown in structural formula (1b).

[0090] [ka]

[0091] In the production method of the present invention, the vinyl selectivity (number of terminal vinyl groups / (number of terminal vinyl groups+number of terminal vinylidene groups)) in the unsaturated structure in the terminal structure of the produced propylene-based polymer can be increased, and the vinyl selectivity can be made 90% or more, and even 95% or more. In the present invention, the number of terminal vinyl groups depends on the molecular weight (Mn), but the number per 1000 monomers may be 0.5 or more, 1.0 or more, or 15 or less. In the present invention, the number of terminal vinylidene groups per 1000 monomers may be 1.0 or less, or may be below the detection limit of less than 0.01 or less per 1000 monomers. Furthermore, since vinyl-terminated propylene polymers can act as macromers, they are copolymerized as monomers during polymerization to form long-chain branches (LCBs) in polymers with LCBs. Since LCBs are macromers with vinyl-terminated groups incorporated into the main chain, the number of LCBs (LCB number) is added to the number of vinyl-terminated groups to calculate the vinyl selectivity.

[0092] (5) Number of long chain branches (LCB) The propylene polymer produced by the production method of the present invention may have a long chain branched (LCB) structure moiety represented by the following structural formula (2a).

[0093] [ka] [However, in structural formula (2a), P 1 , P 2 , P 3 are propylene polymer residues, each having one or more propylene units, and C br indicates the methine carbon at the root of a branched chain having 7 or more carbon atoms, and C a , C b , C c is the methine carbon (C br ) indicates the methylene carbon adjacent to the

[0094] According to the olefin polymerization catalyst of the present invention, the resulting propylene polymer may be polymerized as a macromer in the same manner as propylene, resulting in macromer copolymerization. In this case, the propylene polymer produced by the production method of the present invention has a specific branched structure as shown in structural formula (2a).

[0095] In structural formula (2a), the main chain of the propylene polymer is P 1 -C br -P 2 Line, P 1 -C br -P 3 Line or P 2 -C br -P 3 Therefore, there are three types of lines, C br -P 3 Line C br -P 2 Line or C br -P 1 The line can be the branched chain. 1 , P 2 , P 3 is a C described in structural formula (2a) br is another branched carbon (C br ) may also be contained.

[0096] In the present invention, the number of terminal vinyl groups, the number of terminal vinylidene groups, and the number of long chain branches (LCB) are evaluated as follows. 1 H-NMR measurement and 13C-NMR measurement can be carried out by the following method. [Sample preparation and measurement conditions] 200 mg of sample was placed in an NMR sample tube with an inner diameter of 10 mm along with 2.4 ml of ODCB / deuterated bromide benzene (C6D5Br) = 4 / 1 (volume ratio) and hexamethyldisiloxane, a chemical shift reference substance, and dissolved uniformly in a block heater at 150°C. NMR measurements are performed using a Bruker Biospin AV400 NMR instrument equipped with a 10 mm diameter cryoprobe. To quantify unsaturated ends, 1 H-NMR is used. 1 The H-NMR measurement conditions are a sample temperature of 120°C, a pulse angle of 4.5°, a pulse interval of 2 seconds, and an accumulation count of 512. The chemical shift of the hexamethyldisiloxane proton signal is set to 0.09 ppm, and the chemical shifts of signals due to other protons are based on this. To quantify saturated ends, 13 C-NMR is used. 13 The C-NMR measurement conditions are a sample temperature of 120°C, a pulse angle of 90°, a pulse interval of 15 seconds, an accumulation count of 1024, and broadband decoupling. 13 The C signal was set to 1.98 ppm, and the other 13 The chemical shift of the C signal is based on this. In the present invention, 13 The signals in the C-NMR spectrum are 13 It is sometimes called a "C signal" 1 The signals in the H-NMR spectrum are 1 This is sometimes called the "H signal."

[0097] <How to calculate the number of unsaturated ends> The number of unsaturated ends per 1000 monomers is: 1 The integrated intensity of the H signal is used to determine the value as follows: 1In the 1H-NMR, the proton signals of the unsaturated bonds of the 1-propenyl structure and the 1-butenyl structure shown in the above structural formula (1a) are detected overlapping with the signals at 5.08 to 4.85 ppm and 5.86 to 5.69 ppm in the 1H-NMR spectrum. Therefore, the number of terminal vinyl groups is the sum of the numbers of the 1-propenyl structure and the 1-butenyl structure. The number of terminal vinylidene groups is the number of the vinylidene structures shown in the above structural formula (1b). 1 In the 1H-NMR spectrum, they are detected overlapping with the signals at 5.08 to 4.85 ppm and 5.86 to 5.69 ppm. Therefore, the number of terminal vinyl groups is the sum of the numbers of the 1-propenyl structure and the 1-butenyl structure. The number of terminal vinylidene groups is the number of the vinylidene structures shown in the above structural formula (1b).

[0098] <Calculation method of LCB number> The LCB number is 13 Calculated by the following formula using the signal integral intensities of the carbon at the branching point at 31.7 to 31.7 ppm and the three methylene carbons (Ca, Cb, Cc) at from 44. to 44.0 ppm, 44.8 to 44.7 ppm and 44.9 to 44.8 ppm when the intensity of the methylene carbon of the propylene main chain at 49.0 to 44.3 ppm is normalized to 1000 by 13C-NMR, and it is taken as the number per 1000 monomers. LCB number = [(I 44.1~43.0 + I 44.8~44.7 + I 44.9~44.8 + I 31.7~31.7 ) / 4] / I 49.00~44.33

[0099] Also, the LCB number is 13 The number of methine carbons (C br ) at the root of the branched chain having 7 or more carbons per 1000 monomers calculated by 13C-NMR. The branched chain having more than 6 carbons and the branched chain having 6 or less carbons can be distinguished by the difference in the peak position of the methine carbon at the root of the branch (see Macromol.chem.phys. 2003, Vol. 204, page 1738). In the propylene-based polymer produced by the production method of the present invention, the LCB number is not particularly limited, but may be below the detection limit of less than 0.01 per 1000 monomers. In the propylene-based polymer produced by the production method of the present invention, it may be 0.03 or more per 1000 monomers, and from the viewpoint of acting advantageously in the fields where melt tension is required, it may be 0.1 or more per 1000 monomers.

[0100] The propylene polymer produced by the present invention, which has a high vinyl selectivity, a moderately low molecular weight, and a wide melting point range, can be suitably selected as a macromer and suitably used for producing a propylene polymer having a branched structure. The propylene polymer having a branched structure produced by the present invention can be heated, melt-kneaded, and then cut into pellets to be used as a molding material. The propylene polymer having a branched structure produced by the present invention can be blended with various additives, such as known antioxidants, ultraviolet absorbers, antistatic agents, nucleating agents, lubricants, flame retardants, antiblocking agents, colorants, inorganic or organic fillers, and various synthetic resins, as needed. These pellet-like molding materials can be molded by various known polypropylene molding methods, such as injection molding, extrusion molding, foam molding, and blow molding, to produce various molded products such as industrial injection-molded parts, containers, unstretched films, uniaxially stretched films, biaxially stretched films, sheets, pipes, and fibers. Furthermore, the propylene polymer produced by the present invention, which has a high vinyl selectivity, a moderately low molecular weight and a wide melting point range, can also be used as a compatibilizer or a raw material for hot melt adhesives. [Example]

[0101] 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 measurements and analyses in the following examples were carried out according to the following methods. In the following chemical structural formula, Me represents a methyl group.

[0102] (1) Molecular weight and molecular weight distribution (Mw, Mn, Mw / Mn): Measurement was carried out by gel permeation chromatography (GPC) using the method described above in this specification. (2) Melting point Measurement was carried out by a differential scanning calorimeter (DSC) according to the method described herein above. (3) Vinyl selectivity, number of terminal vinyl groups, number of terminal vinylidene groups 1 H-NMR and 13 Calculation was performed using C-NMR according to the method described above in this specification. (4) Number of LCBs 13 Measurement was performed using C-NMR according to the method described herein above.

[0103] (5) Identification of the structure of metallocene complexes The structures of the compounds disclosed in the synthesis examples are shown by proton nuclear magnetic resonance spectroscopy ( 1 The specific measurement method is as follows: [Sample preparation] Under a nitrogen atmosphere, 5 to 30 mg of sample was weighed into an NMR measurement tube, and a heavy solvent (the type is described in each example) was added thereto so that the liquid level was about 4 to 5 cm from the bottom of the NMR test tube, and the sample was completely dissolved at room temperature. [ 1 H-NMR measurement conditions] Equipment: JEOL JNM-ECS400 type NMR manufactured by JEOL Probe: 5mmφ probe Sample temperature: room temperature Pulse angle: 45° Pulse interval: 5.0 seconds Accumulation count: 32 times Chemical shift: The proton signal of tetramethylsilane was set to 0 ppm or the proton signal of chloroform to 7.26 ppm, and the chemical shifts of signals due to other protons were set to these as the reference.

[0104] [Example 1] Clay-supported evaluation using dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride (Complex A):

[0105] [ka]

[0106] (1-a) Synthesis of dimethyl(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)silane: Under a nitrogen atmosphere, 2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indene (7.0 g, 21 mmol) and tetrahydrofuran (THF, 70 mL) were added to a 200 mL glass reaction vessel and cooled to -70 °C in a dry ice-methanol bath with stirring. A n-butyllithium-n-hexane solution (1.57 mol / L, 14 mL, 21 mmol) was added dropwise to the reaction vessel. After the dropwise addition, the mixture was stirred for 2 hours while gradually warming to room temperature to obtain the lithium compound. Under a nitrogen atmosphere, a THF solution (30 mL) containing dimethyldichlorosilane (5.5 mL, 46 mmol) was added to a separate glass reaction vessel and cooled to -70 °C in a dry ice-methanol bath with stirring. The lithium compound solution was then slowly added. After stirring at room temperature for 1 hour, the solvent and excess dimethyldichlorosilane were removed under reduced pressure. After distillation, THF (30 ml) was added to the residue to give a solution of the chlorosilane compound. Under a nitrogen atmosphere, 2,3-dimethyl-4-(4'-t-butylphenyl)indene (5.9 g, 21 mmol) and THF (70 ml) were added to another 200 ml glass reaction vessel and cooled to -70°C in a dry ice-methanol bath with stirring. To this vessel was added dropwise n-butyllithium-n-hexane solution (1.57 mol / L, 14 ml, 21 mmol). After the dropwise addition, the mixture was stirred for 2 hours while gradually warming to room temperature. The reaction solution was then cooled to -70°C in a dry ice-methanol bath, and 1-methylimidazole (0.08 ml, 1.0 mmol) was added to the reaction solution. The above chlorosilane solution was slowly added to this reaction solution. The mixture was then stirred overnight while gradually warming to room temperature. After stirring, distilled water was added to the reaction mixture, which was then transferred to a separatory funnel and washed with saline until neutral. After washing, anhydrous sodium sulfate was added to the separated organic layer and dried. The anhydrous sodium sulfate was filtered off, and the solvent was removed from the filtrate by distillation under reduced pressure. The resulting crude product was purified using a silica gel column (Kanto Chemical Co., Ltd. silica gel 60N (spherical, neutral), solvent: hexane / diethyl ether) to obtain a pale yellow powder of dimethyl(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)silane (8.7 g, yield: 62%).

[0107] (1-b) Synthesis of dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride (Complex A): Under a nitrogen atmosphere, dimethyl(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)silane (6.1 g, 12 mmol) from (1-a) above and diethyl ether (200 mL) were added to a 500 mL glass reaction vessel and cooled to -70°C in a dry ice-methanol bath with stirring. To this was added dropwise n-butyllithium-n-hexane solution (1.57 mol / L, 17 mL, 26 mmol). After the dropwise addition, the mixture was warmed to room temperature and stirred for 2 hours. After 2 hours, the reaction mixture was concentrated under reduced pressure to approximately 20 mL. To this mixture were then added toluene (300 mL) and diethyl ether (15 mL) and cooled to -70°C in a dry ice-methanol bath with stirring. To this reaction mixture was added 4.2 g (13 mmol). Thereafter, the mixture was stirred overnight while gradually warming to room temperature. After stirring, the solvent was removed under reduced pressure, and the resulting crude product was recrystallized by adding toluene / hexane to obtain yellow crystals of the meso form of dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride (racemic / meso=9 / 91, 2.2 g).

[0108] The above-mentioned procedure was carried out on the obtained mesophase. 1 The identified values ​​obtained by H-NMR (toluene-d8) are shown below. Meso form: δ1.06(s,3H), δ1.17(s,3H), δ1.20(s,18H), δ1.60(s,3H), δ1.96(s,3H), δ2.11(s,3H), δ5.74(d,1H), δ6.55(d,1H), δ6.67(dd,1H), δ6.77(dd,1H), δ6.92(d,1H), δ7.08(d,1H), δ7.25(s,1H), δ7.36(d,2H),δ7.58(d,1H), δ7.67(d,1H), δ7.81(d,2H)

[0109] (1-c) Chemical treatment of ion-exchangeable layered silicate (clay support) In a separable flask, 96% sulfuric acid (1044 g) was added to 3456 g of distilled water. Granulated montmorillonite (600 g, Benclay SL manufactured by Mizusawa Chemical Industries, Ltd.: average particle size 19 μm) was added as an ion-exchange layered silicate to this sulfuric acid aqueous solution. The internal temperature of this slurry was raised to 90°C at a rate of 0.5°C / min over 1 hour, and the reaction was carried out at 90°C for 120 minutes. After the reaction, the reaction slurry was cooled to room temperature over 1 hour, and after cooling, 2400 g of distilled water was added. After filtration, 1230 g of a cake-like solid was obtained. Next, 648 g of lithium sulfate and 1,800 g of distilled water were added to a separable flask to prepare an aqueous solution, to which the entire cake-like solid was added, followed by 522 g of distilled water. The slurry was heated to 90°C at a rate of 0.5°C / min over 1 hour and reacted at 90°C for 120 minutes. After the reaction, the reaction slurry was cooled to room temperature over 1 hour, and after cooling, 1,980 g of distilled water was added and filtered. The filtrate was then repeatedly washed with distilled water until the pH reached 3, and 1,150 g of cake-like solid was obtained by filtration. The cake-like solid was pre-dried for 2 days at 130°C under a nitrogen stream, after which coarse particles of 53 µm or larger were removed, and the solid was placed in a glass container and dried under reduced pressure in an oil bath at 200°C for 2 hours or more to obtain 340 g of chemically treated smectite.

[0110] (1-d) Preparation of clay-supported catalyst (meso form of complex A) Under a nitrogen atmosphere, 1 g of the chemically treated smectite obtained in (1-c) was placed in a 100 ml glass reaction vessel and 6.5 ml of heptane was added to form a slurry. A triisobutylaluminum-n-heptane solution (140 mg / ml, 3.5 ml) was added with stirring and stirred for 1 hour. The mixture was then washed with heptane to a volume of 1 / 100, and finally brought to a total volume of 5 ml. A tri-n-octylaluminum-n-heptane solution (140 mg / ml, 0.6 ml) was added with stirring and allowed to react at room temperature for 5 minutes. A separately prepared solution of Complex A (14 mg, 15 μmol) in toluene (3 ml) was then added with stirring and allowed to react at room temperature for 1 hour. Heptane was then added to adjust the concentration to 50 mg clay / ml, producing a clay-supported catalyst slurry.

[0111] (1-e) Polymerization A 3-L autoclave was thoroughly dried under heating by passing nitrogen through it, and then a triisobutylaluminum-n-heptane solution (140 mg / ml, 5.6 ml) was added. Propylene (750 g) was then added, and the temperature was raised to 70°C. The clay-supported slurry of Complex A (4 ml, 200 mg clay) prepared in (1-d) above was then injected into the autoclave through a feed cylinder. The temperature was maintained at 70°C, and polymerization was carried out for 1 hour. After 1 hour, ethanol was injected through the cylinder to terminate the reaction, and the unreacted monomer was slowly depressurized. The recovered polymer weighed 71 g when dried under reduced pressure. The evaluation results of the obtained polymer are shown in Table 1.

[0112] [Example 2] Clay-supported evaluation using dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4,5-benzoindenyl)hafnium dichloride (Complex B):

[0113] [ka]

[0114] (2-a) Synthesis of dimethyl(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4,5-benzoindenyl)silane: Under a nitrogen atmosphere, 2,3-dimethyl-4-(4'-t-butylphenyl)indene (2.5 g, 9 mmol) and THF (80 ml) were placed in a 200 ml glass reaction vessel and cooled to -70°C in a dry ice-methanol bath while stirring. A n-butyllithium-n-hexane solution (1.51 mol / L, 6.0 ml, 9 mmol) was added dropwise to the vessel. After the dropwise addition, the vessel was gradually warmed to room temperature while stirring for 2 hours to obtain the lithiated product. Under a nitrogen atmosphere, a THF solution (30 ml) containing dimethyldichlorosilane (3.0 ml, 27 mmol) was prepared in a separate glass reaction vessel and cooled to -70°C in a dry ice-methanol bath. The above solution of the lithium compound was then slowly added to the vessel while stirring. After the dropwise addition, the temperature was gradually raised to room temperature and the mixture was stirred for 1 hour. After that, the solvent and excess dimethyldichlorosilane were distilled off under reduced pressure. After distillation, THF (30 ml) was added to the residue to obtain a solution of the chlorosilane compound. Under a nitrogen atmosphere, 2-(5'-methyl-2'-furyl)-4,5-benzoindene (2.2 g, 9 mmol) and THF (80 mL) were added to a 300 mL glass reaction vessel and cooled to -70°C in a dry ice-methanol bath with stirring. A n-butyllithium-n-hexane solution (1.51 mol / L, 6.0 mL, 9 mmol) was added dropwise. After the dropwise addition, the mixture was stirred for 2 hours while gradually warming to room temperature. After stirring for 2 hours, the reaction mixture was cooled to -70°C in a dry ice-methanol bath with stirring, and 1-methylimidazole (0.04 mL, 0.5 mmol) was added. While maintaining the temperature at -70°C, the above chlorosilane solution was slowly added. The mixture was then stirred overnight while gradually warming to room temperature. After stirring, distilled water was added to the reaction mixture, which was then transferred to a separatory funnel and washed with saline until neutral. After washing, anhydrous sodium sulfate was added to the organic layer to dry it. After drying, the anhydrous sodium sulfate was filtered off, and the solvent was removed from the filtrate by distillation under reduced pressure to obtain a pale yellow powder (5.2 g) of dimethyl(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)silane.

[0115] (2-b) Synthesis of dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4,5-benzoindenyl)hafnium dichloride (Complex B): Under a nitrogen atmosphere, dimethyl(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4,5-benzoindenyl)silane (5.2 g, 9 mmol) and diethyl ether (100 ml) were added to a 500 ml glass reaction vessel and cooled to -70°C in a dry ice-methanol bath with stirring. To this mixture was added dropwise n-butyllithium-n-hexane solution (1.51 mol / L, 12.0 ml, 18 mmol). After the dropwise addition, the mixture was warmed to room temperature and stirred for 2 hours. After the reaction, the reaction solution was concentrated under reduced pressure to approximately 20 ml. To the concentrated solution, toluene (150 ml) and diethyl ether (7.5 ml) were added and the mixture was cooled to -70°C in a dry ice-methanol bath with stirring. To this solution, 2.9 g (9 mmol) of hafnium tetrachloride was added. The mixture was then gradually warmed to room temperature and stirred overnight. After stirring, the solvent was removed from the reaction mixture under reduced pressure, and the resulting crude product was recrystallized by adding toluene / hexane to give yellow crystals of racemic (racemic / meso=99 / 1, 1.60 g) and meso (racemic / meso=3 / 97, 0.58 g) dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride.

[0116] The above-mentioned procedure was carried out on the obtained mesophase. 1 The identified values ​​obtained by H-NMR (toluene-d8) are shown below. Racemic: δ0.96(s,3H), δ0.98(s,3H), δ1.18(s,9H), δ1.84(s,3H), δ1.93(s,3H), δ2.20(s,3H), δ5.94(dd,1H), δ6.43(d,1H), δ6.64( dd,1H),δ6.96(dd,1H),δ7.07(dd,2H),7.10-7.32(m,5H),δ7.38(s,1H),δ7.43(d,1H),δ7.51(dd,1H),δ7.75(d,1H),δ7.81(d,1H) Meso form: δ0.90(s,3H), δ1.14(s,3H), δ1.18(s,9H), δ1.66(s,3H), δ1.93(s,3H), δ2.14(s,3H), δ5.88(dd,1H), δ6.66(dd,1H), δ6.79(dd,1H ),δ6.84(d,1H),δ6.98(d,1H),7.12-7.31(m,4H),δ7.38(s,1H),δ7.38(d,2H),δδ7.56(d,1H),7.58(d,1H),δ7.59(d,1H),δ7.78(d,1H)

[0117] (2-c) Preparation of clay-supported catalysts The same procedure as in Example 1(1-d) was carried out except that the racemic form of Complex B (12 mg, 15 μmol) was used instead of Complex A, to obtain a clay-supported catalyst slurry.

[0118] (2-d) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of Complex B prepared in (2-c) (6 ml, 300 mg) was used instead of the clay-supported slurry of Complex A. As a result, 61 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0119] [Example 3] Homogeneous polymerization with aluminoxane (MAO) using racemic complex B: (3-a) Preparation of MAO catalyst solution Under a nitrogen atmosphere, the racemic form of Complex B (11 mg, 13 μmol) from Example 2(2-b) and toluene (10 ml) were added to a 100 ml glass reaction vessel to prepare a solution. MAO-n-hexane solution (10 ml, manufactured by Tosoh Finechem Co., Ltd., MMAO3A, 5.9 wt%-Al) was added thereto with stirring, and the mixture was stirred for 30 minutes to prepare an MAO catalyst solution.

[0120] (3-b) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of Complex A was replaced with the MAO catalyst solution (4 ml, 2.6 μmol) of Complex B prepared in (3-a) above. As a result, 45 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0121] [Example 4] Clay-supported evaluation using mesomorphic complex B: (4-a) Preparation of clay-supported catalyst A clay-supported catalyst slurry was obtained in the same manner as in Example 1(1-d), except that the meso form of Complex B (12 mg, 15 μmol) of Example 2(2-b) was used instead of Complex A.

[0122] (4-b) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of Complex B (6 ml, 300 mg) prepared in (4-a) above was used instead of the clay-supported slurry of Complex A. As a result, 44 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0123] [Example 5] Homogeneous polymerization with MAO using meso form of complex B: (5-a) Preparation of MAO catalyst solution Under a nitrogen atmosphere, the meso form of Complex B (11 mg, 13 μmol) from Example 2(2-b) and toluene (10 ml) were added to a 100 ml glass reaction vessel to prepare a solution. MAO-n-hexane solution (10 ml, Tosoh Finechem, MMAO3A, 5.9 wt%-Al) was added thereto with stirring, and the mixture was stirred for 30 minutes to prepare a MAO catalyst solution.

[0124] (5-b) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of Complex A was replaced with the MAO catalyst solution (4 ml, 2.6 μmol) of Complex B prepared in (5-a) above. As a result, 8 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0125] [Example 6] Clay-supported evaluation using dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)hafnium dichloride (Complex C):

[0126] [ka]

[0127] (6-a) Synthesis of dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)silane: Under a nitrogen atmosphere, 2,3-dimethyl-4-(4'-t-butylphenyl)indene (3.0 g, 11 mmol) and THF (80 mL) were added to a 200 mL glass reaction vessel and cooled to -70 °C in a dry ice-methanol bath with stirring. A n-butyllithium-n-hexane solution (1.56 mol / L, 7.0 mL, 11 mmol) was added dropwise to the reaction vessel. After the dropwise addition, the mixture was gradually warmed to room temperature and stirred for 1.5 hours to obtain the lithium compound. Under a nitrogen atmosphere, a THF solution (80 mL) containing dimethyldichlorosilane (3.9 mL, 33 mmol) was added to a separate glass reaction vessel and cooled to -70 °C in a dry ice-methanol bath with stirring. The lithium compound solution was then slowly added. The mixture was then warmed to room temperature and stirred for 1.5 hours, after which the solvent and excess dimethyldichlorosilane were removed under reduced pressure. After distillation under reduced pressure, THF (80 ml) was added to the residue to give a solution of the chlorosilane compound. Under a nitrogen atmosphere, 2-cyclopropyl-4-(4'-t-butylphenyl)indene (3.1 g, 11 mmol) and THF (80 ml) were placed in a 300 ml glass reaction vessel and cooled to -70°C in a dry ice-methanol bath with stirring. An n-butyllithium-n-hexane solution (1.56 mol / L, 7.0 ml, 11 mmol) was added dropwise to the vessel. After the dropwise addition, the vessel was stirred for 1.5 hours while gradually warming to room temperature. The reaction mixture was cooled to -70°C in a dry ice-methanol bath with stirring, and 1-methylimidazole (0.05 ml, 0.5 mmol) was added. The chlorosilane solution was slowly added to the vessel. The mixture was then stirred overnight while gradually warming to room temperature. After stirring, distilled water was added to the reaction mixture, which was then transferred to a separatory funnel and washed with saline until neutral. After washing, anhydrous sodium sulfate was added to the organic layer to dry it, and the anhydrous sodium sulfate was filtered off. The solvent was then removed from the filtrate by distillation under reduced pressure. The resulting crude product was purified using a silica gel column (Kanto Chemical Co., Ltd. silica gel 60N (spherical, neutral), solvent: hexane / diethyl ether) to obtain a pale yellow powder of dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)silane (6.2 g, yield: 92%).

[0128] (6-b) Synthesis of dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)hafnium dichloride (Complex C): Under a nitrogen atmosphere, dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)silane (2.0 g, 3.2 mmol) and diethyl ether (100 mL) were added to a 500 mL glass reaction vessel and cooled to -70°C in a dry ice-ethanol bath with stirring. To this solution, n-butyllithium-n-hexane solution (1.56 mol / L, 4.0 mL, 6.4 mmol) was added dropwise. After the dropwise addition, the mixture was stirred at -70°C in a dry ice-methanol bath for 1 hour, then warmed to room temperature and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to approximately 20 mL. To the concentrated reaction mixture, toluene (100 mL) and diethyl ether (5 mL) were added, followed by 1.0 g (3.2 mmol) of hafnium tetrachloride with stirring. The mixture was then stirred overnight at room temperature. After stirring, the solvent in the reaction mixture was distilled off under reduced pressure, and the resulting crude product was recrystallized by adding toluene / hexane to the mixture, yielding yellow crystals of the racemic form (racemic / meso=72 / 28, 0.26 g) and meso form (racemic / meso=14 / 86, 63 mg) of dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)hafnium dichloride.

[0129] The above-mentioned test was carried out on the obtained racemic and meso isomers. 1 The identified values ​​obtained by H-NMR (toluene-d8) are shown below. Racemic: δ0.16(m,1H), δ0.54(m,1H), δ0.72(m,1H), δ0.86(m,1H), δ0.95(s,3H), δ1.04(s,3H),δ1.17(s,9H),δ1.20(s,9H),δ1.94(m,1H),δ1.92(s,3H),δ1.93( s,3H),6.82(s,1H),δ6.85(dd,1H),δ7.11(d,2H),δ7.14-7.32(m,3H),δ7.24( d,1H),δ7.36(d,2H),δ7.45(d,1H),δ7.56(d,1H),δ7.84(d,2H),δ7.90(br,1H) Meso form: δ0.15(m,1H), δ0.62(m,1H), δ0.72(m1H), δ0.90(s,3H), δ1.12(s,3H), δ1 .18(s,9H),δ1.21(s,9H),δ1.23(m,1H),δ1.80(m,1H),δ2.03(s,3H),δ2.06(s, 3H),δ6.65(dd,1H),δ6.74(dd,1H),δ6.77(s,1H),δ6.92(d,1H),δ7.14-7.33( m,3H),δ7.12(d,1H),δ7.36(d,2H),δ7.58(t,2H),δ7.78(d,2H),δ7.83(br,1H)

[0130] (6-c) Preparation of clay-supported catalyst (racemic form of complex C) The same procedure as in Example 1 (1-d) was carried out, except that the racemic form (13 mg, 15 μmol) of Complex C (6-b) above was used instead of Complex A, and the catalyst preparation concentration was 25 mg clay / ml of slurry, to obtain a clay-supported catalyst slurry.

[0131] (6-d) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of complex C (2 ml, 50 mg) prepared in (6-c) above was used instead of the clay-supported slurry of complex A. As a result, 44 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0132] [Example 7] Clay-supported evaluation using mesomorphic complex C: (7-a) Preparation of clay-supported catalyst The same procedure as in Example 1(1-d) was carried out, except that the meso form (13 mg, 15 μmol) of Complex C from Example 6(6-b) above was used instead of Complex A, and the catalyst preparation concentration was set to 16.7 mg clay / ml of slurry, to obtain a clay-supported catalyst slurry.

[0133] (7-b) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of complex C (3 ml, 50 mg) prepared in (7-a) above was used instead of the clay-supported slurry of complex A. As a result, 69 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0134] [Example 8] Clay-supported evaluation using dimethylsilylene(2,3-dimethylindenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride (Complex D):

[0135] [ka]

[0136] (8-a) Synthesis of dimethyl(2,3-dimethylindenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)silane: Under a nitrogen atmosphere, 2,3-dimethylindene (2.2 g, 15 mmol) and THF (100 mL) were added to a 300 mL glass reaction vessel and cooled to -70 °C in a dry ice-methanol bath while stirring. To this solution, n-butyllithium-n-hexane solution (1.56 mol / L, 9.8 mL, 15 mmol) was added dropwise. After the dropwise addition, the mixture was gradually warmed to room temperature and stirred for 1 hour to obtain the lithium compound. A THF solution (80 mL) containing dimethyldichlorosilane (5.5 mL, 46 mmol) was prepared in a separate glass reaction vessel and cooled to -70 °C in a dry ice-methanol bath while stirring, and the lithium compound solution was slowly added to the THF solution. After stirring at room temperature for 1 hour, the solvent and excess dimethyldichlorosilane were removed from the reaction mixture by vacuum distillation. To the resulting solution, THF (50 mL) was added to obtain a chlorosilane solution. Under a nitrogen atmosphere, 2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indene (5.0 g, 15 mmol) and THF (80 ml) were added to a 300 ml glass reaction vessel and cooled to -70°C in a dry ice-methanol bath with stirring. To this solution, n-butyllithium-n-hexane solution (1.56 mol / L, 9.8 ml, 15 mmol) was added dropwise. After the dropwise addition, the mixture was stirred for 2 hours while gradually warming to room temperature. The resulting solution was then cooled to -70°C in a dry ice-methanol bath, and 1-methylimidazole (0.06 ml, 0.8 mmol) was added. The chlorosilane solution was slowly added to this solution. The mixture was then stirred overnight while gradually warming to room temperature. After stirring, distilled water was added to the reaction mixture, which was then transferred to a separatory funnel and washed with saline until neutral. After washing, anhydrous sodium sulfate was added to the separated organic layer and dried. The anhydrous sodium sulfate was then filtered off, and the solvent was removed from the filtrate by distillation under reduced pressure. The resulting crude product was purified using a silica gel column (Kanto Chemical Co., Ltd. silica gel 60N (spherical, neutral), solvent: hexane / diethyl ether) to obtain a pale yellow powder of dimethyl(2,3-dimethylindenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)silane (5.0 g, yield: 62%).

[0137] (8-b) Synthesis of dimethylsilylene(2,3-dimethylindenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride (Complex D): Under a nitrogen atmosphere, dimethyl(2,3-dimethylindenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)silane (5.0 g, 9.5 mmol) and diethyl ether (120 ml) were added to a 500 ml glass reaction vessel and cooled to -70°C in a dry ice-methanol bath with stirring. To this solution, n-butyllithium-n-hexane solution (1.56 mol / L, 12 ml, 19 mmol) was added dropwise. After the dropwise addition, the mixture was warmed to room temperature and stirred for 2 hours. The reaction mixture was concentrated under reduced pressure to approximately 20 ml. To the concentrated solution, toluene (300 ml) and diethyl ether (15 ml) were added and cooled to -70°C in a dry ice-methanol bath. To this solution, 3.0 g (9.5 mmol) of hafnium tetrachloride was added. The mixture was then gradually warmed to room temperature and stirred overnight. After stirring, the solvent was removed from the reaction mixture by distillation under reduced pressure, and the resulting crude product was recrystallized by adding toluene / hexane to give yellow crystals of racemic (racemic / meso=89 / 11, 0.31 g) and meso (racemic / meso=8 / 92, 0.43 g) dimethylsilylene(2,3-dimethylindenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)hafnium dichloride.

[0138] The above-mentioned test was carried out on the obtained racemic and meso isomers. 1 The identified values ​​obtained by H-NMR (toluene-d8) are shown below. Racemic: δ0.97(s,3H), δ0.99(s,3H), δ1.17(s,9H), δ1.99(s,3H), δ2.12(s,3H), δ2.22(s,3H), δ5.79(d,1H), δ6.15(d,1H), δ6.5 4(dd,1H),δ6.80(d,1H),δ6.90(dd,1H),δ7.09(dd,1H)δ7.12(s,1H),δ7.25(d,2H),δ7.33(d,2H),δ7.56(d,1H),δ7.80(d,2H) Meso form: δ0.87(s,3H), δ1.12(s,3H), δ1.17(s,9H), δ1.71(s,3H), δ2.08(s,3H), δ2.25(s,3H), δ5.78(d,1H), δ6.62(d,1H), δ6.63(dd,1 H),δ6.72(dd,1H),δ7.06(d,1H),δ7.14(d,1H),δ6.98(dd,1H)δ7.19(s,1H),δ7.31(d,2H),δ7.52(d,1H),δ7.60(d,1H),δ7.73(d,2H)

[0139] (8-c) Preparation of clay-supported catalyst (racemic complex D) The same procedure as in Example 1(1-d) was carried out except that the racemic form of Complex D (12 mg, 15 μmol) of (8-d) above was used instead of Complex A, to obtain a clay-supported catalyst slurry.

[0140] (8-d) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of Complex D (10 ml, 500 mg) prepared in (8-c) above was used instead of the clay-supported slurry of Complex A. As a result, 64 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0141] [Example 9] Clay-supported evaluation using mesomorphic complex D: (9-a) Preparation of clay-supported catalyst The same procedure as in Example 1(1-d) was carried out except that the meso form of Complex D (13 mg, 15 μmol) of Example 8(8-b) was used instead of Complex A, to obtain a clay-supported catalyst slurry.

[0142] (9-b) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of Complex D (6 ml, 300 mg) prepared in (9-a) above was used instead of the clay-supported slurry of Complex A. As a result, 16 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0143] [Example 10] Clay-supported evaluation using dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)zirconium dichloride (Complex E):

[0144] [ka]

[0145] (10-a) Synthesis of dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)zirconium dichloride (Complex E) Under a nitrogen atmosphere, dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)silane (3.2 g, 5 mmol) and diethyl ether (100 mL) were added to a 500 mL glass reaction vessel and cooled to -70°C in a dry ice-ethanol bath with stirring. To this solution, n-butyllithium-n-hexane solution (1.56 mol / L, 7.0 mL, 10 mmol) was added dropwise. After the dropwise addition, the mixture was warmed to room temperature and stirred for 1 hour. The reaction solution was concentrated under reduced pressure to approximately 20 mL. To the concentrated reaction solution, toluene (150 mL) and diethyl ether (7.5 mL) were added and cooled to -70°C in a dry ice-ethanol bath. 1.2 g (5 mmol) of zirconium tetrachloride was added to the reaction solution. The mixture was then gradually warmed to room temperature and stirred overnight. The solvent was removed from the reaction mixture under reduced pressure, and the resulting crude product was recrystallized by adding toluene / hexane to obtain yellow crystals of dimethylsilylene(2,3-dimethyl-4-(4'-t-butylphenyl)indenyl)(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)zirconium dichloride (racemic / meso=59 / 41, 0.15 g).

[0146] The above-mentioned test was carried out on the obtained meso and racemic compounds. 1 The identified values ​​obtained by H-NMR (toluene-d8) are shown below. Racemic: δ0.18(m,1H), δ0.53(m,1H), δ0.71(m,1H), δ0.87(m,1H), δ0.95(s,3H), δ1.03(s, 3H), δ1.17(s,9H), δ1.20(s,9H), δ1.83(s,3H), δ1.85(m,1H), δ1.92(s,3H), δ6.77(dd, 1H), δ6.87(dd,1H),6.88(s,1H),δ7.14(d,1H),δ7.16-7.23(m,1H),δ7.23-7.33(m,2H) ,δ7.26(d,1H),δ7.36(d,2H),δ7.41(d,1H),δ7.51(d,1H),δ7.86(d,2H),δ7.95(br,1H), Meso form: δ0.17(m,1H), δ0.48-0.58(m,1H), δ0.61(m1H), δ0.70(m,1H), δ0.89(s,3H), δ1 .12(s,3H),δ1.18(s,9H),δ1.21(s,9H),δ1.71(m,1H),δ1.95(s,3H),δ2.01(s,3H), δ6.68(dd,1H),δ6.77(dd,1H),δ6.84(s,1H),δ6.87(dd,1H),δ6.94(d,1H),δ7.12(d ,1H),δ7.16-7.33(m,3H),δ7.35(d,2H),δ7.56(d,1H),δ7.81(d,2H),δ7.91(br,1H)

[0147] (10-b) Preparation of clay-supported catalyst (Complex E) The same procedure as in Example 1 (1-d) was carried out, except that Complex E (12 mg, 15 μmol) from (10-a) above was used instead of Complex A, and the catalyst preparation concentration was 15 mg clay / ml of slurry, to obtain a clay-supported catalyst slurry.

[0148] (10-c) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of Complex E (2 ml, 30 mg) prepared in (10-b) above was used instead of the clay-supported slurry of Complex A. As a result, 60 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0149] [Example 11] Clay-supported evaluation using dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6,7-dimethyl-s-indacenyl)hafnium dichloride (Complex F):

[0150] [ka]

[0151] (11-a) Synthesis of 3,5,6,7-tetrahydro-2-methyl-s-indacen-1-one: Under a nitrogen atmosphere, indane (10 g, 85 mmol), CHCl (90 mL), and 2-bromoisobutyl bromide (10 mL, 85 mmol) were added to a 300 mL glass reaction vessel, and the mixture was cooled to 0°C in an ice-water bath while stirring. Aluminum chloride (34 g, 254 mmol) was then slowly added to the reaction vessel. The mixture was then warmed to room temperature and stirred for 4 hours. The reaction mixture was added to a container containing ice, and the mixture was transferred to a separatory funnel for separation. The resulting organic layer was further washed with brine. After separation, anhydrous sodium sulfate was added to the organic layer to dry it, and the anhydrous sodium sulfate was then filtered off. The solvent was removed from the filtrate by distillation under reduced pressure. The resulting crude product was purified using a silica gel column (Kanto Chemical Silica Gel 60N (spherical, neutral), solvent: hexane) to obtain 3,5,6,7-tetrahydro-2-methyl-s-indacen-1-one (15 g, yield: 94%) as a colorless liquid.

[0152] (11-b) Synthesis of 1,2,3,5-tetrahydro-6,7-dimethyl-s-indacene: Under a nitrogen atmosphere, 3,5,6,7-tetrahydro-2-methyl-s-indacen-1-one (3.8 g, 20 mmol) and THF (200 mL) were added to a 300 mL glass reaction vessel and cooled to -30°C in a dry ice-ethanol bath while stirring. A methyllithium-diethyl ether solution (1.13 mol / L, 27 mL, 30 mmol) was added dropwise to the vessel. After the addition, the vessel was warmed to room temperature and stirred for 3.5 hours. Toluene was then added to the reaction solution, which was then transferred to a separatory funnel and washed with a mixture of water and brine. After washing, the organic layer was separated. The organic layer was further washed with water and brine. After separation, anhydrous sodium sulfate was added to the organic layer to dry it. The anhydrous sodium sulfate was then filtered, and the resulting filtrate was concentrated. To the concentrated solution, toluene (200 ml) and p-toluenesulfonic acid (77 mg, 0.4 mmol) were added under a nitrogen atmosphere with stirring. The mixture was then refluxed for 4 hours. The mixture was cooled to room temperature and washed successively with water, aqueous sodium carbonate, and brine. After washing, anhydrous sodium sulfate was added to the separated organic layer for drying. The anhydrous sodium sulfate was then filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The resulting crude product was purified using a silica gel column (Kanto Chemical Silica Gel 60N (spherical, neutral), solvent: hexane) to obtain 1,2,3,5-tetrahydro-6,7-dimethyl-s-indacene (2.7 g, yield: 73%) as a yellow liquid.

[0153] (11-c) Synthesis of dimethyl(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6,7-dimethyl-s-indacenyl)silane: Under a nitrogen atmosphere, 1,2,3,5-tetrahydro-6,7-dimethyl-s-indacene (2.0 g, 11 mmol) and THF (80 mL) were added to a 200 mL glass reaction vessel and cooled to -70 °C in a dry ice-ethanol bath with stirring. A n-butyllithium-n-hexane solution (1.56 mol / L, 7 mL, 11 mmol) was added dropwise. After the dropwise addition, the temperature was gradually raised to room temperature over 1 hour. The mixture was then stirred at room temperature for another 30 minutes to obtain the lithium compound. A THF solution (80 mL) containing dimethyldichlorosilane (3.9 mL, 33 mmol) was cooled to -70 °C in a dry ice-methanol bath with stirring, and the lithium compound solution was slowly added to the mixture. The temperature was then gradually raised to room temperature over 1 hour. After stirring at room temperature for another 30 minutes, the solvent and excess dimethyldichlorosilane were removed under reduced pressure. THF (20 ml) was added to the resulting residue and stirred to give a solution of the chlorosilane compound. Under a nitrogen atmosphere, 2-cyclopropyl-4-(4'-t-butylphenyl)indene (3.1 g, 11 mmol) and THF (80 ml) were added to a 200 ml glass reaction vessel and cooled to -70°C in a dry ice-ethanol bath with stirring. An n-butyllithium-n-hexane solution (1.56 mol / L, 7.0 ml, 11 mmol) was added dropwise to the reaction vessel. After the dropwise addition, the reaction vessel was gradually warmed to room temperature over 2 hours with stirring. The reaction vessel was then cooled to -70°C in a dry ice-methanol bath with stirring, and 1-methylimidazole (0.05 ml, 0.5 mmol) was added to the reaction vessel. The chlorosilane solution was then slowly added to the reaction vessel. The reaction vessel was then gradually warmed to room temperature and stirred overnight. Distilled water was then added to the reaction solution, and the layers were separated. The organic layer was washed with brine until neutral. After separation, anhydrous sodium sulfate was added to the organic layer and dried. The anhydrous sodium sulfate was then filtered, and the solvent was removed from the obtained filtrate by distillation under reduced pressure. The obtained crude product was purified using a silica gel column (Kanto Chemical Co., Ltd. silica gel 60N (spherical, neutral), solvent: hexane / diethyl ether) to obtain a pale yellow powder of dimethyl(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6,7-dimethyl-s-indacenyl)silane (3.1 g, yield 55%).

[0154] (11-d) Synthesis of dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6,7-dimethyl-s-indacenyl)hafnium dichloride (Complex F): Under a nitrogen atmosphere, dimethyl(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6,7-dimethyl-s-indacenyl)silane (3.1 g, 5.93 mmol) and diethyl ether (150 mL) were added to a 300 mL glass reaction vessel and cooled to -70 °C in a dry ice-ethanol bath with stirring. To this was added dropwise n-butyllithium-n-hexane solution (1.56 mol / L, 8 mL, 12 mmol). After the dropwise addition, the mixture was stirred at -70 °C for 1 hour and then gradually warmed to room temperature over 1 hour. The resulting reaction solution was concentrated under reduced pressure to a total volume of approximately 20 mL. After concentration, toluene (150 mL) and diethyl ether (7.5 mL) were added to the concentrated solution and cooled to -70 °C in a dry ice-ethanol bath with stirring. 1.9 g (5.9 mmol) of hafnium tetrachloride was added to the mixture. Thereafter, the temperature was gradually raised to room temperature, and stirring was continued overnight. The solvent was then removed under reduced pressure, and the resulting crude product was recrystallized by adding toluene / hexane to obtain the racemic isomer (racemic / meso=92 / 8,480 mg) and meso isomer (racemic / meso=18 / 82,430 mg) of dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6,7-dimethyl-s-indacenyl)hafnium dichloride.

[0155] The above-mentioned test was carried out on the obtained racemic and meso isomers. 1 The identification values ​​obtained by H-NMR (chloroform-d) are shown below. Racemic: δ0.38-0.49(m,1H), δ0.65-0.78(m,1H), δ0.81-0.98(m,1H), δ0.98-1.09(m,1H), δ1.2 7(s,3H)δ1.32(m,12H),δ1.47(s,3H),δ1.97-2.17(m,3H),δ2.12(s,3H),δ2.25(s,3H),δ2.73 -2.85(m,1H),δ2.85-2.96(m,1H),δ2.96-3.09(m,1H),δ3.09-3.32(m,1H),δ6.43(s,1H),δ7. 00(dd,1H),δ7.24(s,1H),δ7.26(s,1H),δ7.41(d,1H),7.44-7.49(m,1H),δ7.52-7.61(m,3H) Meso form: δ0.35-0.49(m,1H), δ0.65-0.79(m,1H), δ0.81-0.97(m,1H), δ0.97-1.11(m,1H), δ1.29-1.34(m,12H),δ1.35(s,3H),δ1.97-2.17(m,3H),δ1.85-1.96(m,1H),δ2.33(s, 3H), δ2.35(s,3H), δ2.56-2.69(m,1H), δ2.74-3.00(m,4H), δ6.54(s,1H), δ6.76(dd,1 H),δ7.04(d,1H),δ7.13(s,1H),δ7.40(d,2H),δ7.44(s,1H),7.49(d,2H),δ7.68(d,1H)

[0156] (11-e) Preparation of clay-supported catalyst (racemic complex F) A clay-supported catalyst slurry was obtained by the same procedure as in Example 1(1-d), except that the racemic form of Complex F (12 mg, 15 μmol) from Example 11(11-d) above was used instead of Complex A and the concentration was adjusted to 33 mg clay / ml.

[0157] (11-f) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of Complex F prepared in (11-e) above (3 ml, 100 mg) was used instead of the clay-supported slurry of Complex A. As a result, 40 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0158] [Example 12] Clay-supported evaluation using mesomorphic complex F: (12-a) Preparation of clay-supported catalyst A clay-supported catalyst slurry was obtained by the same procedure as in Example 1(1-d), except that the meso form (12 mg, 15 μmol) of Complex F from Example 11(11-d) above was used instead of Complex A and the concentration was adjusted to 20 mg clay / ml.

[0159] (12-b) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of Complex F (2 ml, 40 mg) prepared in (12-a) above was used instead of the clay-supported slurry of Complex A. As a result, 19 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0160] [Example 13] Clay-supported evaluation using dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6-methyl-7-(4'-t-butylphenyl)-s-indacenyl)hafnium dichloride (Complex G):

[0161] [ka]

[0162] (13-a) Synthesis of 1,2,3,5-tetrahydro-6-methyl-7-(4'-t-butylphenyl)-s-indacene: Under a nitrogen atmosphere, 1-bromo-4-t-butyl-benzene (6.3 g, 30 mmol) and diethyl ether (150 ml) were added to a 500 ml glass reaction vessel and cooled to -70 °C in a dry ice-ethanol bath while stirring. A n-butyllithium n-hexane solution (1.56 mol / L, 19 ml, 30 mmol) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour to obtain the lithium derivative. The resulting reaction solution was then cooled to -70 °C in a dry ice-ethanol bath with stirring, and a diethyl ether solution (50 ml) containing 2-methyl-s-indacen-1-one (5.0 g, 27 mmol) was added dropwise with stirring. After the dropwise addition, the mixture was returned to room temperature and stirred for 1 hour. Distilled water was then added to the reaction solution, which was then transferred to a separatory funnel. Hydrochloric acid was then added to wash the reaction solution. After separation, the organic layer was further washed with brine until neutral. After separation, the organic layer was dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was filtered off, and the solvent was removed from the resulting filtrate by distillation under reduced pressure to obtain a crude product. Under a nitrogen atmosphere, the resulting crude product, toluene (300 ml), and p-toluenesulfonic acid (260 mg, 1.3 mmol) were added to a 500 ml glass reaction vessel with stirring, and the mixture was heated to reflux using a Deen-Stark-Trap. After cooling to room temperature, distilled water was added to the reaction mixture, and the solution was transferred to a separatory funnel for separation. The resulting organic layer was washed with aqueous sodium carbonate. After separation, the organic layer was washed with brine until neutral. After separation, anhydrous sodium sulfate was added to the organic layer and dried. The anhydrous sodium sulfate was filtered off, and the solvent was removed from the resulting filtrate by distillation under reduced pressure. The obtained crude product was purified using a silica gel column (Kanto Chemical Silica Gel 60N (spherical, neutral), solvent: hexane) to obtain a colorless powder of 1,2,3,5-tetrahydro-6-methyl-7-(4'-t-butylphenyl)-s-indacene (5.5 g, yield: 68%).

[0163] (13-b) Synthesis of dimethyl(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6-methyl-7-(4'-t-butylphenyl)-s-indacenyl)silane: Under a nitrogen atmosphere, 1,2,3,5-tetrahydro-6-methyl-7-(4'-t-butylphenyl)-s-indacene (3.1 g, 10 mmol) and THF (80 mL) were added to a 200 mL glass reaction vessel and cooled to -70 °C in a dry ice-ethanol bath with stirring. To this was added dropwise a n-butyllithium-n-hexane solution (1.56 mol / L, 6.6 mL, 10 mmol) with stirring. After the dropwise addition, the mixture was gradually heated to -10 °C and stirred for 1 hour. The mixture was then warmed to room temperature and stirred for an additional 30 minutes to obtain the lithiated product. A THF solution (80 mL) containing dimethyldichlorosilane (3.7 mL, 30 mmol) was cooled to -70 °C in a dry ice-methanol bath with stirring, and the lithiated product solution was slowly added to the mixture. The mixture was then gradually heated to -10 °C and stirred for 1 hour, then warmed to room temperature and stirred for an additional 30 minutes. The solvent and excess dimethyldichlorosilane were then removed by distillation under reduced pressure, and THF (20 ml) was added to the resulting crude product to give a solution of the chlorosilane compound. Under a nitrogen atmosphere, 2-cyclopropyl-4-(4'-t-butylphenyl)indene (3.0 g, 10 mmol) and THF (80 mL) were added to a 300 mL glass reaction vessel and cooled to -70 °C in a dry ice-ethanol bath with stirring. A n-butyllithium-n-hexane solution (1.56 mol / L, 6.6 mL, 10 mmol) was added dropwise. After the dropwise addition, the mixture was stirred for 1 hour while gradually warming to room temperature. The reaction mixture was then cooled to -70 °C in a dry ice-ethanol bath with stirring, and 1-methylimidazole (0.04 mL, 0.5 mmol) was added. The chlorosilane solution was then slowly added. The mixture was then gradually warmed to -10 °C and stirred for 1 hour. After 1 hour, the mixture was warmed to room temperature and further stirred overnight. Distilled water was added to the resulting reaction mixture, which was then transferred to a separatory funnel and washed with hydrochloric acid. After separation, the organic layer was further washed with brine until neutral. After separation, anhydrous sodium sulfate was added to the organic layer and dried. The anhydrous sodium sulfate was filtered off, and the solvent was removed from the obtained filtrate by distillation under reduced pressure. The obtained crude product was purified using a silica gel column (Kanto Chemical Co., Ltd. silica gel 60N (spherical, neutral), solvent: hexane / diethyl ether) to obtain a pale yellow powder of dimethyl(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6-methyl-7-(4'-t-butylphenyl)-s-indacenyl)silane (5.5 g, yield: 82%).

[0164] (13-c) Synthesis of dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6-methyl-7-(4'-t-butylphenyl)-s-indacenyl)hafnium dichloride (Complex G): Under a nitrogen atmosphere, dimethyl(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6,7-dimethyl-s-indacenyl)silane (5.5 g, 8.4 mmol) and diethyl ether (200 mL) were added to a 300 mL glass reaction vessel and cooled to -70°C in a dry ice-ethanol bath with stirring. To this was added dropwise n-butyllithium-n-hexane solution (1.56 mol / L, 13 mL, 17 mmol). After the dropwise addition, the mixture was stirred at -70°C for 1 hour, and then gradually warmed to room temperature while stirring for 1 hour. After 1 hour, the reaction mixture was concentrated under reduced pressure to a total volume of approximately 20 mL. After concentration, toluene (250 mL) and diethyl ether (13 mL) were added to the concentrated mixture and cooled to -70°C in a dry ice-ethanol bath with stirring. 2.7 g (8.4 mmol) of hafnium tetrachloride was added thereto, and the mixture was then stirred overnight while gradually warming to room temperature. The solvent was then removed from the reaction mixture by distillation under reduced pressure, and the resulting crude product was recrystallized by adding toluene / hexane to obtain a racemic mixture of dimethylsilylene(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)(1,2,3,5-tetrahydro-6-methyl-7-(4'-t-butylphenyl)-s-indacenyl)hafnium dichloride (racemic / meso=100 / 0.760 mg).

[0165] The above-mentioned test was carried out on the obtained racemic and meso isomers. 1 The identification values ​​obtained by H-NMR (chloroform-d) are shown below. Racemic: δ0.40-0.50(m,1H), δ0.70-0.81(m,1H), δ0.83-0.94(m,1H), δ1.03-1.15(m,1H), δ1.29(s,9H), δ1.33( s,9H),δ1.37(s,3H),δ1.39(s,3H),δ1.97-2.17(m,3H),δ2.12(s,3H),δ1.92-2.04(m,1H),δ2.04-2.15(m,1H) ,δ2.17-2.27(m,1H),δ2.30(s,3H),δ2.76-2.99(m,3H),δ3.11-3.23(m,1H),δ6.42(s,1H),δ6.94(dd,1H),δ7 .21(d,1H),δ7.29(d,2H),δ7.37(d,2H),δ7.39(s,1H),δ7.42(d,2H),δ7.54(s,1H),7.56(d,2H),δ7.62(d,1H) Meso form: δ0.38-0.50(m,1H), δ0.80-0.95(m,1H), δ0.98-1.08(m,1H), δ1.15-1.24(m,1H), δ1.31( s,3H)δ1.33(s,9H),δ1.35(s,9H),δ1.37(s,3H),δ1.51(s,3H),δ1.78-2.15(m,3H),δ2.52(s, 3H), δ2.61-2.87(m,3H), δ2.87-2.99(m,1H), δ6.56(s,1H), δ6.77(dd,1H), δ7.07(d,1H), δ7. 17(s,1H),δ7.35(d,2H),δ7.42(d,2H),δ7.46(d,2H),7.51(d,2H),δ7.54(s,1H),δ7.75(d,1H)

[0166] Clay-supported evaluation using the racemic form of complex G: (13-d) Preparation of clay-supported catalysts A clay-supported catalyst slurry was obtained by the same procedure as in Example 1(1-d), except that the racemic form of Complex G (13 mg, 15 μmol) from Example 13(13-c) above was used instead of Complex A and the concentration was adjusted to 33 mg clay / ml.

[0167] (13-e) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of Complex G (6 ml, 200 mg) prepared in (13-d) above was used instead of the clay-supported slurry of Complex A. As a result, 68 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0168] [Comparative Example 1] (C1-a) Synthesis of dimethylsilylenebis(2-(5'-methyl-2'-furyl)-4-(4'-iso-propylphenyl)indenyl)hafnium dichloride (Complex X): Synthesis was performed with reference to Example 11 of JP 2009-299045 A, and a racemic mixture (racemic / meso=100 / 0) was obtained.

[0169] [ka]

[0170] (C1-b) Preparation of clay-supported catalyst (Complex X) The same procedure as in Example 1(1-d) was carried out except that Complex X (14 mg, 15 μmol) of (C1-a) above was used instead of Complex A, and the catalyst preparation concentration was 20 mg clay / ml of slurry, to obtain a clay-supported catalyst slurry.

[0171] (C1-c) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of complex X (2 ml, 40 mg) prepared in (C1-b) above was used instead of the clay-supported slurry of complex A. As a result, 25 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0172] Comparative Example 2 (C2-a) Synthesis of dimethylsilylene(2-methyl-4-(4'-t-butylphenyl)indenyl)(2-(5'-methyl-2'-furyl)-4-(4'-t-butylphenyl)indenyl)zirconium dichloride (Complex Y): Synthesis was carried out with reference to Example 4 of JP 2008-280360 A, and a racemic mixture (racemic / meso=100 / 0) was obtained.

[0173] [ka]

[0174] (C2-b) Preparation of clay-supported catalyst (complex Y) The same procedure as in Example 1(1-d) was carried out, except that instead of complex A, complex Y (12 mg, 15 μmol) from (C2-a) above was used and the catalyst preparation concentration was 20 mg clay / ml of slurry, to obtain a clay-supported catalyst slurry.

[0175] (C2-c) Polymerization The same procedure as in Example 1 (1-e) was carried out, except that the clay-supported slurry of complex Y prepared in (C2-b) above (3 ml, 60 mg) was used instead of the clay-supported slurry of complex A. As a result, 130 g of polymer was obtained. The evaluation results of the obtained polymer are shown in Table 1.

[0176] [Table 1] In the table, "not detected" means below the detection limit, and "-" means not measured.

[0177] [Consideration] As is clear from Table 1, in Examples 1 to 13, by using the olefin polymerization catalyst containing the metallocene complex of the present invention and the method for producing a propylene polymer, propylene polymers were obtained that had a high vinyl selectivity of 95% or more, a moderately low molecular weight (Mw) of 9,900 to 140,000, and a wide melting point range of 108° C. to 153° C. Furthermore, it was found that in Examples 6, 7, and 10, the catalytic activity was high and propylene polymers could be produced efficiently. In Examples 2 to 5, clay-supported catalysts and MAO catalysts were evaluated for the racemic and meso isomers of the same complex B. The results show that propylene polymers can be efficiently obtained using either MAO or ion-exchanged layered silicate as the catalyst component. From Examples 6 to 7, R 11Complex C, which has a three-membered cyclopropyl group introduced into the nucleus, exhibited high catalytic activity, especially the meso form. Furthermore, when the central metal (M) is Zr and the indenyl ligand in the metallocene complex has a substituent at the 2-position, the polymer obtained by bulk polymerization of propylene is a high molecular weight polymer. However, in Example 10, a polymer having a moderately low molecular weight, high vinyl selectivity, and a moderate melting point was obtained, and furthermore, the catalytic activity was high. Comparative Example 1 is a conventional macromer complex X. When compared under the same polymerization conditions, each Example shows that a propylene polymer having a higher vinyl selectivity, a lower molecular weight, and a lower melting point can be produced than Comparative Example 1. Thus, when compared under the same polymerization conditions, the complex of the present invention shows a higher vinyl selectivity and is superior as a complex for producing a macromer. The complex Y of Comparative Example 2 was R 2 is unsubstituted and R 11 The polymer obtained from this complex Y has a very high molecular weight and is unsuitable for macromer applications. In addition, since a high molecular weight polymer is obtained, it is thought that the elimination reaction during polymerization is suppressed, and the number of terminal vinyl groups is expected to be small. 11 The influence of whether R is a cyclopropyl group or a furyl group on the polymer can be considered as follows, based on the relationship between Complex A (Example 1) and Complex C (Example 7). 11 When R is a cyclopropyl group, the catalytic activity improves and the molecular weight and melting point tend to increase slightly, but the vinyl selectivity is the same, and it is clear that the difference does not affect the polymer structure. Therefore, the difference in the molecular weight of the polymer between complex Y and complex E (complex Y has a much higher molecular weight) is due to the difference in R 2 It arises from the presence or absence of substituents, and R 2 It is speculated that the substituents affect the elimination reactions that occur during polymerization, which change the molecular weight of the polymer. From the comparison between the Examples and Comparative Examples, it can be seen that the 2-position (R 1 ) and 3rd place (R 2 ) and the 2-position of the other indenyl ligand (R 11) and the 3-position (hydrogen atom) have a specific structure in combination, which results in high vinyl selectivity, a moderately low molecular weight, and a low melting point. [Industrial Applicability]

[0178] By using an olefin polymerization catalyst containing the metallocene complex of the present invention, it is possible to produce propylene polymers with high vinyl selectivity, moderately low molecular weights, and a wide melting point range. It is possible to modify the melting point and molecular weight of propylene polymers containing terminal vinyl groups, which is expected to improve transparency and flexibility. Such propylene polymers are useful for macromers. It is expected that by using an olefin polymerization catalyst containing the metallocene complex of the present invention, it is possible to efficiently produce propylene polymers having a branched structure. The improved melt tension of propylene polymers having a branched structure is expected to enable applications in sheet molding, blow molding, thermoforming, foam molding, and other processes that require materials with relatively high melt tension. Furthermore, the side chains of propylene polymers having a branched structure can be made to have a lower melting point, which also makes it possible to improve transparency and flexibility.

Claims

1. A metallocene complex represented by the following general formula [I]: 【Chemical 1】 (In formula [I], M is zirconium or hafnium; Y is a carbon atom or a silicon atom; X １ and X ２ each independently represents an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms; R １ is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, R １１ represents a saturated or unsaturated alicyclic hydrocarbon group having 3 to 5 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a 4- or 5-membered saturated or unsaturated heterocyclic group which contains one heteroatom selected from an oxygen atom and a sulfur atom and which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, R ２ represents an aryl group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 6 carbon atoms, R ３ , R ４ , R ５ , R １３ , R １４ , and R １５ 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 silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms substituted with a halogen atom, a furyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, a thienyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms or a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, a benzofuryl group, or a benzothienyl group, or adjacent substituents may be joined together to form a 5- or 6-membered cyclic structure, which cyclic structure may contain an unsaturated bond, R ６ and R １６ are each independently an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group, an aryl group having 6 to 10 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms substituted with a halogen atom; R ６ and R １６ Both may form a 4- or 5-membered ring containing Y.)

2. In the general formula [I], R ３ , R ４ , R ５ , R １３ , R １４ , and R １５ are each independently a hydrogen atom, an aryl group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms, or adjacent substituents may be joined together to form a 5- or 6-membered cyclic structure, and the cyclic structure may contain an unsaturated bond.

3. In the general formula [I], R １１ is a cycloalkyl group having 3 to 5 carbon atoms which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, a furyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a thienyl group which may be substituted with a hydrocarbon group having 1 to 6 carbon atoms.

4. In the general formula [I], R ２ 2. The metallocene complex according to claim 1, wherein is an alkyl group having 1 to 6 carbon atoms.

5. In the general formula [I], R １ is a hydrogen atom, a methyl group, or an ethyl group, and R ２ 2. The metallocene complex according to claim 1, wherein is a methyl group or an ethyl group.

6. A catalyst for olefin polymerization comprising the following components (A), (B) and (C): Component (A): the metallocene complex according to any one of claims 1 to 5 Component (B): A component containing at least one selected from the group consisting of the following (b-1) and (b-2): (b-1) A component containing a compound that reacts with component (A) to form an ion pair. (b-2) Ion-exchange layered compound Component (C): Alkyl aluminum compound

7. 7. The olefin polymerization catalyst according to claim 6, wherein the component (B) contains an aluminoxane compound or an ion-exchange layered silicate.

8. 8. The olefin polymerization catalyst according to claim 7, wherein the ion-exchanged layered silicate contains montmorillonite as a main component.

9. A method for producing a propylene polymer, comprising polymerizing or copolymerizing propylene in the presence of the olefin polymerization catalyst according to claim 6.

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