JP5105772B2 - Method for producing syndiotactic α-olefin polymer - Google Patents

Description

  The present invention relates to an olefin polymerization catalyst containing a crosslinked metallocene compound having a specific structure, and a method for producing an olefin polymer using the olefin polymerization catalyst.

As a homogeneous catalyst for olefin polymerization, a so-called metallocene compound is well known. The method of polymerizing olefins using metallocene compounds, especially the method of stereoregularly polymerizing α-olefins, has been reported to be a further improvement in polymerization activity and stereoregularity since isotactic polymerization was reported by W. Kaminsky et al. Many improvement studies have been conducted from the viewpoint of improvement (Non-patent Document 1).

As a part of such research, it is a transition metal catalyst with isopropylidene (cyclopentadienyl) (9-fluorene) synthesized from a ligand obtained by crosslinking cyclopentadienyl and fluorenyl with isopropylidene. JA Ewen reported that propylene polymerization in the presence of a catalyst comprising a metallocene compound and an aluminoxane resulted in a polypropylene with a high tacticity such that the syndiotactic pentad fraction exceeded 0.7 ( Non-patent document 2).

As an improvement of this metallocene, an attempt has been made to improve stereoregularity by changing fluoryl to a 2,7-di-tert-butylfluorenyl group (Patent Document 1).
In addition, attempts to improve stereoregularity by changing fluoryl to 3,6-di-tert-butylfluorenyl group (Patent Document 2), and conversion of the cross-linking part connecting cyclopentadienyl and fluorenyl Attempts to do this have been reported (Patent Documents 3 and 4). In addition, dimethylmethylene (3-tert-butyl-5-methylcyclohexane) in which a methyl group is introduced into the 5-position of the cyclopentadienyl ring from dimethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride. Isotactic polypropylene with a higher molecular weight can be obtained with pentadienyl) (fluorenyl) zirconium dichloride (Patent Document 5).

  However, the polymerization performance of these metallocene compounds is not sufficient. Further, the conventional catalyst does not mean that an α-olefin polymer having a somewhat high melting point, which is an index of stereoregularity, cannot be obtained, but a high molecular weight catalyst cannot be obtained. Therefore, it has been desired to produce a polymer having a high melting point and a high molecular weight. It has also been desired to obtain a polymer having a higher melting point than before. Further, in order to enable industrialization, it is desired that an α-olefin polymer having the above characteristics can be produced at a temperature higher than normal temperature, preferably higher than normal temperature. Did not exist.

  In addition, even a catalyst having improved specific α-olefin polymerization performance is not necessarily suitable for other α-olefins such as ethylene polymerization. The catalyst had to be changed, and it was very inconvenient to manufacture.

As a result of intensive studies in view of such circumstances, the present inventors have found that when an α-olefin such as propylene is polymerized using an olefin polymerization catalyst including a specific transition metal catalyst, not only at room temperature. It has been found that an α-olefin polymer having a high melting point can be obtained even in polymerization at a high temperature that can be industrialized, and even when an α-olefin mainly composed of ethylene is polymerized under a high temperature polymerization condition, good activity can be obtained. In addition, the inventors have found that an ethylene polymer having a high molecular weight can be obtained, that is, that the polymer exhibits high performance over a wide range of polymerizations, and the present invention has been completed.
JP-A-4-69394 JP 2000-212194 A Japanese Patent Laid-Open No. 2004-189666 JP 2004-189667 A Special table 2001-526730 gazette Angew. Chem. Int. Ed. Engl. , 24, 507 (1985) J. et al. Am. Chem. Soc. , 1988, 110, 6255

  The problem to be solved by the present invention is that, when an α-olefin such as propylene is polymerized, an α-olefin polymer having a high melting point and a sufficient molecular weight can be obtained not only at room temperature but also at a high temperature. In addition, even when an α-olefin having ethylene as a main component is polymerized under a high temperature condition, an ethylene polymer having a high activity and a high molecular weight can be obtained, that is, production of a wide range of olefin polymers. It is to provide an olefin polymerization catalyst exhibiting high performance against the above. Moreover, it is providing the manufacturing method of an olefin polymer using such a catalyst for olefin polymerization.

The olefin polymerization catalyst of the present invention comprises:
(A) a bridged metallocene compound represented by the following general formula [I], and (B) (b-1) an organoaluminum oxy compound,
(b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and
(b-3) consisting of at least one compound selected from organoaluminum compounds;

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are selected from hydrogen, a hydrocarbon group and a silicon-containing group, and each may be the same or different;
The four groups R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not hydrogen atoms but are selected from hydrocarbon groups and silicon-containing groups, which may be the same or different,
R ² and R ³ may be bonded to each other to form a ring, and R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹¹ and R ^In one or more adjacent group combinations selected from ¹² , the adjacent groups may be bonded to each other to form a ring.

R ¹³ and R ¹⁴ are atoms or substituents selected from the group consisting of a hydrogen atom, a hydrocarbon group excluding a methyl group, and a silicon atom-containing group, and may be the same or different from each other. They may combine to form a ring.

M is Ti, Zr or Hf,
Y is carbon or silicon;
Q is selected from a halogen, a hydrocarbon group, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair, and each may be the same or different,
j is an integer of 1-4. ).

In the general formula [I], R ¹ , R ² , R ³ and R ⁴ are preferably hydrogen.
The olefin polymerization catalyst of the present invention preferably further contains a carrier (C).
The method for producing an olefin polymer of the present invention comprises polymerizing one or more monomers selected from α-olefins having 2 or more carbon atoms in the presence of the olefin polymerization catalyst.

When an α-olefin having 3 or more carbon atoms such as propylene is polymerized using the olefin polymerization catalyst of the present invention, the melting point is high and the molecular weight is sufficiently high not only at room temperature but also at high temperature. An α-olefin polymer can be obtained with good activity, and even when an α-olefin containing at least a part of ethylene is polymerized under the high temperature conditions using the same catalyst, the α-olefin polymer has good activity and is sufficient. High molecular weight ethylene polymers can be obtained, i.e. high performance for the production of a wide range of olefin polymers.
Further, by producing an olefin polymer using such an olefin polymerization catalyst, an α-olefin polymer having a high melting point and a sufficiently high molecular weight can be obtained with good activity even under high temperature conditions. In addition, even when an α-olefin containing at least a part of ethylene is polymerized under high temperature conditions using the same catalyst, an ethylene polymer having a good activity and a sufficiently high molecular weight can be obtained.

The olefin polymerization catalyst of the present invention comprises:
(A) a bridged metallocene compound represented by the general formula [I], and (B) (b-1) an organoaluminum oxy compound,
(b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and
(b-3) It comprises at least one compound selected from organoaluminum compounds.

  BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the invention will be sequentially described with respect to a crosslinked metallocene compound related to an olefin polymerization catalyst of the present invention, an olefin polymerization catalyst containing the crosslinked metallocene compound, and a method of polymerizing in the presence of the olefin polymerization catalyst. .

(A) Bridged metallocene compound (A) The bridged metallocene compound represented by the general formula [1] (also referred to as “component (A)” in this specification) has the following chemical structure features: [m1] to [m2] provided.
[m1] Of the two ligands, one is a cyclopentadienyl group which may have a substituent, and the other is a fluorenyl group having a substituent (hereinafter referred to as “substituted fluorenyl group”). It may be called.)
[m2] The transition metal (M) constituting the metallocene compound is titanium, zirconium or hafnium.

  Hereinafter, after sequentially explaining the cyclopentadienyl group, the substituted fluorenyl group, the bridged portion, and other characteristics which may have a substituent, which are the characteristics of the chemical structure of the bridged metallocene compound according to the present invention, these A preferred bridged metallocene compound having characteristics and examples thereof, and finally, the polymerization method of the present invention using the bridged metallocene compound will be described in detail.

Which may have a substituent cyclopentadienyl group cyclopentadienyl group may or may not be substituted. The unsubstituted cyclopentadienyl group is a cyclopentadienyl group in which R ¹ , R ² , R ³ and R ⁴ possessed by the cyclopentadienyl group moiety in the general formula [I] are all hydrogen atoms. In the substituted cyclopentadienyl group, at ^{least one} of R ¹ , R ² , R ³ and R ⁴ is substituted with a hydrocarbon group (f1) or a silicon-containing group (f2) It may be a cyclopentadienyl group. When two or more of R ¹ , R ² , R ³ and R ⁴ are groups other than hydrogen atoms, these groups may be the same as or different from each other.

As the hydrocarbon group (f1) used for R ^{1 to} R ^4, when the substituent does not form a ring together with other substituents, a hydrocarbon group having 1 to 20 carbon atoms in total ( Hereinafter, “hydrocarbon group (f1 ′)” is also preferable.

In the case where R ² and R ³ are hydrocarbon groups (f1), R ² and R ³ are bonded to each other to form a ring (hereinafter also referred to as “ring (f ′ ″)”). There are cases where it exists. In this case, among R ^{1 to} R ⁴ , it is further preferable that only R ² and R ³ form a ring from the viewpoint of producing a highly stereoregular, for example, syndiotactic poly α-olefin.

For example, when the substituents R ² and R ³ are bonded to each other to form a ring, the ring is formed regardless of whether the above-mentioned preferred R ² and R ³ each have 1 to 20 carbon atoms. The total number of carbon atoms of the two substituents is preferably 2 to 40, more preferably 3 to 30, and still more preferably 4 to 20.

Further, even when the substituents R ² and R ³ are bonded to each other to form a ring, some of the hydrogen atoms directly bonded to the carbon of the substituent are halogen atoms, oxygen-containing groups, nitrogen-containing groups, silicon In this case, the total number of carbon atoms of the two substituents forming the ring is the number of carbon atoms contained in the oxygen-containing group, nitrogen-containing group, and silicon-containing group. Also included.

The hydrocarbon group having 1 to 20 carbon atoms (f1 ′) is an alkyl group, an alkenyl group, an alkynyl group or an aryl group composed only of carbon and hydrogen.
The hydrocarbon group having 1 to 20 carbon atoms (f1 ′) includes, in addition to alkyl groups, alkenyl groups, alkynyl groups, and aryl groups composed only of carbon and hydrogen, a part of hydrogen atoms directly connected to these carbon atoms. Also included are heteroatom-containing hydrocarbon groups in which is substituted with a halogen atom, an oxygen-containing group, a nitrogen-containing group, or a silicon-containing group. As such a hydrocarbon group (f1 ′), a methyl group,
Ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, etc. Linear hydrocarbon group; isopropyl group, t-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, Branched hydrocarbon groups such as 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group Cyclic saturated hydrocarbon groups such as cyclooctyl group, norbornyl group and adamantyl group; cyclic unsaturated hydrocarbon groups such as phenyl group, naphthyl group, biphenyl group, phenanthryl group and anthracenyl group and their nuclear alkyl substituents; benzyl group , Kumi A saturated hydrocarbon group substituted with an aryl group such as methoxy group; methoxy group, ethoxy group, phenoxy group N-methylamino group, trifluoromethyl group, tribromomethyl group, pentafluoroethyl group, pentafluorophenyl group, fluorophenyl group And heteroatom-containing hydrocarbon groups such as chlorophenyl group, bromophenyl group, chlorobenzyl group, fluorobenzyl group, bromobenzyl group, dichlorobenzyl group, difluorobenzyl group, trichlorobenzyl group, trifluorobenzyl group, etc. .

  The silicon-containing group (f2) is a group having a silicon atom covalently bonded to the ring carbon of the cyclopentadienyl group, and specifically an alkylsilyl group or an arylsilyl group. Preferred silicon-containing groups (f2) may include silicon-containing groups (f2 ′) having a total carbon number of 1 to 20 when the substituent does not form a ring with other substituents. Examples thereof include a trimethylsilyl group and a triphenylsilyl group.

In this cyclopentadienyl group, R ¹ and R ⁴ are the same atom or the same group, and R ² and R ³ are bonded to form a ring, or the same atom or the same group. It is preferable that R ¹ and R ⁴ are hydrogen atoms, and it is particularly preferable that all of R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms.

Employed in the polymerization process of substituted fluorenyl groups present invention, the important first point in the fluorenyl group moiety in the general formula chemical formula represented by ^{[I], R 6, R} 7 in the general formula [I], The four groups of R ¹⁰ and R ¹¹ are not hydrogen atoms. R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are selected from a hydrocarbon group and a silicon-containing group, and may be the hydrocarbon group (f1) or the silicon-containing group (f2).

The second important point in the fluorenyl group portion is that R ⁶ and R ⁷ and R ¹⁰ and R ¹¹ are not bonded to each other to form a ring. In the bridged metallocene compound used in the present invention, the four groups R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not hydrogen atoms, and R ⁶ and R ⁷ and R ¹⁰ and R ¹¹ are bonded to each other. By not forming a ring, it was possible to achieve a polymerization activity that could not be achieved by existing polymerization, and to produce an α-olefin polymer having a high melting point of 3 or more carbon atoms, such as a propylene polymer. It is.

R ⁵ , R ⁸ , R ⁹ and R ¹² may be the same or different atoms or groups selected from hydrogen, hydrocarbon group (f1) and silicon-containing group (f2). ^{In the} combination of one or more adjacent groups selected from ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² , the adjacent groups are bonded to each other to form a ring May be formed.

As the hydrocarbon group (f1) used for the substituents R ^{5 to} R ^12, when the substituent is a group that does not form a ring with other substituents, the total carbon number is 1 to 20. A certain hydrocarbon group (hydrocarbon group (f1 ′)) can be preferably exemplified.

In the case where the substituents R ^{5 to} R ¹² are hydrocarbon groups (f1), the substituent is within the range of the above adjacent group combination with other adjacent substituents among the substituents R ^{5 to} R ^12. A case where they are bonded to each other to form a ring is also mentioned. In this case, adjacent substituents among R ^{5 to} R ¹² are bonded to each other to form a ring (ring (f ′ ″)).

Further Examples If each other adjacent substituents of the adjacent group combination substituents R ⁵ to R ¹² in the range of form a ring bonded to each other, adjacent ones of the substituents R ⁵ to R ¹² A case where two are bonded to each other to form a ring is preferable.

For example, when two adjacent substituents are bonded to each other to form a ring (R ⁵ and R ⁶ , R ⁷
And R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , or a combination of one or more adjacent groups selected from R ¹¹ and R ¹² ), each of R ^{5 to} R ¹² described above Preferred carbon number is 1-2
Regardless of being 0, the total number of carbon atoms of the two substituents forming the ring is preferably 2 to 40, more preferably 3 to 30, and further preferably 4 to 20.

  Even when adjacent substituents are bonded to each other to form a ring, some of the hydrogen atoms directly bonded to carbon of the substituent are halogen atoms, oxygen-containing groups, nitrogen-containing groups, and silicon-containing groups. In this case, the total number of carbon atoms of a plurality of substituents forming a ring includes the number of carbon atoms contained in the oxygen-containing group, nitrogen-containing group, and silicon-containing group.

From the viewpoint of synthesis of the catalyst in the present invention, it is preferable that R ⁶ and R ¹¹ are the same atom or the same group, and R ⁷ and R ¹⁰ are the same atom or the same group. Preferred groups as the hydrocarbon group (f1) are the above-described hydrocarbon group (f1 ′) having a total carbon number of 1 to 20, and a ring structure (f ′ ″). Preferred examples of the silicon-containing group (f2) are: The above-mentioned silicon-containing group (f2 ′) having a total carbon number of 1 to 20 when the substituent does not form a ring with other substituents.

In the present invention, not only under normal temperature polymerization conditions but also under high temperature polymerization conditions, it is possible to obtain an α-olefin polymer having a melting point equal to or higher than that of a conventional one and a high molecular weight of 3 or more carbon atoms,
In particular, R ⁶ and R ¹¹ are 1) a hydrocarbon group, and when they do not form a ring with an adjacent group, they are each independently a carbon atom of 2 or more, more preferably 3 or more, particularly preferably 4 or more. It is particularly preferable that it is a hydrogen group, or 2) each of which is a silicon-containing group.

Among silicon-containing groups, a silicon-containing group having a total number of carbon atoms and silicon atoms of 3 or more, preferably 4 or more is preferred. In order to further enhance the effect of the present invention, when R ⁶ is a hydrocarbon that does not form a ring with an adjacent group, and R ⁷ is a hydrocarbon group that does not form a ring with an adjacent group, R ⁶ The number of carbon atoms of is preferably the same as or greater than that of R ⁷ . When R ⁶ is a silicon-containing group and R ⁷ is a silicon-containing group, the total number of silicon atoms and carbon atoms in R ⁶ is the same as or equal to the total number of silicon atoms and carbon atoms in R ^7. The above is preferable. When R ⁶ is a hydrocarbon group that does not form a ring with an adjacent group, and R ⁷ is a silicon-containing group, the number of carbon atoms in R ⁶ is the total number of silicon atoms and carbon atoms in R ^7. Preferably they are the same or higher. When R ⁶ is a silicon-containing group and R ⁷ is a hydrocarbon group that does not form a ring, the total number of silicon atoms and carbon atoms in R ⁶ is equal to or greater than the number of carbon atoms in R ^7. Preferably there is.

R ⁶ and R ¹¹ are preferably an aryl group or a substituted aryl group, and specifically include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a t-butylphenyl group, a naphthyl group, and dimethylphenyl. Group, trimethylphenyl group, biphenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-trifluorophenyl group, m -Trifluorophenyl group, p-trifluorophenyl group and the like.

When R ⁶ and R ¹¹ of the substituted fluorenyl group are either 1) or 2),
When compared under the same polymerization conditions, an α-olefin polymer having 3 or more carbon atoms having a higher melting point and a molecular weight equal to or higher than that of the conventional one can be obtained. Compared with the same polymerization conditions, it also has the advantage that an α-olefin polymer having 3 or more carbon atoms with a melting point equal to or higher than that of a conventional one can be obtained, and an α-olefin polymer having an excellent performance balance. Can be manufactured.

The main chain portion of the bond connecting the cyclopentadienyl group and the substituted fluorenyl group, which may have a covalent bond substituent, is a divalent covalent bond containing one carbon atom or silicon atom.

The important point in the covalently bonded bridge part of the bridged metallocene compound used in the present invention is that the bridge atom Y in the general formula [I] has R ¹³ and R ^14, which are hydrogen atoms,
An atom or substituent selected from a hydrocarbon group excluding a methyl group and a silicon atom-containing group, which may be the same or different from each other, and the substituents may be bonded to each other to form a ring. .

When Y is carbon, R ¹³ and R ¹⁴ are each preferably a hydrocarbon group other than a methyl group or a silicon-containing group. When Y is silicon, R ¹³ and R ¹⁴ are each other than a methyl group. The hydrocarbon group is preferably.

Among this, Y is carbon, R ^13, R ¹⁴ are preferred to have a hydrocarbon group having 2 to 20 carbon atoms.
By combining these covalent bond bridges with the substituted fluorenyl group, it became possible to produce a high melting point propylene polymer under high temperature polymerization conditions that could not be achieved by existing polymerization.

The hydrocarbon group other than methyl group used in R ^13, and R ^14, when R ¹³ and R ¹⁴ do not form a ring with each other, the total number of carbon atoms is 2 to 20 Preferred examples include hydrocarbon groups (hereinafter also referred to as “hydrocarbon groups (f1 ″)”). R ¹³ and R ¹⁴
And is a hydrocarbon group, R ¹³ and R ¹⁴ are bonded to each other to form a ring (ring (f ″ ″)).

The hydrocarbon group having 2 to 20 carbon atoms (f1 ″) is a hydrocarbon group having 1 to 20 carbon atoms (f1 ′) obtained by removing a methyl group.
When R ¹³ and R ¹⁴ are bonded to each other to form a ring, R ¹³ and R ¹⁴ each form a ring structure regardless of the preferable range of 2 to 20 carbon atoms. The total number of carbon atoms of ¹³ and R ¹⁴ is preferably 4 to 40, and this ring structure is one of the preferred embodiments like the hydrocarbon group.

Also, when R ¹³ and R ¹⁴ are bonded to each other to form a ring, a part of the hydrogen atoms directly bonded to the carbon of R ¹³ or R ¹⁴ are halogen atoms, oxygen-containing groups, nitrogen-containing groups, It may be substituted with a silicon-containing group. In this case, the total number of carbon atoms of a plurality of substituents forming a ring is the number of carbon atoms contained in the oxygen-containing group, nitrogen-containing group, and silicon-containing group. Include numbers.

Examples of the hydrocarbon group (f1 ″) include an alkyl group, a substituted alkyl group (including a halogen-substituted alkyl group), a cycloalkyl group, a substituted cycloalkyl group (including a halogen-substituted alkyl group), an arylalkyl group, and a substituted aryl. Alkyl group (including halogen-substituted arylalkyl group and halogenated alkyl group-substituted arylalkyl group), alkylaryl group, substituted alkylaryl group (including halogen-substituted alkylaryl group and halogenated alkyl group-substituted alkylaryl group), aryl group (Aromatic group) Preferred are a divalent hydrocarbon group (meaning a structure in which R ¹³ and R ¹⁴ are combined to form a ring), a substituted divalent hydrocarbon group, and the like. Also preferred are substituted aryl groups (including halogen-substituted aryl groups and halogenated alkyl group-substituted aryl groups). Here, in the substituted arylalkyl group and the substituted alkylaryl group, the substituent may be bonded to the aryl site or may be bonded to the alkyl site.

  The silicon-containing group (f2) is a group having a silicon atom covalently bonded to the ring carbon of the cyclopentadienyl group, and specifically an alkylsilyl group or an arylsilyl group. For example, when the substituent does not form a ring with other substituents, examples of the silicon-containing group having 1 to 20 carbon atoms (f2 ′) may include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and the like. it can.

R ¹³ and R ¹⁴ include, among these, an alkyl group such as an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, etc. An aryl group such as a phenyl group, a biphenyl group and a naphthyl group; an alkylaryl group such as an o-tolyl group, an m-tolyl group and a p-tolyl group; an arylalkyl group such as a benzyl group and a phenylbenzyl group; Halogen atoms such as m- (trifluoromethyl) phenyl group, p- (trifluoromethyl) phenyl group, bis (trifluoromethyl) phenyl group, m-chlorophenyl group, p-chlorophenyl group and dichlorophenyl group are introduced into the substituent. Substituted aryl group; m-chlorobenzyl group,
Halogen atoms such as p-chlorobenzyl group, m-fluorobenzyl group, p-fluorobenzyl group, m-bromobenzyl group, p-bromobenzyl group, dichlorobenzyl group, difluorobenzyl group, trichlorobenzyl group, trifluorobenzyl group Is preferably a substituted alkylaryl group in which is introduced into the substituent, and when a substituent is introduced into the aromatic group of the aryl group or arylalkyl group, those in the meta and / or para positions are preferred.

  Among these, an alkyl group, an arylalkyl group, a substituted arylalkyl group (including a halogen-substituted arylalkyl group and a halogenated alkyl group-substituted arylalkyl group), and an alkylaryl group are more preferable. In particular, in this case, in addition to the above characteristics, an α-olefin polymer having a higher melting point and a higher molecular weight can be produced at a temperature of room temperature or higher.

As the bridged metallocene compound used in the present invention, those in which R ¹³ and R ¹⁴ are the same are preferably used because of their ease of production.
Other Features of Bridged Metallocene Compound In the general formula [I], Q is halogen, a hydrocarbon group having 1 to 10 carbon atoms, and 1 carbon atom.
Zero or less neutral, conjugated or non-conjugated dienes, anionic ligands, and neutral ligands capable of coordinating with lone pairs are selected in the same or different combinations. Specific examples of the halogen include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2 , 2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1 1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like.

Specific examples of neutral, conjugated or non-conjugated dienes having 10 or less carbon atoms include s-cis- or s-
Trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl -1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s -Cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans- and η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene.

Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.

  Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane.

j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other.
Preferred bridged metallocene compounds and examples thereof Specific examples of Group 4 transition metal compounds represented by the above general formula [I] are shown below, but the scope of the present invention is not particularly limited thereby.
Di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl (2,7-di ( 2,4,6-trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di n-Butylmethylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-di (4- Methylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride Di-n-butylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-di (4-tert-butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,

Diisobutylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl (2,7-di (2,4,6- Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutyl Methylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,3, 6,7-tetra-tert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert-butylfluorenyl) zirconium di Chloride, diisobutylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-di (4-tert -Butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,

Dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride [otherly 1,3-diphenylisopropylidene (cyclopentadienyl) (2, Also referred to as 7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride. Other names are omitted], dibenzylmethylene (cyclopentadienyl (2,7-di (2,4,6-trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) ) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, dibenzylmethylene ( Cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3 , 6-Ditert-butylfluorenyl)
Zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di (4-tert-butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,

Diphenethylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6- Ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-) Til) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (2,7 -Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (2 , 7-Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluoride Nyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) ) (2,7-Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butyl Fluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,

(Benzyl) (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (n-butyl) methylene (cyclopentadiene) Enyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopropylidene (cyclopenta Dienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluoride) Oleenyl) zirconium di Loride, cyclobutylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-diphenyl-3 , 6-Ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclohexane) Pentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butyl) Fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) ( 2,7 -Dimethyl-3,6-ditert-
Butyl fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butyl fluorenyl) zirconium dichloride,

Dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3, 6-dimethyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dicumyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopenta Dienyl) (2,7-dimethyl-3,6-dicumyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di (trimethylsilyl) -butyl Fluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di (trimethylsilyl) -butylfluorenyl) zirconium dichloride, Benzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-diphenyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6 -Diphenyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dibenzyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadi) Enyl) (2,7-dimethyl-3,6-dibenzyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (
2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl)
Zirconium dichloride,

Diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-
Di-tert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (
Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6 -Di-tert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m -Chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7 -Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) Zirconium dichloride, di (m-trifluoromethyl) Ru-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6- Ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, Di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (Cyclopentadienyl) (2,7-diphenyl-3,6- tert-butylfluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,

Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2 , 7-Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-
Naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-
Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl)
Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3 , 6-Ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di ( Naphthylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-
Di-tert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p -Isopropylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7- Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride Diphenylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-diphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,

Di (4-chlorobenzyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di (3-chlorobenzyl) methylene (cyclopentadienyl) ( 2,7-diphenyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di (4-bromobenzyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-dimethyl-butylfluorene Nyl) zirconium dichloride, di (3-bromobenzyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di (4-fluorobenzyl) methylene (cyclo Pentadienyl) (2,7-diphenyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di (3-fluorobenzyl) methylene (cyclopentadienyl) (2,7-di Enyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di (4-chlorobenzyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride , Di (4-chlorobenzyl) methylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di (4-chlorobenzyl) methylene (cyclopentadienyl) (2,7-di {p-tolyl} -3,6-dimethyl-butylfluorenyl) zirconium dichloride, di (4-chlorobenzyl) methylene (cyclopentadienyl) (2,7-di {o-tolyl } -3,6-Dimethyl-butylfluorenyl) zirconium dichloride, di (
4-phenylbenzyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-
Butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di {p-chlorophenyl} -3,6-ditert-butylfluorenyl) zirconium dichloride, di (4-chlorobenzyl) ) Methylene (cyclopentadienyl) (2,7-di {p-chlorophenyl} -3,6-ditert-butylfluorenyl) zirconium dichloride and the like.

Furthermore, the compounds described above in which “zirconium” is changed to “hafnium” or “titanium”, “dichloride” is “difluoride”, “dibromide”, “diaiodide”, “dichloride” is “dimethyl” or “methyl”. The metallocene compound and the like converted to “ethyl” are also metallocene compounds related to the olefin polymerization catalyst of the present invention. In particular, a syndiotactic α-olefin polymer having a high melting point can be synthesized by using a metallocene compound having a Cs symmetric structure among the above catalyst structures.

The (A) bridged metallocene compound according to the present invention can be produced by a known method, and the production method is not particularly limited. Examples of known production methods include the production methods described in the pamphlets of WO2001 / 27124 and WO2004 / 087775 by the present applicant.

The above metallocene compounds can be used alone or in combination of two or more.
Olefin Polymerization Catalyst Next, a preferred embodiment when the above-described (A) bridged metallocene compound is used as a polymerization catalyst in the olefin polymerization method of the present invention will be described.

When the bridged metallocene compound of the present invention is used as an olefin polymerization catalyst, the catalyst component includes (A) a bridged metallocene compound represented by the general formula [1], and (B) (b-1) an organoaluminum oxy compound, b-2) It is composed of at least one compound selected from a compound that forms an ion pair by reacting with the bridged metallocene compound (A) and (b-3) an organoaluminum compound. Furthermore, it is comprised from the (C) particulate carrier as needed. Hereinafter, each component will be specifically described.

(b-1) Organoaluminum oxy compound (b-1) Organoaluminum oxy compound (also referred to as “component (b-1)” in the present specification) used in the present invention can be a conventionally known aluminoxane as it is. . Specifically, the following general formula [2]

（上記式[２]において、Rは、それぞれ独立に炭素数1〜10の炭化水素基、nは2以上の整数を示す。）

(In the above formula [2], R is each independently a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.)

And / or general formula [3]

(Wherein, in the above formula [3], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more). In particular, R is a methyl group. A methylaluminoxane having n of 3 or more, preferably 10 or more is used. These aluminoxanes may be mixed with some organoaluminum compounds. A characteristic property in the high temperature solution polymerization of the present invention is that a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can also be applied. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like It can be suitably used. The “benzene-insoluble” organoaluminum oxy compound used in the high-temperature solution polymerization of the present invention means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 5% or less. Is 2% or less, and is insoluble or hardly soluble in benzene.

  Examples of the organoaluminum oxy compound used in the present invention include modified methylaluminoxane as shown in [4] below.

(Here, R is a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represents an integer of 2 or more.)
This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound [4] is generally called MMAO. Such MMAO can be prepared by the methods listed in US4960878 and US5041584. In addition, from Tosoh Finechem Co., etc., MMAO is prepared using trimethylaluminum and triisobutylaluminum and R is an isobutyl group.
And TMAO are commercially produced. Such MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, it is different from those insoluble or hardly soluble in benzene such as [2] and [3] above. It is soluble in aliphatic hydrocarbons and alicyclic hydrocarbons.

  Furthermore, as an organoaluminum oxy compound used in the present invention, an organoaluminum oxy compound containing boron represented by the following general formula [5] can be exemplified.

(In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group.)
(b-2) A compound that reacts with the bridged metallocene compound (A) to form an ion pair A compound (b-2) that reacts with the bridged metallocene compound (A) to form an ion pair (hereinafter referred to as “ionic compound”) Or may be abbreviated as “component (b-2)”). JP-A-1-501950, JP-A-1-502036, JP-A-3-17905, JP-A-3-179006 And Lewis acids, ionic compounds, borane compounds, carborane compounds and the like described in JP-A-3-207703, JP-A-3-207704, USP5321106, and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

  In the present invention, the ionic compound preferably employed is a compound represented by the following general formula [6].

In the formula, R ^{e +} includes H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^{f to} R ⁱ may be the same as or different from each other, and are organic groups, preferably aryl groups.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl And dialkyl ammonium cations such as ammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

Among the above, as R ^{e +} , a carbenium cation, an ammonium cation, and the like are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl And phenyl) carbenium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and the like.
Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-
Butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) Borate, tripropylammonium tetrakis (
Pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4-tri Fluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, di Octadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethyl) Tilphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate And dioctadecylmethylammonium.

Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis ( 3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5- Ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, etc. .

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

In addition, ionic compounds disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can also be used without limitation.
The ionic compound (b-2) as described above can be used as a mixture of two or more.

(b-3) Organoaluminum Compound Forms an Olefin Polymerization Catalyst (b-3) Organoaluminum Compound (
Also referred to as “component (b-3)”. Examples of the compound include an organoaluminum compound represented by the following general formula [7] and a complex alkylated product of a Group 1 metal and aluminum represented by the following general formula [8].

R ^a _m Al (OR ^b ) _n H _p X _q ... [7]
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is a number 0 ≦ n <3, p is a number 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3.

Specific examples of such compounds include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum;
Tri-branched alkyl aluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisopropylaluminum hydride, diisobutylaluminum hydride;
Isoprenyl aluminum represented by general formula (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y, z are positive numbers, z ≦ 2x), etc. Alkenylaluminum of
Alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminum having an average composition represented by the general formula Ra _2.5 Al (ORb) _0.5 ;
Alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

M ² AlR ^a ₄ ... [8]
(Wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). Alkylate complex of aluminum and aluminum. Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

A compound similar to the compound represented by the general formula [8] can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

From the viewpoint of availability, trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.
In the olefin polymerization catalyst according to the present invention, the catalyst component includes (A) a bridged metallocene compound represented by the general formula [1], and (B) (b-1) an organoaluminum oxy compound, (b- 2) A compound that reacts with the bridged metallocene compound (A) to form an ion pair, and (b-3) at least one compound selected from organoaluminum compounds, and optionally support (C). It can also be used.

(C) Carrier The carrier (C) used in the present invention (also referred to herein as “component (C)”) is an inorganic or organic compound, and is a granular or particulate solid. Among these, as the inorganic compound, porous oxides, inorganic chlorides, clays, clay minerals or ion-exchangeable layered compounds are preferable.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ and B _2.
O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or composites or mixtures containing these are used, for example natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO _{2 -V 2 O 5, SiO 2} -Cr 2 O 3, etc. can be used SiO ₂ -TiO ₂ -MgO. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.
Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 3 to 300 μm, preferably 10 to 300 μm, more preferably 20 to 200 μm. The specific surface area is 50 to 1000 m ² / g, preferably 10
It is desirable to be in the range of 0 to 700 m ² / g and the pore volume to be in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Moreover, after dissolving inorganic chloride in solvent, such as alcohol, what was made to deposit into a fine particle form with a depositing agent can also be used.

The clay used in the present invention is usually composed mainly of clay minerals. The ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. . Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used. Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated. Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And an ion exchange layered compound include α-Zr (HAsO ₄ ) _2.
H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α Of polyvalent metals such as —Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O Examples thereof include crystalline acid salts.

Such a clay, clay mineral or ion-exchange layered compound preferably has a pore volume of not less than 0.1 cc / g and not less than 0.3-5 cc / g, as measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 ⁴ Å by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.
In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Etc. These compounds are used alone or in combination of two or more. Further, when these compounds were intercalated, they were obtained by hydrolysis of metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymer, Si
A colloidal inorganic compound such as O ₂ can coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers. Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

  Clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  When ion exchange layered silicate is used, in addition to its function as a carrier, it can also reduce the amount of organoaluminum oxy compounds such as alkylaluminoxane by utilizing its ion exchange properties and layer structure. Is possible. The ion-exchange layered silicate is naturally produced mainly as a main component of clay mineral, but is not limited to a natural product, and may be an artificial synthetic product. Specific examples of clay, clay mineral, and ion-exchange layered silicate include kaolinite, montmorillonite, hectorite, bentonite, smectite, vermiculite, teniolite, synthetic mica, synthetic hectorite, and the like.

Examples of the organic compound include granular or fine particle solids having a particle size in the range of 3 to 300 μm, preferably 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers or copolymers produced with a main component as a main component, or polar functional groups obtained by copolymerizing or graft polymerizing polar monomers such as acrylic acid, acrylic acid ester, and maleic anhydride to these polymers A polymer or modified product having These particulate carriers can be used alone or in combination of two or more.

In the olefin polymerization catalyst according to the present invention, the catalyst component includes (A) a bridged metallocene compound represented by the general formula [1], and (B) (b-1) an organoaluminum oxy compound, (b- 2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and (b-3) at least one compound selected from organoaluminum compounds, and optionally a carrier (C),
A specific organic compound component (D) as described later may be included as necessary.

(D) Organic Compound Component In the present invention, (D) the organic compound component (also referred to as “component (D)” in the present specification) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. used. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the component (A) alone to the polymerization vessel.
(2) A method in which component (A) and component (B) are added to the polymerization vessel in any order.
(3) A method in which the catalyst component having component (A) supported on carrier (C) and component (B) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having component (B) supported on carrier (C) and component (A) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which component (A) and component (B) are supported on a carrier (C) is added to a polymerization vessel.

In each of the above methods (2) to (5), at least two or more of the catalyst components may be contacted in advance.
In each of the above methods (4) and (5) in which the component (B) is supported, the unsupported component (B) may be added in any order as necessary. In this case, the components (B) may be the same or different.

  The solid catalyst component in which the component (A) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

In the olefin polymerization method according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above.
In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof, and the olefin itself is used as a solvent. You can also.

When the olefin polymerization is carried out using the olefin polymerization catalyst as described above, the component (A) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² , per liter of the reaction volume. It is used in such an amount that it becomes a mole.

Component (b-1) has a molar ratio [(b-1) / M] of component (b-1) to all transition metal atoms (M) in component (A) of usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (b-2) has a molar ratio [(b-2) / M] of component (b-2) to transition metal atom (M) in component (A) usually from 1 to 10, preferably It is used in such an amount as to be 1-5. Component (b-3) has a molar ratio [(b-3) / M] of the aluminum atoms in component (b-3) to the total transition metals (M) in component (A) usually 10 to 10. The amount used is 5000, preferably 20-2000.

Component (D) has a molar ratio [(D) / (b-1)] of usually 0 when component (B) is component (b-1).
. When the component (B) is the component (b-2) in an amount such as 01 to 10, preferably 0.1 to 5, the molar ratio (D) / (b-2)] is usually 0.01. -10, preferably 0.1-5, and when component (B) is component (b-3), the molar ratio [(D) / (b-3)] is usually 0. 01-2,
Preferably it is used in such an amount as to be 0.005-1.

Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually −50 to
It is +200 degreeC, Preferably it is 0-170 degreeC, More preferably, it is 25-170 degreeC, More preferably, it is the range of 40-170 degreeC. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the component (B) to be used. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

In the present invention, the olefin supplied to the polymerization reaction is one or more monomers selected from α-olefins having 2 or more carbon atoms. The α-olefin has 2 to 2 carbon atoms.
0 linear or branched α-olefins such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like.
In the polymerization method of the present invention, a cyclic olefin having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1 , 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene;
Α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride and bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride Polar monomers such as acids, and metal salts such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts, calcium salts;
Methyl acrylate, acrylate-n-butyl, acrylate acrylate, isopropyl acrylate, acrylate acrylate, isobutyl acrylate, tert-butyl acrylate, 2-n-butyl hexyl acrylate, methyl methacrylate Α, β-unsaturated carboxylic acid esters such as methacrylic acid-n-butyl, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate;
Examples thereof include unsaturated glycidyl such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.
Vinylcyclohexane, diene or polyene;
Aromatic vinyl compounds such as mono or polyalkyl such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, on-butylstyrene, mn-butylstyrene, pn-butylstyrene styrene;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene;
Polymerization can also be carried out in the presence of 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene or the like in the reaction system.

  In the production method of the present invention, as an example, 100 to 90 mol%, preferably 100 to 91 mol% of a structural unit derived from one monomer (e.g., propylene) selected from α-olefins having 3 to 20 carbon atoms, More preferably, the structural unit derived from a monomer other than the above monomer is 10 to 0, which is at least one selected from 100 to 96 mol% and an α-olefin having 2 to 20 carbon atoms (excluding propylene). It can be used for the production of a polymer containing mol%, preferably 9 to 0 mol%, more preferably 4 to 0 mol%. An example of this is the production of a propylene homopolymer. Such an α-olefin polymer preferably has a syndiotactic structure. For example, the rrrr value measured by the method described later is preferably 70% or more, and more preferably 85% or more.

  In addition, as an example, the production method of the present invention includes 50 to 0 structural units derived from one or more monomers selected from 100 to 50 mol% of structural units derived from ethylene and an α-olefin having 3 to 20 carbon atoms. It can be used for the production of a polymer consisting of mol%. Examples of this include the production of ethylene homopolymers.

Of course, it can be used for production of other polymers.
Next, a method for measuring physical properties and properties of a polymer obtained by olefin polymerization in the presence of a catalyst containing the transition metal compound of the present invention will be described.

[Intrinsic viscosity ([η])]
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of granulated pellets are dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity ηsp is measured in the same manner. This dilution operation is further repeated twice, and the value of ηsp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity.

[Η] = lim (ηsp / C) (C → 0)
[Melting point (Tm)]
By a differential scanning calorimetry (DSC), a polymer sample held at 200 ° C. for 10 minutes is cooled to 30 ° C., held for 5 minutes, and then calculated from the crystal melting peak when the temperature is raised at 10 ° C./minute. In the propylene polymer described in the examples of the present application, when one or two peaks are observed and two peaks are detected, the low temperature side peak is Tm ₁ and the high temperature side peak is T
Indicated as m ₂ . For one was expressed as Tm _2.

Stereoregularity (rrrr) is calculated from ¹³ C-NMR spectrum measurement.
That rrrr fraction, ¹³ total methyl C-NMR Prrrr in the spectrum (the absorption intensity derived from methyl groups of the third unit in the site in propylene units continuously 5 units and syndiotactic bond) and Pw (propylene unit It is calculated | required by following formula (1) from the absorption intensity of the absorption intensity derived from a group.

rrrr fraction (%) = 100 × Prrrr / Pw (1)
The NMR measurement is performed as follows, for example. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. And ¹³ C-NMR measurement is performed at 120 degreeC using the JEOL GX-500 type | mold NMR measuring apparatus. The number of integration is 10,000 times or more.
[Example]
Hereinafter, the present invention will be described more specifically based on synthesis examples and examples, but the present invention is not limited to these examples. Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclohexylene (cyclo Pentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (
3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyloctahydro) Dibenzofluorenyl) zirconium dichloride was synthesized by the method described in the following patent document. JP 2000-212194 A, JP 2004-168744 A, JP 2004-189666 A.

The structure of the compound obtained in the synthesis example was determined using 270 MHz ¹ H-NMR (JEOL GSH-270), FD-mass spectrometry (JEOL SX-102A), or the like.

[Synthesis Example 1]
Synthesis of dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride (i) 2,7-dibromo-3,6-ditert-butyl- Synthesis of fluorene 15.22 g (54.7 mmol) of 3,6-ditert-butyl-fluorene synthesized in a 300 mL three-necked flask under a nitrogen atmosphere according to the method described in Bull. Chem. Soc. Jpn., 59, 97 (1986) ) And 170 mL of propylene carbonate were added and stirred. To this solution, 20.52 g (115 mmol) of N-bromosuccinimide was added, and the mixture was heated and stirred at 80 ° C. for 5 hours. Then, it is allowed to cool naturally and the reaction solution is 800 mL of water.
After stirring at room temperature for 15 minutes, the precipitated solid was filtered off. The resulting solid was washed 5 times with 10 mL of ethanol. Thereafter, a mixed solution of n-hexane and a small amount of dichloromethane was added to the solid, heated to 60 ° C., dissolved, and allowed to stand at −20 ° C. overnight. The precipitated crystals were washed 3 times with 5 mL of hexane to obtain the desired product (yield 21.16 g, yield 76%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.60 (s, tBu (Flu), 18H), 3.75 (s, Flu-9H, 2H), 7.73 (s, Flu, 2H), 7.81 (s, Flu, 2H).
MS (FD): M / z 436 (M ⁺ ).

(Ii) Synthesis of 2,7-diphenyl-3,6-ditert-butyl-fluorene Under a nitrogen atmosphere, in a 300 mL three-necked flask, 8.15 g of 2,7-dibromo-3,6-ditert-butyl-fluorene ( 18.7 mmol) and Pd (PPh ₃ ) 1.08 g (0.93 mmol) were added 120 mL of dehydrated 1,2-dimethoxyethane and stirred at room temperature for 20 minutes. To this solution was added a solution of phenylboric acid (5.01 g, 41.1 mmol) in ethanol (20 mL) and stirred at room temperature for 20 minutes, and then 2.0 mol / L sodium carbonate aqueous solution (37.4 mL, 74.8 mmol) was added. Thereafter, the mixture was heated to reflux for 18 hours, allowed to cool naturally, and then quenched with dilute hydrochloric acid in an ice bath. Ether was added to extract the soluble part, and the organic layer was washed twice with saturated aqueous sodium hydrogen carbonate solution, twice with water and twice with saturated brine, and then dried over magnesium sulfate. Thereafter, the solvent was distilled off, and the obtained solid was separated by column chromatography to obtain the desired product (yield 4.36 g, yield 54%).
. The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.29 (s, tBu (Flu), 18H), 3.78 (s, Flu-9H, 2H), 7.16 (s, Flu, 2H), 7.34 (br, PhFlu, 10H), 7.97 (s, Flu, 2H).
MS (FD): M / z 430 (M ⁺ ).

(Iii) Synthesis of 6,6-dibenzofulvene Under a nitrogen atmosphere, 8.0 g (121 mmol) of cyclopentadiene and 100 mL of dehydrated tetrahydrofuran were added to a 500 mL three-necked flask and stirred. The mixed solution was cooled in an ice bath, and 80 mL (125.6 mmol) of a hexane solution of n-butyllithium having a concentration of 1.57 mol / L was added. The mixture was then stirred at room temperature for 3 hours, and the resulting white slurry was cooled in an ice bath, and then a solution of 25.0 g (118 mmol) of 1,3-diphenyl-2-propanone in 50 mL of dehydrated tetrahydrofuran was added. The mixture was then stirred at room temperature for 12 hours, and the resulting yellow solution was quenched with a saturated aqueous ammonium chloride solution. Soluble components were extracted by adding 100 mL of n-hexane, and the organic phase was washed with water and saturated brine and then dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to obtain the desired product as a yellow solid (yield 3.7 g, yield 12%). The target product was identified by ¹ H-NMR.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 3.69 (s, PhCH _2, 4H), 6.60-6.72 (m, Cp, 4H),
_{7.13-7.32 (m, PhCH 2, 10H} ).

(Iv) Synthesis of dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) 2,7-diphenyl-3,6-ditert-butylfluorene under nitrogen atmosphere 1.60 g (3.71 mmol) was added with dehydrated tetrahydrofuran mL and stirred. The solution was cooled in an ice bath, and 2.65 mL (4.13 mmol) of a 1.56 mol / L n-butyllithium hexane solution was added. Stir at room temperature for 2 hours. The obtained red solution was cooled to −78 ° C. in a dry ice-methanol bath, and a solution of 1.06 g (4.10 mmol) of 6,6-dibenzofulvene in 20 mL of tetrahydrofuran was added dropwise over 20 minutes. Thereafter, the mixture was stirred for 18 hours while gradually warming to room temperature. To the resulting black-red solution, 60 mL of 1N hydrochloric acid was added to terminate the reaction. Diethyl ether (80 mL) was added to carry out liquid separation, and a soluble part was extracted. The organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, once with saturated brine, and dried over magnesium sulfate. The solvent was distilled off and the residue was purified by silica gel chromatography to obtain the desired product as a white yellow powder (yield 0.59 g, yield 23%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.25 (s, tBu (Flu), 18H), 2.66 (br, CpH, 1H), 3.22 (br, CH ₂ Ph, 4H), 4.41 (br, Flu-9H, 1H), 5.85-6.51 (m, Cp, 4H), 6.82-7.40
(m, Ph (Flu) and CH ₂ Ph and Flu, 22H), 7.67 (s, Flu, 2H).
MS (FD): M / z 688 (M ⁺ ).

(V) Dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-
Synthesis of (butylfluorenyl) zirconium dichloride Under nitrogen atmosphere, 100 mL Schlenk tube was charged with dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) 0.59 g (0.855 mmol) ), 40 mL of dehydrated diethyl ether was added and stirred. The mixed slurry solution was cooled in an ice bath, 1.21 mL (1.88 mmol) of a hexane solution of n-butyllithium having a concentration of 1.56 mol / L was added, and the mixture was stirred for 45 hours while gradually warming to room temperature. The red reaction solution was cooled to −78 ° C. with a dry ice / methanol bath, and 0.200 g (0.858 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 42 hours while gradually warming to room temperature to obtain a red-orange suspension. After the solvent was distilled off under reduced pressure, it was dissolved in n-hexane under nitrogen, washed with n-hexane through a glass filter packed with celite, and the orange powder not dissolved in n-hexane was extracted with dichloromethane. The solvent in the dichloromethane-dissolved portion was distilled off, washed with diethyl ether / cold n-pentane, and dried to obtain the desired product as an orange powder (yield 515 mg, yield 71%). Identification of the target is ¹ H-NMR, FD
Performed by -MS spectrum.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.30 (s, tBu (Flu), 18H), 3.82 (d, J = 15.5 Hz, CH ₂ Ph, 2H), 3.93 (d, J = 15.5 Hz, CH ₂ Ph, 2H), 5.80 (t, J = 2.6 Hz, Cp, 2H), 6.25 (t, J = 2.6 Hz, Cp, 2H), 6.97-7.34 (m, Ph (Flu) and CH ₂ Ph, 20H), 7.37 (s, Flu, 2H),
8.32 (s, Flu, 2H).
MS (FD): M / z 848 (M ⁺ ).

[Synthesis Example 2]
Di (n-butyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-
Synthesis of (butylfluorenyl) zirconium dichloride
(i) Synthesis of 6,6-di (n-butyl) fulvene Under a nitrogen atmosphere, 15 mL of methanol and 11.8 mL (146 mmol) of pyrrolidine were added to a 200 mL three-necked flask. The mixture was cooled in an ice bath, and 20.21 g (144 mmol) of 5-nonanone and 11.0 mL (146 mmol) of cyclopentadiene were added and stirred at room temperature for 22 hours. Soluble components were extracted by adding 100 mL of diethyl ether and 100 mL of water, and this organic layer was washed twice with water and once with saturated brine, and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to obtain the desired product as a yellow oil (yield 22.53 g, yield 82%). The target product was identified by ¹ H-NMR.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 0.93 (t, J = 7.3 Hz, CH ₂ CH ₂ CH ₂ CH _3, 6H), 1.38 (sex, J = 7.3 Hz, CH ₂ CH ₂ CH ₂ CH _3, 4H), 1.53 (quin, J = 7.3 Hz, CH ₂ CH ₂ CH ₂ CH _3, 4H), 2.53 (t, J = 7.3 Hz, CH ₂ CH ₂ CH ₂ CH _3, 4H) , 6.40-6.57 (m, Cp, 4H).

(Ii) Synthesis of di (n-butyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) 2, synthesized in Synthesis Example 1 (ii) under a nitrogen atmosphere 30 ml of dehydrated tetrahydrofuran was added to 1.51 g (3.51 mmol) of 7-diphenyl-3,6-ditert-butyl-fluorene and stirred. The solution was cooled in an ice bath, and 2.50 mL (3.90 mmol) of a 1.56 mol / L n-butyllithium hexane solution was added. Stir at room temperature for 2 hours. The obtained deep red solution was cooled to −78 ° C. with a dry ice-methanol bath, and a solution of 6,6-di (n-butyl) fulvene in 0.757 g (3.98 mmol) in tetrahydrofuran was added dropwise over 15 minutes. Thereafter, the mixture was stirred for 18 hours while gradually warming to room temperature. 50 mL of 1N hydrochloric acid was added to the obtained red solution to terminate the reaction. Diethyl ether (100 mL) was added to perform liquid separation, and a soluble component was extracted. The organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, once with saturated brine, and dried over magnesium sulfate. The target product was obtained as a white powder by distilling off the solvent and recrystallization from hexane (yield 1.54 g, yield 70%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 0.72 (t, J = 7.3 Hz, CH ₂ CH ₂ CH ₂ CH _3, 6H), 0.86-1.24 (m, CH ₂ CH ₂ CH ₂ CH _3, 8H), 1.26 (s, tBu (Flu), 18H), 1.57-1.72 (m, CH ₂ CH ₂ CH ₂ CH _3, 4H), 2.68 (br, CpH, 1H), 3.97 (br, Flu -9H, 1H), 5.70-6.55 (m, Cp, 4H), 6.78 (s, Flu, 2H), 7.15-7.50 (m, Ph (Flu), 10H), 7.81 (s, Flu, 2H).
MS (FD): M / z 620 (M ⁺ ).

(Iii) Synthesis of di (n-butyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride Dinitrogen was added to a 100 mL Schlenk tube under a nitrogen atmosphere. (N-Butyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) 0.71 g (1.15 mmol) and dehydrated diethyl ether 30 mL were added and stirred. The mixed slurry solution was cooled in an ice bath, 1.62 mL (2.53 mmol) of a 1.56 mol / L n-butyllithium hexane solution was added, and the mixture was stirred for 47 hours while gradually warming to room temperature. This red-orange reaction solution is dried in a dry ice / methanol bath.
After cooling to 78 ° C., 0.265 g (1.14 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 42 hours while gradually warming to room temperature to obtain a red suspension. After the solvent was distilled off under reduced pressure, it was dissolved in n-hexane under nitrogen, washed with n-hexane through a glass filter packed with celite, and the red powder not dissolved in n-hexane was extracted with dichloromethane. The solvent in the dichloromethane-dissolved part was distilled off, and recrystallization was performed with dichloromethane / n-hexane to obtain the desired product as an orange powder (yield 217 mg, yield 24%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 0.82 (t, J = 7.3 Hz, CH ₂ CH ₂ CH ₂ CH _3, 6H), 1.12-1.70 (m, CH ₂ CH ₂ CH ₂ CH _3, 8H), 1.24 (s, tBu (Flu), 18H), 2.30-2.60 (m, CH ₂ CH ₂ CH ₂ CH _3, 4H), 5.53 (t, J = 2.6 Hz, Cp, 2H), 6.26 (t, J = 2.6 Hz, Cp, 2H), 7.15-7.40 (m, Ph (Flu) and Flu, 12H), 8.19 (s, Flu, 2H).
MS (FD): M / z 780 (M ⁺ ).

[Synthesis Example 3]
Di (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butyl)
Synthesis of ( tilfluorenyl) zirconium dichloride (i) Synthesis of 2,7-dimethyl-3,6- ditert -butyl-fluorene 2,7-Dibromo- 3,6- synthesized in Synthesis Example 1 (i) under nitrogen atmosphere To tert-butyl-fluorene (5.03 g, 11.5 mmol) and PdCl ₂ (dppf) · CH ₂ Cl ₂ (0.196 g, 0.24 mmol), 100 mL of dehydrated tert-butyl methyl ether was added and stirred. The solution was cooled in an ice bath, and 19.2 mL (57.6 mmmol) of a methyl ether bromide diethyl ether solution having a concentration of 3 mol / L was added dropwise over 15 minutes. Heating reflux was performed for 5 days. After natural cooling, 1N hydrochloric acid was added dropwise in an ice bath to complete the reaction. Diethyl ether was added for liquid separation, and the organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with saturated brine, and dried over magnesium sulfate. The solvent was distilled off, and separation by silica gel chromatography was performed to obtain the target product as a white powder (yield 2.07 g, yield 63%). The target product was identified by ¹ H-NMR.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.50 (s, tBu (Flu), 18H), 2.60 (s, Me (Flu) _,
6H), 7.26 (s, Flu, 2H), 7.75 (s, Flu, 2H).

(Ii) Synthesis of di (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorene) Under a nitrogen atmosphere, 2,7-dimethyl-3,6-di Dehydrated tetrahydrofuran was added to 0.783 g (2.55 mmol) of tert-butyl-fluorene and stirred. The solution was cooled in an ice bath, and 1.85 mL (2.85 mmol) of a hexane solution of 1.54 mol / L n-butyllithium was added. Stir at room temperature for 2 hours. The obtained orange solution was cooled to −78 ° C. in a dry ice-methanol bath, and 0.571 g (3.00 mmol) of 6,6-di (n-butyl) fulvene synthesized in (i) of Synthesis Example 2 was added to dehydrated tetrahydrofuran 15 The mL solution was added dropwise over 20 minutes and stirred for 2 hours. 100 mL of 1N hydrochloric acid was added to the resulting orange solution to terminate the reaction. Diethyl ether (100 mL) was added to perform liquid separation, and a soluble component was extracted. The organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, once with saturated brine, and dried over magnesium sulfate. The target product was obtained as a white powder by distilling off the solvent and recrystallizing from diethyl ether / methanol (yield 0.63 g, yield 50%).
. The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 0.76 (t, J = 7.3 Hz, CH ₂ CH ₂ CH ₂ CH _3, 6H), 0.80-1.90 (m, CH ₂ CH ₂ CH ₂ CH _3, 10H), 1.46 (s, tBu (Flu), 18H), 2.50 (s, Me (Flu) _, 6H), 3.00 (br, CpH, 1H), 4.01 (br, Flu-9H, 1H), 5.85-6.70 (m, Cp, 4H), 6.93 (s, Flu, 2H), 7.60 (s, Flu, 2H).
MS (FD): M / z 496 (M ⁺ ).

(Iii) Di (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-
Synthesis of di-tert-butylfluorenyl) zirconium dichloride Under a nitrogen atmosphere, di (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butyl) was added to a 100 mL Schlenk tube. Fluorene) 0.614 g (1.24 mmol) and dehydrated diethyl ether 30 mL were added and stirred. The mixed slurry solution was cooled in an ice bath, 1.78 mL (2.74 mmol) of a 1.54 mol / L n-butyllithium hexane solution was added, and the mixture was stirred for 16 hours while gradually warming to room temperature. This red-orange reaction solution is dried in a dry ice / methanol bath.
After cooling to 78 ° C., 0.239 g (1.02 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 22 hours while gradually warming to room temperature to obtain a reddish brown suspension. After the solvent was distilled off under reduced pressure, it was dissolved in n-hexane under nitrogen, washed with n-hexane through a glass filter packed with celite, and the red powder not dissolved in n-hexane was extracted with dichloromethane. The solvent in the dichloromethane-dissolved portion was distilled off and recrystallized from dichloromethane / n-hexane to obtain the desired product as an orange powder (yield 286 mg, yield 41%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 0.99 (t, J = 7.3 Hz, CH ₂ CH ₂ CH ₂ CH _3, 6H), 1.30-1.78 (m, CH ₂ CH ₂ CH ₂ CH _3, 8H), 1.46 (s, tBu (Flu), 18H), 2.53 (s, Me (Flu) _, 2.60-2.80 (m, CH ₂ CH ₂ CH ₂ CH _3, 4H), 5.60 (t, J = 2.6 Hz, Cp, 2H), 6.21 (t, J = 2.6 Hz, Cp, 2H), 7.38 (s, Flu, 2H), 7.95 (s, Flu, 2H).
MS (FD): M / z 656 (M ⁺ ).

[Synthesis Example 4]
Synthesis of di- (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride (i) 6,6-di (p-chlorophenyl) Synthesis of fulvene A reaction vessel equipped with a dropping funnel was charged with 40 mL of dehydrated tetrahydrofuran and 2.15 mL (25.89 mmol) of cyclopentadiene under a nitrogen atmosphere. 18 mL (28.47 mmol) of the solution was slowly added dropwise and stirred. Thereafter, 30 mL of a tetrahydrofuran solution in which 5.00 g (19.91 mmol) of 4,4′-dichlorobenzophenone was dissolved was added to the dropping funnel, and the solution was slowly added dropwise. The reaction solution was extracted with diethyl ether, and the organic layer was washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification was performed on a silica gel column to obtain the desired product (yield 3.37 g, yield 57%). The target product was identified by ¹ H-NMR.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 6.21-6.24 (m, 2H), 6.60-6.63 (m, 2H), 7.23 (d, 2H, J = 8.1 Hz), 7.37 (d , 2H, J = 8.6 Hz).

(Ii) Di- (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-
Synthesis of 3,6-ditert-butylfluorene) In a 200 mL 3-neck flask under nitrogen atmosphere, 2,7-diphenyl- synthesized in Synthesis Example 1 (ii)
3,6-ditert-butylfluorene (3.5 g, 8.1 mmol) and dehydrated tetrahydrofuran (100 mL) were added and stirred. This solution was cooled to −78 ° C. in a dry ice-methanol bath, and 5.7 mL (8.87 mmol) of a hexane solution of 1.56 mol / L n-butyllithium was added dropwise. The mixture was then stirred at room temperature for 3 hours, and the resulting solution was again cooled to −40 ° C., and a solution of 6,6-di (p-chlorophenyl) fulvene in 2.22 g (7.39 mmol) in tetrahydrofuran was added dropwise and stirred at room temperature for 5 hours. did. Then, it was quenched with dilute hydrochloric acid aqueous solution. To the reaction solution, 100 mL of n-hexane was added to extract a soluble component, and the organic layer was washed with a saturated sodium hydrogen carbonate solution, water, and a saturated saline solution, and dried over magnesium sulfate. Thereafter, the solvent was concentrated and washed with n-hexane and methanol to obtain the desired product (yield 3.2 g, yield 54%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.2 (s, 18H), 2.9 (s, 2H), 5.2 (s, 1H), 6.0 (d, 1H), 6.2 (d, 1H ), 6.3 (s, 1H), 6.6 (s, 2H), 6.9 (s, 10H), 7.2-7.4 (m + s, 8H), 7.6 (s, 2H),
MS (FD): M / z 729 (M ⁺ )

(iii) Synthesis of di- (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tertbutyl-fluorenyl) zirconium dichloride In a nitrogen atmosphere, di ( 1.0 g (1.4 mmol) of p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butyl-fluorene) and 60 mL of dehydrated diethyl ether were added and stirred. The solution was cooled to −78 ° C. in a dry ice / methanol bath, and 1.8 mL (2.88 mmol) of a 1.56 mol / L n-butyllithium hexane solution was added dropwise, followed by stirring at room temperature for 20 hours. Then, after cooling to −60 ° C. with a dry ice / methanol bath, 0.37 g (1.59 mmol) of zirconium tetrachloride was added and stirred at room temperature for 20 hours. After distilling off the solvent under reduced pressure, the residue was extracted with n-hexane and dichloromethane under nitrogen, and the target product was obtained by recrystallization from each solution (yield 0.47 g, yield 38%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.2 (s, 18H), 5.4 (m, 2H), 5.8 (s, 2H), 6.3 (m, 2H), 7-7.2 (s + m + m , 6H), 7.5-7.7 (m, 12H), 8.3 (s, 2H)
MS (FD): M / z 888 (M ⁺ )

[Synthesis Example 5]
Synthesis of di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butyl-fluorenyl) zirconium dichloride
(i) Synthesis of di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butyl-fluorene) Synthesis Example 3 in a 200 mL three-necked flask under a nitrogen atmosphere 2,7-dimethyl-3 synthesized in i),
2.6 g (8.48 mmol) of 6-ditert-butyl-fluorene and 100 mL of dehydrated tetrahydrofuran were added and stirred. This mixed solution was cooled to −78 ° C. with an ice bath, 5.7 mL (8.9 mmol) of a hexane solution of n-butyllithium having a concentration of 1.56 mol / L was added dropwise, and then stirred at room temperature for 3 hours. Thereafter, the obtained solution was cooled to −40 ° C. with a dry ice / methanol bath to dissolve 2.78 g (9.33 mmol) of 6,6-di (p-chlorophenyl) fulvene synthesized in (i) of Synthesis Example 4. 60 mL of tetrahydrofuran solution was added dropwise. Then, it stirred for 1 hour, heating up gradually to room temperature. To the reaction solution was added 100 mL of 1N hydrochloric acid, and 100 mL of n-hexane was added to extract the soluble component. The organic layer was washed with water and saturated brine, and then dried over magnesium sulfate. Thereafter, the solvent was distilled off, and the residue was recrystallized from n-hexane to obtain the desired product (yield 4.4 g, yield 86%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.3 (s, 18H), 2.3 (s, 6H), 3.0 (s, 2H), 5.2 (s, 2H), 6.1-6.3 (s , 4H), 6.7 (s, 2H), 7.0 (s, 6H), 7.4 (s, 2H)
MS (FD): M / z 604 (M ⁺ )

(Ii) Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-
Synthesis of 3,6-ditert-butyl-fluorenyl) zirconium dichloride Under a nitrogen atmosphere, a 100 mL Schlenk tube was charged with di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert -Butyl-fluorene) 1.0 g (1.65 mmol) and dehydrated diethyl ether 50 mL were added and stirred. This mixed slurry solution is cooled to −40 ° C. in a dry ice / methanol bath, added with 2.2 mL (3.38 mmol) of a hexane solution of n-butyllithium having a concentration of 1.56 mol / L, and gradually warmed to room temperature for 22 hours. Stir. The reaction solution was cooled to −78 ° C. with a dry ice / methanol bath, and 0.38 g (1.65 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 20 hours while gradually warming to room temperature. After distilling off the solvent under reduced pressure, about 30 mL of n-hexane was added under nitrogen, and after stirring, insoluble matters were removed by Celite filtration. Furthermore, this insoluble matter was dissolved in dichloromethane, and the insoluble matter was removed by Celite filtration. The solution extracted with n-hexane was concentrated, and the precipitated solid was washed with n-hexane and n-pentane to obtain the desired product (yield 0.122 g, yield 10%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.5 (s, 18H), 2.3 (s, 6H), 5.6 (m, 2H), 6.0 (m, 2H), 6.3 (m, 2H ), 7.3 (dd, 2H), 7.4 (dd, 2H), 7.7 (dd, 2H), 7.8 (dd, 2H), 8.1 (s, 2H)
MS (FD): M / z 764 (M ⁺ )

[Synthesis Example 6]
Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl)
(3) Synthesis of 6,6-di (m-trifluoromethylphenyl) fulvene in 70 mL of dehydrated tetrahydrofuran under nitrogen atmosphere and 2.08 mL of cyclopentadiene (i) Synthesis of 6,6-ditert-butylfluorenyl ) zirconium dichloride 25.14mmol)
Was added and stirred. The solution was cooled to 0 ° C., and 16.3 mL (25.77 mmol) of a hexane solution of n-butyllithium having a concentration of 1.58 mol / L was added dropwise. After stirring at room temperature for 20 hours, the solution was cooled again to 0 ° C., and 4.08 g (12.6 mmol) of 3,3′-ditrifluoromethylbenzophenone in 30 mL of dehydrated tetrahydrofuran was added dropwise over 15 minutes. Stir at room temperature for 2.5 hours, 1N
The reaction was terminated with hydrochloric acid. Liquid separation was performed, the aqueous layer was extracted twice with diethyl ether, combined with the previous organic layer, washed with a saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, and then dried over magnesium sulfate. The target product was obtained by distilling off the solvent and separating by silica gel chromatography (yield 1.2 g, yield 26%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 6.17-6.21 (m, 2H), 6.64-6.66 (m, 2H), 7.44-7.58 (m, 6H), 7.68 (d, 2H) .
MS (FD): m / z 366 (M ⁺ ).

(Ii) Synthesis of di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorene) Synthesis into a 300 mL 3-neck flask under nitrogen atmosphere 2.1 g (6.85 mmol) of 2,7-diphenyl-3,6-ditert-butyl-fluorene synthesized in Example 1 (ii) and 60 mL of dehydrated tetrahydrofuran were added and stirred. This solution was cooled to 0 ° C., and 4.83 mL (7.5 mmol) of a hexane solution of n-butyllithium having a concentration of 1.56 mol / L was added. Then, it stirred at room temperature for 2 hours. The resulting solution was cooled to −78 ° C. with a dry ice / methanol bath, and then 2.39 g (6.52 mmol) of 6,6-di (m-trifluoromethylphenyl) fulvene dissolved in 50 mL of dehydrated tetrahydrofuran was added over 15 minutes. It was dripped.
After stirring for 10 minutes, 1N hydrochloric acid was added to the reaction solution to stop the reaction. Oil-water separation was performed, and the aqueous layer was extracted twice with 50 mL of diethyl ether. The organic layer was combined with the previous organic layer, washed with a saturated aqueous sodium hydrogen carbonate solution, water, and saturated brine, and then dried over magnesium sulfate. The solvent was distilled off, and 4.8 g of the residue was dissolved in 15 mL of dichloromethane and added dropwise to 300 mL of methanol. The methanol solution was cooled to 0 ° C., and the resulting crystals were filtered off to obtain the desired product (yield 2.3 g, yield 50%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.37 (s, 18H), 2.35 (s, 6H) 3.16 (s, 1H), 5.30 (s, 1H), 6.38-6.52 (m, 2H), 6.86 (m, 2H), 7.06-7.28 (m, 12H).
MS (FD): m / z 673 (M ⁺ ).

(Iii) Synthesis of di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride 100 mL Schlenk under nitrogen atmosphere Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorene) 0.672 g (1 mmol) and dehydrated diethyl ether 40 mL were added to the tube and stirred. did. This solution is cooled to −78 ° C. with a dry ice / methanol bath, and 1.3 mL of a hexane solution of n-butyllithium having a concentration of 1.56 mol / L.
(2.05 mmol) was added, and the mixture was stirred at room temperature for 19 hours until the cloudy solution became amber and transparent. The reaction solution was cooled again to −78 ° C. with a dry ice / methanol bath, and 0.23 g (1 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 23 hours while gradually warming to room temperature. The solvent was distilled off under reduced pressure, about 50 mL of n-hexane was added under nitrogen, and insoluble materials were removed by Celite filtration.
The obtained n-hexane solution was concentrated to about 5 mL and allowed to stand at −18 ° C. for 24 hours. The precipitated solid was filtered and washed with n-hexane and n-pentane to obtain the desired product as an orange powder. (Yield 0.2g, Yield 24%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.44 (s, 18H), 2.20 (s, 6H), 5.59 (d, 2H),
5.80 (m, 2H), 6.31 (m, 2H), 7.19-8.14 (m, 10H).
MS (FD): m / z 833 (M ⁺ ).

[Synthesis Example 7]
Synthesis of cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride
(I) Synthesis of cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) 2,7-diphenyl- synthesized in Synthesis Example 1 (ii) under nitrogen atmosphere 30 mL of dehydrated tetrahydrofuran was added to 1.14 g (2.65 mmol) of 3,6-ditert-butyl-fluorene and stirred. The solution was cooled in an ice bath, and 1.90 mL (2.96 mmol) of a 1.56 mol / L n-butyllithium hexane solution was added. Stir at room temperature for 2 hours. The obtained deep red solution was cooled to −78 ° C. with a dry ice-methanol bath, and a solution of 0.49 g (3.35 mmol) of cyclohexylfulvene synthesized in accordance with the method described in JP-A-2000-26490 in a 20 mL tetrahydrofuran solution over 15 minutes. It was dripped. Thereafter, the mixture was stirred for 19 hours while gradually warming to room temperature. 30 mL of 1N hydrochloric acid was added to the resulting deep red solution to terminate the reaction. Diethyl ether (100 mL) was added to perform liquid separation, and a soluble component was extracted. The organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, once with saturated brine, and dried over magnesium sulfate. The target product was obtained as a pale yellow powder by distilling off the solvent and recrystallization from diethyl ether and methanol (yield 0.98 g, yield 64%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.26 (s, tBu (Flu), 18H), 0.90-1.85 (m, C6,
10H), 2.75 (br, CpH, 1H), 3.79 (br, Flu-9H, 1H), 5.80-6.52 (m, Cp, 4H), 6.73 (s, Flu, 2H), 7.20-7.60 (m, Ph (Flu), 10H), 7.82 (s, Flu, 2H).
MS (FD): M / z 577 (M ⁺ ).

(Ii) Synthesis of cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride Under a nitrogen atmosphere, cyclohexylidene (cyclohexane) was added to a 100 mL Schlenk tube. Pentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) 0.98 g (1.70 mmol) and dehydrated diethyl ether 40 mL were added and stirred. This mixed slurry solution was cooled to 0 ° C. in an ice bath, and 2.40 mL (3.74 mmol) of a 1.56 mol / L n-butyllithium hexane solution was added, followed by stirring for 23 hours while gradually warming to room temperature. This red reaction solution was -78 ° C in a dry ice / methanol bath.
After cooling to 0.391 g (1.68 mmol) of zirconium tetrachloride. Thereafter, the mixture was stirred for 22 hours while gradually warming to room temperature to obtain an orange suspension. After the solvent was distilled off under reduced pressure, it was dissolved in n-hexane under nitrogen, washed with n-hexane through a glass filter packed with celite, and the red powder not dissolved in n-hexane was extracted with dichloromethane. The solvent in the dichloromethane-dissolved part was distilled off and washed with cold diethyl ether / cold n-hexane to obtain the desired product as an orange solid (yield 0.71 g, yield 57%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.25 (s, tBu (Flu), 18H), 1.45-1.90 (m, C6,
6H), 2.10-2.35 (m, C6, 2H), 2.85-3.00 (m, C6, 2H), 5.55 (t, J = 2.6 Hz, Cp, 2H), 6.29 (t, J = 2.6 Hz, Cp, 2H), 7.15-7.45 (m, Ph (Flu) and Flu, 12H), 8.22 (s, Flu, 2H).
MS (FD): M / z 736 (M ⁺ ).

[Synthesis Example 8]
Synthesis of dibenzylmethylene (cyclopentadienyl) (2,7-di [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride
(I) Synthesis of 2,7-di (2-naphthyl) -3,6-ditert-butyl-fluorene 2,7-dibromo-3,6-di synthesized in Synthesis Example 1 (i) under nitrogen atmosphere Dehydrated 1,2-dimethoxyethane (45 mL) was added to tert-butyl-fluorene (3.02 g, 6.92 mmol) and Pd (PPh ₃ ) (0.40 g, 0.35 mmol), and the mixture was stirred at room temperature for 20 minutes. To this solution, a solution of 2.62 g (15.2 mmol) of 2-naphthalene boric acid in 15 mL of ethanol was added. After stirring at room temperature for 20 minutes, 13.8 mL (27.7 mmol) of a 2.0 mol / L sodium carbonate aqueous solution was added. Heating under reflux was performed for 21 hours. After naturally cooling, the reaction was terminated with 1N hydrochloric acid in an ice bath. Dichloromethane was added for liquid separation, and the aqueous layer was extracted twice with diethyl ether and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over magnesium sulfate. The solvent was distilled off and separation by silica gel chromatography was performed. To the resulting white yellow powder, a mixed solution of n-hexane and a small amount of dichloromethane was added, and heated to 65 ° C. to completely dissolve it. After standing at room temperature overnight, the precipitated crystals were washed 3 times with 10 mL of n-hexane to obtain the desired product as a white powder (yield 2.71 g, yield 74%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.32 (s, tBu (Flu), 18H), 3.81 (s, Flu-9H, 2H), 7.22 (s, Flu, 2H), 7.46 -7.52 (m, NapFlu, 6H), 7.77-7.90 (m, NapFlu, 8H), 8.03 (s, Flu, 2H).
MS (FD): M / z 530 (M ⁺ ).

(Ii) Synthesis of dibenzylmethylene (cyclopentadienyl) (2,7-di [2-naphthyl] -3,6-ditert-butylfluorene) 2,7-di (2-naphthyl) under nitrogen atmosphere 80 mL of dehydrated tert-butyl methyl ether was added to 0.82 g (1.54 mmol) of -3,6-ditert-butyl-fluorene and stirred. The solution was cooled in an ice bath, and 1.10 mL (1.76 mmol) of a hexane solution of 1.60 mol / L n-butyllithium was added. Stir at room temperature for 22 hours. To the obtained yellow suspension, 0.44 g (1.70 mmol) of 6,6-dibenzofulvene synthesized in Synthesis Example 1 (iii) was added. Heating to reflux was carried out for 19 hours. 30 mL of 1N hydrochloric acid was added to the obtained light orange brown solution to terminate the reaction. Diethyl ether (100 mL) was added to perform liquid separation, and a soluble component was extracted. The organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, once with saturated brine, and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to obtain the desired product as a pale yellow solid (yield 0.64 g, 53%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.28 (s, tBu (Flu), 18H), 2.65 (br, CpH, 1H), 3.28 (br, CH ₂ Ph, 4H), 4.46 (br, Flu-9H, 1H), 5.85-6.48 (m, Cp, 4H), 6.80-7.92
(m, Nap (Flu) and CH ₂ Ph and Flu, 26H).
MS (FD): M / z 788 (M ⁺ ).

(Iii) Synthesis of dibenzylmethylene (cyclopentadienyl) (2,7-di [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride into a 100 mL Schlenk tube under nitrogen atmosphere Dibenzylmethylene (cyclopentadienyl) (2,7-di [2-naphthyl] -3,6-ditert-butylfluorene) 0.64 g (0.811 mmol) and dehydrated diethyl ether 40 mL were added and stirred. The mixed slurry solution was cooled in an ice bath, 1.14 mL (1.82 mmol) of a 1.60 mol / L n-butyllithium hexane solution was added, and the mixture was stirred for 42 hours while gradually warming to room temperature. This red reaction solution was -78 ° C in a dry ice / methanol bath.
After cooling to 0.180 g (0.772 mmol) of zirconium tetrachloride. Thereafter, the mixture was stirred for 47 hours while gradually warming to room temperature to obtain an orange suspension. After the solvent was distilled off under reduced pressure, it was dissolved in n-hexane under nitrogen, washed with n-hexane through a glass filter packed with celite, and the red powder not dissolved in n-hexane was extracted with dichloromethane. The solvent in the dichloromethane-dissolved part was distilled off and washed with diethyl ether / n-hexane to obtain the desired product as a red-orange powder (yield 379 mg, yield 49%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.35 (s, tBu (Flu), 18H), 3.72-4.00 (m, CH ₂ Ph, 4H), 5.83 (br, Cp, 2H) , 6.52 (br, Cp, 2H), 6.95-7.90 (m, Nap (Flu) and CH ₂ Ph,
26H), 8.40 (s, Flu, 2H).
MS (FD): M / z 948 (M ⁺ ).

[Synthesis Example 9]
Synthesis of dibenzylmethylene (cyclopentadienyl) (2,7-di [p-tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride
(I) Synthesis of 2,7-di (p-tolyl) -3,6-ditert-butyl-fluorene 2,7-dibromo-3,6-di synthesized in Synthesis Example 1 (i) under nitrogen atmosphere To 8.00 g (18.3 mmol) of tert-butyl-fluorene and 1.05 g (0.909 mmol) of Pd (PPh ₃ ), 120 mL of dehydrated 1,2-dimethoxyethane was added and stirred at room temperature for 20 minutes. To this solution was added 20 mL of ethanol in 5.50 g (40.5 mmol) of 4-methylphenylboric acid. After stirring for 20 minutes at room temperature, 36.8 mL (73.6 mmol) of 2.0 mol / L sodium carbonate aqueous solution was added. Heating under reflux was performed for 21 hours. After natural cooling, 1N hydrochloric acid was added in an ice bath to terminate the reaction. Dichloromethane was added for liquid separation, and the aqueous layer was extracted twice with diethyl ether and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over magnesium sulfate. The solvent was distilled off and separation by silica gel chromatography was performed. A small amount of a mixed solution of n-hexane and ethanol was added to the obtained white yellow powder, heated to 65 ° C. and allowed to stand at room temperature for 1 hour, and then the precipitated crystals were cooled 10 times with 2 mL of cold ethanol and cooled n-hexane. 2 in 1 mL
This was washed 0 times to obtain the target product as a white powder (yield 6.95 g, yield 83%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.29 (s, tBu (Flu), 18H), 2.41 (s, MePhFlu,
6H), 3.76 (s, Flu-9H, 2H), 7.12-7.26 (m, Flu and MePhFlu 10H), 7.95 (s, Flu, 2H).
MS (FD): M / z 458 (M ⁺ ).

(Ii) Synthesis of dibenzylmethylene (cyclopentadienyl) (2,7-di [p-tolyl] -3,6-ditert-butylfluorene) 2,7-di (p-tolyl) under nitrogen atmosphere 100 mL of dehydrated tert-butyl methyl ether was added to 1.30 g (2.84 mmol) of -3,6-ditert-butyl-fluorene and stirred. The solution was cooled in an ice bath, and 2.10 mL (3.36 mmol) of 1.60 mol / L n-butyllithium in hexane was added. Stir at room temperature for 21 hours. To the resulting black-yellow suspension, 0.808 g (3.12 mmol) of 6,6-dibenzofulvene synthesized in Synthesis Example 1 (iii) was added. Heating to reflux was carried out for 19 hours. 30 mL of 1N hydrochloric acid was added to the obtained reddish brown solution to terminate the reaction. Diethyl ether (100 mL) was added to perform liquid separation, and a soluble component was extracted. The organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, once with saturated brine, and dried over magnesium sulfate. The solvent was distilled off, and the residue was separated by column chromatography. The obtained white yellow powder was washed once with 10 mL of cold hexane, 3 times with 5 mL of cold ethanol, and 3 times with 2 mL of cold hexane to obtain the desired product as a white powder (yield 1.04 g, yield 51%). ). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.25 (s, tBu (Flu), 18H), 2.38 (s, MePhFlu,
6H), 2.69 (br, CpH, 1H), 3.27 (br, CH ₂ Ph, 4H), 4.40 (br, Flu-9H, 1H), 5.80-6.48
(m, Cp, 4H), 6.80-7.30 (m, MePh (Flu) and CH ₂ Ph and Flu, 20H), 7.66 (s, Flu, 2H).
MS (FD): M / z 717 (M ⁺ ).

(Iii) Dibenzylmethylene (cyclopentadienyl) (2,7-di [p-tolyl] -3,6-ditert
-Butylfluorenyl) zirconium dichloride synthesis Under a nitrogen atmosphere, a 100 mL Schlenk tube was charged with dibenzylmethylene (cyclopentadienyl) (2,7-di [p-tolyl] -3,6-ditert-butylfluorene ) 1.04 g (1.45 mmol) and 60 mL of dehydrated diethyl ether were added and stirred. The mixed slurry solution is cooled in an ice bath to obtain 1.60 mol / L.
N-butyllithium hexane solution (2.00 mL, 3.20 mmol) was added, and the mixture was stirred for 51 hours while gradually warming to room temperature. This red-orange reaction solution was -78 ° C in a dry ice / methanol bath.
After cooling, 0.363 g (1.60 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 43 hours while gradually warming to room temperature to obtain an orange suspension. After the solvent was distilled off under reduced pressure, it was dissolved in n-hexane under nitrogen, washed with n-hexane through a glass filter packed with celite, and the orange powder not dissolved in n-hexane was extracted with dichloromethane. The solvent in the dichloromethane-dissolved part was distilled off and washed with diethyl ether / n-hexane to obtain the desired product as an orange powder (yield 744 mg, yield 58%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.32 (s, tBu (Flu), 18H), 2.37 (s, MePhFlu,
6H), 3.86 (d, J = 15.5 Hz, CH ₂ Ph, 2H), 3.94 (d, J = 15.5 Hz, CH ₂ Ph, 2H), 5.81 (t, J = 2.6 Hz, Cp, 2H), 6.46 (t, J = 2.6 Hz, Cp, 2H), 6.90-7.40 (m, MePh (Flu) and CH ₂ Ph and Flu, 20H), 8.32 (s, Flu, 2H).
MS (FD): M / z 876 (M ⁺ ).

[Synthesis Example 10]
Synthesis of dibenzylmethylene (cyclopentadienyl) (2,7-di [o-tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride
(I) Synthesis of 2,7-di (p-tolyl) -3,6-ditert-butyl-fluorene 2,7-dibromo-3,6-di synthesized in Synthesis Example 1 (i) under nitrogen atmosphere tert-butyl-fluorene 3.50 g (8.02 mmol), Pd ₂ (dba) ₃ 0.186 g (0.20 mmol), P (tBu) ₃ 0.115 g (0.57 mmol), tripotassium phosphate 6.81 g (32.1 mmol) Add 50 mL and add 20 mL at room temperature.
Stirring was performed for a minute. To this solution, a solution of 2.73 g (20.0 mmol) of o-tolylboronic acid in 15 mL of dehydrated tetrahydrofuran was added. Thereafter, heating under reflux was performed for 72 hours. After natural cooling, 1N hydrochloric acid was added in an ice bath to terminate the reaction. Diethyl ether was added for liquid separation, and the aqueous layer was extracted twice with diethyl ether and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over magnesium sulfate. The solvent was distilled off, and separation by silica gel chromatography was performed to obtain the desired product as a white powder (yield 0.532 g, yield 14%). The target product was identified by ¹ H-NMR.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.27 (s, tBu (Flu), 18H), 2.07 (s, Me (o-tolyl), 6H), 3.79 (s, Flu-9H , 2H), 7.07 (s, Flu, 2H), 7.19-7.25 (m, o-tolylFlu, 10H), 8.00 (s, Flu, 2H).

(Ii) Synthesis of dibenzylmethylene (cyclopentadienyl) (2,7-di [o-tolyl] -3,6-ditert-butylfluorene) 2,7-di (p-tolyl) under nitrogen atmosphere 40 mL of dehydrated tert-butyl methyl ether was added to 0.92 g (2.00 mmol) of -3,6-ditert-butyl-fluorene and stirred. The solution was cooled in an ice bath and 1.45 mL (2.20 mmol) of a hexane solution of 1.52 mol / L n-butyllithium was added. Stir at room temperature for 4 hours. The resulting red solution was cooled in an ice bath and synthesized in Synthesis Example 1 (iii).
A solution of 0.58 g (2.24 mmol) of 6-dibenzofulvene in 20 mL of THF was added dropwise over 25 minutes. The mixture was stirred for 18 hours while gradually warming to room temperature, and then heated to reflux for 3 hours. The resulting black-red solution was allowed to cool naturally, and 1N hydrochloric acid was added in an ice bath to terminate the reaction. Diethyl ether was added for liquid separation, and the aqueous layer was extracted twice with diethyl ether and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over magnesium sulfate. The solvent was distilled off and separation was performed by silica gel chromatography to obtain a yellow powder. A mixed solvent of hexane and ethanol was added to the yellow powder, and the whole was dissolved by heating to 60 ° C. Let stand at -20 ° C overnight. The precipitated crystals were washed with ethanol to obtain the target product as a pale yellow powder (yield 0.57 g, yield 40%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.21-1.23 (m, tBu (Flu), 18H), 1.96-1.99 (m, CH ₃ (o-tolyl), 3H), 2.14- 2.19 (m, CH ₃ (o-tolyl), 3H), 2.66 (br, CpH, 1H), 3.06-3.34 (br, CH ₂ Ph, 4H), 4.45 (br, Flu-9H, 1H), 5.80- 6.48 (br, Cp, 4H), 6.75-7.20 (m, o-tolyl (Flu) and CH ₂ Ph and Flu, 20H), 7.64-7.79 (m, Flu, 2H).
MS (FD): M / z 716 (M ⁺ ).

(Iii) Synthesis of dibenzylmethylene (cyclopentadienyl) (2,7-di [o-tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride into a 50 mL Schlenk tube under nitrogen atmosphere Dibenzylmethylene (cyclopentadienyl)
(2,7-Di [o-tolyl] -3,6-ditert-butylfluorene) 0.36 g (0.50 mmol) and dehydrated diethyl ether 25 mL were added and stirred. The mixed slurry solution was cooled in an ice bath, 0.72 mL (1.09 mmol) of a hexane solution of n-butyllithium having a concentration of 1.52 mol / L was added, and the mixture was stirred for 40 hours while gradually warming to room temperature. The red reaction solution was cooled to −78 ° C. with a dry ice / methanol bath, and 0.251 g (1.08 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 17 hours while gradually warming to room temperature to obtain a red-orange suspension. The solvent was dried under reduced pressure, dissolved in n-hexane under nitrogen, washed with n-hexane through a glass filter packed with celite, and the orange powder that was not dissolved in n-hexane was extracted with dichloromethane. The solvent in the dichloromethane-dissolved part was distilled off, washed with diethyl ether / cold n-pentane, and dried to obtain the desired product as a dark pink powder (yield 167 mg, 38%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.28-1.33 (m, tBu (Flu), 18H), 1.68, 1.87, 2.16 (s, s, s, CH ₃ (o-tolyl) , 6H), 3.34-4.30 (m, CH ₂ Ph, 4H), 5.73-5.82 (m, Cp, 2H), 6.45-6.48 (m, Cp, 2H), 6.95-7.30 (m, o-tolyl (Flu ) and CH ₂ Ph, 18H), 7.48 (s, Flu, 2H), 8.37-8.41 (m, Flu, 2H).
MS (FD): M / z 876 (M ⁺ ).

[Synthesis Example 11]
Synthesis of di (4-chlorobenzyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride
(i) Synthesis of bis (4-chlorobenzyl) ketone In a nitrogen atmosphere, in a 500 mL three-necked flask, 15.12 g (73.3 mmol) of dicyclohexylcarbodiimide and 2.24 g (18.3 mmol) of dimethylaminopyridine were added. mL was added and stirred at room temperature. To this solution, 12.50 g (73.3 mmol) of 4-chlorophenylacetic acid dissolved in 120 mL of anhydrous dichloromethane was added dropwise. After stirring at room temperature for 3 days, the precipitated white crystals were filtered off with a Kiriyama funnel. The filtrate was concentrated, and the residue was separated by silica gel column chromatography to obtain a white crystal / yellow oil mixture. Ethanol was added to this mixture and heated to 50 ° C. to dissolve everything, and then allowed to stand overnight at room temperature. The precipitated crystals were washed with a small amount of ethanol to obtain the target product as a white powder (yield 5.52 g, yield 54%). The target product was identified by ¹ H-NMR.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 3.69 (s, 4-Cl-PhCH _2, 4H), 7.05 (d, 4-Cl-PhCH ₂ , 4H), 7.28 (d, 4 -Cl-PhCH _2, 4H).

(Ii) Synthesis of 6,6-di (4-chlorobenzyl) fulvene Under a nitrogen atmosphere, 0.66 g (9.22 mmol) of lithium cyclopentadiene and 10 mL of dehydrated THF were added to a 100 mL three-necked flask and stirred. This solution was cooled with a dry ice / methanol bath (−78 ° C.), and 2.50 g (8.96 mmol) of bis (4-chlorobenzyl) ketone dissolved in 15 mL of dehydrated THF was added dropwise. Stir for 17 hours while gradually warming to room temperature, and add 1 to the resulting black-brown solution.
N hydrochloric acid was added to terminate the reaction. Hexane was added for liquid separation, and the aqueous layer was extracted twice with hexane and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to obtain the desired product as a yellow powder (yield 0.65 g, yield 22%).
). The target product was identified by ¹ H-NMR.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 3.65 (s, PhCH _2, 4H), 6.64 (s, Cp, 4H), 7.02 (d, 4-Cl-PhCH ₂ , 4H), 7.23 (d, 4-Cl- PhCH 2, 4H).

(Iii) Synthesis of di (4-chlorobenzyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) Synthesized in Synthesis Example 1 (ii) under a nitrogen stream 2 Then, 15 mL of anhydrous THF was added to 0.69 g (1.60 mmol) of 7,7-diphenyl-3,6-ditert-butyl-fluorene and stirred. This solution was cooled with a methanol / dry ice bath (−78 ° C.), and 1.26 mL (1.92 mmol) of a hexane solution of 1.52 mol / L n-butyllithium was added. The mixture was stirred for 19 hours while gradually warming to room temperature. The resulting deep red solution was cooled in a dry ice / methanol bath (-78 ° C) and dissolved in 10 mL of THF.
Di (4-chlorobenzyl) fulvene 0.62 g (1.88 mmol) was added dropwise over 20 minutes. The mixture was stirred for 30 minutes, and 1N hydrochloric acid was added to the resulting deep red solution to terminate the reaction. Hexane was added for liquid separation, and the aqueous layer was extracted twice with hexane and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over magnesium sulfate. The solvent was distilled off to obtain a white yellow powder. The white yellow powder was washed with a mixed solvent of hexane and ethanol to obtain the target product as a white powder (yield 0.80 g, yield 66%). Identification of the target is ¹ H-N
MR and FD-MS spectra were used.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.27 (s, tBu (Flu), 18H), 2.70 (br, CpH, 1H), 3.12 (br, 4-Cl-PhCH ₂ , 4H ), 4.34 (s, Flu-9H, 1H), 5.87-6.62 (m, Cp, 4H), 6.70-7.30 (m, Ph (Flu) and 4-Cl-PhCH ₂ and Flu, 20H), 7.67 (br , Flu, 2H).
MS (FD): M / z 756 (M ⁺ ).

(Iv) Synthesis of di (4-chlorobenzyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride into a 50 mL Schlenk tube under nitrogen atmosphere Di (4-chlorobenzyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) 0.79 g (1.01 mmol) and anhydrous diethyl ether 40 mL were added and stirred. Cool this mixed slurry solution in a dry ice / methanol bath (-78 ° C), add 1.45 mL (2.20 mmol) of a 1.52 mol / L n-butyllithium hexane solution, and gradually warm to room temperature for 18 hours. Stir. The red reaction solution was cooled in a dry ice / methanol bath (−78 ° C.), and 0.32 g (1.37 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 22 hours while gradually warming to room temperature to obtain an orange suspension. The solvent was dried under reduced pressure, filtered through a glass filter packed with celite under nitrogen, washed with a small amount of diethyl ether, and the filtrate was concentrated to give an orange solid. Extraction was performed with a mixed solvent of diethyl ether / hexane / pentane, and the solvent in the dissolved portion was distilled off, followed by drying to obtain the desired product as a dark pink powder (yield 366 mg, yield 40%). The object was identified by ¹ H-NMR and FD-MS spectra.
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.32 (s, tBu (Flu), 18H), 3.70 (d, J = 15.5 Hz, 4-Cl-PhCH ₂ , 2H), 3.86 ( d, J = 15.5 Hz, 4-Cl-PhCH ₂ , 2H), 5.79 (t, J = 2.6 Hz, Cp, 2H), 6.48 (t, J = 2.6 Hz, Cp, 2H), 6.92-7.33 (m , Ph (Flu) and 4-Cl-PhCH ₂ and Flu, 20H), 8.35 (s, Flu, 2H).
MS (FD): M / z 916 (M ⁺ ).

-Propylene polymerization-
250 ml of toluene in a 500 ml glass autoclave thoroughly purged with nitrogen
The propylene was circulated in an amount of 150 liter / hour and kept at 25 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30-ml branch flask with a sufficient nitrogen substitution, and a toluene solution of methylaluminoxane (Al = 1.53 mol / l) was converted to aluminum atoms so as to be 5.00 mmol. In addition, a toluene solution of dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride is converted to zirconium atoms so that the concentration becomes 5.0 μmol. And stirred for 20 minutes. This solution was added to toluene in a glass autoclave in which propylene had been circulated, and polymerization was started. Propylene gas was continuously supplied at a rate of 150 liters / hour, polymerization was carried out at 25 ° C. for 10 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 6.32 g of polymer was obtained. The polymerization activity is 7.58 kg-PP / mmol-Zr · hr, and [η] of the obtained polymer is 2.54 dl / g, Tm ₁ = 157.0 ° C., Tm ₂ = 162.0 ° C., rrrr = 95.3%.

-Propylene polymerization-
The same procedure as in Example 1 was performed except that the temperature in the autoclave before the polymerization reaction and during the polymerization reaction was maintained at 50 ° C., and the polymerization time was 15 minutes. The obtained polymer was 12.74 g, the polymerization activity was 10.19 kg-PP / mmol-Zr · hr, the [η] of the polymer was 1.64 dl / g, Tm ₁ = 142.9 ° C., Tm ₂ = 150 It was 1 ° C.

-Propylene polymerization-
To a glass autoclave with a capacity of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, propylene was circulated in an amount of 150 liters / hour, and kept at 25 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30-ml branch flask with a sufficient nitrogen substitution, and a toluene solution of methylaluminoxane (Al = 1.53 mol / l) was converted to aluminum atoms so as to be 5.00 mmol. In addition, a toluene solution of di (n-butyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride is converted to a zirconium atom to 5. It added so that it might become 0 micromol, and it stirred for 20 minutes. This solution was added to toluene in a glass autoclave in which propylene had been circulated, and polymerization was started. Propylene gas was continuously supplied at a rate of 150 liters / hour, polymerization was carried out at 25 ° C. under normal pressure for 25 minutes, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 7.35 g of polymer was obtained. The polymerization activity is 3.53 kg-PP / mmol-Zr · hr, and [η] of the obtained polymer is 2.43 dl / g, Tm ₁ = 154.9 ° C., Tm ₂ = 160.0 ° C. rrrr = 95.2%.

-Propylene polymerization-
The same procedure as in Example 3 was performed except that the temperature in the autoclave before the polymerization reaction and during the polymerization reaction was maintained at 50 ° C. The obtained polymer was 11.00 g and the polymerization activity was 5.28 kg-
PP / mmol-Zr · hr, and the polymer [η] was 1.54 dl / g, Tm ₁ = 138.6 ° C., and Tm ₂ = 146.2 ° C.

-Propylene polymerization-
In Example 1, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6
Polymerization time of 2-ditert-butylfluorenyl) zirconium dichloride to di (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride The catalyst solution was prepared and polymerized in the same manner as in Example 1 except that was changed to 40 minutes. As a result, 3.31 g of polymer was obtained. Polymerization activity is 0.99 kg-PP /
The obtained polymer had [η] of 2.52 dl / g, Tm ₁ = 142.6 ° C., and Tm ₂ = 151.8 ° C.

-Propylene polymerization-
In Example 1, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (p-chlorophenyl) methylene (cyclopentadienyl) (2 , 7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was prepared and polymerized in the same manner as in Example 1 except that the polymerization time was changed to 30 minutes. As a result, 8.35 g of polymer was obtained. The polymerization activity was 3.34 kg-PP / mmol-Zr · hr, and the polymer [η] was 5.98 dl / g and Tm ₂ = 153.3 ° C.

-Propylene polymerization-
In Example 2, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (p-chlorophenyl) methylene (cyclopentadienyl) (2 , 7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was prepared and polymerized in the same manner as in Example 2 except that the polymerization time was changed to 40 minutes. As a result, 2.90 g of a polymer was obtained. The polymerization activity was 0.87 kg-PP / mmol-Zr · hr, and the obtained polymer [η] was 3.22 dl / g, Tm ₁ = 139.1 ° C., and Tm ₂ = 143.8 ° C. .

-Propylene polymerization-
In Example 1, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (p-chlorophenyl) methylene (cyclopentadienyl) (2 , 7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride was prepared and polymerized in the same manner as in Example 1 except that the polymerization time was changed to 60 minutes. As a result, 7.30 g of polymer was obtained. The polymerization activity was 1.46 kg-PP / mmol-Zr · hr, and the obtained polymer [η] was 5.96 dl / g, Tm ₁ = 142.6 ° C., and Tm ₂ = 149.0 ° C. .

-Propylene polymerization-
In Example 1, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (m-trifluoromethyl-phenyl) methylene (cyclopentadiene). The catalyst solution was prepared and polymerized in the same manner as in Example 1 except that the polymerization time was changed to (enyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride. went. As a result, 2.90 g of a polymer was obtained. The polymerization activity was 0.58 kg-PP / mmol-Zr · hr, and the obtained polymer [η] was 4.64 dl / g, Tm ₁ = 135.7 ° C., Tm ₂ = 141.9 ° C. .

-Propylene polymerization-
In Example 1, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6
-Ditert-butylfluorenyl) zirconium dichloride to cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride with polymerization time of 15 minutes A catalyst solution was prepared and polymerized in the same manner as in Example 1 except for the change. As a result, 6.55 g of polymer was obtained. Polymerization activity is 5.24 kg-PP / m
mol-Zr · hr. [η] of the obtained polymer was 2.17 dl / g, Tm ₁ = 153.7 ° C., and Tm ₂ = 157.7 ° C.

-Propylene polymerization-
In Example 1, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to cyclohexylidene (cyclopentadienyl) (2,7-diphenyl). A catalyst solution was prepared and polymerized in the same manner as in Example 2 except that the polymerization time was changed to -3,6-ditert-butylfluorenyl) zirconium dichloride for 15 minutes. As a result, 5.64 g of polymer was obtained. Polymerization activity is 4.51 kg-PP / m
The obtained polymer had [η] of 1.42 dl / g, Tm ₁ = 136.9 ° C., and Tm ₂ = 145.8 ° C.

-Propylene polymerization-
To a glass autoclave with a capacity of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, propylene was circulated in an amount of 150 liters / hour, and kept at 25 ° C. for 20 minutes. Next, 2.0 mmol of a 1.0 mmol / ml toluene solution of triisobutylaluminum in terms of aluminum atoms was added, and dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-) was added thereto. A toluene solution of tert-butylfluorenyl) zirconium dichloride was added to 5.0 μmol in terms of zirconium atom, and finally, a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added to 0. 020 mmol / liter was added to initiate the polymerization. Propylene gas was continuously supplied at a rate of 150 liters / hour, polymerization was carried out at 25 ° C. for 20 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 10.56 g of a polymer was obtained. The polymerization activity was 6.34 kg-PP / mmol-Zr · hr.
η] was 1.25 dl / g, Tm ₁ = 144.9 ° C., and Tm ₂ = 151.8 ° C.

[Comparative Example 1]
-Propylene polymerization-
In Example 1, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (3,6-diphenyl). A catalyst solution was prepared and polymerized in the same manner as in Example 1 except that the polymerization time was changed to tert-butylfluorenyl) zirconium dichloride to 15 minutes. As a result, 8.94 g of polymer was obtained. The polymerization activity is 7.15 kg-PP / mmol-Zr · hr, and [η] of the obtained polymer is 2.12 dl / g, Tm ₁ = 150.2 ° C., Tm ₂ = 155.2 ° C., rrrr = 94.1%.

[Comparative Example 2]
-Propylene polymerization-
In Example 2, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (3,6-diphenyl). A catalyst solution was prepared and polymerized in the same manner as in Example 2 except that the compound was changed to tert-butylfluorenyl) zirconium dichloride. As a result, 8.23 g of polymer was obtained. The polymerization activity was 6.58 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer was 1.23 dl / g, Tm ₁ = 132.2 ° C., Tm ₂ = 142.1 ° C. .

[Comparative Example 3]
-Propylene polymerization-
In Example 1, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzo). A catalyst solution was prepared and polymerized in the same manner as in Example 1 except that the polymerization time was changed to fluorenyl) zirconium dichloride for 60 minutes. As a result, 0.06 g of polymer was obtained. Polymerization activity is 0.02 kg-PP / m
mol-Zr · hr, and [η] of the obtained polymer was 1.61 dl / g, Tm ₁ = 149.1 ° C., and Tm ₂ = 153.7 ° C.

[Comparative Example 4]
-Propylene polymerization-
In Example 1, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dimethylmethylene (cyclopentadienyl) (3,6-ditert A catalyst solution was prepared and polymerized in the same manner as in Example 1 except that the polymerization time was changed to -butylfluorenyl) zirconium dichloride to 30 minutes. As a result, 1.70 g of a polymer was obtained. The polymerization activity was 0.68 kg-PP / mmol-Zr · hr, and the obtained polymer had Tm ₂ = 150.1 ° C.

[Comparative Example 5]
-Propylene polymerization-
In Example 2, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dimethylmethylene (cyclopentadienyl) (3,6-ditert The catalyst solution was prepared and polymerized in the same manner as in Example 2 except that the polymerization time was changed to -butylfluorenyl) zirconium dichloride to 60 minutes. As a result, 2.65 g of a polymer was obtained. The polymerization activity was 0.53 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer was 1.22 dl / g and Tm ₂ = 131.0 ° C.

[Comparative Example 6]
-Propylene polymerization-
In Example 1, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzo A catalyst solution was prepared and polymerized in the same manner as in Example 1 except that the polymerization time was changed to fluorenyl) zirconium dichloride to 45 minutes. As a result, 2.38 g of a polymer was obtained. Polymerization activity is 0.63 kg-PP / m
[η] of the obtained polymer was 2.15 dl / g, Tm ₁ = 150.1 ° C., Tm ₂ = 155.4 ° C., and rrrr = 94.2%. .

[Comparative Example 7]
-Propylene polymerization-
In Example 2, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzo A catalyst solution was prepared and polymerized in the same manner as in Example 2 except that the polymerization time was changed to fluorenyl) zirconium dichloride to 45 minutes. As a result, 2.14 g of a polymer was obtained. Polymerization activity is 0.57 kg-PP / m
mol-Zr · hr, and the obtained polymer [η] is 1.32 dl / g, Tm ₁ = 125.
. It was 4 ° C. and Tm ₂ = 136.1 ° C.

[Comparative Example 8]
-Propylene polymerization-
In Example 2, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofur A catalyst solution was prepared and polymerized in the same manner as in Example 2 except that the polymerization time was changed to oleenyl) zirconium dichloride to 60 minutes. As a result, 0.75 g of polymer was obtained. Polymerization activity is 0.15 kg-PP / m
mol-Zr · hr, and [η] of the obtained polymer was 1.85 dl / g, Tm ₁ = 98.0 ° C., and Tm ₂ = 104.0 ° C.

[Reference Example 13]
-Ethylene polymerization-
400 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, and ethylene was circulated in an amount of 100 liters / hour and kept at 75 ° C. for 10 minutes. To this, a toluene solution of methylaluminoxane (Al = 1.21 mol / l) was added in an amount of 1.3 mmol in terms of aluminum atoms, and then dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl). Polymerization was initiated by adding a toluene solution of -3,6-ditert-butylfluorenyl) zirconium dichloride to 2.0 μmol in terms of zirconium atoms. Ethylene gas was continuously supplied at a rate of 100 liters / hour, polymerization was carried out at 75 ° C. for 6 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 4.59 g of polymer was obtained. The polymerization activity was 23.0 kg-PE / mmol-Zr · hr, and the [η] of the polymer obtained was 3.69 dl / g.

[Reference Example 14]
-Ethylene polymerization-
400 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, and ethylene was circulated in an amount of 100 liters / hour and kept at 75 ° C. for 10 minutes. To this, a toluene solution of methylaluminoxane (Al = 1.21 mol / l) was added in an amount of 0.52 mmol in terms of aluminum atoms, and then di (n-butyl) methylene (cyclopentadienyl) (2 , 7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride in toluene was converted to zirconium atoms to 0.8 μmol, and polymerization was started. Ethylene gas was continuously supplied at a rate of 100 liters / hour, polymerization was carried out at 75 ° C. for 3 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 2.70 g of polymer was obtained. The polymerization activity was 67.5 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 4.32 dl / g.

[Reference Example 15]
-Ethylene polymerization-
In Reference Example 14, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (n-butyl) methylene (cyclopentadienyl) (2 , 7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride was used in the same manner as in Reference Example 14 to prepare and polymerize a catalyst solution. As a result, 4.72 g of polymer was obtained. The polymerization activity was 118.0 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 3.53 dl / g.

[Reference Example 16]
-Ethylene polymerization-
In Reference Example 14, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (p-chlorophenyl) methylene (cyclopentadienyl) (2 , 7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride was used in the same manner as in Reference Example 14 to prepare and polymerize a catalyst solution. As a result, 3.68 g of polymer was obtained. The polymerization activity was 92.0 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 7.32 dl / g.

[Reference Example 17]
-Ethylene polymerization-
In Reference Example 14, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (m-trifluoromethyl-phenyl) methylene (cyclopentadiene). The catalyst solution was prepared and polymerized in the same manner as in Reference Example 14 except that the polymerization time was changed to 2 min for (enyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride. went. As a result, 4.24 g of polymer was obtained. The polymerization activity was 159.0 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 7.61 dl / g.

[Reference Example 18]
-Ethylene polymerization-
In Reference Example 13, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to cyclohexylidene (cyclopentadienyl) (2,7-diphenyl). The catalyst solution was prepared and polymerized in the same manner as in Reference Example 13 except that the polymerization time was changed to -3,6-ditert-butylfluorenyl) zirconium dichloride to 4 minutes. As a result, 4.07 g of polymer was obtained. The polymerization activity was 30.5 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 4.05 dl / g.

[Comparative Example 9]
-Ethylene polymerization-
In Reference Example 13, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzo A catalyst solution was prepared and polymerized in the same manner as in Reference Example 13 except that the polymerization time was changed to fluorenyl) zirconium dichloride for 2 minutes. As a result, 1.21 g of polymer was obtained. The polymerization activity was 18.2 kg-PE / mmol-Zr · hr, and the [η] of the obtained polymer was 2.23 dl / g.

[Comparative Example 10]
-Ethylene polymerization-
In Reference Example 13, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzo A catalyst solution was prepared and polymerized in the same manner as in Reference Example 13 except that the polymerization time was changed to fluorenyl) zirconium dichloride to 2.5 minutes. As a result, 1.76 g of polymer was obtained. The polymerization activity was 21.1 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 2.62 dl / g.

[Comparative Example 11]
-Ethylene polymerization-
In Reference Example 13, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofuro The catalyst solution was prepared and polymerized in the same manner as in Reference Example 13 except that the polymerization time was changed to 3 min for oleenyl) zirconium dichloride. As a result, 4.15 g of polymer was obtained. The polymerization activity was 41.5 kg-PE / mmol-Zr · hr.

-Preparation of supported catalyst-
A stirring bar was attached to a 100 ml three-necked flask thoroughly purged with nitrogen, and 0.501 g of silica-supported methylaluminoxane (Al = 16.1 wt%) was added thereto. To this was added 15 ml of dehydrated toluene at room temperature, and 10 ml of toluene solution of 10.2 mg of dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride with stirring. Was added and stirred for 1 hour. The obtained slurry was filtered, and the powder on the filter was washed once with 10 ml of dehydrated toluene and then three times with 10 ml of dehydrated hexane. The washed powder was dried under reduced pressure for 2 hours to obtain 0.422 g of powder, which was mixed with 3.80 g of mineral oil to obtain a 10.0 wt% slurry.

-Propylene bulk polymerization-
A magnetic stirrer chip was placed in a 50 ml branch flask thoroughly purged with nitrogen, and 0.596 g of the supported catalyst slurry prepared in Example 19 and 1.0 mmol of hexane solution of triisobutylaluminum (Al = 1.0 M) were added thereto. Then, 5.0 ml of dehydrated hexane was added, and the mixture was introduced into an SUS autoclave having an internal volume of 2000 ml that was sufficiently purged with nitrogen. Thereafter, 500 g of liquid propylene was charged and polymerization was carried out at 70 ° C. for 40 minutes, and then the autoclave was cooled and propylene was purged to stop the polymerization. The obtained syndiotactic polypropylene was 38.7 g, and the polymerization activity was 45.8 kg-PP / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.99 dl / g, Mw = 72800, Mw / Mn = 1.87, Tm ₁ = 135.9 ° C., Tm ₂ = 145.7 ° C.

-Propylene bulk polymerization-
Polymerization was carried out under the same conditions as in Example 20 except that 0.194 g of the supported catalyst slurry prepared in Example 19 was used, 500 g of liquid propylene was charged, and 0.3 NL of hydrogen was added. The obtained syndiotactic polypropylene was 42.2 g, and the polymerization activity was 153.5 kg-PP / mmol-Zr · hr. As a result of polymer analysis, [η] = 1.00 dl / g, Mw = 74200, Mw / Mn = 1.99, Tm ₁ = 134.6 ° C., and Tm ₂ = 145.8 ° C.

[Comparative Example 12]
-Preparation of supported catalyst-
A stirring rod was attached to a 100 ml three-necked flask thoroughly purged with nitrogen, and 0.506 g of methylaluminoxane (Al = 16.1 wt%) on silica was added thereto. To this was added 15 ml of dehydrated toluene at room temperature, and 10 ml of a toluene solution of 10.3 mg of isopropylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride was added with stirring and stirred for 1 hour. . The obtained slurry was filtered, and the powder on the filter was washed once with 10 ml of dehydrated toluene and then three times with 10 ml of dehydrated hexane. The washed powder was dried under reduced pressure for 2 hours to obtain 0.410 g of powder, which was mixed with 3.69 g of mineral oil to make a 10.0 wt% slurry.

[Comparative Example 13]
-Propylene bulk polymerization-
A magnetic stirrer chip was placed in a 50 ml branch flask thoroughly purged with nitrogen, and 0.205 g of the supported catalyst slurry prepared in Comparative Example 12 above and 1.0 mmol of a hexane solution of triisobutylaluminum (Al = 1.0 M). Then, 5.0 ml of dehydrated hexane was added, and the mixture was introduced into an SUS autoclave having an internal volume of 2000 ml that was sufficiently purged with nitrogen. Thereafter, 500 g of liquid propylene was charged and polymerization was carried out at 70 ° C. for 40 minutes, and then the autoclave was cooled and propylene was purged to stop the polymerization. The polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained syndiotactic polypropylene was 6.9 g, and the polymerization activity was 16.9 kg-PP / mmol-Zr · hr. As a result of polymer analysis, [η] = 1.15 dl / g, Mw = 88200, Mw / Mn = 1.76, Tm ₁ = 126.
It was 9 ° C. and Tm ₂ = 136.9 ° C.

[Comparative Example 14]
-Propylene bulk polymerization-
Polymerization was carried out under the same conditions as in Comparative Example 13, except that 0.198 g of the supported catalyst slurry prepared in Comparative Example 12 was used, 500 g of liquid propylene was charged, and 0.3 NL of hydrogen was added. The obtained syndiotactic polypropylene was 168.9 g, and the polymerization activity was 429.7 kg-PP / mmol-Zr · hr. As a result of polymer analysis, [η] = 1.07 dl / g, Mw = 84700, Mw / Mn = 1.96, Tm ₁ = 12.3 ° C., T
m ₂ = 136.4 ° C.

-Propylene polymerization-
N-heptane 400 in a 500 ml glass autoclave thoroughly purged with nitrogen
ml was charged and propylene was circulated in an amount of 150 liters / hour and kept at 25 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30 ml-branched flask with an internal volume sufficiently purged with nitrogen, 5.00 mmol of a toluene solution of methylaluminoxane (Al = 1.53 mol / L), and then dibenzylmethylene (cyclopentadiene). A toluene solution of 5.0 μmol of (enyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was added and stirred for 20 minutes. This solution was added to n-heptane in a glass autoclave in which propylene had been circulated to initiate polymerization. 1 propylene gas
After continuously feeding at an amount of 50 liters / hour and performing polymerization at 25 ° C. under normal pressure for 7.5 minutes,
A small amount of methanol was added to terminate the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 9.00 g of polymer was obtained. The polymerization activity was 14.40 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer was 2.73 dl / g and Tm ₂ = 159.0 ° C.

-Propylene polymerization-
The same procedure as in Example 22 was performed except that the temperature in the autoclave before the polymerization reaction and during the polymerization reaction was kept at 50 ° C., and the polymerization time was 31 minutes. The obtained polymer was 19.60 g, the polymerization activity was 7.59 kg-PP / mmol-Zr · hr, the [η] of the polymer was 1.72 dl / g, Tm ₁ = 149.9 ° C., Tm ₂ = 154 8 ° C.

-Propylene polymerization-
To a glass autoclave with a capacity of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, propylene was circulated in an amount of 150 liters / hour, and kept at 25 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30-ml branch flask with a sufficient nitrogen substitution, and a toluene solution of methylaluminoxane (Al = 1.53 mol).
/ L) 5.00 mmol, then dibenzylmethylene (cyclopentadienyl) (2,7- [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride in 5.0 μmol in toluene. Added and stirred for 20 minutes. This solution was added to toluene in a glass autoclave in which propylene had been circulated, and polymerization was started. Propylene gas was continuously supplied at a rate of 150 liters / hour, polymerization was performed at 25 ° C. for 15 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 12.19 g of polymer was obtained. The polymerization activity was 9.75 kg-PP / mmol-Zr · hr, and the obtained polymer [η] was 2.27 dl / g, Tm ₁ = 156.5 ° C., Tm ₂ = 161.0 ° C. .

-Propylene polymerization-
The same procedure as in Example 24 was performed except that the temperature in the autoclave before the polymerization reaction and during the polymerization reaction was kept at 50 ° C., and the polymerization time was 20 minutes. The obtained polymer was 12.30 g, the polymerization activity was 7.38 kg-PP / mmol-Zr · hr, the [η] of the polymer was 1.43 dl / g, Tm ₁ = 143.0 ° C., Tm ₂ = 150 It was 6 ° C.

-Propylene polymerization-
In Example 23, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (2,7- [ A catalyst solution was prepared and polymerized in the same manner as in Example 23, except that 2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride was changed to a polymerization time of 15 minutes. As a result, 5.75 g of polymer was obtained. Polymerization activity is 4.60 kg-
PP / mmol-Zr · hr. [Η] of the obtained polymer was 1.59 dl / g, Tm ₁ = 147.2 ° C., and Tm ₂ = 154.1 ° C.

-Propylene polymerization-
In Example 24, dibenzylmethylene (cyclopentadienyl) (2,7- [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (2 , 7- [p-Tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride, the catalyst solution was prepared and polymerized in the same manner as in Example 24 except that the polymerization time was changed to 10 minutes. went. As a result, 29.81 g of a polymer was obtained. The polymerization activity was 35.77 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer was 1.00 dl / g, Tm ₁ = 155.1 ° C., Tm ₂ = 160.0 ° C. .

-Propylene polymerization-
In Example 25, dibenzylmethylene (cyclopentadienyl) (2,7- [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (2 , 7- [p-Tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride, and the catalyst solution was prepared and polymerized in the same manner as in Example 25 except that the polymerization time was changed to 15 minutes. went. As a result, 39.08 g of polymer was obtained. The polymerization activity was 31.26 kg-PP / mmol-Zr · hr, and the polymer [η] was 0.71 dl / g, Tm ₁ = 140.5 ° C., and Tm ₂ = 148.9 ° C. .

-Propylene polymerization-
In Example 23, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3
, 6-Ditert-butylfluorenyl) zirconium dichloride to dibenzylmethylene (cyclopentadienyl) (2,7- [p-tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride, A catalyst solution was prepared and polymerized in the same manner as in Example 23 except that the polymerization time was changed to 15 minutes. As a result, 7.42 g of polymer was obtained. Polymerization activity is 5.94 kg-P.
P / mmol-Zr · hr. [Η] of the obtained polymer was 1.87 dl / g, Tm ₁ = 147.2 ° C., and Tm ₂ = 153.6 ° C.

-Propylene polymerization-
In Example 24, dibenzylmethylene (cyclopentadienyl) (2,7- [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (2 , 7- [o-Tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride, and the catalyst solution was prepared and polymerized in the same manner as in Example 24 except that the polymerization time was changed to 5 minutes. went. As a result, 2.24 g of polymer was obtained. Polymerization activity is 5.38 kg-P
P / mmol-Zr · hr. [Η] of the obtained polymer was 3.63 dl / g and Tm ₂ = 156.0 ° C.

-Propylene polymerization-
In Example 25, dibenzylmethylene (cyclopentadienyl) (2,7- [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (2 , 7- [o-Tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride, the catalyst solution was prepared and polymerized in the same manner as in Example 25 except that the polymerization time was changed to 8 minutes. went. As a result, 3.98 g of a polymer was obtained. Polymerization activity is 5.97 kg-P
P / mmol-Zr · hr. [Η] of the obtained polymer was 2.46 dl / g, Tm ₁ = 138.4 ° C., and Tm ₂ = 145.8 ° C.

-Propylene polymerization-
In Example 22, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (2,7- [ The catalyst solution was prepared and polymerized in the same manner as in Example 22 except that the polymerization time was changed to o-tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride for 9 minutes. As a result, 3.75 g of polymer was obtained. Polymerization activity is 5.00kg-PP
/ Mmol-Zr · hr, [η] of the obtained polymer was 3.88 dl / g, and the obtained polymer was Tm ₂ = 156.2 ° C.

-Propylene polymerization-
In Example 23, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (2,7- [ A catalyst solution was prepared and polymerized in the same manner as in Example 23, except that the polymerization time was changed to o-tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride. As a result, 6.66 g of a polymer was obtained. Polymerization activity is 4.00 kg-P
P / mmol-Zr · hr, and Tm ₁ = 141.9 ° C. and Tm ₂ = 149.0 ° C.

[Reference Example 34]
-Ethylene polymerization-
400 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, and ethylene was circulated in an amount of 100 liters / hour and kept at 75 ° C. for 10 minutes. To this, 1.3 mmol of a toluene solution of methylaluminoxane (Al = 1.21 mol / l) was added, and then dibenzylmethylene (cyclopentadienyl) (2,7- [2-naphthyl] -3,6-di- Polymerization was initiated by adding 2.0 μmol of a toluene solution of tert-butylfluorenyl) zirconium dichloride. Ethylene gas was continuously supplied at a rate of 100 liters / hour, polymerization was carried out at 75 ° C. for 4 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 3.76 g of polymer was obtained. The polymerization activity was 28.2 kg-PE / mmol-Zr · hr, and the [η] of the obtained polymer was 3.74 dl / g.

[Reference Example 35]
-Ethylene polymerization-
In Reference Example 34, dibenzylmethylene (cyclopentadienyl) (2,7- [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (2 , 7- [p-Tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride, and the catalyst solution was prepared and polymerized in the same manner as in Reference Example 34 except that the polymerization time was changed to 5 minutes. went. As a result, 6.00 g of polymer was obtained. The polymerization activity was 36.0 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 4.58 dl / g.

[Reference Example 36]
-Ethylene polymerization-
In Reference Example 34, dibenzylmethylene (cyclopentadienyl) (2,7- [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride was converted to dibenzylmethylene (cyclopentadienyl) (2 , 7- [o-Tolyl] -3,6-ditert-butylfluorenyl) zirconium dichloride, and the catalyst solution was prepared and polymerized in the same manner as in Reference Example 34 except that the polymerization time was changed to 6 minutes. went. As a result, 4.41 g of polymer was obtained. The polymerization activity was 22.1 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 6.37 dl / g.

-Propylene polymerization-
In Example 24 dibenzylmethylene (cyclopentadienyl) (2,7- [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (4-chlorobenzyl) methylene (cyclopenta A catalyst solution was prepared and polymerized in the same manner as in Example 24, except that it was changed to (dienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride. As a result, 6.54 g of polymer was obtained. Polymerization activity is 5.23 kg-PP / m
mol-Zr · hr. [η] of the obtained polymer was 2.29 dl / g, Tm ₁ = 157.6 ° C., and Tm ₂ = 163.0 ° C.

-Propylene polymerization-
In Example 25, dibenzylmethylene (cyclopentadienyl) (2,7- [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (4-chlorobenzyl) methylene (cyclopenta Preparation of a catalyst solution and polymerization in the same manner as in Example 25 except that the polymerization time was changed to dienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride and the polymerization time was changed to 15 minutes. Went. As a result, 6.17 g of polymer was obtained. The polymerization activity was 4.94 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer was 1.48 dl / g, Tm ₁ = 146.6 ° C., Tm ₂ = 154.1 ° C. .

-Propylene polymerization-
In Example 22, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (4-chlorobenzyl) methylene (cyclopentadienyl) ( A catalyst solution was prepared and polymerized in the same manner as in Example 22 except that the polymerization time was changed to 2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride for 8 minutes. As a result, 2.76 g of a polymer was obtained. The polymerization activity was 4.14 kg-PP / mmol-Zr · hr, and the polymer [η] was 2.68 dl / g and Tm ₂ = 160.5 ° C.

-Propylene polymerization-
In Example 23, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (4-chlorobenzyl) methylene (cyclopentadienyl) ( A catalyst solution was prepared and polymerized in the same manner as in Example 23 except that the polymerization time was changed to 2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride and the polymerization time was changed to 10 minutes. As a result, 1.69 g of a polymer was obtained. The polymerization activity was 2.03 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer was 1.55 dl / g, Tm ₁ = 150.2 ° C., Tm ₂ = 156.8 ° C. .
[Comparative Example 15]

-Propylene polymerization-
N-Hexane 400 in a 500 ml glass autoclave thoroughly purged with nitrogen
ml was charged and propylene was circulated in an amount of 150 liters / hour and kept at 45 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30 ml-branched flask with an internal volume sufficiently purged with nitrogen. Enyl) (3,6-ditert-butylfluorenyl) zirconium dichloride in toluene 5.0 μmo
was added and stirred for 20 minutes. This solution was added to toluene in a glass autoclave in which propylene had been circulated, and polymerization was started. Propylene gas was continuously supplied at a rate of 150 liter / hour, polymerization was carried out at 45 ° C. for 30 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 2.15 g of a polymer was obtained. The polymerization activity was 0.86 kg-PP / mmol-Zr · hr, and the obtained polymer [η] was 1.31 dl / g, Tm ₁ = 134.1 ° C., and Tm ₂ = 143.5 ° C. .

[Reference Example 41]
-Ethylene polymerization-
In Reference Example 34, dibenzylmethylene (cyclopentadienyl) (2,7- [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride was converted to di (4-chlorobenzyl) methylene (cyclopenta Preparation and polymerization of the catalyst solution in the same manner as in Reference Example 34 except that the polymerization time was changed to dienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride and the polymerization time was changed to 6 minutes. Went. As a result, 2.00 g of polymer was obtained. The polymerization activity was 10.0 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 3.36 dl / g.

[Reference Example 42]
-Ethylene polymerization-
400 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, and ethylene was circulated in an amount of 100 liters / hour and kept at 75 ° C. for 10 minutes. To this, 0.52 mmol of a toluene solution of methylaluminoxane (Al = 1.21 mol / l) was added, and then di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-). Polymerization was initiated by adding 0.8 μmol of a toluene solution of tert-butylfluorenyl) zirconium dichloride. Ethylene gas was continuously supplied at a rate of 100 liters / hour, polymerization was carried out at 75 ° C. for 6 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 0.42 g of polymer was obtained. The polymerization activity was 5.3 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 8.44 dl / g.

Table 1 shows the results of Examples 1 to 12 and Comparative Examples 1 to 8 related to propylene polymerization, Table 2 shows the results of Reference Examples 13 to 18 and Comparative Examples 9 to 11 related to ethylene polymerization, and the results related to propylene polymerization. The results of Examples 22 to 33, 37 to 40 and Comparative Example 15 are summarized in Table 3, and the results of Reference Examples 34 to 36, 41 and 42 relating to ethylene polymerization are summarized in Table 4.

Catalyst a: Dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-
Butylfluorenyl) zirconium dichloride catalyst b: Di (n-butyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride catalyst c: Di (n -Butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride catalyst d: di (p-chlorophenyl) methylene (cyclopentadienyl) (2, 7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride catalyst e: di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylful) Olenyl) zirconium dichloride catalyst f: di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride Medium g: cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-
Butylfluorenyl) zirconium dichloride catalyst h: Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride catalyst i: Cyclohexylidene (cyclopentadienyl) (octamethylocta Hydrodibenzofluorenyl) zirconium dichloride catalyst j: Dimethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride catalyst k: Dibenzylmethylene (cyclopentadienyl) (octamethylocta Hydrodibenzofluorenyl) zirconium dichloride catalyst l: Diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride

Catalyst a: Dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-
Butylfluorenyl) zirconium dichloride catalyst b: Di (n-butyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-dite
rt-Butylfluorenyl) zirconium dichloride catalyst c: Di (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride catalyst e: Di (P-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride catalyst f: di (m-trifluoromethyl-phenyl) methylene (cyclopenta Dienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride catalyst g: cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-
Butylfluorenyl) zirconium dichloride catalyst i: cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride catalyst k: dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofur) Olenyl) zirconium dichloride catalyst l: Diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride

Catalyst a: Dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-
Butylfluorenyl) zirconium dichloride catalyst h: Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride catalyst m: Dibenzylmethylene (cyclopentadienyl) (2,7 -[2-Naphtyl] -3,6-ditert-butylfluorenyl) zirconium dichloride catalyst n: dibenzylmethylene (cyclopentadienyl) (2,7- [p-tolyl] -3,6-ditert -
Butylfluorenyl) zirconium dichloride catalyst o: dibenzylmethylene (cyclopentadienyl) (2,7- [o-tolyl] -3,6-ditert-
Butylfluorenyl) zirconium dichloride catalyst p: di (4-chlorobenzyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

Catalyst d: Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride catalyst m: Dibenzylmethylene (cyclopentadienyl) ( 2,7- [2-naphthyl] -3,6-ditert-butylfluorenyl) zirconium dichloride catalyst n: dibenzylmethylene (cyclopentadienyl) (2,7- [p-tolyl] -3,6 -Di-tert-
Butylfluorenyl) zirconium dichloride catalyst o: dibenzylmethylene (cyclopentadienyl) (2,7- [o-tolyl] -3,6-ditert-
Butylfluorenyl) zirconium dichloride catalyst p: di (4-chlorobenzyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

  The catalyst for olefin polymerization of the present invention is excellent in polymerization activity and has a great merit for the olefin polymerization industry.

Claims (7)

(A) a bridged metallocene compound represented by the following general formula [I], and (B) (b-1) an organoaluminum oxy compound,
(b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and
(b-3) propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, in the presence of an olefin polymerization catalyst composed of at least one compound selected from organoaluminum compounds , One or more selected from 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene a process for producing a syndiotactic α-olefin polymer, wherein a monomer of α-olefin is polymerized;

Wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, R ⁵ , R ⁸ , R ⁹ and R ¹² are selected from hydrogen, hydrocarbon groups, alkylsilyl groups and arylsilyl groups; Each may be the same or different,
The four groups R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not hydrogen atoms but are selected from hydrocarbon groups, alkylsilyl groups and arylsilyl groups, which may be the same or different, and R ⁷ and R ¹⁰ The hydrocarbon groups as are ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n- Linear hydrocarbon groups, branched hydrocarbon groups, cyclic saturated hydrocarbon groups, cyclic unsaturated hydrocarbon groups and their nuclear alkyl substituents, saturated hydrocarbon groups substituted with aryl groups, and heteroatoms selected from decanyl groups Any group selected from the containing hydrocarbon groups,
In the combination of one or more adjacent groups selected from R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² , the adjacent groups are bonded to each other. A ring may be formed.
R ⁶ and R ⁷ are not bonded to form a ring, and R ¹⁰ and R ¹¹ are not bonded to each other to form a ring.
R ¹³ and R ¹⁴ are atoms or substituents selected from the group consisting of a hydrogen atom, a hydrocarbon group having 2 to 20 carbon atoms, an alkylsilyl group, and an arylsilyl group, and may be the same or different from each other; The substituents may be bonded to each other to form a ring.
M is Ti, Zr or Hf,
Y is carbon,
Q is selected from a halogen, a hydrocarbon group, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair, and each may be the same or different,
j is an integer of 1-4. ). The method for producing a syndiotactic α- olefin polymer according to claim 1 , wherein the olefin polymerization catalyst further comprises a carrier (C). In the general formula [I], R ⁶ And R ¹¹ Are the same atom or the same group, and R ⁷ And R ^Ten Are the same atom or the same group, The manufacturing method of the syndiotactic alpha-olefin polymer of Claim 1 or 2 characterized by the above-mentioned. In the general formula [I], R ⁶ And R ¹¹ The method for producing a syndiotactic α-olefin polymer according to any one of claims 1 to 3, wherein is an aryl group or a substituted aryl group. In the general formula [I], R ¹³ And R ¹⁴ Is a C2-C20 hydrocarbon group, The manufacturing method of the syndiotactic alpha-olefin polymer in any one of Claims 1-4 characterized by the above-mentioned. In the general formula [I], R ¹³ And R ¹⁴ Are ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, m-tolyl, p-tolyl, benzyl A group selected from a group, m- (trifluoromethyl) phenyl group, p- (trifluoromethyl) phenyl group, bis (trifluoromethyl) phenyl group, m-chlorophenyl group, p-chlorophenyl group and dichlorophenyl group The method for producing a syndiotactic α-olefin polymer according to claim 1, wherein: The method for producing a syndiotactic α-olefin polymer according to any one of claims 1 to 6, wherein the bridged metallocene compound (A) is a metallocene compound having a Cs symmetric structure.