JP5866788B2 - Novel half metallocene complex, olefin polymerization catalyst containing the same, and olefin or ethylene polymerization method using the same - Google Patents

Description

  The present invention relates to a novel half-metallocene complex, an olefin polymerization catalyst containing the same, and an olefin or ethylene polymerization method using the same, and more particularly, the olefin copolymer is excellent in copolymerizability and has a high molecular weight olefin copolymer. The present invention relates to a novel half metallocene complex forming an olefin polymerization catalyst capable of producing a polymer, an olefin polymerization catalyst containing the same, and an olefin or ethylene polymerization method using the same.

Olefin copolymers represented by ethylene / α-olefin copolymers or propylene / α-olefin copolymers have excellent mechanical properties, and polymers with a wide range of physical properties from hard to soft are produced. Its uses are widely used from industrial use to daily life materials as films and sheets, fibers and corrosive cloths, various containers and molded articles, and modifiers.
Generally, copolymers of comonomers such as 1-butene and 1-hexene are more flexible, low temperature impact, environmental stress crack resistance, and transparency than ethylene homopolymer and propylene homopolymer. It is known that such performance is excellent. In order to further improve these performances, it is necessary to increase the comonomer content in the copolymer while maintaining the high molecular weight. In addition, it is known that when a complex catalyst typified by a metallocene catalyst is used, the distribution of the comonomer introduced into the copolymer becomes uniform and the above performance is further improved.
Therefore, in producing an olefin copolymer having these performances, a high molecular weight olefin copolymer can be produced in a temperature range of 50 to 300 ^° C. which is efficient in an industrial process, and from the viewpoint of process load. There is a demand for a complex catalyst excellent in copolymerizability that can produce a copolymer having a high comonomer content even at a low comonomer concentration. However, when the olefin copolymerization is carried out using a complex catalyst typified by a metallocene catalyst, there is a drawback that the molecular weight of the copolymer decreases as the comonomer content in the copolymer obtained generally increases. Have been reported (for example, see Non-Patent Document 1).

From the 1990s, it has been found that a catalyst using a half metallocene complex using one cyclopentadienyl derivative as a ligand is superior in copolymerizability to a metallocene catalyst (for example, Patent Documents 1 and 2; (See Patent Documents 2 and 3). Thereafter, as a result of intensive research, it has been reported that the molecular weight of the resulting copolymer is improved by introducing a substituent onto the cyclopentadienyl ligand (for example, Patent Document 3). To 6).
However, studies by the present inventors have revealed that when these half-metallocene catalysts are used for olefin copolymerization, the polymer produced has an insufficient molecular weight, although it is excellent in copolymerizability.

  Under such circumstances, the complex catalyst that eliminates the problems of the complex catalyst in the prior art and can produce a high-molecular-weight olefin copolymer while having excellent copolymerization at an industrially advantageous polymerization temperature and polymerization conditions. There has been a demand for the development of a system catalyst and, further, a method for producing an olefin polymer using the same.

Japanese Patent No. 2994746 Japanese Patent No. 2535249 Japanese Patent No. 3795072 Japanese Patent No. 4454698 Special Table 2000-516608 JP 2005-519969 A

Macromol. Chem. Phys. 1996, 197, 3091-3097 Chem. Rev. 1998, 98, 2587-2598 Prog. Polym. Sci. 2008, 33, 797-819

  In view of the problems of the prior art described above, an object of the present invention is to provide a high-molecular-weight olefin copolymer without lowering the copolymerizability compared to conventional complex catalysts at an industrially advantageous polymerization temperature and polymerization conditions. It is another object of the present invention to provide a half metallocene complex capable of producing a olefin, a catalyst for olefin polymerization containing the same, and a method for polymerizing olefin or ethylene using the same.

  As a result of intensive studies to solve the above problems, the present inventors have determined that a half metallocene complex having a specific substituent, that is, a half metallocene having a specific heteroaromatic ring at the 2-position of the cycloalkadienyl ring. By using the complex, it has been found that a copolymer having excellent copolymerizability and a high molecular weight can be obtained, and the present invention has been completed.

  That is, according to the first aspect of the present invention, there is provided a half metallocene complex represented by the following general formula [I]:

［式中、Ｍはチタン、ジルコニウム、またはハフニウムであり、Ｑは炭素数１〜２０の炭化水素基を有していてもよいシリレン基またはゲルミレン基であり、Ｚはアミド基である。
Ｘ及びＹは、σ共有結合性補助配位子を示し、同一でも異なってもよく、ｎとｍの和は０〜２であり、Ｌは中性のルイス塩基でありｋは０〜２であり、ｎとｍとｋの和は０〜４である。
Ｒ^１は１つ以上の置換基を有するフリル基又はチエニル基である。また、該フリル基又はチエニル基が複数の置換基を有する場合、各置換基は同じでも異なっていてもよく、該フリル基またはチエニル基に結合する置換基は、炭素数１〜２０のアルキル基もしくは炭素数１〜２０の珪素含有アルキル基、炭素数１〜２０のハロゲン原子含有アルキル基、炭素数１〜６のアルコキシ基、炭素数６〜１８のアリール基もしくは炭素数６〜１８のハロゲン化アリール基である。
Ｒ^２は、水素、炭素数１〜８のアルキル基、炭素数１〜８のハロゲン原子含有アルキル基、炭素数１〜２０の珪素含有アルキル基、炭素数６〜１８のアリール基または炭素数６〜１８のハロゲン化アリール基であり、
Ｒ ^３ 及びＲ ^４ は、インデニル環を形成する。］

[Wherein, M is titanium, zirconium or hafnium, Q is a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and Z is an amide group.
X and Y represent σ covalent auxiliary ligands, which may be the same or different, the sum of n and m is 0 to 2, L is a neutral Lewis base, and k is 0 to 2. Yes, the sum of n, m, and k is 0-4.
R ¹ is a furyl group or a thienyl group having one or more substituents. When the furyl group or thienyl group has a plurality of substituents, each substituent may be the same or different, and the substituent bonded to the furyl group or thienyl group is an alkyl group having 1 to 20 carbon atoms. Alternatively, a silicon-containing alkyl group having 1 to 20 carbon atoms, a halogen atom-containing alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogenated group having 6 to 18 carbon atoms. An aryl group.
R ² is hydrogen, an alkyl group having 1 to 8 carbon atoms, a halogen atom-containing alkyl group having 1 to 8 carbon atoms, a silicon-containing alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or 6 carbon atoms. halogenated aryl groups der of ~ 18 is,
R ³ and R ⁴ form an indenyl ring. ]

According to a second invention of the present invention, there is provided a half metallocene complex according to the first invention, wherein M is titanium in the general formula [I].

Furthermore, according to the third aspect of the present invention, there is provided an olefin polymerization catalyst characterized in that it comprises the following components (A) and (B) and, if necessary, (C).
Component (A): Half metallocene complex according to either the first or second invention Component (B): Compound or ion-exchange layered silicate or inorganic silicate that reacts with component (A) to form an ion pair (C): Organoaluminum compound

According to a fourth aspect of the present invention, there is provided an olefin polymerization catalyst according to the third aspect , wherein the component (B) is a boron compound.

Furthermore, according to the fifth invention of the present invention, using the olefin polymerization catalyst according to the third or fourth invention, homopolymerization of olefin, copolymerization of two or more kinds of olefins, or olefin and polymerizable unsaturated. Provided is a method for polymerizing olefins, which comprises copolymerizing hydrocarbons.

According to the sixth invention of the present invention, ethylene homopolymerization or copolymerization of ethylene and one or more α-olefins is carried out using the olefin polymerization catalyst according to the third or fourth invention. A method for polymerizing ethylene is provided.

By using the half metallocene complex of the present invention as a polymerization catalyst, it is possible to obtain a high-molecular-weight olefin copolymer in olefin copolymerization while maintaining excellent copolymerizability as compared with conventional complex catalyst systems. it can.
As a result, an olefin copolymer excellent in flexibility, impact resistance, and transparency can be produced under industrially efficient polymerization conditions, and the half metallocene complex of the present invention and olefin polymerization including the half metallocene complex. The olefin polymerization method using the catalyst for olefin and the olefin polymerization catalyst is very useful from an industrial viewpoint.

It considers below that the half metallocene complex of this invention has the effect of said this invention.
That is, the half metallocene complex constituting the basic structure of the present invention is a novel transition metal compound, characterized by the electronic and steric structure of the ligand, thereby exhibiting excellent olefin copolymerizability. However, the catalytic function leading to high molecular weight polymers is manifested.
The half metallocene complex is composed of a transition metal compound represented by the above general formula [I]. In the present invention, the half metallocene complex is combined with a co-catalyst to form a polymerization catalyst. Used as a catalyst component.

By using the transition metal compound of the present invention as a catalyst component for olefin polymerization, it is possible to efficiently incorporate an α-olefin, which is a comonomer, particularly in ethylene copolymerization, as demonstrated by the comparison of Examples and Comparative Examples described later. Furthermore, it is possible to realize a half metallocene complex catalyst for olefin copolymerization that can give a high molecular weight polymer.
The reason is not necessarily clear, but the transition metal compound represented by the general formula [I] in the present invention has a sterically unique structure having a specific heteroaromatic substituent at the 2-position of the cycloalkadienyl ring. There are certain basic features, and it can be inferred that these features bring about the specificity of the present invention.
In particular, by arranging a heteroaromatic substituent at the 2-position of the cycloalkadienyl ring, the β-hydrogen elimination reaction after insertion of the comonomer, which causes the decrease in molecular weight, is sterically suppressed, and the resulting polymer It is thought to increase the molecular weight. In general, a sterically bulky substituent hinders the coordination of the monomer and lowers the copolymerizability, but the heteroaromatic substituent at the 2-position rotates its planar cyclic structure during the coordination / insertion of the monomer. Thus, it is considered that the excellent copolymerizability of the conventional half metallocene complex can be maintained by minimizing steric hindrance so as not to interfere with the coordination and insertion of the comonomer. As a result, it can be considered that an excellent effect of giving a high molecular weight polymer can be obtained without impairing the copolymerizability.

  As demonstrated by the comparison between Examples and Comparative Examples described later, in the structure in which a methyl group is arranged at the 2-position of the cyclopentadienyl ring and the structure in which a hydrogen atom is arranged at the 2-position of the indenyl ring, the polymer elimination reaction Is not in an arrangement that can sufficiently suppress In contrast to this result, in the structure having a cyclo ring and an indenyl ring in which the specific heteroaromatic substituent found in the present invention is located at the 2-position, the above-described polymer elimination reaction suppression and monomer coordination / insertion are possible. It is thought that it was possible to achieve both avoidance of inhibition. In addition, if a specific heteroaromatic substituent is arranged at the 2-position, it is effective even with a cyclopentadienyl ring and an indenyl ring, so a half having a specific heteroaromatic substituent at the 2-position A metallocene complex can be considered to exert the same effect.

  Hereinafter, the transition metal compound (half metallocene complex) of the present invention, an olefin polymerization catalyst containing the half metallocene complex, an olefin polymerization method using the olefin polymerization catalyst, and the like will be described in detail.

1. Transition metal compounds (half metallocene complexes)
The transition metal compound (half metallocene complex) of the present invention is represented by the following general formula [I], and has a specific heteroaromatic substituent at the 2-position of the cyclic ligand.

In the general formula [I], M is titanium, zirconium, or hafnium, and Q may have a divalent hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms. A silylene group or a germylene group, and Z is an amide group, phosphide group, oxygen atom, sulfur atom, phenyleneoxy group or alkylidene group.
X and Y represent σ covalent auxiliary ligands, which may be the same or different, the sum of n and m is 0 to 2, L is a neutral Lewis base, and k is 0 to 2. Yes, the sum of n, m, and k is 0-4. Note that n + m + 2 represents the oxidation number of the central metal M.
R ¹ represents a 5- to 10-membered heteroaromatic substituent containing a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom, and the heteroaromatic substituent contains 1 to 5 hetero atoms; When containing multiple heteroatoms, each heteroatom may be the same or different and the heteroaromatic substituent is directly attached to the cycloalkadienyl group via a carbon atom. In addition, the heteroaromatic substituent has one or more substituents bonded to the heteroaromatic ring, and when it has a plurality of substituents, each substituent may be the same or different. When the number of heteroatoms contained in the aromatic ring is 1, the position of the substituent bonded to the heteroaromatic ring is other than the atom directly bonded to the carbon atom bonded to the cycloalkadienyl group. The substituent bonded to the heteroaromatic ring is an alkyl group having 1 to 20 carbon atoms or a silicon-containing alkyl group having 1 to 20 carbon atoms, a halogen atom-containing alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. , An aryl group having 6 to 18 carbon atoms or a halogenated aryl group having 6 to 18 carbon atoms.

  In the general formula [I], M is titanium, zirconium, or hafnium, preferably titanium or hafnium, and more preferably titanium.

  Q is a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms. Specific examples include dimethylsilylene group, diethyl Silylene group, di-i-propylsilylene group, diphenylsilylene group, methylphenylsilylene group, methyl-i-propylsilylene group, dimethylgermylene group, diethylgermylene group, di-i-propylgermylene group, diphenylgermylene Group, methylphenylgermylene group, methyl-i-propylgermylene group, dimethylmethylene group, ethylene group, 1,2-dimethylethylene group, 1-phenylethylene group, 1,2-diphenylethylene group, silacyclobutane group, Silacyclopentane group, 2,5-dimethylsilacyclopentane group, silacyclohexane group, silafur Ren group, such as phenylene group can be mentioned. Among these, a dimethylsilylene group, a di-i-propylsilylene group, a diphenylsilylene group, a silacyclobutane group, a silacyclopentane group, a silacyclohexane group, and a phenylene group are preferable, and a dimethylsilylene group and a diphenylsilylene group are particularly preferable. Group, silacyclohexane group.

  Z is an amide group, phosphide group, oxygen atom, sulfur atom, phenyleneoxy group or alkylidene group, preferably an amide group, phenyleneoxy group or oxygen atom, and most preferably an amide group.

  X and Y each represent a σ covalent bond auxiliary ligand, which may be the same or different, and is not particularly limited, but preferred X and Y are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and 1 carbon atom. -20 substituted amino group, C1-C20 nitrogen-containing hydrocarbon group, C1-C20 silicon-containing hydrocarbon group, C1-C20 oxygen-containing hydrocarbon group, C1-C20 halogen Examples thereof include a hydrocarbon group. X and Y may have a crosslinked structure. Specifically, chlorine atom, bromine atom, iodine atom, fluorine atom, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, phenyl group, benzyl group, dimethylamino group, diethylamino group, trimethylsilyl Examples thereof include a methyl group, a methoxy group, and a phenoxy group. Among these, a halogen atom and a C1-C8 hydrocarbon group are preferable, and a chlorine atom, a methyl group, i-butyl group, and a benzyl group are especially preferable.

  L represents a neutral Lewis base, which may be the same or different, and is not particularly limited, and examples thereof include ethers, amines, phosphines, dienes, and thioethers. Among these, preferred are Ethers, amines and dienes are preferred, and ethers and dienes are most preferred.

In the general formula [I], R ¹ represents a 5- to 10-membered heteroaromatic substituent containing a nitrogen atom, an oxygen atom or a sulfur atom as a heteroatom, and the heteroatom contained in the heteroaromatic substituent The number is from 1 to 5, and when it contains a plurality of heteroatoms, each heteroatom may be the same or different, and the heteroaromatic substituent is directly bonded to the cycloalkadienyl group by a carbon atom To do. In addition, the heteroaromatic substituent has one or more substituents bonded to the heteroaromatic ring, and when it has a plurality of substituents, each substituent may be the same or different. When the heteroatom number contained in the aromatic ring is 1, the position of the substituent bonded to the heteroaromatic ring is other than the atom directly bonded to the carbon atom bonded to the cycloalkadienyl group. The bonded substituent is an alkyl group having 1 to 20 carbon atoms or a silicon-containing alkyl group having 1 to 20 carbon atoms, a halogen atom-containing alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 carbon atoms. Or an aryl group having 18 to 18 carbon atoms or a halogenated aryl group having 6 to 18 carbon atoms. Among these substituents, an alkyl group having 1 to 20 carbon atoms or a siliconized alkyl group having 1 to 20 carbon atoms is preferable.

  Specific examples of the alkyl group having 1 to 20 carbon atoms that can be bonded to the heteroaromatic ring include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl group. , T-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, n-decyl group, n -A dodecyl group etc. can be mentioned.

  The silicon-containing alkyl group having 1 to 20 carbon atoms that can be bonded to the heteroaromatic ring is one in which a silicon atom is substituted on a carbon atom on the skeleton of the alkyl group. Specific examples include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, a trimethylsilylmethyl group, and a 2-trimethylsilylethyl group.

Moreover, as a halogen atom of a C1-C20 halogen-containing alkyl group which can be couple | bonded with this hetero aromatic ring, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom is mentioned, A C1-C20 halogen-containing alkyl In the group, a hydrogen atom on the skeleton of an alkyl group having 1 to 20 carbon atoms is substituted with a halogen atom.
Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2 -Trifluoroethyl group, 2,2,1,1-tetrafluoroethyl group, pentafluoroethyl group, pentachloroethyl group, pentafluoropropyl group, nonafluorobutyl group, 5-chloropentyl group, 5,5,5 -Trichloropentyl, 5-fluoropentyl, 5,5,5-trifluoropentyl, 6-chlorohexyl, 6,6,6-trichlorohexyl, 6-fluorohexyl, 6,6,6-tri Fluorohexyl group, 8-fluorooctyl group, 8,8,8-trifluorooctyl group, etc. It is possible.

  Specific examples of the alkoxy group having 1 to 6 carbon atoms that can be bonded to the heteroaromatic ring include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s -Butoxy group, t-butoxy group, n-pentoxy group, n-pentoxy group, n-hexyloxy group, cyclopropoxy group, cyclobutoxy group, cyclopentoxy group, cyclohexyloxy group and the like can be mentioned.

  Specific examples of the aryl group having 6 to 18 carbon atoms that can be bonded to the heteroaromatic ring include phenyl group, methylphenyl group, n-propylphenyl group, i-propylphenyl group, n-butylphenyl group, i-butyl. Examples thereof include a phenyl group, a s-butylphenyl group, a t-butylphenyl group, an n-hexylphenyl group, a trimethylphenyl group, a pentamethylphenyl group, a biphenyl group, and a naphthyl group.

Moreover, as a halogen atom of a C6-C18 halogenated aryl group which can couple | bond with this hetero aromatic ring, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A C6-C18 halogenated aryl halide is mentioned. In the group, a hydrogen atom on the skeleton of an aryl group having 6 to 18 carbon atoms is substituted with a halogen atom.
Specific examples include a pentafluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, a perfluoronaphthyl group, and a perfluorobiphenyl group.

Specific examples of R ¹ include 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5-trimethylsilyl-2-furyl group, 5-tert-butyl-2-furyl group, and 5-methoxy-2. -Furyl group, 4,5-dimethyl-2-furyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5-trimethylsilyl-2-thienyl group, 5-tert-butyl-2- Thienyl group, 5-methoxy-2-thienyl group, 4,5-dimethyl-2-thienyl group, 1-methyl-2-imidazolyl group, 1-methyl-5-imidazolyl group, 2-methyl-4-oxazolyl group, Examples thereof include 2-methyl-4-thiazolyl group and 1-methyl-4-pyrazolyl group. Among these, 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5-trimethylsilyl-2-furyl group, 5-tert-butyl-2-furyl group, 5-methoxy-2 are preferable. -Furyl group, 4,5-dimethyl-2-furyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5-trimethylsilyl-2-thienyl group, 5-tert-butyl-2- A thienyl group, a 5-methoxy-2-thienyl group and a 4,5-dimethyl-2-thienyl group, more preferably a 5-methyl-2-furyl group, a 5-trimethylsilyl-2-furyl group, and a 5-tert group. -Butyl-2-furyl group, 4,5-dimethyl-2-furyl group, 5-methyl-2-thienyl group, 5-trimethylsilyl-2-thienyl group, 5-tert-butyl-2-thienyl group, , 5-dimethyl-2-thienyl group, most preferred is 5-methyl-2-furyl group, 4,5-dimethyl-2-furyl group, 5-methyl-2-thienyl group, 4,5-dimethyl group. A 2-thienyl group.

R ² , R ³ , and R ⁴ are hydrogen, an alkyl group having 1 to 8 carbon atoms, a halogen atom-containing alkyl group having 1 to 8 carbon atoms, a silicon-containing alkyl group having 1 to 8 carbon atoms, and 6 to 18 carbon atoms. An aryl group or a halogenated aryl group having 6 to 18 carbon atoms, which may be the same as or different from each other, and may form a 5- to 10-membered ring with both adjacent Rs, and a 5- to 10-membered ring is an unsaturated bond May be included.

Specific examples of the alkyl group having 1 to 8 carbon atoms in R ^{2 to} R ⁴ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, Examples thereof include a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Moreover, as a halogen atom of a C1-C8 halogen atom containing alkyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A C1-C8 halogen-containing alkyl group is C1-C1. A hydrogen atom on the skeleton of the alkyl group of 8 is substituted with a halogen atom.
Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2 -Trifluoroethyl group, 2,2,1,1-tetrafluoroethyl group, pentafluoroethyl group, pentachloroethyl group, pentafluoropropyl group, nonafluorobutyl group, 5-chloropentyl group, 5,5,5 -Trichloropentyl, 5-fluoropentyl, 5,5,5-trifluoropentyl, 6-chlorohexyl, 6,6,6-trichlorohexyl, 6-fluorohexyl, 6,6,6-tri Fluorohexyl group, 8-fluorooctyl group, 8,8,8-trifluorooctyl group, etc. It is possible.

  The silicon-containing alkyl group having 1 to 20 carbon atoms is one in which a silicon atom is substituted for a carbon atom on the skeleton of the alkyl group. Specific examples include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, a trimethylsilylmethyl group, and a 2-trimethylsilylethyl group.

  Specific examples of the aryl group having 6 to 18 carbon atoms include phenyl group, methylphenyl group, n-propylphenyl group, i-propylphenyl group, n-butylphenyl group, i-butylphenyl group, and s-butylphenyl group. , T-butylphenyl group, n-hexylphenyl group, trimethylphenyl group, pentamethylphenyl group, biphenyl group, naphthyl group, and the like.

Examples of the halogen atom of the halogenated aryl group having 6 to 18 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and the halogenated aryl group having 6 to 18 carbon atoms is an aryl having 6 to 18 carbon atoms. A hydrogen atom on the skeleton of the group is substituted with a halogen atom.
Specific examples include a pentafluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, a perfluoronaphthyl group, and a perfluorobiphenyl group.

Moreover, R < ² >, R < ³ >, R < ⁴ > may form a 5-10 membered ring by both adjacent R, and a 5-10 membered ring may form an unsaturated bond. Specific examples of the cycloalkadienyl ring formed by R ² , R ³ , and R ⁴ forming a ring include an indenyl ring, a benzoindenyl ring, a tetrahydroindenyl ring, and an azulenyl ring.

Specific examples of half metallocene complexes:
Preferred specific examples of the transition metal compound of the present invention are shown below. Titanium dimethyl is selected as a representative example, and its name is exemplified in the compounds of the structural formula shown below.
The compound of this structural formula is called dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium.

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

Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -cyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl-2-furyl) -Cyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -cyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4-methylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl-2 -Furyl) -4-methylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4-methylcyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4-tert-butylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl -2-furyl) -4-tert-butylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4-tert-butylcyclopentadienyl }] Titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4-phenylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl-2 -Furyl) -4-phenylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4-phenylcyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl -2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -3,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl -2-furyl) -3,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -3,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5 -Methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -3,4,5 -Trimethylcyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -tetrahydroindenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl-2-furyl)- Tetrahydroindenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -tetrahydroindenyl}] titanium,

Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl-2-furyl) -indenyl} ] Titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4-phenylindenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl-2-furyl) ) -4-phenylindenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4-phenylindenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4,7-diphenylindenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl-2 -Furyl) -4,7-diphenylindenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,7-diphenylindenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl-2-furyl)- Benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -benzoindenyl}] titanium,

Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4H-azulenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl-2-furyl)- 4H-azulenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4H-azurenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4-phenyl-4H-azulenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methyl-2 -Furyl) -4-phenyl-4H-azurenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4-phenyl-4H-azurenyl}] titanium,

Dimethyl [dimethylsilylene (tert-butylamide) {2- (4,5-dimethyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (4 , 5-dimethyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (4,5-dimethyl-2-furyl) -4,5 -Dimethylcyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-tert-butyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5 -Tert-butyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2-5-tert-butyl-2-furyl) -4,5- Dimethylcyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-trimethylsilyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-trimethylsilyl) -2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-trimethylsilyl-2-furyl) -4,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methoxy-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methoxy -2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methoxy-2-furyl) -4,5-dimethylcyclopentadienyl }] Titanium,

Dimethyl [dimethylsilylene (tert-butylamide) {2- (4,5-dimethyl-2-thienyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (4 , 5-dimethyl-2-thienyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (4,5-dimethyl-2-thienyl) -4,5 -Dimethylcyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-tert-butyl-2-thienyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5 -Tert-butyl-2-thienyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2-5-tert-butyl-2-thienyl) -4,5- Dimethylcyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-trimethylsilyl-2-thienyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-trimethylsilyl) -2-thienyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-trimethylsilyl-2-thienyl) -4,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methoxy-2-thienyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methoxy -2-thienyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methoxy-2-thienyl) -4,5-dimethylcyclopentadienyl }] Titanium,

Dimethyl [dimethylsilylene (tert-butylamide) {2- (1-methyl-2-imidazolyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (1-methyl -2-imidazolyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (1-methyl-2-imidazolyl) -4,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (1-methyl-5-imidazolyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (1-methyl -5-imidazolyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (1-methyl-5-imidazolyl) -4,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (2-methyl-4-oxazolyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (2-methyl -4-oxazolyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (2-methyl-4-oxazolyl) -4,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (2-methyl-4-thiazolyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (2-methyl -4-thiazolyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (2-methyl-4-thiazolyl) -4,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (1-methyl-4-pyrazolyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (1-methyl -4-pyrazolyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (1-methyl-4-pyrazolyl) -4,5-dimethylcyclopentadienyl }] Titanium,

Dimethyl [dimethylsilylene (tert-butylamide) {2- (4,5-dimethyl-2-thienyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (4,5-dimethyl-2-thienyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (4,5-dimethyl-2-thienyl) -3,4,5-trimethylcyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-tert-butyl-2-thienyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-tert-butyl-2-thienyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2-5-tert-butyl-2-thienyl)- 3,4,5-trimethylcyclopentadienyl}] titanium dimethyl [dimethylsilylene (tert-butylamide) {2- (5-trimethylsilyl-2-thienyl) -3,4,5-trimethylcyclopentadienyl}] titanium , Dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-trimethylsilyl-2-thienyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-trimethylsilyl-2-thienyl)- 3,4,5-trimethylcyclopentadienyl}] titanium,

Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methoxy-2-thienyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5 -Methoxy-2-thienyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methoxy-2-thienyl) -3,4,5 -Trimethylcyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (1-methyl-2-imidazolyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (1 -Methyl-2-imidazolyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (1-methyl-2-imidazolyl) -3,4,5 -Trimethylcyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (2-oxazolyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (2-oxazolyl)- 3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (2-oxazolyl) -3,4,5-trimethylcyclopentadienyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (2-thiazolyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (2-thiazolyl)- 3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (2-thiazolyl) -3,4,5-trimethylcyclopentadienyl}] titanium,

Dimethyl [dimethylsilylene (tert-butylamide) {2- (4,5-dimethyl-2-thienyl) -indenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (4,5-dimethyl-2-thienyl) ) -Indenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (4,5-dimethyl-2-thienyl) -indenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-tert-butyl-2-thienyl) -indenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-tert-butyl-2-thienyl) ) -Indenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2-5-tert-butyl-2-thienyl) -indenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-trimethylsilyl-2-thienyl) -indenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-trimethylsilyl-2-thienyl) -indenyl} ] Titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-trimethylsilyl-2-thienyl) -indenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methoxy-2-thienyl) -indenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methoxy-2-thienyl) -indenyl} ] Titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methoxy-2-thienyl) -indenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (1-methyl-2-imidazolyl) -indenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (1-methyl-2-imidazolyl) -indenyl} ] Titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (1-methyl-2-imidazolyl) -indenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (2-oxazolyl) -indenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (2-oxazolyl) -indenyl}] titanium, dimethyl [dimethylsilylene ( Cyclododecylamide) {2- (2-oxazolyl) -indenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (2-thiazolyl) -indenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (2-thiazolyl) -indenyl}] titanium, dimethyl [dimethylsilylene ( Cyclododecylamide) {2- (2-thiazolyl) -indenyl}] titanium,

Dimethyl [dimethylsilylene (tert-butylamide) {2- (4,5-dimethyl-2-thienyl) -benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (4,5-dimethyl-2 -Thienyl) -benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (4,5-dimethyl-2-thienyl) -benzoindenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-tert-butyl-2-thienyl) -benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-tert-butyl-2 -Thienyl) -benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2-5-tert-butyl-2-thienyl) -benzoindenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-trimethylsilyl-2-thienyl) -benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-trimethylsilyl-2-thienyl)- Benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-trimethylsilyl-2-thienyl) -benzoindenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methoxy-2-thienyl) -benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (5-methoxy-2-thienyl)- Benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methoxy-2-thienyl) -benzoindenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (1-methyl-2-imidazolyl) -benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (1-methyl-2-imidazolyl)- Benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclododecylamide) {2- (1-methyl-2-imidazolyl) -benzoindenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (2-oxazolyl) -benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (2-oxazolyl) -benzoindenyl}] titanium, dimethyl [Dimethylsilylene (cyclododecylamide) {2- (2-oxazolyl) -benzoindenyl}] titanium,
Dimethyl [dimethylsilylene (tert-butylamide) {2- (2-thiazolyl) -benzoindenyl}] titanium, dimethyl [dimethylsilylene (cyclohexylamide) {2- (2-thiazolyl) -benzoindenyl}] titanium, dimethyl [Dimethylsilylene (cyclododecylamide) {2- (2-thiazolyl) -benzoindenyl}] titanium,

Dimethyl [diphenylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [diphenylsilylene (cyclohexylamide) {2- (5-methyl -2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [diphenylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [diphenylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium, dimethyl [diphenylsilylene (cyclohexylamide) {2- (5-methyl-2-furyl) -indenyl} ] Titanium, dimethyl [diphenylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium,
Dimethyl [diphenylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [diphenylsilylene (cyclohexylamide) {2- (5 -Methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [diphenylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -3,4,5 -Trimethylcyclopentadienyl}] titanium,

Dimethyl [diethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [diethylsilylene (cyclohexylamide) {2- (5-methyl -2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [diethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [diethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium, dimethyl [diethylsilylene (cyclohexylamide) {2- (5-methyl-2-furyl) -indenyl} ] Titanium, dimethyl [diethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium,
Dimethyl [diethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [diethylsilylene (cyclohexylamide) {2- (5 -Methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [diethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -3,4,5 -Trimethylcyclopentadienyl}] titanium,

Dimethyl [methylene (tert-butylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [methylene (cyclohexylamide) {2- (5-methyl-2 -Furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [methylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium ,
Dimethyl [methylene (tert-butylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium, dimethyl [methylene (cyclohexylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium , Dimethyl [methylene (cyclododecylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium,
Dimethyl [methylene (tert-butylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [methylene (cyclohexylamide) {2- (5-methyl -2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [methylene (cyclododecylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclo Pentadienyl}] titanium,

Dimethyl [dimethylmethylene (tert-butylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylmethylene (cyclohexylamide) {2- (5-methyl -2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [dimethylmethylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [dimethylmethylene (tert-butylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium, dimethyl [dimethylmethylene (cyclohexylamide) {2- (5-methyl-2-furyl) -indenyl} ] Titanium, dimethyl [dimethylmethylene (cyclododecylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium,
Dimethyl [dimethylmethylene (tert-butylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylmethylene (cyclohexylamide) {2- (5 -Methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [dimethylmethylene (cyclododecylamide) {2- (5-methyl-2-furyl) -3,4,5 -Trimethylcyclopentadienyl}] titanium,

Dimethyl [diphenylethylene (tert-butylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [diphenylethylene (cyclohexylamide) {2- (5-methyl -2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [diphenylethylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl }] Titanium,
Dimethyl [diphenylethylene (tert-butylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium, dimethyl [diphenylethylene (cyclohexylamide) {2- (5-methyl-2-furyl) -indenyl} ] Titanium, dimethyl [diphenylethylene (cyclododecylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium,
Dimethyl [diphenylethylene (tert-butylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [diphenylethylene (cyclohexylamide) {2- (5 -Methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [diphenylethylene (cyclododecylamide) {2- (5-methyl-2-furyl) -3,4,5 -Trimethylcyclopentadienyl}] titanium,

Dimethyl [ethylene (tert-butylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [ethylene (cyclohexylamide) {2- (5-methyl-2 -Furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [ethylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium ,
Dimethyl [ethylene (tert-butylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium, dimethyl [ethylene (cyclohexylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium , Dimethyl [ethylene (cyclododecylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium,
Dimethyl [ethylene (tert-butylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [ethylene (cyclohexylamide) {2- (5-methyl -2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium, dimethyl [ethylene (cyclododecylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclo Pentadienyl}] titanium,

[Dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium 2,5-hexadiene, [dimethylsilylene (cyclohexylamide) {2- ( 5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium 2,5-hexadiene, [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4, 5-dimethylcyclopentadienyl}] titanium 2,5-hexadiene,
[Dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium 2,5-hexadiene, [Dimethylsilylene (cyclohexylamide) {2- (5-methyl-2-furyl) -Indenyl}] titanium 2,5-hexadiene, [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium 2,5-hexadiene,
[Dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium 2,5-hexadiene, [dimethylsilylene (cyclohexylamide) {2 -(5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium 2,5-hexadiene, [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) ) -3,4,5-trimethylcyclopentadienyl}] titanium 2,5-hexadiene,

[Dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium 1,4-diphenylbutadiene, [dimethylsilylene (cyclohexylamide) {2- (5-Methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium 1,4-diphenylbutadiene, [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl)- 4,5-dimethylcyclopentadienyl}] titanium 1,4-diphenylbutadiene,
[Dimethylsilylene (tert-butyramide) {2- (5-methyl-2-furyl) -indenyl}] titanium 1,4-diphenylbutadiene, [Dimethylsilylene (cyclohexylamide) {2- (5-methyl-2-furyl) ) -Indenyl}] titanium 1,4-diphenylbutadiene, [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium 1,4-diphenylbutadiene,
[Dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium 1,4-diphenylbutadiene, [dimethylsilylene (cyclohexylamide) { 2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium 1,4-diphenylbutadiene, [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2 -Furyl) -3,4,5-trimethylcyclopentadienyl}] titanium 1,4-diphenylbutadiene,

[Dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium 2,3-dimethylbutadiene, [dimethylsilylene (cyclohexylamide) {2- (5-Methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium 2,3-dimethylbutadiene, [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl)- 4,5-dimethylcyclopentadienyl}] titanium 2,3-dimethylbutadiene,
[Dimethylsilylene (tert-butyramide) {2- (5-methyl-2-furyl) -indenyl}] titanium 2,3-dimethylbutadiene, [Dimethylsilylene (cyclohexylamide) {2- (5-methyl-2-furyl) ) -Indenyl}] titanium 2,3-dimethylbutadiene, [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium 2,3-dimethylbutadiene,
[Dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium 2,3-dimethylbutadiene, [dimethylsilylene (cyclohexylamide) { 2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl}] titanium 2,3-dimethylbutadiene, [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2 -Furyl) -3,4,5-trimethylcyclopentadienyl}] titanium 2,3-dimethylbutadiene,

  Dimethyl [dimethylsilylene (3-tert-butyl-5-methyl-2-phenyleneoxy) {2- (5-methyl-2-furyl) -3,4,5-trimethylcyclopentadienyl} titanium, dimethyl [dimethyl Silylene (3-tert-butyl-5-methyl-2-phenyleneoxy) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl} titanium, dimethyl [dimethylmethylene (3-tert -Butyl-5-methyl-2-phenyleneoxy) {2- (5-methyl-2-furyl) -indenyl} titanium, [dimethylsilylene (3-tert-butyl-5-methyl-2-phenyleneoxy) {2 -(5-Methyl-2-furyl) -4,5-dimethylcyclopentadienyl} titanium 2,5-hexadiene

Dimethyl [phenylene (cyclohexylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [phenylene (cyclohexylamide) {2- (5-methyl-2- Furyl) -indenyl}] titanium, dimethyl [phenylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [phenylene (cyclododecylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium,
Dimethyl [phenylene (2-mesitylenesulfonylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [phenylene (2-mesitylenesulfonylamide) {2- ( 5-methyl-2-furyl) -indenyl}] titanium, dimethyl [phenylene (p-toluenesulfonylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, Dimethyl [phenylene (p-toluenesulfonylamide) {2- (5-methyl-2-furyl) -indenyl}] titanium, dimethyl [phenylene (methylsulfonylamide) {2- (5-methyl-2-furyl) -4 , 5-Dimethylcyclopentadienyl}] titanium, dimethyl [phenylene (methyls Honiruamido) {2- (5-methyl-2-furyl) - indenyl}] titanium,
Dimethyl [phenylene (tert-butylcarboxamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [phenylene (tert-butylcarboxamide) {2- ( 5-methyl-2-furyl) -intenyl}] titanium,
Dimethyl [phenylene (diphenylphosphinoamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [phenylene (diphenylphosphinoamide) {2- (5- Methyl-2-furyl) -indenyl}] titanium dimethyl [phenylene (diisopropylphosphinoamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium, dimethyl [phenylene ( Diisopropylphosphinoamide) {2- (5-methyl-2-furyl) -indenyl}] titanium,
Dimethyl [phenylene (2,3,4,5-tetramethylcyclopentadienyl) oxy] titanium.

Synthesis method of transition metal compounds (half metallocene complexes):
The transition metal compound of the present invention can be synthesized by any method depending on the type of substituent or bond. As typical known documents relating to the synthesis of the half metallocene complex, for example, Japanese Patent No. 3275211, Japanese Patent No. 3341117, Japanese Patent Publication No. 9-509149, Japanese Patent Publication No. 2003-501436 can be cited. An example of a typical synthetic route for carrying out the synthesis of the transition metal compound of the present invention is shown below.

  In the above synthesis route, the cycloalkadiene derivative 1 having a heteroaromatic substituent is anionized with butyllithium or the like, then treated with excess dichloromethylsilane to introduce a chlorodimethylsilyl group, and excess dichlorodimethylsilane is removed. After the removal, the ligand 3 is obtained by reacting a lithiated compound prepared separately by reacting tert-butylamine with n-butyllithium or the like. After treating the ligand 3 with 4 equivalents of MeLi, the transition metal complex 4 is obtained by reacting with the titanium tetrachloride.

  A typical synthesis example of a cycloalkadiene derivative having a heteroaromatic substituent necessary in the above synthesis route is shown below.

Method for synthesizing indene derivatives having heteroaromatic groups:
In the above synthesis route, the furylated indene compound 1 can be synthesized by carrying out a coupling reaction of 2-bromoindene (5) and 5-methyl-2-furylboronic acid in the presence of a catalyst typified by palladium. Alternatively, 1 can be similarly obtained by reacting 2-indanone and lithiated 5-methyl-2-furan, and then proceeding with a dehydration reaction by treatment with an acid or the like.

Method for synthesizing a cyclopentadiene derivative having a heteroaromatic group:
8 can be synthesized by reacting 5-methyl-2-furan obtained by lithiation of the cyclopentadienone derivative 7 in the above synthesis route and then proceeding with a dehydration reaction by treatment with an acid or the like.

  The transition metal compound into which other substituents are introduced in the above synthesis route can be synthesized by using furan derivatives, 2-bromoindene derivatives, and cyclopentadienone derivatives having different substituents.

2. Olefin Polymerization Catalyst The transition metal compound of the present invention forms a catalyst component for olefin polymerization, and the catalyst component can be used as an olefin polymerization catalyst. For example, it is preferable to use the half metallocene complex as a component (A) as an olefin polymerization catalyst described below.

(1) Components of Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention includes the following components (A) and (B), and (C) as necessary.
Component (A): Transition metal compound represented by general formula [I] Component (B): Compound that reacts with component (A) to form an ion pair or ion-exchangeable layered silicate or inorganic silicate Component (C) : Organoaluminum compound

(2) About each component The transition metal compound represented by the general formula [I] of the component (A) may use two or more compounds represented by the same or different general formula [I].

The component (B) will be described below.
The component (B) is a compound that reacts with the component (A) to form an ion pair, or an ion-exchange layered silicate or inorganic silicate. Examples of such a component (B) include an aluminum oxy compound, A boron compound, an ion-exchange layered silicate, silica, silica alumina, etc. can be mentioned, Preferably it is an aluminum oxy compound or a boron compound, More preferably, it is a boron compound. These components (B) may be used alone or in combination of two or more.

The organoaluminum oxy compound as one of the components (B) has Al—O—Al bonds in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy compound is usually obtained by reacting an organoaluminum compound with water or an aromatic carboxylic acid.
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. Preference is given to using aromatic hydrocarbons.

  As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any of the compounds represented by the following general formula [II] can be used, but trialkylaluminum is preferably used.

[Chemical 6]
^{_{R a t AlX a 3-t}} [II]

(In the formula, R ^a represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, aralkyl group or the like having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and X ^a represents a hydrogen atom or a halogen atom. , T represents an integer of 1 ≦ t ≦ 3.)

The alkyl group of the trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. A methyl group and an isobutyl group are preferable, and a methyl group is more preferable.
Two or more of the above organoaluminum compounds can be mixed and used.

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

  In an aluminum oxy compound, what is represented by the following general formula can also be illustrated.

The compound represented by the general formula [III] is 10: 1 of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula: R ^c B (OH) _2. It can be obtained by a reaction of ˜1: 1 (molar ratio). In the general formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

In addition, as component (B) that reacts with the metallocene complex of component (A) to form an ion pair,
Boron compounds such as borane compounds and borate compounds are also included.
Specific examples of the borane compound include triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, tris (p- Fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris (3 , 5
―Ditrifluoromethylphenyl) borane, Tris (2,6-ditrifluoromethylphenyl) borane, Tris (pentafluorophenyl) borane, Tris (perfluoronaphthyl) borane, Tris (perfluorobiphenyl), Tris (perfluoroanthryl) ) Borane, tris (perfluorobinaphthyl) borane and the like.
Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (
2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenyl) borane, tris (perfluoroanthryl) borane, tris (perfluorobinaphthyl) Borane is more preferable, and tris (2,6-ditrifluoromethylphenyl) is more preferable.
Borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, and tris (perfluorobiphenyl) borane are preferred.

  When the borate compound is specifically represented, the first example is a compound represented by the following general formula [IV].

[Chemical 8]
^{[L 1 -H] + [BR} d R e X b X c] - [IV]

In the formula [IV], L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium, or phosphonium. Examples of ammonium include trialkylammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.

Examples of anilinium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium.
Furthermore, examples of the phosphonium include triarylphosphonium, tributylphosphonium, triarylphosphonium such as tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

In the formula [IV], R ^d and R ^e are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and are connected to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, or a halogen such as fluorine, chlorine, bromine or iodine is preferable.
Furthermore, ^Xb and ^Xc are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted carbon atom containing 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by halogen atoms. It is a hydrogen group.

  Specific examples of the compound represented by the general formula [IV] include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5- Ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6- Ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluorophene) L) borate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5 -Ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium Tetra (pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethyl Ammonium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, di (1 -Propyl) ammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate and the like.

Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro) Naphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylaniliniumtetra (2,6-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium Tetra (perfluoronaphthyl) borate is preferred.

  Moreover, the 2nd example of a borate compound is represented by the following general formula [V].

[Chemical 9]
^{[L 2] + [BR d} R e X b X c] - [V]

In the formula [V], L ² represents carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium. Examples include cations and protons. R ^d , R ^e , X ^b and X ^c are the same as defined in the general formula [IV].

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

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

More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluoro) Methylphenyl) borate, NaB (C ₆ F ₅ ) ₄ , NaB (2,6- (CF ₃ ) ₂ -Ph) ₄ , H ⁺ B (C ₆ F ₅ ) ₄ -2 diethyl ether, H ⁺ B ( _{2,6- (CF 3) 2 -Ph)} 4 · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ^{_{ether, H + B (C 10 F}} 7) 4 -2 diethyl ether is mentioned.
Further, as the component (B) of the olefin polymerization catalyst, a mixture of the organoaluminum oxy compound and the borane compound or borate compound can be used. Further, two or more of the above borane compounds and borate compounds can be used in combination.

An ion-exchange layered silicate (hereinafter, sometimes simply referred to as “silicate”) has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other and have a binding force. Refers to a silicate compound in which the ions to be exchanged are exchangeable. Various known silicates are known, and are specifically described in Shiramizu Haruo "Clay Mineralogy" Asakura Shoten (1995).
In the present invention, those preferably used as the component (B) belong to the mica or smectite group, and specifically include montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite and the like. it can. Among these, montmorillonite is preferable in terms of the activity and molecular weight of the rubber component.
Since most silicates are naturally produced mainly as the main component of clay minerals, they often contain impurities (such as quartz and cristobalite) other than ion-exchanged layered silicates. Hybrids may be contained in the smectite silicate.

Granulation of ion-exchange layered silicate:
Silicates may be used in a dry state or in a slurry state in a liquid. In addition, the shape of the ion-exchange layered silicate is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or a shape by operations such as pulverization, granulation, and classification. You may use the processed ion exchange layered silicate. Of these, the use of granulated silicate is particularly preferred because it gives good polymer particle properties.
The shape processing of the ion-exchange layered silicate such as granulation, pulverization, and classification may be performed before the acid treatment, or the shape may be processed after the acid treatment.

  Examples of the granulation method used here include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation method, emulsion granulation method. , Submerged granulation method, compression molding granulation method, and the like, but are not particularly limited. Preferred examples include agitation granulation method, spray granulation method, rolling granulation method, and fluidization granulation method, and particularly preferred are agitation granulation method and spray granulation method.

  When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene is used as a dispersion medium for the raw slurry. Preferably, water is used as a dispersion medium. The concentration of the component (B) in the raw slurry liquid for spray granulation from which spherical particles are obtained is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight. . Although the inlet temperature of the hot air of spray granulation from which spherical particles are obtained varies depending on the dispersion medium, taking water as an example, the temperature is 80 to 260 ° C, preferably 100 to 220 ° C.

In granulation, in order to obtain a carrier having high particle strength and to improve propylene polymerization activity, the silicate is refined as necessary. The silicate may be refined by any method. As a method for miniaturization, either dry pulverization or wet pulverization is possible.
Preferably, wet pulverization using water as a dispersion medium and utilizing the swellability of silicate, for example, a forced stirring method using polytron or the like, a dyno mill, a pearl mill, or the like. The average particle size before granulation is 0.01 to 3 μm, preferably 0.05 to 1 μm.

  Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. Examples of the binder used include magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycols and the like.

  The spherical particles obtained as described above preferably have a compression fracture strength of 0.2 MPa or more in order to suppress crushing and fine powder generation in the polymerization step. The particle size of the granulated ion-exchange layered silicate is in the range of 0.1 to 1000 μm, preferably 1 to 500 μm. There is no particular limitation on the pulverization method, and either dry pulverization or wet pulverization may be used.

Acid treatment:
The silicate used in the present invention is used after being subjected to an acid treatment, but may be treated by combining other chemical treatments. Other chemical treatments include alkali treatment, salt treatment, organic matter treatment, and the like.
The acid treatment of the silicate can change the acid strength of the solid. In addition to the effect of ion exchange and removal of surface impurities, the acid treatment also has an effect of eluting part of cations such as Al, Fe, Mg, Li having a crystal structure.
Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, and phthalic acid. Two or more of these may be used simultaneously. Of these, inorganic acids are preferable, sulfuric acid, hydrochloric acid and nitric acid are preferable, and sulfuric acid is more preferable.
In addition, a method in which acid treatment and salt treatment are combined is particularly preferable, a method in which acid treatment is performed after salt treatment, a method in which salt treatment is performed after acid treatment, a method in which salt treatment and acid treatment are performed simultaneously, salt treatment There is a method of performing salt treatment and acid treatment at the same time after the treatment.

The treatment conditions with the acid are usually selected from the conditions where the acid concentration is 0.1 to 30% by weight, the treatment temperature is the temperature range from room temperature to the boiling point of the solvent used, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the conditions under which at least a part is eluted. The acid is generally used as an aqueous solution. For example, when sulfuric acid is used, the treatment temperature is preferably 80 ° C. to 100 ° C., and the treatment time is preferably 0.5 hours or more and less than 5 hours.
By performing the salt treatment at the same time, the surface area and interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, or the like. For example, a layered substance in a state where the layers are expanded can be obtained by replacing the exchangeable ions between the layers with other large and bulky ions using ion exchange.
When the acid treatment is performed, shape control may be performed by pulverization or granulation before, during, or after the treatment. Further, other chemical treatments such as alkali treatment, organic compound treatment, and organometallic treatment may be used in combination.

The salt used for the ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of 1 to 14 atoms, and preferably selected from the group consisting of 1 to 14 atoms. And a compound comprising a cation containing at least one atom and an anion derived from at least one atom or atomic group selected from the group consisting of a halogen atom, an inorganic acid and an organic acid. Is a cation containing at least one atom selected from the group consisting of group 2 to 14 atoms, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , At least one anion selected from the group consisting of ClO ₃ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OH, OOCH, OOCCH ₂ CH ₃ , C ₆ H ₅ O ₇ ; Is a compound consisting of Two or more of these salts may be used simultaneously.

The silicate thus obtained preferably has a pore volume with a radius of 20 mm or more measured by a mercury intrusion method of 0.1 cc / g or more, particularly 0.3 to 5 cc / g. Such silicates contain adsorbed water and interlayer water when treated in aqueous solution. Here, adsorbed water is water adsorbed on the silicate surface or crystal fracture surface, and interlayer water is water existing between crystal layers.
The silicate is preferably used after removing adsorbed water and interlayer water as described above. The dehydration method is not particularly limited, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. The heating temperature is a temperature range in which the adsorbed water and interlayer water do not remain, and is usually 100 ° C. or higher, preferably 150 ° C. or higher, but high temperature conditions that cause structural destruction are not preferable. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the weight loss of the silicate after dehydration and drying is preferably 3% by weight or less as a value when sucked for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. In the present invention, when a silicate having a weight loss adjusted to 3% by weight or less is used, the same weight loss state is maintained even when contacting the component (A) and the component (C). It is preferable to handle them.

Composition of silicate after acid treatment:
The acid-treated silicate that is the component (B) according to the present invention has an Al / Si atomic ratio of 0.01 to 0.29, preferably 0.03 to 0.25, and more preferably. Is preferably in the range of 0.05 to 0.23 in view of the activity of the polymerization catalyst and the molecular weight of the rubber component.
The Al / Si atomic ratio is an index of the acid treatment strength of the clay portion, and the method for controlling the Al / Si atomic ratio is controlled by adjusting the acid species for acid treatment, the acid concentration, the acid treatment time, and the temperature. can do.
Aluminum and silicon in the silicate are measured by a method in which a calibration curve is prepared by a chemical analysis method by JIS method and quantified by fluorescent X-rays.

Next, the component (C) will be described.
An example of the organoaluminum compound as the component (C) is represented by the following general formula.

[Chemical Formula 10]
R ^f _t AlX ^d _3-t [VI]

In general formula [VI], ^Rf represents a hydrocarbon group having 1 to 20 carbon atoms, ^Xd represents hydrogen, halogen, an alkoxy group, or a siloxy group, and t represents an integer of 1 ≦ t ≦ 3.
Specific examples of the organoaluminum compound represented by the general formula include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, diethylaluminum monomethoxy. And halogen containing alkoxy or alkoxy-containing alkylaluminum. Of these, trialkylaluminum is preferred. Two or more of the above organoaluminum compounds may be used in combination.

(3) Catalyst Preparation Method In the method for preparing an olefin polymerization catalyst according to the present invention, the contact method of component (A), component (B) and component (C) is not particularly limited, but the following method is used. Can be illustrated.
(I) Method of adding component (C) after contacting component (A) and component (B) (ii) After contacting component (A) and component (C), component (B) (Iii) Method of adding component (A) after contacting component (B) and component (C) (iv) Contacting each component (A), (B), (C) simultaneously Let
(V) The component (A) is contacted with the component (B) in the absence of the component (C).

Further, different components may be used as a mixture in each component, or the components may be contacted in different orders. In addition, you may perform this contact at the time of the prepolymerization by an olefin or the polymerization of an olefin not only at the time of catalyst preparation.
Alternatively, the component (B) and the component (C) may be contacted and then the mixture of the component (A) and the component (C) may be added, and the components may be divided and brought into contact with each component.
The contact of each of the components (A), (B), and (C) is preferably performed in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, and xylene in an inert gas such as nitrogen. . The contact can be carried out at a temperature between −20 ° C. and the boiling point of the solvent, and particularly preferably at a temperature between 0 ^° C. and the boiling point of the solvent.

  In the polymerization catalyst according to the present invention, preferred examples of the component (B) include boron compounds and organoaluminum oxy compounds, with boron compounds being particularly preferred. In the case of component (B) an organoaluminum oxy compound, the molar ratio of component (A) to component (B) is 1: 0.1 to 1: 10,000. When component (B) is a boron compound, the molar ratio of component (A) to component (B) is preferably in the range of 1: 0.1 to 1: 100. When component (C) is used, the molar ratio of component (A) to component (C) is preferably in the range of 1: 0.1 to 1: 10,000.

  In the polymerization catalyst according to the present invention, when the component (B) is a silicate, the preferred amounts of the component (A), the component (B) and the component (C) are used as the component (A) with respect to 1 g of the component (B). The half metallocene compound (complex) of 0.001 to 10 mmol, more preferably 0.001 to 1 mmol. The amount of the component (C) used is an Al / half metallocene compound molar ratio of 0.1 or more and 100,000 or less, preferably 1 or more and 10,000 or less. These use ratios show examples of normal ratios, and the present invention is limited by the range of use ratios described above as long as the catalyst meets the purpose of the present invention. Must not.

When component (B) is other than silicate, component (A), component (B) and / or component (C) of the present invention can be supported on a fine particle carrier other than silicate and used for polymerization. Examples of the fine particle carrier to be used include an inorganic carrier, a particulate polymer carrier, and a mixture thereof. As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof can be used.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.

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

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

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

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

(4) Catalyst preparation method using fine particle carrier other than silicate From half metallocene complex (component A), compound that reacts with half metallocene complex (component A) to form ion pairs (component B), and fine particle carrier The contact method of each component when obtaining the olefin polymerization catalyst to be obtained is not particularly limited, and for example, the following methods can be arbitrarily employed.

(I) After contacting the half metallocene complex (component A) and the compound (component B) that reacts with the half metallocene complex (component A) to form an ion pair, the fine particle carrier is contacted.
(II) After contacting the half metallocene complex (component A) and the fine particle carrier, the compound that reacts with the half metallocene compound (A) to form an ion pair (component B) is contacted.
(III) The compound (component B) that reacts with the half metallocene complex (component A) to form an ion pair and the fine particle carrier are contacted, and then the half metallocene complex (component A) is contacted.

Of these contact methods, (I) and (III) are preferred, and (I) is most preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually having 6 to 12 carbon atoms), heptane, hexane, decane and dodecane. In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane, a method of bringing each component into contact with stirring or non-stirring is employed.
This contact is usually −100 ° C. to 200 ° C., preferably −50 ° C. to 100 ° C., more preferably 0 ° C. to 50 ° C., for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably. It is desirable to carry out in 30 minutes to 12 hours.

  In addition, as mentioned above, certain components are soluble when contacting the half metallocene complex (component A) or the compound (component B) that reacts with the half metallocene complex (component A) to form an ion pair (component B). Either an aromatic hydrocarbon solvent that is hardly soluble or an aliphatic or alicyclic hydrocarbon solvent in which a certain component is insoluble or hardly soluble can be used.

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

  In the present invention, the use ratio of the half metallocene complex (component A), the compound (component B) that reacts with the half metallocene complex (component A) to form an ion pair, and the fine particle carrier is not particularly limited. A range is preferred.

When using an organoaluminum oxy compound as the compound (component B) that reacts with the half metallocene complex (component A) to form an ion pair, the organoaluminum oxy compound for the transition metal (M) in the half metallocene complex (component A) The atomic ratio (Al / M) of aluminum is usually in the range of 1 to 100,000, preferably 5 to 1000, more preferably 50 to 400. When a borane compound or a borate compound is used, half metallocene is used. The atomic ratio (B / M) of boron to the transition metal (M) in the complex is usually selected in the range of 0.01 to 100, preferably 0.1 to 50, more preferably 0.2 to 10. It is desirable.
Further, when a mixture of an organoaluminum oxy compound, a borane compound, and a borate compound is used as the compound (component B) that forms an ion pair, for each compound in the mixture, the transition metal (M) It is desirable to select at the same usage ratio as above.

  The amount of the fine particle carrier used is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, based on the transition metal in the half metallocene complex (component A). 1 g.

  Any one of the above contact methods (I) to (III) is prepared by combining the half metallocene complex (component A), the compound (B) that reacts with the half metallocene complex (component A) to form a cationic half metallocene compound, and the fine particle carrier. Then, the catalyst for olefin polymerization can be obtained as a solid catalyst by removing the solvent or washing and slurrying with an inert solvent. The removal of the solvent is desirably performed under normal pressure or reduced pressure at 0 to 200 ° C., preferably 20 to 150 ° C. for 1 minute to 50 hours, preferably 10 minutes to 10 hours.

The olefin polymerization catalyst can also be obtained by the following method.
(IV) The half metallocene complex (component A) and the fine particle carrier are contacted to remove the solvent, and this is used as a solid catalyst component, which is contacted with an organoaluminum oxy compound, borane compound, borate compound or a mixture thereof under polymerization conditions. Let
(V) An organoaluminum oxy compound, borane compound, borate compound or a mixture thereof and a fine particle carrier are contacted to remove the solvent, which is used as a solid catalyst component, and contacted with a half metallocene complex (component A) under polymerization conditions. Let
In the case of the contact methods (IV) and (V), the same conditions as described above can be used for the component ratio, contact conditions, and solvent removal conditions.

  Before using the catalyst containing the components (A), (B) and (C) as a catalyst for olefin polymerization (main polymerization), ethylene, propylene, 1-butene, 1-hexene, 1 -Prepolymerization treatment for preliminarily polymerizing a small amount of an olefin such as octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene or the like may be performed. As the prepolymerization method, a known method can be used.

3. Olefin Polymerization Method In the present invention, the polymerization form is such that the polymerization catalyst containing the half metallocene complex represented by the above general formula [I] can be efficiently contacted with the monomer to polymerize or copolymerize the olefin. Any style can be adopted.
Specifically, a slurry method and a solution method using an inert solvent, a bulk polymerization method using an olefin monomer as a solvent substantially without using an inert solvent, or keeping each monomer in a gaseous state substantially without using a liquid solvent. A gas phase polymerization method can be employed.
As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. The combination of the polymerization formats is not particularly limited, and a solution polymerization two-stage, bulk polymerization two-stage, gas phase polymerization after bulk polymerization, and two-stage gas phase polymerization are possible. It is also possible to manufacture with.

Polymerized monomer:
In the present invention, the olefin refers to an unsaturated hydrocarbon that can be expressed by the chemical formula C _n H _2n , and the α-olefin refers to the double bond in the α-position (between the endmost carbon and the next carbon) of the olefin. It points to something. Specific examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene, Examples include 3-methyl-1-butene, isobutene, 2-butene, 2-methyl-1-pentene, and 2-ethyl-2-pentene.
Specific examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl- Examples thereof include 1-pentene and 3-methyl-1-butene.

  In the present invention, the polymerizable unsaturated hydrocarbon refers to a hydrocarbon compound having at least one carbon-carbon double bond, specifically, vinylcycloalkane, aromatic vinyl compound, non-conjugated diene, conjugated diene, cyclic Examples include olefins.

  Specific examples of the vinylcycloalkane include vinylcyclopentane and vinylcyclohexane, and specific examples of the aromatic vinyl compound include styrenes. Specific examples of non-conjugated dienes include 1,4-hexadiene, 1,5-hexadiene, 1,7-heptadiene, 1,7-octadiene, 4-vinyl-1-cyclohexene, 5-vinyl-norbornene, 5- Ethylidene-2-norbornene and the like can be mentioned, and specific examples of the conjugated diene include butadiene, isoprene, 1,4-cyclohexadiene and the like. In addition, specific examples of cyclic olefins include norbornenes, cyclohexene, cyclopentene and the like.

Moreover, even if a component for removing water, a so-called scavenger, is added to the polymerization system, the polymerization can be carried out without any trouble.
Such scavengers include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, organoaluminum compounds such as trioctylaluminum, the organoaluminum oxy compounds, and the organoaluminum compounds modified with alcohols or phenols. Modified organoaluminum compounds, organozinc compounds such as diethyl zinc and dibutyl zinc, organomagnesium compounds such as diethylmagnesium, dibutylmagnesium and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum are preferable, and triisobutylaluminum, trihexylaluminum, and trioctylaluminum are particularly preferable.

  The molecular weight of the produced polymer can be adjusted by changing the polymerization conditions such as the polymerization temperature, the concentration of the olefin monomer, and the molar ratio of the catalyst. Further, the molecular weight can be adjusted effectively by adding hydrogen, the above-mentioned scavengers or the like as a chain transfer agent to the polymerization reaction system.

  The present invention can also be applied to a multistage polymerization system having two or more stages having different polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature without any trouble.

4). Ethylene Homopolymerization Method and Copolymerization Method In the present invention, more preferable polymerization using the above-mentioned olefin polymerization catalyst includes ethylene homopolymerization or ethylene / α-olefin copolymerization. Further, as a preferable polymerization method, a solution method using an inert solvent or a polymerization method using an olefin monomer as a solvent without substantially using an inert solvent is preferable. The polymerization temperature is generally 0-300 ^° C, preferably 50-250 ^° C.

The α-olefins which are comonomers include those having 3 to 30 carbon atoms, preferably 3 to 8 carbon atoms, specifically, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl- Examples include 1-pentene and the like.
As for the α-olefins, two or more types of α-olefins can be copolymerized with ethylene.
The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. When ethylene and another α-olefin are copolymerized, the amount of the other α-olefin can be arbitrarily selected within a range of 90 mol% or less of the total monomers, but is preferably 50 mol% or less. Of course, a small amount of a comonomer other than ethylene or α-olefin can be used. In this case, aromatic vinyls such as styrene, 4-methylstyrene, 4-dimethylaminostyrene, 1,4-butadiene, 1, Dienes such as 5-hexadiene, 1,4-hexadiene, 1,7-octadiene, 4-vinyl-1-cyclohexene, 5-vinyl-norbornene, 5-ethylidene-2-norbornene, and cyclic compounds such as norbornene and cyclopentene And polymerizable unsaturated hydrocarbon compounds.

In the following, the present invention will be described in more detail with reference to examples and comparative examples, and the superiority of the present invention and the superiority in the structure of the present invention will be demonstrated, but the present invention is limited by these examples. It is not a thing.
In addition, the measuring methods of various physical properties of the polymers obtained in the examples and comparative examples are as follows.

(1) Melt flow rate (MFR)
The measured value at a test temperature of 190 ° C. and a nominal load of 2.16 kg was shown as MFR according to JIS K7210 (2004 edition), Annex A, Table 1-Condition D.
(2) Gel permeation chromatography (GPC)
The generated ethylene polymer was subjected to gel permeation chromatography (GPC) under the following conditions to determine the number average molecular weight (Mn) and the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) was calculated.
[Gel permeation chromatographic measurement conditions]:
Apparatus: Waters Alliance GPC2000 model Column: Shodex-HT806M,
Solvent: 1,2-dichlorobenzene,
Flow rate: 1 ml / min
Temperature: 145 ° C
Universal rating using monodisperse polystyrene fraction.
Measurement was performed under the above-mentioned conditions, and a chromatogram was recorded at a sampling interval of 1 second. This chromatogram by Sadao Mori “Size Exclusion Chromatography” (Kyoritsu Shuppan) Chapter 4 p. The differential molecular weight distribution curve and the average molecular weight value (Mn, Mw) were calculated by the method described in 51-60. However, in order to correct the molecular weight dependency of dn / dc, the height H from the baseline in the chromatogram was corrected by the following equation. Chromatogram recording (data acquisition) and average molecular weight calculation were carried out on a PC in which Microsoft Windows XP (registered trademark) XP was installed using an in-house program (created with Visual Basic 6.0 from Microsoft).
H ′ = [1.032 + 189.2 / M (PE)] × H
In addition, the following formula was used for the molecular weight conversion from polystyrene to polyethylene.
M (PE) = 0.468 × M (PS)

(3) Density Density was measured according to Method A (underwater substitution method) among the test methods described in JIS K7112 (2004 edition).

The molecular weight of the polymer obtained by carrying out the above measurements (1) and (2) can be evaluated. That is, it can be said that a polymer having a smaller MFR value obtained from measurement (1) and a polymer having a larger weight average molecular weight obtained by measurement (2) have a higher molecular weight.
In addition, by carrying out the above measurement (3), it is possible to evaluate the size of the comonomer in the copolymer, that is, the content of 1-hexene which is an α-olefin in this example and the comparative example. This is because the higher the comonomer content, the lower the density. In other words, by comparing the density of polymers obtained under the same monomer ratio using different catalysts, the copolymerizability (performance capable of efficiently incorporating a comonomer) can be evaluated. .

[Example 1]
(1) Synthesis of dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) indenyl}] titanium (1-1) Synthesis of 2- (5-methyl-2-furyl) indene − A 1.57 mol / L n-butyllithium / n-hexane solution (44 mL, 69 mmol) was added dropwise to a solution of 2-methylfuran 6.0 mL (67 mmol) in dimethylmethoxyether (75 mL) cooled to 78 ^° C. Stir at room temperature for 2 hours. After stirring, 125 mL of dimethylmethoxyether was added and cooled to −78 ^° C., triisopropyl borate (16.9 mL, 73 mmol) was added, and the mixture was stirred at room temperature overnight. After stirring, 170 mL of water, 15.5 g (146 mmol) of sodium carbonate, 10.0 g (51.3 mmol) of 2-bromoindene, 5.0 g (4.33 mmol) of tetrakis (triphenylphosphino) palladium were added in this order. While removing low boiling point components, the mixture was stirred at 85 ^° C. for 4 hours.
The reaction solution was poured into ice water, and extracted with ether three times. The ether phase was washed with saturated brine until neutral. Sodium sulfate was added thereto and left overnight, and the reaction solution was dried. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 9.2 g of 2- (5-methyl-2-furyl) indene. Yield 92%.

(1-2) chloro {2- (5-methyl-2-furyl) indenyl} cooled to synthesize -78 ^o C dimethylsilane 2- (5-methyl-2-furyl) indene (10.0 g, 50. 9 mol) in tetrahydrofuran was added dropwise with a 2.5 mol / L n-butyllithium / n-hexane solution (22.4 mL, 56 mmol), followed by stirring at room temperature for 4 hours. After stirring, the reaction solution was added dropwise to a tetrahydrofuran solution of dichlorodimethylsilane (32.8 g, 255 mmol) cooled to −78 ^° C., and stirred at room temperature for 12 hours. After the reaction, the solvent and unreacted dichlorodimethylsilane were distilled off under reduced pressure, extracted with n-hexane, and insoluble matter was filtered off. The filtrate was concentrated under reduced pressure and distilled to obtain 7.5 g of chloro {2- (5-methyl-2-furyl) indenyl} dimethylsilane. Yield 51%.

(1-3) Synthesis of (tert-Butylamide) {2- (5-Methyl-2-furyl) indenyl} dimethylsilane Tetrabutylamine (1.71 g, 23.4 mmol) in tetrahydrofuran cooled to −78 ^° C. A 2.5 mol / L n-butyllithium / n-hexane solution (9.8 mL, 25 mmol) was added dropwise thereto, followed by stirring at room temperature for 4 hours. After stirring, the reaction solution was added dropwise to a tetrahydrofuran solution of chloro (2- (5-methyl-2-furyl) indenyl) dimethylsilane (7.5 g, 23.4 mmol) cooled to −78 ^° C., and the mixture was stirred at room temperature for 12 hours. Stir. After the reaction, the solvent was distilled off under reduced pressure and extracted with n-hexane, and then insoluble matter was filtered off. The filtrate was concentrated under reduced pressure and then distilled to obtain 3.6 g of (tert-butylamide) {2- (5-methyl-2-furyl) indenyl} dimethylsilane. Yield 47%.

(1-4) Synthesis of dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) indenyl}] titanium (tert-Butylamide) {2- (5-methyl) cooled to 0 ^o C After adding 1.06 mol / L methyllithium / diethyl ether solution (33.0 mL, 35.0 mmol) dropwise to a diethyl ether solution of 2-furyl) indenyl} dimethylsilane (2.60 g, 7.9 mmol), room temperature For 4 hours. After stirring, the reaction solution was added dropwise to an n-hexane solution of titanium tetrachloride (0.90 mL, 8.2 mmol) cooled to 0 ^° C., and stirred at room temperature for 30 minutes. After the reaction, the reaction solvent was distilled off under reduced pressure, and the product was extracted with n-hexane, followed by celite filtration. The solvent of the filtrate was distilled off under reduced pressure, redissolved in diethyl ether / n-pentane, and then left in a freezer to leave dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl). ) Indenyl}] 1.55 g of yellow crystals of titanium were obtained. Yield 48%.
¹ HNMR (C ₆ D ₆ ) δ = 7.59 (d, 1H), 7.45 (d, 1H), 7.15 (s, 1H), 7.07 (t, 1H), 6.89 ( t, 1H), 6.36 (d, 1H), 5.78 (d, 1H), 2.02 (s, 3H), 1.45 (s, 9H), 1.09 (s, 3H), 0.63 (s, 3H), 0.47 (s, 3H), 0.00 (s, 3H) ppm.

(2) Ethylene / 1-hexene copolymerization using dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) indenyl}] titanium 2.3 L sufficiently dried and substituted with nitrogen 1000 mL of toluene and 58 mL of 1-hexene were placed in a stainless steel autoclave (stirring and equipped with a temperature controller), and the temperature was raised to 150 ^° C. After the temperature in the reactor was stabilized, the pressure was increased to 0.7 MPaG with nitrogen, and further pressurized to 2.7 MPaG with ethylene. Thereafter, 0.1 mmol of tri (n-octyl) aluminum was injected with nitrogen, and dimethyl [dimethylsilylene (tert-butylamide) {2- (5-methyl-2-furyl) indenyl}] dimethyltitanium 1.5 μmol-toluene 1 mL The solution and the cocatalyst [Me ₂ N (H) C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ ] 1.0 μmol-toluene 1 mL solution were contacted at room temperature / nitrogen and then stirred at room temperature for 10 minutes. Was injected to start polymerization. Then, after stirring for 5 minutes while controlling the internal pressure to be 2.7 MPa, the reaction was stopped by injecting ethanol with nitrogen, and the polymer was obtained by drying after cooling. Polymer yield 2.4 g.
Polymer index: density = 0.9134 g / cm ³ , MFR = 0.1 g / 10 min, weight average molecular weight M _w = 254,000, M _w / M _n = 7.54.

[Example 2]
(1) Synthesis of dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) indenyl}] titanium (1-1) (cyclododecylamide) {2- (5-methyl-2- Synthesis of furyl) indenyl} dimethylsilane 1.57 mol / L n-butyllithium in a tetrahydrofuran solution of 2- (5-methyl-2-furyl) indene (2.36 g, 12.0 mmol) cooled to −78 ^° C. A / n-hexane solution (7.8 mL, 12.2 mmol) was added dropwise, followed by stirring at room temperature for 2 hours. After stirring, the reaction solution was added dropwise to an n-hexane solution of dichlorodimethylsilane (7.2 mL, 60 mmol) cooled to −78 ^° C., and stirred at room temperature for 1.5 hours. After the reaction, the solvent and unreacted dichlorodimethylsilane were distilled off under reduced pressure and redissolved in tetrahydrofuran (solution A).
A 1.57 mol / L n-butyllithium / n-hexane solution (7.8 mL, 12.2 mmol) was added dropwise to a tetrahydrofuran solution of cyclododecylamine (2.20 g, 12.0 mmol) cooled to −78 ^° C. Thereafter, the mixture was stirred at room temperature for 5 hours. The reaction solution was added dropwise to the solution A cooled to −78 ^° C., and then stirred at room temperature for 3 hours. After the reaction, the solvent was distilled off under reduced pressure, and the product was extracted with diethyl ether, followed by celite filtration. The filtrate was distilled off under reduced pressure and dried to obtain 5.22 g of (cyclododecylamide) {2- (5-methyl-2-furyl) indenyl} dimethylsilane as an orange oil. Quantitative yield.

(1-2) Synthesis of dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) indenyl}] titanium (cyclododecylamide) {2- (5-methyl) cooled to 0 ^o C 2-furyl) indenyl} dimethylsilane (2.61 g, 6.00 mmol) in diethyl ether was added dropwise with a 1.06 mol / L methyllithium / diethyl ether solution (25.0 mL, 26.5 mmol) at room temperature. For 3.5 hours. After stirring, the reaction solution was added dropwise to an n-hexane solution of titanium tetrachloride (0.65 mL, 5.9 mmol) cooled to 0 ^° C., and stirred at room temperature for 30 minutes. After the reaction, the reaction solvent was distilled off under reduced pressure, and the product was extracted with n-hexane, followed by celite filtration. The solvent of the filtrate was distilled off under reduced pressure, redissolved in n-pentane, and allowed to stand in a freezer so that dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) indenyl }] 1.38 g of titanium black crystals were obtained. Yield 45%.
By recrystallizing 1.05 g of the black crystals in diethyl ether, 865 mg (28% yield) of yellow crystals were obtained.
¹ HNMR (C ₆ D ₆ ) δ = 7.62 (d, 1H), 7.51 (d, 1H), 7.14 (s, 1H), 7.04 (dd, 1H), 6.89 ( dd, 1H), 6.37 (d, 1H), 5.78 (d, 1H), 5.26 (d, 1H), 1.8-1.1 (m, 22H), 2.03 (s , 3H), 1.06 (s, 3H), 0.66 (s, 3H), 0.46 (s, 3H), 0.00 (s, 3H) ppm.

(2) Ethylene / 1-hexene copolymerization using dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) indenyl}] titanium Dimethyl [dimethylsilylene (cyclododecylamide) { 2- (5-methyl-2-furyl) indenyl}] titanium, the amount of complex used is 0.9 μmol, and the promoter [Me ₂ N (H) C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ The polymerization operation was carried out in the same manner as in Example 1 except that the amount used was 0.6 μmol. Polymer yield 3.0 g.
Polymer index: density = 0.8944 g / cm ³ , MFR = 0.02 g / 10 min, weight average molecular weight M _w = 402,000, M _w / M _n = 2.92.

[Example 3] (Reference Example)
(1) Synthesis of dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium (1-1) 1- (5-methyl Synthesis of 2-furyl) -3,4-dimethylcyclopentadiene 1- (5-Methyl-2-furyl) -3,4-dimethylcyclopentadiene was synthesized according to the synthesis method in the example of Japanese Patent No. 3675509.

(1-2) Synthesis of chloro {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl} dimethylsilane 1- (5-methyl-2-furyl cooled to −78 ^° C. ) A 2.5 mol / L n-butyllithium / n-hexane solution (27.8 mL, 69.5 mmol) was added dropwise to a tetrahydrofuran solution of 3,4-dimethylcyclopentadiene (11 g, 63 mmol), and then 4 at room temperature. Stir for hours. After stirring, the reaction solution was added dropwise to a tetrahydrofuran solution of dichlorodimethylsilane (24.5 g, 189 mmol) and N-methylimidazole (0.26 g, 3.16 mmol) cooled to −78 ^° C., and stirred at room temperature for 16 hours. did. After the reaction, the solvent and unreacted dichlorodimethylsilane were distilled off under reduced pressure, extracted with n-hexane, and insoluble matter was filtered off. The filtrate was concentrated under reduced pressure and distilled to obtain 15.1 g of chloro (2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl) dimethylsilane. Yield 90%.

(1-3) (cyclododecyl amido) {2- (5-methyl-2-furyl) -4,5-dimethyl-cyclopentadienyl} cyclo dodecylamine cooled synthesis -78 ^o C dimethylsilane (4. A 2.5 mol / L n-butyllithium / n-hexane solution (10 mL, 25 mmol) was added dropwise to a 4 g, 24 mmol) tetrahydrofuran solution, and the mixture was stirred at room temperature for 4 hours. After stirring, the reaction solution was cooled to −78 ^° C. to a tetrahydrofuran solution of chloro (2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl) dimethylsilane (6.4 g, 24 mmol). The solution was added dropwise and stirred at room temperature for 16 hours. After the reaction, the solvent was distilled off under reduced pressure and extracted with n-hexane, and then insoluble matter was filtered off. The filtrate was distilled off under reduced pressure to obtain 9.0 g of (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl} dimethylsilane. Yield 90%.

(1-4) Synthesis of dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium {Cyclododecyl cooled to 0 ^o C Amide) (2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl) dimethylsilane (3.31 g, 8.00 mmol) in diethyl ether solution at 1.06 mol / L methyllithium / A diethyl ether solution (32 mL, 34 mmol) was added dropwise, and the mixture was stirred at room temperature for 3.5 hours. After stirring, the reaction solution was added dropwise to an n-hexane solution of titanium tetrachloride (0.90 mL, 8.2 mmol) cooled to 0 ^° C., and stirred at room temperature for 30 minutes. After the reaction, the reaction solvent was distilled off under reduced pressure, and the product was extracted with n-hexane, followed by celite filtration. After concentrating the solvent of the filtrate under reduced pressure, the solution was allowed to stand in a freezer, whereby dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl. }] 2.96 g of titanium black crystals were obtained. Yield 76%.
¹ HNMR (C ₆ D ₆ ) = 6.64 (s, 1H), 6.22 (d, 1H), 5.77 (d, 1H), 5.39 (m, 1H), 2.05 (s , 3H), 2.03 (s, 3H), 1.8-1.2 (m, 22H), 0.92 (s, 3H), 0.62 (s, 3H), 0.47 (s, 3H), 0.27 (s, 3H) ppm.

(2) Ethylene / 1-hexene copolymerization using dimethyl [dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium [Dimethylsilylene (cyclododecylamide) {2- (5-methyl-2-furyl) -4,5-dimethylcyclopentadienyl}] titanium is used, the amount of complex used is 0.3 μmol, and the promoter [Me ₂ A polymerization operation was performed in the same manner as in Example 1 except that the amount of N (H) C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ ] was changed to 0.2 μmol. Polymer yield 4.0 g.
Polymer index: density = 0.8919 g / cm ³ , MFR = 0.023 g / 10 min, weight average molecular weight M _w = 423,000, M _w / M _n = 2.71.

[Comparative Example 1] (1) Synthesis of dimethyl {dimethylsilylene (tert-butylamide) (2,3,4,5-tetramethylcyclopentadienyl)} titanium The compound was synthesized with reference to JP-T-2003-501436.
(2) Ethylene / 1-hexene copolymerization using dimethyl {dimethylsilylene (tert-butylamide) (2,3,4,5-tetramethylcyclopentadienyl)} titanium Dimethyl {dimethylsilylene (tert-butylamide) as a complex ) (2,3,4,5-tetramethylcyclopentadienyl)} titanium, the amount of complex used is 0.3 μmol, and the promoter [Me ₂ N (H) C ₆ H ₅ ] [B (C ₆ The same polymerization operation as in Example 1 was performed except that the amount of F ₅ ) ₄ ] used was 0.2 μmol. Polymer yield 8.0g.
Polymer index: density = 0.9115 g / cm ³ , MFR = 0.42 g / 10 min, weight average molecular weight M _w = 166,000, M _w / M _n = 3.32.

[Comparative Example 2]
(1) Synthesis of dimethyl {dimethylsilylene (cyclododecyl) (2,3,4,5-tetramethylcyclopentadienyl)} titanium The compound was synthesized with reference to the synthesis method of JP-T-2003-501436.
(2) Ethylene / 1-hexene copolymerization using dimethyl {dimethylsilylene (cyclododecyl) (2,3,4,5-tetramethylcyclopentadienyl)} titanium dimethyl {dimethylsilylene (cyclododecyl) ( 2,3,4,5-tetramethylcyclopentadienyl)} titanium, the amount of complex used is 0.3 μmol, and the promoter [Me ₂ N (H) C ₆ H ₅ ] [B (C ₆ F _{5 4} ) The same polymerization operation as in Example 1 was carried out except that the amount used of ₄ ] was 0.2 μmol. Polymer yield 10.6 g.
Polymer index: density = 0.8883 g / cm ³ , MFR = 0.49 g / 10 min, weight average molecular weight M _w = 148,000, M _w / M _n = 2.82.

[Comparative Example 3]
(1) Synthesis of dimethyl {dimethylsilylene (tert-butylamide) (1-indenyl)} titanium was synthesized with reference to JP-T-2003-501436.
(2) Ethylene / 1-hexene copolymerization using dimethyl {dimethylsilylene (tert-butylamide) (1-indenyl)} titanium Dimethyl {dimethylsilylene (tert-butylamide) (1-indenyl)} titanium as a complex The amount of the complex used was 0.3 μmol, and the amount of the promoter [Me ₂ N (H) C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ ] used was 0.2 μmol. A polymerization operation was performed. Polymer yield 4.4 g.
Polymer index: density = 0.9103 g / cm ³ , MFR = 0.82 g / 10 min, weight average molecular weight M _w = 14,000, M _w / M _n = 1.91.

[Comparative Example 4]
(1) Synthesis of dimethyl [dimethylsilylene (tert-butylamide) {3- (5-methyl-2-furyl) indenyl}] titanium (1-1) Synthesis of 1- (5-methyl-2-furyl) indene J . Organomet. Chem. 2001, volume 621, pages 197-206 were synthesized with reference.

(1-2) (tert-butylamido) {3- (5-methyl-2-furyl) indenyl} cooled to synthesize -78 ^o C dimethylsilane 1- (5-methyl-2-furyl) indene (2. A 1.57 mol / L n-butyllithium / n-hexane solution (7.8 mL, 12.2 mmol) was added dropwise to a tetrahydrofuran solution (36 g, 12.0 mmol), followed by stirring at room temperature for 2 hours. After stirring, the reaction solution was added dropwise to an n-hexane solution of dichlorodimethylsilane (7.2 mL, 60 mmol) cooled to −78 ^° C., and stirred at room temperature for 1.5 hours. After the reaction, the solvent and unreacted dichlorodimethylsilane were distilled off under reduced pressure and redissolved in tetrahydrofuran (solution A).
A 1.57 mol / L n-butyllithium / n-hexane solution (7.8 mL, 12.2 mmol) was added dropwise to a tetrahydrofuran solution of tert-butylamine (1.26 mL, 12.0 mmol) cooled to −78 ^° C. Then, it stirred at room temperature for 4.5 hours. The reaction solution was added dropwise to the solution A cooled to −78 ^° C., and then stirred at room temperature for 17 hours. After the reaction, the solvent was distilled off under reduced pressure, and the product was extracted with diethyl ether, followed by celite filtration. The filtrate was distilled off under reduced pressure and dried to obtain 3.91 g of (tert-butylamide) {3- (5-methyl-2-furyl) indenyl} dimethylsilane as an orange oil. Quantitative yield.

(1-3) Synthesis of dimethyl [dimethylsilylene (tert-butylamide) {3- (5-methyl-2-furyl) indenyl}] titanium (tert-Butylamide) {2- (5-methyl) cooled to 0 ^o C 2-Furyl) indenyl} dimethylsilane (2.60 g, 7.9 mmol) in diethyl ether was added dropwise with a 1.06 mol / L methyllithium / diethyl ether solution (32 mL, 34 mmol) and then stirred at room temperature for 4 hours. did. After stirring, the reaction solution was added dropwise to an n-hexane solution of titanium tetrachloride (0.90 mL, 8.2 mmol) cooled to 0 ^° C., and stirred at room temperature for 30 minutes. After the reaction, the reaction solvent was distilled off under reduced pressure, the product was extracted with n-pentane, and then filtered through Celite. The solvent of the filtrate was distilled off under reduced pressure to obtain yellowish black oil of dimethyl [dimethylsilylene (tert-butylamide) {3- (5-methyl-2-furyl) indenyl}] titanium.
¹ HNMR (C ₆ D ₆ ) = 8.27 (d, 1H), 7.52 (d, 1H), 7.23 (t, 1H), 6.94 (t, 1H), 6.60 (s , 1H), 6.51 (d, 1H), 5.93 (d, 1H), 2.07 (s, 3H), 1.45 (s, 9H), 0.82 (s, 3H), 0 .58 (s, 3H), 0.49 (s, 3H), -0.01 (s, 3H) ppm.

(2) Ethylene / 1-hexene copolymerization using dimethyl [dimethylsilylene (tert-butylamide) {3- (5-methyl-2-furyl) indenyl}] titanium Dimethyl [dimethylsilylene (tert-butylamide) { 3- (5-methyl-2-furyl) indenyl}] titanium, the amount of complex used is 0.3 μmol, and the promoter [Me ₂ N (H) C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ The polymerization operation was carried out in the same manner as in Example 1 except that the amount used was 0.2 μmol. Polymer yield 5.0 g.
Polymer index: density = 0.9043 g / cm ³ , MFR = 1.45 g / 10 min, weight average molecular weight M _w = 110,000, M _w / M _n = 2.20.

[Comparative Example 5]
(1) Synthesis of dimethyl [dimethylsilylene (cyclododecylamide) {3- (5-methyl-2-furyl) indenyl}] titanium (1-1) (cyclododecylamide) {3- (5-methyl-2- Synthesis of furyl) indenyl} dimethylsilane 1.57 mol / L n-butyllithium in a tetrahydrofuran solution of 1- (5-methyl-2-furyl) indene (1.57 g, 8.00 mmol) cooled to −78 ^° C. / N-Hexane solution (5.2 mL, 8.2 mmol) was added dropwise, followed by stirring at room temperature for 2 hours. After stirring, the reaction solution was added dropwise to an n-hexane solution of dichlorodimethylsilane (4.8 mL, 40 mmol) cooled to −78 ^° C., and stirred at room temperature for 2 hours. After the reaction, the solvent and unreacted dichlorodimethylsilane were distilled off under reduced pressure and redissolved in tetrahydrofuran (solution A).
A 1.57 mol / L n-butyllithium / n-hexane solution (5.2 mL, 8.2 mmol) was added dropwise to a tetrahydrofuran solution of cyclododecylamine (1.47 g, 8.02 mmol) cooled to −78 ^° C. Thereafter, the mixture was stirred at room temperature for 5 hours. The reaction solution was added dropwise to the solution A cooled to −78 ^° C., and then stirred at room temperature for 17 hours. After the reaction, the solvent was distilled off under reduced pressure, and the product was extracted with diethyl ether, followed by celite filtration. The filtrate was distilled off under reduced pressure and dried to obtain 3.49 g of (cyclododecylamide) {3- (5-methyl-2-furyl) indenyl} dimethylsilane as an orange oil. Quantitative yield.

(1-2) Synthesis of dimethyl [dimethylsilylene (cyclododecylamide) {3- (5-methyl-2-furyl) indenyl}] titanium (cyclododecylamide) {3- (5-methyl) cooled to 0 ^o C 2-furyl) indenyl} dimethylsilane (3.49 g, 8.00 mmol) in diethyl ether was added dropwise with a 1.06 mol / L methyllithium / diethyl ether solution (32 mL, 34 mmol) and then stirred at room temperature for 4 hours. did. After stirring, the reaction solution was added dropwise to an n-hexane solution of titanium tetrachloride (0.90 mL, 8.2 mmol) cooled to 0 ^° C., and stirred at room temperature for 30 minutes. After the reaction, the reaction solvent was distilled off under reduced pressure, and the product was extracted with n-hexane, followed by celite filtration. The solvent of the filtrate was distilled off under reduced pressure, redissolved in diethyl ether, and allowed to stand in a freezer, so that dimethyl [dimethylsilylene (cyclododecylamide) {3- (5-methyl-2-furyl) indenyl} ] 0.96 g of titanium black crystals were obtained. Yield 23%.
The black crystals were recrystallized in diethyl ether to obtain 0.22 g (5.4% yield) of yellow crystals.
¹ HNMR = 8.30 (d, 1H), 7.55 (d, 1H), 7.20 (t, 1H), 6.95 (t, 1H), 6.65 (s, 1H), 6. 52 (s, 1H), 5.93 (d, 1H), 5.17 (t, 1H), 2.07 (s, 3H), 1.8-1.1 (m, 22H), 0.80 (S, 3H), 0.59 (s, 3H), 0.41 (s, 3H), 0.00 (s, 3H) ppm.

(2) Ethylene / 1-hexene copolymerization using dimethyl [dimethylsilylene (cyclododecylamide) {3- (5-methyl-2-furyl) indenyl}] titanium Dimethyl [dimethylsilylene (cyclododecylamide) { The same polymerization procedure as in Example 1 was performed except that 3- (5-methyl-2-furyl) indenyl}] titanium was used. Polymer yield 5.0 g.
Polymer index: density = 0.901 g / cm ³ , MFR = 0.42 g / 10 min, weight average molecular weight M _w = 156,000, M _w / M _n = 2.37.

[Consideration of Comparison Results of Examples and Comparative Examples]
As is clear from Tables 1 and 2, by comparing Example 3 (Reference Example) with Comparative Examples 1 and 2, and Examples 1 and 2 with Comparative Example 3, the catalyst of the present invention has low density and high molecular weight. That is, it can be seen that an ethylene copolymer having both a high 1-hexene content and a high molecular weight can be provided. Moreover, it is clear that it is indispensable in order to increase the molecular weight of the polymer in which the 2-position heteroaromatic substituent is formed by comparing Example 1 and Comparative Example 4, and Example 2 and Comparative Example 5. . It is clear that this catalyst is excellent in copolymerization at industrially advantageous polymerization temperatures and conditions, and is in a well-balanced catalyst capable of producing a high molecular weight ethylene copolymer.

As is clear from the above, by using the half metallocene complex of the present invention as a polymerization catalyst, in the olefin copolymerization, while maintaining excellent olefin copolymerizability compared with conventional complex catalyst systems, An olefin copolymer can be obtained. In particular, a low density and high molecular weight ethylene copolymer can be produced.
As a result, an olefin copolymer excellent in flexibility, impact resistance, and transparency can be produced under industrially efficient polymerization conditions, and the half metallocene complex of the present invention and olefin polymerization including the half metallocene complex. The olefin polymerization method using the catalyst for olefin and the catalyst for olefin polymerization has extremely great industrial value.

Claims (6)

A half metallocene complex represented by the following general formula [I]:

[Wherein, M is titanium, zirconium or hafnium, Q is a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and Z is an amide group.
X and Y represent σ covalent auxiliary ligands, which may be the same or different, the sum of n and m is 0 to 2, L is a neutral Lewis base, and k is 0 to 2. Yes, the sum of n, m, and k is 0-4.
R ¹ is a furyl group or a thienyl group having one or more substituents. When the furyl group or thienyl group has a plurality of substituents, each substituent may be the same or different, and the substituent bonded to the furyl group or thienyl group is an alkyl group having 1 to 20 carbon atoms. Alternatively, a silicon-containing alkyl group having 1 to 20 carbon atoms, a halogen atom-containing alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogenated group having 6 to 18 carbon atoms. An aryl group.
R ² is hydrogen, an alkyl group having 1 to 8 carbon atoms, a halogen atom-containing alkyl group having 1 to 8 carbon atoms, a silicon-containing alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or 6 carbon atoms. ~ 18 halogenated aryl groups,
R ³ and R ⁴ together form a benzene ring. ] The half metallocene complex according to claim 1, wherein M in the general formula [I] is titanium. An olefin polymerization catalyst comprising the following components (A) and (B), and (C) as necessary.
Component (A): Half metallocene complex component (B) according to claim 1 or 2: Compound that reacts with component (A) to form an ion pair, or an ion-exchange layered silicate or inorganic silicate component (C) : Organoaluminum compound 4. The olefin polymerization catalyst according to claim 3, wherein the component (B) is a boron compound. Using the olefin polymerization catalyst according to claim 3 or 4, olefin homopolymerization, copolymerization of two or more types of olefins, or copolymerization of olefins and polymerizable unsaturated hydrocarbons. Polymerization method. An ethylene polymerization method comprising ethylene homopolymerization or copolymerization of ethylene and one or more α-olefins using the olefin polymerization catalyst according to claim 3 or 4.