JP2005336092A - New transition metal compound and method for producing propylene-based polymer by using the same transition metal compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new C1 symmetric transition metal compound capable of producing a readily soluble propylene-based polymer highly having terminal vinyl bonds and capable of readily carrying out conversion of functional groups and a catalyst for α-olefin polymerization containing the metal compound. <P>SOLUTION: The present invention provides a new C1 symmetric transition metal compound, a catalyst for olefin polymerization containing the metal compound and a method for producing an α-olefin polymer by using the catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel transition metal compound useful as a propylene-based polymerization catalyst component, a method for producing a propylene-based polymer, and more specifically, a novel transition metal compound for propylene-based polymerization having a vinyl group at a terminal, and a terminal The present invention relates to a method for producing a propylene polymer having a vinyl group.

  Propylene polymers are used in a wide range of fields because of their excellent mechanical properties, heat resistance, chemical resistance, water resistance, and the like. In the production of the polymer, since hydrogen is often used for molecular weight adjustment, the polymer terminal is a saturated hydrocarbon group having poor reaction activity. On the other hand, when hydrogen is not added, a polymer having a terminal unsaturated group is obtained. However, since it is an isobutenyl structure generated by β-hydrogen elimination, the polymer terminal has sufficient reaction activity. In addition, there is a disadvantage that the ratio of the polymer having a terminal unsaturated group is reduced by hydrogen generated in the system. Propylene polymers with vinyl groups at the ends, even with the same unsaturated bonds, can be used as macromers, and have special functions such as compatibilizers, adhesives and paintability by modifying the ends. It can be used as a polymer. For this reason, various studies have been made to produce such special polymers. In particular, many studies using metallocene complexes have been conducted. This is because the metallocene complex can produce a stereospecific polymer by controlling the reaction field, can exhibit a high polymerization activity, and can give a polymer with a narrow molecular weight distribution. In the case of a propylene-based polymer having a vinyl group at the terminal produced in this way and having a remarkably low stereoregularity (atactic), it may be difficult to handle due to its stickiness. On the other hand, when the stereoregularity becomes remarkably high, the polymer becomes difficult to dissolve in an organic solvent, and therefore the reaction conditions for introducing a functional group into the polymer become severe. For this reason, development of a propylene polymer having a vinyl group at the terminal and a method for producing the same is desired.

  Recently, there is a report that a polymer having terminal vinyl is produced by high-temperature polymerization of propylene using a metallocene complex. However, the obtained polymer has high stereoregularity and cannot always be said to have high solubility. Further, since the polymerization conditions are high, the generated terminal vinyl group may be isomerized inside, and it is not always preferable for producing a polymer having terminal vinyl (for example, Patent Document 1). ).

Further, it has been reported that when 1,2-ethanediylbis (1- (4,7-dimethylindenyl)) zirconium or the like is used, polypropylene having a terminal vinyl group is produced, but the ratio is low (for example, Non-Patent Document 1).
Further, terminal vinyl group-containing propylene polymers are produced using dichloro [dimethylsilylenebis (2-isopropyl-4-phenyl-4H-azurenyl)] hafnium, etc., but the content of the terminal vinyl groups is satisfactory. It did not go (for example, refer to Patent Document 2)
JP-T-2001-525461 JP 11-349634 A Polym. Prepr., 38, 776 (1997)

In addition to being usable as a macromer, the present invention has a vinyl group in such an amount that it can be used as a polymer having a special function excellent in compatibilizing agent, adhesive, paintability, etc. by modifying the terminal. It aims at providing the novel transition metal compound used as the catalyst component for manufacturing the propylene polymer made into the terminal, and the manufacturing method.

  As a result of diligent investigations in view of the above circumstances, the present inventors have found that an azulenyl group having various substituents at positions 2 and 4 of azulene and a cyclopenta having four hydrocarbon substituents as a ligand for a polymerization catalyst. By using a C1-symmetric transition metal compound having a novel structure in which a dienyl group is cross-linked, it was found that a propylene-based polymer having a considerable amount of a vinyl group at the terminal was obtained, and the present invention was completed.

  That is, the first gist of the present invention resides in a C1-symmetric transition metal compound represented by the following general formula (I).

In general formula (I), R ^{1 to} R ⁴ are all the same hydrocarbon group, halogenated hydrocarbon group or silicon-containing hydrocarbon group, and R ⁹ is a hydrocarbon group, halogenated hydrocarbon group or silicon. -Containing hydrocarbon group, or R ¹ and R ² and R ³ and R ⁴ combine to form a divalent hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group, and R ⁹ is aromatic Group hydrocarbon group:
R ⁵ is a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group: R ⁶ is a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group: R ⁷ has 4 carbon atoms
A saturated or unsaturated divalent hydrocarbon group of ˜9: R ⁸ is a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group: n is 0 or less than twice the number of carbon atoms of R ⁷ Integer (however, when n is 2 or more, R ⁷ may be bonded to each other at any position to form a ring structure)
: Q represents a bridging group: X and Y each independently represent a ligand that forms a σ bond with M: M represents a transition metal of Groups 4 to 6 in the periodic table.

The second gist of the present invention resides in an olefin polymerization catalyst component containing a C1-symmetric transition metal compound represented by the above general formula (I).
The third gist of the present invention resides in an α-olefin polymerization catalyst comprising the following components (A) and (D) and optionally a component (E).
Component (A): C1-symmetric transition metal compound represented by the above general formula (I) Component (D): Compound component selected from the group consisting of an ion-exchange layered compound excluding silicate or inorganic silicate (E ): Organoaluminum compound The fourth gist of the present invention resides in a method for producing a propylene polymer, characterized in that any one of the above-mentioned catalysts and an α-olefin are brought into contact with each other for polymerization or copolymerization.

The fifth gist of the present invention resides in a propylene-based polymer having a vinyl group at the terminal, characterized by satisfying the following conditions (1) to (3).
(1) The number average molecular weight Mn measured by GPC is 20,000 or more and less than 100,000.
^{(2) In 13} C-NMR, a peak derived from the carbon atom of the methyl group of the propylene unit chain part consisting of a head-to-tail bond was observed, and the peak top chemical attributed to the pentad represented by mm mm When the shift is 21.8 ppm, the ratio of the peak area S ₁ having 21.8 ppm as the peak top to the total area S of peaks appearing at 19.8 ppm to 22.2 ppm is 70% or more and 99% or less. is there.
(3) The ratio of the terminal vinyl group to the terminal olefin is 80% or more.

    According to the present invention, it is possible to provide a propylene-based polymer that can be easily converted into a functional group.

Hereinafter, the present invention will be described in detail.
1. C1 Symmetry Transition Metal Complex (1) C1 Symmetry Transition Metal Complex An olefin is polymerized using a novel C1 symmetry transition metal compound represented by the following general formula (I) as a catalyst component.

One of the features of the present invention lies in the combination of R ^{1 to} R ⁴ and R ^{9 in} the general formula (I).
Or 2).
1) R ^{1 to} R ⁴ are all the same hydrocarbon group, halogenated hydrocarbon group or silicon-containing hydrocarbon group, and R ⁹ is a hydrocarbon group, halogenated hydrocarbon group or silicon-containing hydrocarbon group. is there.

Carbon number of R < ¹ > -R < ⁴ > is 1-12 normally, 1-10 are preferable, 1-8 are more preferable, and 1-6 are especially preferable.
Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl and cyclopentyl. In addition to alkyl groups such as cyclohexyl, alkenyl groups such as vinyl, propenyl, and cyclohexenyl, phenyl groups and the like can be mentioned.

Specific examples of the silicon-containing hydrocarbon group include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl.
The halogenated hydrocarbon group is a group in which a halogen atom is substituted at an arbitrary position of the above hydrocarbon group, and the halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2, 2, 2-trifluoroethyl, 2, 2, 1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 2-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2 -, 3-, 4-bromophenyl, 2, 4-, 3, 5-, 2, 6, 6-, 2, 5-difluorophenyl, 2, 4-, 3, 5-, 2, 6, 6, 2, 5 -Dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophene Nil and the like. (Note that in this specification, a part of the compound may be omitted unless misunderstanding occurs. For example, “2-, 3-, 4-fluorophenyl” may be referred to as “2-fluorophenyl”. ”,“ 3-fluorophenyl ”, and“ 4-fluorophenyl ”.)
At this time, R ⁹ is a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group. It is sufficient that the size does not hinder the polymerization reaction, and the carbon number is usually 1 to 40, more preferably 1 to 30, and particularly preferably 1 to 20.

  Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, Alkyl groups such as cyclohexyl and methylcyclohexyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, arylalkenyl groups such as trans-styryl, phenyl, tolyl, dimethylphenyl and ethyl Examples include aryl groups such as phenyl, trimethylphenyl, t-butylphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl and anthryl.

Examples of the halogenated hydrocarbon group include those in which a halogen atom is substituted at an arbitrary position of the above hydrocarbon group, and the halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2, 2, 2-trifluoroethyl, 2, 2, 1 , 1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, 2-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4-bromophenyl, 2, 4-, 3, 5-, 2, 6, 6, 2, 5-difluorophenyl 2, 4, 3, 5, 5, 2, 6, 6, 2, dichlorophenyl, 2, 4, 6 trifluorophenyl, 2, 4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 4-fluoronaphthyl, 4-chloronaphthyl, 2,4-difluoronaphthyl, heptafluoro-1-naphthyl, heptachloro-1-naphthyl, 2-, 3-, 4-trifluoromethylphenyl, 2-, 3-, 4-trichloromethylphenyl, 2,4-, 3,5-, 2,6-, 2,5-bis (trifluoromethyl) phenyl, 2,4- 3,5-, 2,6-, 2,5-bis (trichloromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl, 2, , 4-bis (trifluoromethyl) naphthyl group, and the like.

  Specific examples of silicon-containing hydrocarbon groups include trialkylsilyl groups such as trimethylsilyl, triethylsilylethyl, and t-butyldimethylsilyl groups, trialkylsilylmethyl groups such as trimethylsilylmethyl and triethylsilylmethyl, dimethylphenylsilylmethyl, diethyl Examples thereof include di (alkyl) (aryl) silylmethyl groups such as phenylsilylmethyl and dimethyltolylsilylmethyl, and trialkylphenyl groups such as trimethylsilylphenyl.

  Among these, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, methylcyclohexyl, Propenyl, cyclohexenyl, benzyl, phenylethyl, phenylpropyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2, 2, 2-trifluoroethyl, 2, 2, 1, 1- Tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, trimethylsilyl, triethylsilylethyl, t-butyldimethyl Siri , Trimethylsilylmethyl, triethylsilylmethyl, diethylphenylsilylmethyl, dimethyltolylsilylmethyl, methyl, ethyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclopentyl, cyclohexyl, benzyl, More preferred are trifluoromethyl, pentafluoroethyl, pentafluoropropyl, nonafluorobutyl, trimethylsilyl, methyl, ethyl, i-propyl, n-butyl, s-butyl, t-butyl, cyclohexyl, benzyl, trifluoromethyl, trimethylsilyl. Is particularly preferred.

Specific examples of the substituent condensed to the cyclopentadienyl ring formed by R ⁷ and the carbon to which R ⁹ is bonded (the one closer to the bridging group is the 1-position) include pentamethylene, hexa A divalent saturated hydrocarbon group such as methylene, 1-pentenylene, 2-pentenylene, 1,3-pentadienylene, 1,4-pentadienylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 1,3-hexadienylene, 1 Divalent unsaturated hydrocarbon groups such as 1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene, 1,3,5-hexatrienylene, and the like. Of these, a pentamethylene group, a 1,3-pentadienylene group, a 1,4-pentadienylene group or a 1,3,5-hexatrienylene group is preferable, and a pentamethylene group, a 1,3-pentadienylene group or 1,4- A pentadienylene group is more preferable, and a pentamethylene group and a 1,3-pentadienylene group are particularly preferable.

2) R ¹ and R ² and R ³ and R ⁴ are combined to form a divalent hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group, and R ⁹ is an aromatic hydrocarbon group. is there.
The carbon number of the divalent group formed by combining R ¹ and R ² and R ³ and R ⁴ is usually 3 or more, preferably 4 or more, and usually 9 or less, preferably 6 or less. As the kind of divalent group, a hydrocarbon group is preferable. Specific examples of the divalent hydrocarbon group include dimethylene, trimethylene, tetramethylene, heptamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, trimethylene, tetramethylene and heptamethylene are preferred, and tetramethylene is particularly preferred. preferable.

The divalent group may have a substituent such as a hydrocarbon group, a silicon-containing hydrocarbon group, or a halogenated hydrocarbon group. In this case, the hydrocarbon group, silicon-containing hydrocarbon group or halogenated hydrocarbon group usually has 1 to 10 carbon atoms, preferably 1 to 8 and most preferably 1 to 6.
Specific examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, Cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, methylcyclohexyl, alkenyl groups such as vinyl, propenyl, cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, arylalkenyl groups such as trans-styryl, phenyl, Examples include aryl groups such as tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl, 2-naphthyl and the like.

  Specific examples of the silicon-containing hydrocarbon group include trialkylsilyl groups such as trimethylsilyl, triethylsilyl and t-butyldimethylsilyl, trialkylsilylmethyl groups such as trimethylsilylmethyl and triethylsilylmethyl, dimethylphenylsilylmethyl and dimethyltolyl. Examples thereof include di (alkyl) (aryl) silylmethyl groups such as silylmethyl.

The halogen atom of the halogenated hydrocarbon group is not particularly limited, but is usually fluorine, chlorine or bromine, with chlorine or fluorine being preferred. Examples of the halogenated hydrocarbon group include compounds in which a halogen atom is substituted at an arbitrary position of the above hydrocarbon group. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2, 2, 2-trifluoroethyl, 2, 2, 1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, 2- 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4-bromophenyl, 2, 4-, 3, 5-, 2, 6, 6, 2, 5-difluoro Phenyl, 2,4-, 3,5-, 2,6-, 2,5-dichlorophenyl, 2,4,6-trifluorophenyl, 2, , 4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 4-fluoronaphthyl, 4-chloronaphthyl, 2,4-difluoronaphthyl, heptafluoro-1-naphthyl, heptachloro-1-naphthyl, 2-, 3- 4-trifluoromethylphenyl, 2-, 3-, 4-trichloromethylphenyl, 2, 4-, 3, 5-, 2, 6, 6, 2, 5-bis (trifluoromethyl) phenyl, 2, 4 -, 3, 5-, 2,6-, 2,5-bis (trichloromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl group and the like.

Among these, alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl and t-butyl, cycloalkyl groups such as cyclohexyl and methylcyclohexyl, phenyl and the like Aryl group, trialkylsilyl group such as trimethylsilyl, triethylsilyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2, 2, 2-trifluoroethyl, 1, 1, 2, 2 -Halogenated hydrocarbon groups such as tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, 2-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl are preferred. , Methyl, ethyl,
alkyl groups such as n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, cyclohexyl, phenyl group, trimethylsilyl group, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl More preferred are alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, cyclohexyl, phenyl group, and trimethylsilyl group.

At this time, R ⁹ is an aromatic hydrocarbon group. It is sufficient that the size does not hinder the polymerization reaction, and the carbon number is usually 1 to 40, more preferably 1 to 30, and particularly preferably 1 to 20.
Specific examples include aryl groups such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl and 2-naphthyl.

R ⁵ represents a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group. R ⁵ may be long in size which does not inhibit the reaction, the carbon number thereof is usually 1 to 12, 1 to 10 by weight, more preferably 1-8, 1-6 are particularly preferred.
Specific examples of the hydrocarbon group represented by R ⁵ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclo Examples include alkyl groups such as propyl, cyclopentyl and cyclohexyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, as well as phenyl groups.

Specific examples of the silicon-containing hydrocarbon group represented by R ⁵ include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl.
The halogenated hydrocarbon group represented by R ⁵ is a group in which a halogen atom is substituted at an arbitrary position of the hydrocarbon group, and the halogen atom is any one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Also good. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2, 2, 2-trifluoroethyl, 2, 2, 1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 2-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2 -, 3-, 4-bromophenyl, 2, 4-, 3, 5-, 2, 6, 6-, 2, 5-difluorophenyl, 2, 4-, 3, 5-, 2, 6, 6, 2, 5 -Dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophene Nil and the like.

Among these, hydrocarbon groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl and phenyl are particularly preferable.
R ⁶ is a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group, and hydrogen is particularly preferable.
Of the hydrocarbon group, silicon-containing hydrocarbon group or halogenated hydrocarbon group, a hydrocarbon group is preferred. The size should just be a thing which is not bulky more than necessary, and carbon number is 1-6 normally, and 1-4 are preferable. Specific examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclo Examples include cycloalkyl groups such as propyl, cyclopentyl and cyclohexyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, as well as aryl groups such as phenyl.

R ⁷ is a saturated or unsaturated divalent hydrocarbon group having 4 or more carbon atoms. Usually 4 carbon atoms
-9, preferably 4-6, particularly preferably 4, so that the condensed ring formed is 7-12
It becomes a member ring, and a preferable condensed ring is a 7 to 10 membered ring, and a particularly preferable condensed ring is a 7 membered ring.
R ⁸ need not be a particularly bulky group and represents a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group. Carbon number of a hydrocarbon group and a silicon-containing hydrocarbon group or a halogenated hydrocarbon group is usually 1-20, preferably 1-15, and most preferably 1-10.

  Specific examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclo Cycloalkyl groups such as propyl, cyclopentyl, cyclohexyl and methylcyclohexyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, arylalkenyl groups such as trans-styryl, phenyl and tolyl , Aryl groups such as dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl and 2-naphthyl.

  Specific examples of silicon-containing hydrocarbon groups include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, trialkylsilylmethyl groups such as trimethylsilylmethyl, triethylsilylmethyl, dimethylphenylsilylmethyl, dimethyltolylsilyl And di (alkyl) (aryl) silylmethyl groups such as methyl.

The halogenated hydrocarbon group is a compound in which a halogen atom is substituted at an arbitrary position of the above hydrocarbon group. Halogen is preferably fluorine, chlorine or bromine, among which fluorine or chlorine is preferred. Specific examples of the halogen-valent hydrocarbon include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2, 2, 1, 1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenyl Ethyl, 2-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4-bromophenyl, 2, 4-, 3, 5-, 2, 6, 2, , 5-difluorophenyl, 2, 4-, 3, 5, 5-, 2, 6-, 2,5-dichlorophenyl, 2, 4, 6-trifluoro Orophenyl, 2, 4, 6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 4-fluoronaphthyl, 4-chloronaphthyl, 2,4-difluoronaphthyl, heptafluoro-1-naphthyl, heptachloro-1-naphthyl, 2- 3-, 4-trifluoromethylphenyl, 2-, 3-, 4-trichloromethylphenyl, 2, 4-, 3, 5-, 2,6-, 2,5-bis (trifluoromethyl) phenyl, 2, 4-, 3, 5-, 2, 6, 6, 2, 5-bis (trichloromethyl) phenyl, 2, 4, 6-tris (trifluoromethyl) phenyl group, and the like.

n is 0 or an integer less than or equal to 2 times the carbon number of R ⁷ , and preferably 0 to 5. If n is 2 or greater, plural groups R ⁸ are may be the same as or different from each other. Moreover, when n is an integer greater than or equal to 2, R < ⁸ > may respectively connect and a new ring structure may be formed.
Q is a bridging group, and specific examples thereof include a divalent hydrocarbon group, or a silylene group, an oligosilylene group, or a germylene group, which may have a hydrocarbon group, It is any one of a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group, an oligosilylene group, or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above silylene group, oligosilylene group or germylene group, they may be bonded to each other to form a ring structure.

Specific examples of Q include alkylene groups such as methylene, dimethylmethylene, 1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene and the like. An arylalkylene group such as diphenylmethylene; a silylene group; an alkylsilylene group such as dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene; an aryl such as diphenylsilylene Silylene group; alkyl oligosilylene group such as tetramethyldisilylene; germylene group; alkylgermylene group in which silicon of silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; arylgermylene Examples include groups. Among these, an alkylene group having 1 to 20 carbon atoms, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable. , 2-ethylene, 1,4-tetramethylene, dimethylsilylene, diethylsilylene, diphenylsilylene, dimethylgermylene, diethylgermylene, diphenylgermylene are particularly preferred.

  X and Y are each independently a ligand that forms a σ bond with M. Specific examples thereof include a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing hydrocarbon group, an oxygen-containing hydrocarbon group, an amino group, a substituted amino group, or a nitrogen-containing hydrocarbon group. The hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, oxygen-containing hydrocarbon group, substituted amino group, and nitrogen-containing hydrocarbon group preferably have 1 to 20 carbon atoms.

The halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, Alkyl groups such as cyclohexyl and methylcyclohexyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, arylalkenyl groups such as trans-styryl, phenyl, tolyl, dimethylphenyl and ethyl Examples include aryl groups such as phenyl, trimethylphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl, and anthryl.

Specific examples of the oxygen-containing hydrocarbon group include alkoxy groups such as methoxy, ethoxy, propoxy, cyclopropoxy and butoxy, aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and arylalkoxy groups such as phenylmethoxy and naphthylmethoxy. And oxygen-containing heterocyclic groups such as a furyl group.
Specific examples of the substituted amino group or nitrogen-containing hydrocarbon group include alkylamino groups such as methylamino, dimethylamino, ethylamino and diethylamino, arylamino groups such as phenylamino and diphenylamino, and N-methyl-N-phenylamino. And N-alkyl-N-arylamino groups such as, and the like, and nitrogen-containing heterocyclic groups such as pyrazolyl and indolyl.

Examples of the halogenated hydrocarbon group include those in which a halogen atom is substituted at an arbitrary position of the above hydrocarbon group, and the halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2, 2, 2-trifluoroethyl, 2, 2, 1 , 1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, 2-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4-bromophenyl, 2, 4-, 3, 5-, 2, 6, 6, 2, 5-difluorophenyl 2, 4, 3, 5, 5, 2, 6, 6, 2, dichlorophenyl, 2, 4, 6 trifluorophenyl, 2, 4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 4-fluoronaphthyl, 4-chloronaphthyl, 2,4-difluoronaphthyl, heptafluoro-1-naphthyl, heptachloro-1-naphthyl, 2-, 3-, 4-trifluoromethylphenyl, 2-, 3-, 4-trichloromethylphenyl, 2,4-, 3,5-, 2,6-, 2,5-bis (trifluoromethyl) phenyl, 2,4- 3,5-, 2,6-, 2,5-bis (trichloromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl, 2, , 4-bis (trifluoromethyl) naphthyl group, and the like.

Specific examples of silicon-containing hydrocarbon groups include trialkylsilylmethyl groups such as trimethylsilylmethyl and triethylsilylmethyl, and di (alkyl) (aryl) silylmethyl groups such as dimethylphenylsilylmethyl, diethylphenylsilylmethyl, and dimethyltolylsilylmethyl. Etc.
Preferred X and Y are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group. Among these, a hydrogen atom, a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a benzyl group, a dimethylamino group or a diethylamino group is particularly preferable.

M represents a transition metal of Groups 4 to 6 of the periodic table, preferably, a Group 4 transition metal of titanium, zirconium, or hafnium, more preferably zirconium or hafnium.
Among the C1 symmetric transition metal compounds according to the present invention, a C1 symmetric transition metal compound represented by the following general formula (II) or (III), in which R ⁷ has 4 carbon atoms, is preferable.

In general formula (II), R < ¹ > -R < ⁶ >, R < ⁹ >, Q, X, and Y are synonymous with general formula (I). R ^{10 to} R ¹³ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group, or a halogenated hydrocarbon group, and adjacent substituents may form a ring with each other. M is a transition metal of Groups 4 to 6 of the periodic table, and Group 4 is preferred.

In general formula (III), R < ¹ > -R < ⁶ >, R < ⁹ >, Q, X, and Y are synonymous with general formula (I). R ^{14 to} R ²¹ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group, or a halogenated hydrocarbon group, and adjacent substituents may form a ring with each other. M is a transition metal of Groups 4 to 6 of the periodic table, and Group 4 is preferred.
Among the compounds represented by the general formula (II) or (III) according to the present invention, specific examples of those in which M is hafnium include the following transition metal compounds (1) to (92). Specific compounds (1) and (13) thereof are shown in the following formula (IV).
(Abbreviation: OHFlu: 1,2,3,4,5,6,7,8-octahydro-9-fluorenyl. TMCp: 2,3,4,5-tetramethylcyclopentadienyl. Azu: 4H-1- Azulenyl. THAzu: 5,6,7,8-tetrahydro-4H-1-azurenyl.)

(1) Dichloro [dimethylsilylene (OHFlu) (2-methyl-4-phenyl-Azu)] hafnium (2) Dichloro [dimethylsilylene (OHFlu) (2-methyl-4- (4-chlorophenyl) -Azu)] Hafnium (3) dichloro [dimethylsilylene (OHFlu) (2-ethyl-4-phenyl-Azu)] hafnium (4) dichloro [dimethylsilylene (OHFlu) (2-ethyl-4- (4-chlorophenyl) -Azu) ] Hafnium (5) dichloro [dimethylsilylene (OHFlu) (2-isopropyl-4-phenyl-Azu)] hafnium (6) dichloro [dimethylsilylene (OHFlu) (2-isopropyl-4- (4-chlorophenyl) -Azu] )] Hafnium (7) dichloro [dimethylsilylene (2,7-di) t-butyl-OHFlu) (2-methyl-4-phenyl-Azu)] hafnium (8) dichloro [dimethylsilylene (2,7-di-t-butyl-OHFlu) (2-methyl-4- (4-chlorophenyl) ) -Azu)] hafnium (9) dichloro [dimethylsilylene (2,7-di-t-butyl-OHFlu) (2-ethyl-4-phenyl-Azu)] hafnium (10) dichloro [dimethylsilylene (2,7) -Di-t-butyl-OHFlu) (2-ethyl-4- (4-chlorophenyl) -Azu)] hafnium (11) dichloro [dimethylsilylene (2,7-di-t-butyl-OHFlu) (2-isopropyl -4-phenyl-Azu)] hafnium (12) dichloro [dimethylsilylene (2,7-di-t-butyl-OHFlu) (2- Sopropyl-4- (4-chlorophenyl) -Azu)] hafnium (13) dichloro [dimethylsilylene (TMCp) (2,4-dimethyl-Azu)] hafnium (14) dichloro [dimethylsilylene (TMCp) (2-methyl -4-Isopropyl-Azu)] hafnium (15) dichloro [dimethylsilylene (TMCp) (2-methyl-4-n-butyl-Azu)] hafnium (16) dichloro [dimethylsilylene (TMCp) (2-methyl) -4-t-butyl-Azu)] hafnium (17) dichloro [dimethylsilylene (TMCp) (2-methyl-4-trimethylsilyl-Azu)] hafnium (18) dichloro [dimethylsilylene (TMCp) (2-methyl) -4-phenyl-Azu)] hafnium (19) dichloro [dimethylsilane Ren (TMCp) (2-methyl-4- (4-chlorophenyl) -Azu)] hafnium (20) dichloro [dimethylsilylene (TMCp) (2-ethyl-4-methyl-Azu)] hafnium (21) dichloro [21] Dimethylsilylene (TMCp) (2-ethyl-4-isopropyl-Azu)] hafnium (22) dichloro [dimethylsilylene (TMCp) (2-ethyl-4-n-butyl-Azu)] hafnium (23) dichloro [23] Dimethylsilylene (TMCp) (2-ethyl-4-t-butyl-Azu)] hafnium (24) dichloro [dimethylsilylene (TMCp) (2-ethyl-4-trimethylsilyl-Azu)] hafnium (25) dichloro [25] Dimethylsilylene (TMCp) (2-ethyl-4-phenyl-Azu)] hafnium (2 ) Dichloro [dimethylsilylene (TMCp) (2-ethyl-4- (4-chlorophenyl) -Azu)] hafnium (27) dichloro [dimethylsilylene (TMCp) (2-isopropyl-4-methyl-Azu)] hafnium (28) Dichloro [dimethylsilylene (TMCp) (2,4-diisopropyl-Azu)] hafnium (29) Dichloro [dimethylsilylene (TMCp) (2-isopropyl-4-n-butyl-Azu)] hafnium (30) dichloro [Dimethylsilylene (TMCp) (2-isopropyl-4-t-butyl-Azu)] hafnium (31) dichloro [dimethylsilylene (TMCp) (2-isopropyl-4-trimethylsilyl-Azu)] hafnium (32) dichloro [ Dimethylsilylene (TMCp) (2-isopropyl (Lopyl-4-phenyl-Azu)] hafnium (33) dichloro [dimethylsilylene (TMCp) (2-isopropyl-4- (4-chlorophenyl) -Azu)] hafnium (34) dichloro [isopropylene (OHFlu) (2 -Methyl-4-phenyl-Azu)] hafnium (35) dichloro [isopropylene (2,7-di-t-butyl-OHFlu) (2-methyl-4-phenyl-Azu)] hafnium (36) dichloro [iso Propylene (TMCp) (2-methyl-4-phenyl-Azu)] hafnium (37) dichloro [diphenylsilylene (OHFlu) (2-methyl-4-phenyl-Azu)] hafnium (38) dichloro [diphenylsilylene (2) , 7-di-t-butyl-OHFlu) (2-methyl-4-phenyl-A zu)] hafnium (39) dichloro [diphenylsilylene (TMCp) (2,4-dimethyl-Azu)] hafnium (40) dichloro [diphenylsilylene (TMCp) (2-methyl-4-t-butyl-Azu) ] Hafnium (41) dichloro [diphenylsilylene (TMCp) (2-methyl-4-fell-Azu)] hafnium (42) dichloro [dimethylgermylene (OHFlu) (2,4-dimethyl-A zu)] hafnium (43 ) Dichloro [dimethylgermylene (OHFlu) (2-methyl-4-t-butyl-Azu)] hafnium (44) dichloro [dimethylgermylene (OHFlu) (2-methyl-4-phenyl-Azu)] hafnium ( 45) Dichloro [dimethylgermylene (TMCp) (2,4-dimethyl-Azu) ] Hafnium (46) dichloro [dimethylgermylene (TMCp) (2-methyl-4-t-butyl-Azu)] hafnium (47) dichloro [dimethylgermylene (TMCp) (2-methyl-4-phenyl- Azu)] hafnium (48) dichloro [dimethylsilylene (OHFlu) (2-methyl-4-phenyl-THAzu)] hafnium (49) dichloro [dimethylsilylene (OHFlu) (2-methyl-4- (4-chlorophenyl)] -THAzu)] hafnium (50) dichloro [dimethylsilylene (OHFlu) (2-ethyl-4-phenyl-THAzu)] hafnium (51) dichloro [dimethylsilylene (OHFlu) (2-ethyl-4- (4-chlorophenyl) ) -THAzu)] hafnium (52) dichloro [dimethylsilane] Ren (OHFlu) (2-isopropyl-4-phenyl-THAzu)] hafnium (53) dichloro [dimethylsilylene (OHFlu) (2-isopropyl-4- (4-chlorophenyl) -THAzu)] hafnium (54) dichloro [dimethyl Silylene (2,7-di-t-butyl-OHFlu) (2-methyl-4-phenyl-THAzu)] hafnium (55) dichloro [dimethylsilylene (2,7-di-t-butyl-OHFlu) (2- Methyl-4- (4-chlorophenyl) -THAzu)] hafnium (56) dichloro [dimethylsilylene (2,7-di-t-butyl-OHFlu) (2-ethyl-4-phenyl-THAzu)] hafnium (57 ) Dichloro [dimethylsilylene (2,7-di-t-butyl-OHFlu) (2- Til-4- (4-chlorophenyl) -THAzu)] hafnium (58) dichloro [dimethylsilylene (2,7-di-t-butyl-OHFlu) (2-isopropyl-4-phenyl-THAzu)] hafnium (59 ) Dichloro [dimethylsilylene (2,7-di-t-butyl-OHFlu) (2-isopropyl-4- (4-chlorophenyl) -THAzu)] hafnium (60) dichloro [dimethylsilylene (TMCp) (2,4 -Dimethyl-THA zu)] hafnium (61) dichloro [dimethylsilylene (TMCp) (2-methyl-4-isopropyl-THAzu)] hafnium (62) dichloro [dimethylsilylene (TMCp) (2-methyl-4-n -Butyl-THAzu)] hafnium (63) dichloro [dimethylsilylene ( MCp) (2-methyl-4-t-butyl-THAzu)] hafnium (64) dichloro [dimethylsilylene (TMCp) (2-methyl-4-trimethylsilyl-THAzu)] hafnium (65) dichloro [dimethylsilylene ( TMCp) (2-methyl-4-phenyl-THAzu)] hafnium (66) dichloro [dimethylsilylene (TMCp) (2-methyl-4- (4-chlorophenyl) -THAzu)] hafnium (67) dichloro [dimethylsilylene (TMCp) (2-ethyl-4-methyl-THAzu)] hafnium (68) dichloro [dimethylsilylene (TMCp) (2-ethyl-4-isopropyl-THAzu)] hafnium (69) dichloro [dimethylsilylene (TMCp) (2-ethyl-4-n-butyl-THAz )] Hafnium (70) dichloro [dimethylsilylene (TMCp) (2-ethyl-4-t-butyl-THAzu)] hafnium (71) dichloro [dimethylsilylene (TMCp) (2-ethyl-4-trimethylsilyl-THAzu) )] Hafnium (72) dichloro [dimethylsilylene (TMCp) (2-ethyl-4-phenyl-THAzu)] hafnium (73) dichloro [dimethylsilylene (TMCp) (2-ethyl-4- (4-chlorophenyl)- THAzu)] hafnium (74) dichloro [dimethylsilylene (TMCp) (2-isopropyl-4-methyl-THAzu)] hafnium (75) dichloro [dimethylsilylene (TMCp) (2,4-diisopropyl-THAzu)] hafnium ( 76) Dichloro [dimethylsilyl (TMCp) (2-Isopropyl-4-n-butyl-THAzu)] hafnium (77) dichloro [dimethylsilylene (TMCp) (2-isopropyl-4-t-butyl-THAzu)] hafnium (78) dichloro [dimethylsilylene (TMCp) (2-Isopropyl-4-trimethylsilyl-THAzu)] hafnium (79) dichloro [dimethylsilylene (TMCp) (2-isopropyl-4-phenyl-THAzu)] hafnium (80) dichloro [dimethylsilylene (TMCp) ) (2-Isopropyl-4- (4-chlorophenyl) -THAzu)] hafnium (81) dichloro [isopropylene (OHFlu) (2-methyl-4-phenyl-THAzu)] hafnium (82) dichloro [isopropylene (2) , 7-ji-t-bu Til-OHFlu) (2-methyl-4-phenyl-THAzu)] hafnium (83) dichloro [isopropylene (TMCp) (2,4-dimethyl-THAzu)] hafnium (84) dichloro [isopropylene (TMCp) ( 2-methyl-4-t-butyl-THAzu)] hafnium (85) dichloro [isopropylene (TMCp) (2-methyl-4-phenyl-THAzu)] hafnium (86) dichloro [diphenylsilylene (OHFlu) (2- Methyl-4-phenyl-THAzu)] hafnium (87) dichloro [diphenylsilylene (2,7-di-t-butyl-OHFlu) (2-methyl-4-phenyl-THAzu)] hafnium (88) dichloro [diphenyl Silylene (TMCp) (2-methyl-4-phenyl-THA zu)] hafnium (89) dichloro [dimethylgermylene (OHFlu) (2-methyl-4-phenyl-THAzu)] hafnium (90) dichloro [dimethylgermylene (TMCp) (2,4-dimethyl-TH Azu) ] Hafnium (91) dichloro [dimethylgermylene (TMCp) (2-methyl-4-t-butyl-THAzu)] hafnium (92) dichloro [dimethylgermylene (TMCp) (2-methyl-4-phenyl- THAzu)] hafnium In order to use the C1-symmetric transition metal compound according to the present invention as a polymerization catalyst component, among the above-mentioned transition metal compounds (1) to (92), dichloro [dimethylsilylene (OHFlu) (2- Methyl-4-phenyl-THAzu)] hafnium, dichloro [dimethylsilylene (2,7-di) -T-butylOHFlu) (2-methyl-4-phenyl-THAzu)] hafnium, dichloro [dimethylsilylene (TMCp) (2,4-dimethyl-THAzu)] hafnium, dichloro [dimethylsilylene (TMCp) (2-methyl -4-phenyl-THAzu)] hafnium, dichloro [dimethylsilylene (TMCp) (2-ethyl-4-methyl-THAzu)] hafnium, dichloro [dimethylsilylene (TMCp) (2-ethyl-4-phenyl-THAzu)] Hafnium is preferred, and dichloro [dimethylsilylene (OHFlu) (2-methyl-4-phenyl-Azu)] hafnium, dichloro [dimethylsilylene (2,7-di-t-butylOHFlu) (2-methyl-4- Phenyl-Azu)] hafnium, dichloro [di Tylsilylene (TMCp) (2,4-dimethyl-Azu)] hafnium, dichloro [dimethylsilylene (TMCp) (2-methyl-4-phenyl-Azu)] hafnium, dichloro [dimethylsilylene (TMCp) (2-ethyl-4 -Methyl-Azu)] hafnium, dichloro [dimethylsilylene (TMCp) (2-ethyl-4-phenyl-Azu)] hafnium are also preferred.

When the C1 symmetric transition metal compound according to the present invention is used as a polymerization catalyst component, it may be used in combination of two or more thereof, and as an aspect thereof, two or more types may be mixed and used. It may be used to start the polymerization, and at the end of the first stage of polymerization or before the start of the second stage of polymerization, another transition metal compound may be newly added to continue the polymerization.
Further, a compound in which the central metal M of the compounds of the formulas (1) to (92) exemplified above is replaced with zirconium instead of hafnium can be used as the polymerization catalyst component.
(2) Method for Synthesizing Transition Metal Compound The C1-symmetric transition metal compound according to the present invention can be synthesized by any known method suitable for the purpose of the substituent or bond. A typical synthesis route is as shown in the following reaction formula. Incidentally, H ₂ R ^a and H ₂ R ^b in the reaction formulas, respectively, show the following such a structure.

(R ^{1 to} R ⁹ and n have the same meaning as defined in formula (I).)

Further, the metal salt of the above-mentioned cyclopentadienyl compound such as HR ^b Li can be synthesized by a method involving an addition reaction of an aryl group or the like as described in European Patent No. 694418, for example. Also good. Specifically, an aryl lithium compound or an alkyl lithium compound and an azulene compound are reacted in an inert solvent to form a lithium salt of a dihydroazurenyl compound. Examples of the alkyl lithium compound include methyl lithium, isopropyl lithium, n-butyl lithium, t-butyl lithium, and examples of the aryl lithium compound include phenyl lithium and chlorophenyl lithium. As the inert solvent, hexane, benzene, toluene, diethyl ether, diisopropyl ether, tetrahydrofuran, or a mixed solvent thereof is used.

The compound of the general formula (III) can also be obtained by hydrogenating the compound of the general formula (II). The solvent used in the hydrogenation may be any solvent that does not undergo hydrogenation or decompose the compound of the general formula (II). For example, halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane are preferred.
There are no particular limitations on the reaction temperature, reaction pressure, and reaction time, but usually optimum settings can be made in consideration of productivity and process capability from the following ranges. The reaction temperature is usually 0 ° C. or higher, preferably 10 ° C. or higher, and is usually 70 ° C. or lower, preferably 50 ° C. or lower. The reaction pressure is usually 0.01 MPa or more, preferably 0.03 MPa or more, most preferably 0.05 MPa or more, and usually 20 MPa or less, preferably 15 MPa or less, and most preferably 12 MPa or less. The reaction time is usually 0.1 hours or more, preferably 0.2 hours or more, most preferably 0.3 hours or more, and usually 30 hours or less, preferably 25 hours or less, most preferably 20 hours or less. . As the hydrogenation catalyst, platinum, platinum oxide, palladium, ruthenium, rhodium or a conventionally known transition metal catalyst can be used.
2. Olefin Polymerization Catalyst The C1-symmetric transition metal compound according to the present invention can be used as a catalyst component for olefin polymerization, and is particularly preferably used as a catalyst component for producing an α-olefin polymer. In order to use as a catalyst for the production of an α-olefin polymer, as a co-catalyst, (1) an organoaluminum oxy compound and (2) a C1 symmetric transition metal compound according to the present invention are reacted with the component as a cation. One or more substances selected from the group consisting of an ionic compound that can be exchanged with (3) a Lewis acid, (4) an ion-exchange layered compound excluding silicate, or an inorganic silicate are used. Is preferred.

Moreover, the alpha-olefin polymerization catalyst characterized by including the following component (A) and (B) and the component (C) arbitrarily is more preferable.
Component (A): C1-symmetric transition metal compound according to the present invention Component (B): an organic aluminum oxy compound, an ionic compound capable of reacting with component (A) to convert component (A) into a cation Alternatively, one or more compounds selected from the group consisting of Lewis acids Component (C): Fine particle carrier Hereinafter, Component (B) and Component (C) will be described.
Component (B): one or more compounds selected from the group consisting of an organoaluminum oxy compound, an ionic compound capable of reacting with component (A) to convert component (A) into a cation, or a Lewis acid;
(1) Organoaluminum oxy compound Specific examples of the organoaluminum oxy compound include compounds represented by the following general formulas (V), (VI), and (VII).

In each general formula, R ²² represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. Further, the plurality of R ²² may be the same or different. P represents an integer of 0 to 40, preferably 2 to 30.

  The compounds represented by the general formulas (V) and (VI) are also called aluminoxanes, and are obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminums with water. Specifically, (a) obtained from one kind of trialkylaluminum and water, obtained from methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, (b) obtained from two kinds of trialkylaluminum and water. And methylethylaluminoxane, methylbutylaluminoxane, and methylisobutylaluminoxane. Of these, methylaluminoxane and methylisobutylaluminoxane are preferred. A plurality of the above aluminoxanes can be used in combination. And said aluminoxane can be prepared on various conditions as well-known.

The compound represented by the general formula (VII) is 10: 1 to 1: 1 (one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the following general formula (VIII): (Molar ratio) reaction. In the general formulas (VII) and (VIII), R ²³ represents a hydrocarbon residue or halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
R ²³ B (OH) ₂ (VIII)
Specifically, the following reaction products are obtained: (a) a 2: 1 reaction product of trimethylaluminum and methylboronic acid, (b) a 2: 1 reaction product of triisobutylaluminum and methylboronic acid, (c) Examples include 1: 1: 1 reactant of trimethylaluminum, triisobutylaluminum and methylboronic acid, (d) 2: 1 reactant of trimethylaluminum and ethylboronic acid, (e) 2: 1 reactant of triethylaluminum and butylboronic acid, and the like. be able to.
(2) An ionic compound capable of reacting with a transition metal compound to convert the component into a cation A compound represented by the following general formula (IX) is exemplified.
[K] ^{e +} [Z] ^e- (IX)
In general formula (IX), K is a cation component, and examples thereof include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. Moreover, the cation of the metal which is easy to reduce itself, the cation of an organic metal, etc. are mentioned.

  Specific examples of the cation include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, Triphenylphosphonium, trimethylphosphonium, tris (dimethylphenyl) phosphonium, tris (dimethylphenyl) phosphonium, tris (methylphenyl) phosphonium, triphenylsulfonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, Gold ion, platinum ion, copper ion, palladium ion, mercury ion, ferrocenium ion, etc. .

  In the above general formula (IX), Z is an anion component, which is a component (generally a non-coordinating component) that becomes a counter anion with respect to the cation species into which the transition metal compound is converted. Examples of Z include an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic arsenic compound anion, and an organic antimony compound anion. Specific examples include the following compounds. (A) tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis {3,5-bis (trifluoromethyl) phenyl} boron, tetrakis {3,5-di (t-butyl) ) Phenyl} boron, tetrakis (pentafluorophenyl) boron, etc. (b) tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) aluminum, tetrakis {3,5-bis (trifluoromethyl) phenyl} aluminum , Tetrakis {3,5-di (t-butyl) phenyl} aluminum, tetrakis (pentafluorophenyl) aluminum and the like.

(C) tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis {3,5-bis (trifluoromethyl) phenyl} gallium, tetrakis {3,5-di (t-butyl) ) Phenyl} gallium, tetrakis (pentafluorophenyl) gallium, etc. (d) tetraphenyl phosphorus, tetrakis (pentafluorophenyl) phosphorus, etc. (e) tetraphenyl arsenic, tetrakis (pentafluorophenyl) arsenic, etc. (f) tetra Examples thereof include phenylantimony, tetrakis (pentafluorophenyl) antimony, (g) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate and the like.
(3) Lewis acid In particular, as the Lewis acid capable of converting a transition metal compound into a cation, various organic boron compounds, metal halogen compounds, solid acids and the like are exemplified, and specific examples thereof include the following compounds. (A) organoboron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron, tris (pentafluorophenyl) boron, (b) aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, Metals such as magnesium bromide, magnesium iodide, magnesium chlorobromide, magnesium chloroiodide, magnesium bromoiodide, magnesium chloride hydride, magnesium chloride hydroxide, magnesium bromide hydroxide, magnesium chloride alkoxide, magnesium bromide alkoxide Examples thereof include halogen compounds, (c) solid acids such as alumina and silica / alumina.

Component (C): Fine particle carrier A fine particle carrier may coexist as an optional component. The fine particle carrier is made of an inorganic or organic compound, and is usually a fine particle carrier having a particle diameter of 5 μm or more, preferably 10 μm or more, and usually 5 mm or less, preferably 2 mm or less.
Examples of inorganic carriers include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ ,
Oxides such as ZnO, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂
And composite metal oxides such as —Cr ₂ O ₃ and SiO ₂ —Al ₂ O ₃ —MgO. These specific surface areas are usually 20 m ³ / g or more, preferably 50 m ³ / g or more, and usually 1,000 m ³ / g or less, preferably 700 m ³ / g or less. The pore volume is usually 0.1 cm ² / g
As mentioned above, Preferably it is 0.3 cm < ² > / g or more, More preferably, it is 0.8 cm < ² > / g or more.

Examples of the organic carrier include (co) polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturation such as styrene and divinylbenzene. Examples thereof include porous polymer fine particle carriers made of (co) polymers such as hydrocarbons.
In addition, an α-olefin polymerization catalyst characterized by containing the following component (A) and component (D) and optionally component (E) is also preferably used.

Component (A): C1-symmetric transition metal compound according to the present invention Component (D): Compound selected from the group consisting of an ion-exchange layered compound excluding silicate and inorganic silicate Component (E): Organoaluminum compound Component (D) and component (E) will be described.

Component (D): A compound selected from the group consisting of ion-exchange layered compounds excluding silicates and inorganic silicates. Ion-exchange layered compounds excluding silicates have weak bonding forces due to their ionic bonds. It is a compound that has a crystal structure that is stacked in parallel with each other and that contains exchangeable ions.

Examples of the ion-exchangeable layered compound excluding silicate include an ion-crystalline compound having a layered crystal structure such as a hexagonal close-packed type, an antimony type, a CdCl ₂ type, and a CdI ₂ type. Specifically, α-Zr (HAsO ₄ ) · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) Examples thereof include crystalline acidic salts of polyvalent metals such as ₂ · H ₂ O.

Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. A synthetic product may be used for these, and the mineral produced naturally may be used.
Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, chrysotile, lizardite and antigolite serpentine. Stone group, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, etc. Examples include clay, gyrome clay, hysingelite, pyrophyllite, and ryokdeite group. These may form a mixed layer.

Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.
Among these specific examples, preferably, kaolins such as dickite, nacrite, kaolinite, anorcite, halosites such as metahalosite, halosite, chrysotile, lizardite, serpentine such as antigolite, montmorillonite, Sauconite, beidellite, nontronite, saponite, hectorite and other smectites, vermiculite minerals such as vermiculite, illite, sericite, mica minerals such as sea chlorite, synthetic mica,
Synthetic hectorite, synthetic saponite, synthetic teniolite, and particularly preferably montmorillonite, sauconite, beidellite, nontronite, saponite, smectite such as hectorite, vermiculite mineral such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite, Synthetic teniolite.

These ion-exchange layered compounds excluding silicates or inorganic silicates may be used as they are. However, acid treatment with hydrochloric acid, nitric acid, sulfuric acid, etc. and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , It is preferable to carry out salt treatment such as Li ₂ SO ₄ , MgSO ₄ , ZnSO ₄ , Ti (SO ₄ ) ₂ , Zr (SO ₄ ) ₂ , Al ₂ (SO ₄ ) ₃ . In the treatment, the corresponding acid and base may be mixed to produce a salt in the reaction system. In addition, shape control such as pulverization and granulation may be performed, and granulation is preferable in order to obtain a solid catalyst component having excellent particle fluidity. The above components are usually used after being dehydrated and dried. As these co-catalyst components, it is preferable to use an ion-exchange layered compound or inorganic silicate excluding the silicate (4) in terms of catalyst performance such as polymerization activity.

Component (E): Organoaluminum compound In the polymerization catalyst according to the present invention, it is an optional component of the promoter. Such an organoaluminum compound is AlR ²⁴ _m Z _3-m (wherein R ²⁴ is a hydrocarbon group having 1 to 20 carbon atoms, Z is hydrogen, halogen, alkoxy group or aryloxy group, m is 0) <Number of m ≦ 3).

Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, or halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride, diethylaluminum ethoxide, diethylaluminum hydride, diisobutylaluminum Hydrogen-containing organoaluminum compounds such as hydride. In addition, aluminoxane such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred. Two or more of these optional components may be used in combination. Moreover, you may add this arbitrary component newly after superposition | polymerization start.
3. Method for Producing Olefin Polymerization Catalyst The catalyst according to the present invention can be obtained by contacting the above transition metal compound and, if necessary, a co-catalyst, but the contact method is not particularly limited. This contact may be performed not only during catalyst preparation but also during prepolymerization or polymerization of propylene.

Further, the fine particle carrier may be allowed to coexist or contact when the catalyst components are in contact with each other or after the contact.
The contact may be performed in an inert gas such as nitrogen, or may be performed in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene. It is preferable to use those solvents which have been subjected to an operation for removing poisoning substances such as water and sulfur compounds. The contact temperature is between -20 ° C. and the boiling point of the solvent used, and particularly preferably between room temperature and the boiling point of the solvent used.

  The ratio of each catalyst component used is not particularly limited, but when an ion-exchange layered compound excluding silicate or an inorganic silicate is used as a promoter component, the transition metal compound is 0 per 1 g of the promoter component. 0.0001 to 10 mmol, preferably 0.001 to 5 mmol, and by setting the organoaluminum compound as an optional component to be 0 to 10,000 mmol, preferably 0.01 to 100 mmol, the point of polymerization activity, etc. A favorable result can be obtained. The atomic ratio of the transition metal in the transition metal compound to the aluminum in the organoaluminum compound as an optional component is 1: 0 to 1,000,000, preferably 1: 0.1 to 100,000. Similarly, it is preferable in terms of polymerization activity.

The catalyst thus obtained may be used after washing with an inert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, toluene, xylene, or may be used without washing. Good.
At the time of washing, the above-described organoaluminum compound may be newly used in combination as necessary. The amount of the organoaluminum compound used in this case is preferably 1: 0 to 10,000 in terms of the atomic ratio of aluminum in the organoaluminum compound to the transition metal in the transition metal compound.

As the catalyst, a prepolymer obtained by preliminarily polymerizing an α-olefin having a low molecular weight such as ethylene or propylene and washing it as necessary can also be used. This prepolymerization may be carried out in an inert gas such as nitrogen, or in an inert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, toluene, or xylene.
4). Olefin Polymerization Method As the raw material olefin, an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, is used, and specific examples thereof include ethylene, propylene, 1-butene, 4-methyl- Examples include 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Among them, ethylene, propylene and 1-hexene are preferable. Butene is mentioned.

  Examples of other olefin monomers copolymerizable with α-olefin include butadiene, 1,4-hexadiene, 1,5-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene, 1 , Conjugated and non-conjugated dienes such as 9-decadiene, and cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, norbornene and dicyclopentadiene.

In the polymerization, so-called multistage polymerization in which conditions are changed in multiple stages, for example, so-called block copolymerization in which propylene is polymerized in the first stage and ethylene and propylene are copolymerized in the second stage is possible.
A solvent may or may not be used in the reaction. Specific examples of the solvent include n-pentane, n-hexane, n-heptane, n-octane, n-decane, benzene, toluene, xylene, cyclohexane and methyl. Hydrocarbons such as cyclohexane and dimethylcyclohexane, halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, tetrachloroethane, chlorobenzene and o-dichlorobenzene, n-butyl acetate, methyl isobutyl ketone, tetrahydrofuran and cyclohexanone And polar solvents such as dimethyl sulfoxide. Of these, hydrocarbons are preferred. Moreover, you may use the mixture of the compound described here as a solvent.

The catalyst for polyolefin production of the present invention is applied not only to solvent polymerization using the above-described solvents, but also to liquid-phase solventless polymerization, gas phase polymerization, and melt polymerization that substantially use no solvent. The polymerization method may be either continuous polymerization or batch polymerization.
Although the catalyst concentration is not particularly limited, for example, when the reaction method is solution polymerization, it is usually 100 g or less, preferably 50 g or less, and most preferably 25 g or less with respect to 1 L of the reaction solution. Usually, it is 0.01 mg or more, preferably 0.05 mg or more, and most preferably 0.1 mg or more.

The polymerization temperature, polymerization pressure, and polymerization time are not particularly limited, but usually optimum settings can be made in consideration of productivity and process capability from the following ranges. That is, the polymerization temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, more preferably 70 ° C. or higher, particularly preferably 80 ° C. or higher, and usually 150 ° C. or lower, preferably 100 ° C. or lower. The polymerization pressure is usually 0.01 MPa or more, preferably 0.05 MPa or more, most preferably 0.1 MPa or more, and is usually 100 MPa or less, preferably 20 MPa or less, and most preferably 5 MPa or less. The polymerization time is usually 0.1 hours or more, preferably 0.2 hours or more, most preferably 0.3 hours or more, and usually 30 hours or less, preferably 25 hours or less, more preferably 20 hours or less, most preferably Preferably it is 15 hours or less.
5). Propylene Polymer In this way, a polyolefin is obtained. When propylene is used as an olefin, a propylene polymer having a vinyl group at the terminal is obtained.
(1) Number average molecular weight The number average molecular weight Mn of the propylene-based polymer is 500 or more, preferably 1,000 or more, more preferably 5,000 or more, and usually 200,000 or less, preferably 150, in terms of GPC weight average. 000 or less, more preferably 100,000 or less.

If the weight average molecular weight is small, the stickiness becomes worse and the handling becomes worse.
(2) Proportion of pentad expressed in mmmm The propylene-based polymer observes a peak derived from the carbon atom of the methyl group of the propylene unit chain part composed of a head-to-tail bond in ¹³ C-NMR, and in mmmm When the chemical shift of the peak top of the peak attributed to the pentad represented is 21.8 ppm, the peak having a peak top of 21.8 ppm with respect to the total area S of peaks appearing at 19.8 ppm to 22.2 ppm The area S ₁ ratio is 70% or more, preferably 80% or more, and is usually 99%.
% Or less.

The ratio of mmmm of the propylene polymer in the present invention means the ratio of mmmm in the propylene polymerized portion in the propylene polymer. The ratio of mmmm is the peak of the peak attributed to the pentad represented by mmmm, as measured by ¹³ C-NMR, observing the peak derived from the carbon atom of the methyl group of the propylene unit chain part consisting of the head-to-tail bond. When the top chemical shift is 21.8 ppm, it is obtained by the ratio of the peak area S ₁ having 21.8 ppm as the peak top to the total area S of peaks appearing at 19.8 ppm to 22.2 ppm.

Here, the ¹³ C-NMR measurement method of the propylene-based polymer of the present invention is as follows. 100-500 mg of sample is completely dissolved in about 10 ml of NMR sample tube using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene is added as a lock solvent and homogenized, and then measurement is performed at 130 ° C. by a proton complete decoupling method. The measurement conditions are a flip angle of 90 ° and a pulse interval of 5T ₁ or more (T ₁ is the longest value of the spin-lattice relaxation time of the methyl group). In the propylene polymer, since the spin-lattice relaxation time of the methylene group and methine group is shorter than that of the methyl group, the recovery of the magnetization of all the carbons is 99% or more under this measurement condition.

The chemical shift is a methyl branch of 10 types of pentads (mmmm, mmmr, rmrr, mmrr, mmrm, rmrr, rmrm, rrrr, rrrr, mrrm) of propylene unit linkages composed of head-to-tail bonds. The absolute chemical configuration of all is the same, that is, the chemical shift of the peak based on the methyl group of the third unit of the 5-unit propylene unit expressed in mmmm is set as 21.8 ppm, and other carbon peaks are set based on this. Determine the chemical shift. According to this standard, for example, in the case of other five propylene units, the chemical shift of the peak based on the methyl group of the third unit is generally as follows. That is, mmmr: 21.5 to 21.7 ppm, rmmr: 21.3 to 21.5 ppm, mmrr: 21.0 to 21.1 ppm, mmrm and rmrr: 20.8 to 21.0 ppm, rmrm: 20.6 to 20.8 ppm, rrrr: 20.3-20
. 5 ppm, rrrm: 20.1 to 20.3 ppm, mrrm: 19.9 to 20.1 ppm. The chemical shift of the peak derived from these pentads varies somewhat depending on the NMR measurement conditions, and the peak is not necessarily a single peak, but a complex splitting pattern based on a fine structure ( It should be noted that the split pattern) is often shown.

In order for the olefin polymer to be produced to satisfy these conditions, a conventionally known method used when polymerization is performed using a known metallocene catalyst can be used. That is, in order to adjust the molecular weight, a method of adjusting the molecular weight by controlling the polymerization temperature, or a method of adjusting the molecular weight by controlling the monomer concentration. In order to adjust the pentad, the reaction temperature, raw material concentration, solvent and the like may be adjusted.
(3) Terminal vinyl group The propylene-based polymer has at least 10% or more vinyl group at the terminal, preferably 40% or more, more preferably 60% or more, still more preferably 80% or more, particularly 90% or more. Those having very high terminal vinyl groups can be obtained. In the present invention, the ratio having a vinyl group at the terminal is the ratio of the polymer chain having a vinyl group at the terminal to the total polymer chain.

The proportion of the polymer chain having a vinyl group at the terminal can be determined by determining the terminal structure of the propylene polymer by ¹³ C-NMR and ¹ H-NMR. ¹ H-NMR may be measured according to a conventional method. The homopolymer of propylene includes the following terminal structures (I) to (VI).

The attribution of the partial structure was based on the following non-patent literature.
Macromolecules, 25, 3356 (1992).
Macromolecules, 31, 3783 (1998).
Organometallics, 20, 3436 (2001).
The abundance ratio of the olefin of each terminal structure is determined from the integrated value of the following peak values obtained from ¹ H-NMR measurement. The terminal structure (I) is δ 4.78 to 4.66 (2H) B1), the terminal structure (II) is δ 4.98 to 4.97 (1H) B2), and the terminal structure (III) is δ 4.89 to 5. 07 (2H) B3) (when terminal structure (II) is present, peaks overlap so that δ 5.70-5.90 (1H) B3) ′), and terminal structure (IV) is δ 5.35-5.55. (1H) B
4).

The proportion of the terminal structure (III) in all olefins can be obtained from the following formula.
100 * B3) / (B1) + 2 * B2) + B3) + 2 * B4))
(When determining the proportion of other partial structures, pay attention to the ratio of hydrogen, B3 of the molecule)
Replace the integral value of the substructure you want to find at. )
The abundance ratio of each terminal structure is determined from the integrated value of the following peaks obtained from ¹³ C-NMR measurement. Terminal structure (I) is δ111.6 (position 1) A1), terminal structure (II) is δ18.0 (position 1 (trans position)) A2), and terminal structure (III) is δ115.6 (position 1) A3 ), Terminal structure (IV) is δ124.0 (position 2) A4), terminal structure (V) is δ14.6 (position 1) A5), and terminal structure (VI) is δ26.0 (position 1) A6).

The proportion of terminal vinyl (terminal structure (III)) in all polymer chains can be obtained from the following formula. 100 * A3) / {(1/2) (A1) + A2) + A3) + A4) + A5) + A6))}
(When calculating the ratio of other partial structures, the integral value of the partial structure to be calculated may be replaced at the position A3 of the molecule). )
In addition, the ratio of the terminal partial structure (terminal structure (V) and / or (VI)) having only an alkyl group can be obtained by the following formula.

100 * (1/2) * {(A5) + A6))-(A1) + A2) + A3) + A4))} / {(1/2) (A1) + A2) + A3) + A4) + A5) + A6))}
The proportion of the polymer chain whose terminal portion is composed solely of an alkyl group (terminal structure (V) and / or (VI)) is preferably 20% or less, and more preferably 15% or less.
When the catalyst of the present invention is used, a novel propylene polymer having a vinyl group at the terminal satisfying the following conditions (a) to (c) can be obtained.
(A) The number average molecular weight Mn measured by GPC is 1,000 or more and less than 100,000.
(B) In ¹³ C-NMR, a peak derived from the carbon atom of the methyl group of the propylene unit chain part consisting of a head-to-tail bond was observed, and the peak top chemical attributed to the pentad represented by mmmm When the shift is 21.8 ppm, the ratio of the peak area S ₁ having 21.8 ppm as the peak top to the total area S of peaks appearing at 19.8 ppm to 22.2 ppm is 70% or more and 99% or less. is there.
(C) The ratio of the terminal vinyl group to the terminal olefin is 90% or more.

Moreover, the novel propylene polymer which has the vinyl group at the terminal satisfy | filling the following conditions (d)-(f) is obtained.
(D) The number average molecular weight Mn measured by GPC is 20,000 or more and less than 100,000.
(E) In ¹³ C-NMR, a peak derived from the carbon atom of the methyl group of the propylene unit chain part consisting of a head-to-tail bond was observed, and the peak top chemical attributed to the pentad represented by mm mm When the shift is 21.8 ppm, the ratio of the peak area S ₁ having 21.8 ppm as the peak top to the total area S of peaks appearing at 19.8 ppm to 22.2 ppm is 70% or more and 99% or less. is there.
(F) The ratio of the terminal vinyl group to the terminal olefin is 80% or more.

Moreover, the novel propylene polymer which has the vinyl group at the terminal which satisfy | fills the following conditions (g)-(i) is obtained.
(G) The number average molecular weight Mn measured by GPC is 60,000 or more and less than 100,000.
(H) In ¹³ C-NMR, a peak derived from the carbon atom of the methyl group of the propylene unit chain part consisting of a head-to-tail bond was observed, and the peak top chemical attributed to the pentad represented by mmmm When the shift is 21.8 ppm, the ratio of the peak area S ₁ having 21.8 ppm as the peak top to the total area S of peaks appearing at 19.8 ppm to 22.2 ppm is 70% or more and 99% or less. is there.
(I) The ratio of the terminal vinyl group to the terminal olefin is 60% or more.
(4) Positional Irregular Units The propylene-based polymer of the present invention mainly includes positional irregular units based on 2,1-inserted propylene monomers and / or 1,3-inserted propylene monomers. It may be present in the chain. The sum of the ratios of the position irregular units based on 2,1-insertion and 1,3-insertion relative to the total propylene insertion may be a physical property satisfying the use of the produced polymer, and the ratio is 0.01%. Above, preferably 0.03% or more, usually 3% or less, preferably 2.5% or less.

The abundance ratio of the position irregular units in the propylene-based polymer is determined as follows.
The polymerization of propylene usually proceeds with a 1,2-insertion where the methylene group binds to the active site of the catalyst, but in rare cases it may have a 2,1-insertion or a 1,3-insertion. The propylene monomer polymerized by 2,1-insertion forms position irregular units represented by the following partial structures (I) and (II) in the polymer main chain. The propylene monomer polymerized by 1,3-insertion forms a position irregular unit represented by the following partial structure (III) in the polymer main chain.

  The ratio of the 2,1-inserted propylene monomer to the total propylene insertion and the ratio of the 1,3-inserted propylene monomer are calculated by the following equations.

In the formula, ΣI (xy) represents the sum of integral intensities of signals appearing from xppm to yppm in the ¹³ C-NMR spectrum, and ΣI (CH ₃ ) represents the integral of signals derived from all methyl groups excluding terminals. Intensity sum. This is obtained by the following equation.

The signal appearing at 14.5 to 18.0 ppm is derived from the carbon of the methyl group of 2,1-inserted propylene, and the signal appearing at 19.5 to 24.4 ppm is 1,2-inserted. Derived from the carbon of the methyl group of propylene. The signal appearing at 27.5 to 28.0 ppm is derived from two methylene carbons in 1,3-inserted propylene.
(5) Copolymerization component The proportion of propylene in the propylene-based polymer is not particularly limited, but is usually 50 mol% or more, preferably 60 mol%, more preferably 70 mol% or more, and further preferably 80 mol% or more.

The copolymer component is not particularly limited, but ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, Α-olefins such as octadecene and 1-eicosene; conjugates of butadiene, 1,4-hexadiene, 1,5-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene, 1,9-decadiene, etc. And non-conjugated dienes; and cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, norbornene, and dicyclopentadiene. The carbon number of the copolymerization component is usually 2 or more, usually 15 or less, preferably 8 or less. Among these, α-olefins are preferable, α-olefins having 2 to 6 carbon atoms are more preferable, and ethylene and 1-butene are particularly preferable.
6). Uses The obtained propylene-based polymer can be used as various industrial raw materials because it has a highly reactive terminal vinyl group.

  Alkanol can be obtained by hydroborating the terminal vinyl polymer, followed by oxidation and hydrolysis. The hydroboration reaction may be carried out, for example, by adding an excess borane / tetrahydrofuran solution to the amount of terminal vinyl and reacting at 30 to 80 ° C. for 1 to 8 hours. The oxidation reaction is preferably performed using hydrogen peroxide, oxygen or the like. Moreover, it is preferable to perform a hydrolysis reaction in presence of alkalis, such as sodium hydroxide and potassium hydroxide.

  An alkylene oxide can be obtained by reacting the terminal vinyl polymer with a peracid. Examples of the peracid used here include perbenzoic acid, metachloroperbenzoic acid, perphthalic acid, performic acid, and peracetic acid. The reaction between the terminal vinyl oligomer and the peracid may be carried out using 0 to 50 ° C. for 1 to 50 hours using an excess of peracid and using a solvent such as chloroform and cyclohexane. By this reaction, a polymer having an epoxy group at the terminal is obtained.

If the terminal vinyl polymer is reacted with maleic anhydride, a polymer having maleic acid added to the terminal can be obtained. This reaction is preferably carried out in a solvent such as toluene or o-dichlorobenzene at 100 to 250 ° C. for 5 to 50 hours.
The modified polymer can be used as a polymer having a special function excellent in compatibilizer, adhesive, paintability and the like.

  In addition, the functional group of the polymer modified in this manner can be used as a polymerization starting point of a polar monomer or the like. A block copolymer produced by polar monomer block copolymerization can also be used as a polymer having a special function excellent in compatibilizer, adhesive, paintability and the like.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, the catalyst synthesis step and the polymerization step are all performed under a purified nitrogen atmosphere, and the solvent is molecular sieve (M
After dehydration in S-4A), the product was degassed by bubbling with purified nitrogen.
Moreover, in order to evaluate the physical property of the obtained polymer, molecular weight and melting | fusing point were measured on the conditions as described in (1) and (2), and the < ¹³ > C-NMR spectrum was measured on the conditions in a specification. (1) Measurement of molecular weight:
The weight average molecular weight obtained by GPC was measured. As the GPC apparatus, “150CV type” manufactured by Waters was used. The solvent was orthodichlorobenzene, and the measurement temperature was 135 ° C.
(2) Melting point measurement:
Using DSC ("TA2000 type" manufactured by DuPont), the temperature was raised and lowered from 20 to 200 ° C. at 10 ° C./min once and then obtained by measurement at the second temperature increase.
[Synthesis Example 1]
Dichloro [dimethylsilylene (1,2,3,4,5,6,7,8-octahydro-9-fluorenyl) (2-methyl-4-phenyl-5,6,7,8-tetrahydro-4H-1- Synthesis of azulenyl)] hafnium (1) Synthesis of 2,3-cyclotetramethyleneindan-1-one A 500 mL round bottom flask equipped with a reflux condenser, thermometer, and dropping funnel was charged with polyphosphoric acid (200 g) and benzoic acid (50 0.0 g, 0.409 mol). A mechanical stirrer was attached to the flask, and the contents were heated to 80 ° C. while stirring slowly. While maintaining the temperature at 90 ° C. or higher, cyclohexene (45 mL, 0.433 mol) was added dropwise using a dropping funnel, and the dark red reaction mixture was further stirred at 80-90 ° C. for 3.5 hours. The reddish brown mixture was allowed to cool to about 35 ° C. and poured into 300 mL of saturated ammonium sulfate solution with vigorous stirring. The mixture was cooled to room temperature and extracted three times with diethyl ether (200 mL). The extract was washed with saturated aqueous sodium carbonate solution (200 mL x 2) and saturated brine, dried over magnesium sulfate, and filtered. The solvent was removed with an evaporator to obtain 78 g of a crude product. The crude product was passed through a silica gel-60 column using n-hexane / ethyl acetate (v / v = 100/5) as an eluent. The product fractions were collected and the solvent was removed by evaporator to give a red oil (34 g, 43% yield).
(2) Synthesis of 1-hydroxy-2,3-cyclotetramethyleneindan 2,3-cyclotetramethyleneindan-1-one (30.0 g, 0.161 mol) was added to tetrahydrofuran / methanol (v / v = 2/1). 270 mL) and cooled to 0 ° C. Sodium borohydride (9.15 g, 0.242 mol) was introduced in portions at 0 ° C. over 105 minutes. The mixture was stirred at room temperature overnight, then dropped on ice (200 g), and adjusted to pH = 1 with 1N hydrochloric acid. The organic layer was separated and the aqueous layer was extracted 3 times with ether (300 mL). The organic layers were combined, washed with saturated brine, dried over magnesium sulfate, and filtered. The solvent was distilled off with a rotary evaporator to obtain an orange oil. This was recrystallized from n-hexane, washed and dried to obtain a white powder (6.38 g, 0.0339 mol, yield 21.0%).
(3) Synthesis of 2,3-cyclotetramethyleneindene 1-hydroxy-2,3-cyclotetramethyleneindane (10.0 g, 53.1 mmol) was dissolved in toluene (100 mL), and p-toluenesulfonic acid, one Hydrate (0.1 g) was introduced. The mixture was refluxed for 2 hours, washed with sodium hydrogen carbonate at room temperature, then with brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed with a rotary evaporator to obtain a brown oil (9.01 g). This was developed with a silica gel-60 column using n-hexane as a solvent to remove the coloring component, and _Rf = 0.
47 fractions were collected. The obtained fraction was dried and pale yellow oil (7
. 10 g) was obtained. This was recrystallized from n-hexane, washed and dried to obtain a white powder (5.19 g, yield 57.4%).
(4) Synthesis of lithium [2,3-cyclotetramethylene indenyl] salt 2,3-cyclotetramethylene indene (5.17 g, 30.4 mmol) was dissolved in n-hexane (110 mL), and n -N-hexane solution of butyllithium (1.58
M, 20 mL, 31.6 mmol) was added dropwise. The mixture was stirred at room temperature overnight and then refluxed for 4 hours. Thereafter, the supernatant was removed with a cannula at 55 ° C. The white solid was washed twice with 55 ° C. dehydrated n-hexane (50 mL) and dried to a constant weight. A white solid (5.27 g, yield 98.4%) was obtained.
(5) Synthesis of dimethylsilyl (2,3-cyclotetramethylene-1-indenyl) chloride (4) The salt (4.53 g, 25.7 mmol) prepared in (4) was dissolved in dehydrated tetrahydrofuran (125 mL). The solution was added dropwise over 110 minutes to a dehydrated tetrahydrofuran (125 mL) solution of dimethylsilyl dichloride (30 mL, 250 mmol) cooled to −5 to 0 ° C. After stirring at 0 ° C. for 15 minutes, the mixture was stirred at room temperature for 1 hour. Under reduced pressure, the solvent and unreacted dimethylsilyl dichloride were distilled off, and dehydrated n-hexane (40 mL) was introduced into the residue and suspended. After the solid portion was allowed to settle, the liquid portion was extracted with a cannula, and the solid portion was washed twice with dehydrated hexane (13 mL). The liquid parts were combined and dried under reduced pressure until a constant weight was reached. An orange oil (6.72 g, 99.6% yield) was obtained.
(6) Synthesis of lithium [2-methyl-4-phenylazurenyl] salt 2-Methylazulene (2.65 g, 18.7 mmol) was dissolved in dehydrated hexane (70 mL), cooled to 0 ° C., and then at the same temperature. The solution of phenyllithium in cyclohexane / diethyl ether (0.94M, 19.9 mL, 18.7 mmol) was added dropwise. After completion of dropping, the reaction was allowed to proceed at room temperature for 2 hours. Thereafter, the mother liquor was extracted, and the precipitate was washed with dehydrated hexane (20 mL × 2). And lithium salt (4.24g, 18.7mmol) was obtained by drying.
(7) Synthesis of dimethyl (2,3-cyclotetramethylene-1-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl) silane Dimethylsilyl (2,3-cyclotetra) prepared in (5) Methylene-1-indenyl) chloride (4.92 g, 18.7 mmol) was dissolved in dehydrated tetrahydrofuran / dehydrated diethyl ether (v / v = 1/1, 60 mL). It was introduced at 0 ° C. into a solution of N-methylimidazole (25 μL) added to a solution of lithium salt prepared in (1) in dehydrated tetrahydrofuran / dehydrated diethyl ether (v / v = 1/1, 60 mL), The mixture was stirred at 0 ° C. for 1 hour and further at room temperature for 3 hours. After completion of the stirring, the volatile component was distilled off under reduced pressure to obtain a dark oil. The product showed R _f1 = 0.64 and R _f2 = 0.46 by TLC (hexane development). Water (100 mL) was introduced here and extracted with n-hexane. The extract was dried over anhydrous magnesium sulfate and filtered to obtain a brown oil. This was developed with silica gel-60 inactivated with tetrahydrofuran (n-hexane development). The dark purple band was fractionated to obtain a ligand (6.42 g, 14.4 mmol, yield 77.0%).
(8) Ligand obtained by synthesis (7) of dilithio [(2,3-cyclotetramethylene-1-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl) dimethylsilane] (6. 42 g, 14.4 mmol) was dissolved in dehydrated n-hexane (200 mL), cooled to 0 ° C., and then n-hexane solution of n-butyllithium (1.57 M, 19.2 mL, 30.1 mmol) at the same temperature. Was dripped. After completion of dropping, the mixture was stirred overnight at room temperature and further refluxed for 6 hours. The yellowish brown suspension was cannulated filtered, and the residue was washed twice with dehydrated hexane (30 mL) and dried to obtain a pale orange powder (6.41 g, 14.0 mmol, yield 97.0%).
(9) Synthesis of dichloro [dimethylsilylene (2,3-cyclotetramethylene-1-indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)] hafnium Ligand obtained in (8) Salt (0.918 g, 2.00 mmol) and hafnium tetrachloride (0.641 g, 2.00 mmol) were weighed in a nitrogen atmosphere glove box and introduced into a 300 mL round bottom flask. The flask was cooled to -10 ° C. While stirring, dehydrated toluene (120 mL) and dehydrated diethyl ether (20 mL) were added to obtain a homogeneous solution. The temperature was slowly raised to room temperature and stirred overnight. After completion of the stirring, the reaction solution was filtered through Celite, and the Celite was further washed twice with dehydrated toluene (15 mL). This solid was washed twice with dehydrated pentane (10 mL), washed three times with dehydrated pentane / dehydrated diethyl ether (v / v = 1/1, 10 mL), dried and brown solid (0.830 g, 1.20 mmol, Yield 60%).
(10) Dichloro [dimethylsilylene (1,2,3,4,5,6,7,8-octahydro-9-fluorenyl) (2-methyl-4-phenyl-5,6,7,8-tetrahydro-4H -1-Azulenyl)] The complex (142 mg, 0.204 mmol) produced in the synthesis (9) of hafnium was dissolved in dehydrated methylene chloride (20 mL), and platinum oxide (20 mg) was added. The mixture was stirred under hydrogen (0.3 MPa) for 1 hour. The resulting suspension was filtered through celite, washed with dehydrated methylene chloride (15 mL), and the filtrate was concentrated. This was dissolved in dehydrated hexane to remove insoluble matters, the solvent was distilled off, and further dissolved in dehydrated toluene to remove insoluble matters and dried to obtain the desired product (28.6 mg, 0.041 mmol, yield 20. 1%) was obtained.
¹ H-NMR (CDCl ₃ ): δ0.89 (s, 3H), 0.90 (s, 3H), 1.08-2.00 (m, 14H), 2.12 (s, 10H),
2.20-2.80 (m, 4H), 4.41 (d, J = 11 Hz, 1H), 5.66 (s, 1H), 7.16-7.45 (m, 5H).
NCI-MS (M) (702).
[Synthesis Example 2]
Synthesis of dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-methyl-4-phenyl-4H-1-azulenyl)] hafnium 2-methylazulene (1.94 g, 13. 7 mmol) was dissolved in dehydrated hexane (50 mL), cooled to 0 ° C., and a cyclohexane / diethyl ether solution of phenyllithium (0.94 M, 14.9 mL, 14.0 mmol) was added dropwise at the same temperature. After completion of dropping, the reaction was allowed to proceed at room temperature for 2 hours. Thereafter, the mother liquor was extracted, and the precipitate was washed with dehydrated hexane (20 mL × 2). Dehydrated tetrahydrofuran (40 mL) was added to the suspension and cooled to 0 ° C. To the solution, a solution of dimethylsilyl (2,3,4,5-tetramethylcyclopentadienyl) chloride (2.93 g, 13.6 mmol) in Aldrich and dehydrated hexane (40 mL) and N-methylimidazole (20 μL) Was added. After stirring at room temperature for 2 hours, water was added and the desired compound was extracted with diethyl ether. The extracted solution was dehydrated with magnesium sulfate and then dried to obtain an unpurified product of the target ligand.
The ligand obtained above was dissolved in dehydrated tetrahydrofuran (50 mL) and cooled to 5 ° C. with an ice bath. The n-hexane solution (1.58M, 16.6 mL, 26.2 mmol) of n-butyllithium was slowly dripped here at the same temperature. After completion of dropping, the ice bath was removed and the mixture was stirred for 3 hours, and the solvent was distilled off under reduced pressure. Dehydrated toluene (60 mL) and dehydrated tetrahydrofuran (5 mL) were added to the residue obtained after evaporation, and then cooled to -78 ° C. Thereto was slowly added hafnium tetrachloride (4.21 g, 13.1 mmol). Thereafter, the cooling bath was removed and the mixture was stirred overnight. After completion of stirring, the reaction solution was filtered. A brown powder was obtained by concentrating the filtrate. The target complex was extracted from this brown powder with dehydrated toluene / dehydrated hexane (100 mL / 200 mL). After the extraction solution was dried, the obtained solid was suspended and washed with dehydrated n-hexane (40 mL × 5 times), suspended and washed with dehydrated ether (50 mL × 3), and dried under reduced pressure. Further, dehydrated toluene was added to the obtained powder, the precipitate was filtered off, and the filtrate was concentrated. The obtained powder was washed with dehydrated hexane (25 mL × 3) and dehydrated diethyl ether (25 mL × 3) to obtain the target complex (1.19 g, 1.84 mmol, yield 14%).
¹ H-NMR (CDCl ₃ ): δ0.97 (s, 3H), 1.00 (s, 3H), 2.03 (s, 3H), 2.10 (s, 3H), 2.11 (s, 3H), 2.12 (s, 3H), 2.15 (s, 3H), 5.08 (d, J = 4.1 Hz, 1H), 5.74 (s, 1H), 5.82-5.95 (m, 2H), 6.05 (dd, J = 11.4, 6.33 Hz, 1H ), 6.77 (d, J = 11.4 Hz, 1H), 7.26
-7.47 (m, 5H).
NCI-MS (M) (646).
[Synthesis Example 3]
Synthetic synthesis of dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-methyl-4-phenyl-5,6,7,8-tetrahydro-4H-1-azurenyl)] hafnium Dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-methyl-4-phenyl-4H-1-azulenyl)] hafnium (137 mg, 0.21 mmol) prepared in Example 2 was used. Dissolved in dehydrated methylene chloride (20 mL), platinum oxide (40 mg) was added. The mixture was stirred under hydrogen (0.2 MPa) at 20 ° C. for 3 hours. The resulting suspension was filtered through celite, washed with dehydrated methylene chloride (15 mL), and the filtrate was concentrated. The crude product was washed twice with dehydrated pentane (10 mL) and dried under reduced pressure to obtain dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-methyl-4-phenyl-5). , 6,7,8-tetrahydro-4H-1-azurenyl)] hafnium (118 mg, 0.182 mmol, 86% yield).
¹ H-NMR (CDCl ₃ ): δ0.95 (s, 3H), 0.96 (s, 3H), 1.99 (s, 3H), 2.00 (s, 3H), 2.04 (s, 3H), 2.11 (s, 3H), 2.11 (s, 3H), 1.08-2.27 (m, 7H), 2.88 (dd, J = 14.4, 6.33 Hz, 1H), 4.40 (d, J = 11.1 Hz, 1H), 5.64 (s, 1H ), 7.19-7.43 (m, 5H).
NCI-MS (M) (650).
[Synthesis Example 4]
Synthesis of dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium 2-methylazulene (1.94 g, 13.7 mmol) Was dissolved in dehydrated tetrahydrofuran (50 mL), cooled to 5 ° C., and then methyl lithium in diethyl ether (1.20 M, 12.4 mL, 14.9 mmol) was added dropwise at the same temperature. After completion of dropping, the reaction was allowed to proceed at room temperature for 2 hours. A solution of dimethylsilyl (2,3,4,5-tetramethylcyclopentadienyl) chloride (3.11 g, 14.5 mmol) in dehydrated tetrahydrofuran (50 mL) and N-methylimidazole (40 μL) was added to the solution. Was added. After stirring at room temperature for 2 hours, water was added and the desired compound was extracted with diethyl ether. The extracted solution was dehydrated with magnesium sulfate and then dried to obtain an unpurified product of the target ligand.
The ligand obtained above was dissolved in dehydrated tetrahydrofuran (60 mL) and cooled to 5 ° C. with an ice bath. The n-hexane solution (1.58M, 18.0 mL, 28.4 mmol) of n-butyllithium was slowly dripped here at the same temperature. After completion of dropping, the ice bath was removed and the mixture was stirred for 3 hours, and the solvent was distilled off under reduced pressure. Dehydrated toluene (60 mL) and dehydrated tetrahydrofuran (5 mL) were added to the residue obtained after evaporation, and then cooled to -78 ° C. Thereto was slowly added hafnium tetrachloride (4.55 g, 14.2 mmol). Thereafter, the cooling bath was removed and the mixture was stirred overnight. After completion of stirring, the reaction solution was filtered. A brown powder was obtained by concentrating the filtrate. The target complex was extracted from this brown powder with dehydrated toluene / dehydrated hexane (30 mL / 120 mL, 20 mL / 60 mL). After the extract solution was dried, the resulting solid was suspended and washed with dehydrated n-hexane (20 mL × 5 times), suspended and washed with dehydrated diethyl ether (15 mL × 3), and dried under reduced pressure. . Furthermore, dehydrated toluene / dehydrated hexane (30 mL / 100 mL) was added to the obtained powder, the precipitate was filtered off, and the filtrate was concentrated. The obtained powder was washed with dehydrated hexane (20 mL × 3) and dehydrated diethyl ether (15 mL × 3) to obtain the target complex (0.31 g, 0.50 mmol, yield 4%).
¹ H-NMR (CDCl ₃ ): δ0.98 (s, 6H), 1.49 (d, J = 7.1 Hz, 3H), 2.06 (s, 3H), 2.07 (s,
3H), 2.09 (s, 3H), 2.15 (s, 3H), 2.26 (s, 3H), 3.49-3.55 (m, 1H), 5.43 (dd, J = 10.1, 4.50 Hz, 1H), 5.80-5.84 (m, 1H), 6.12 (dd, J = 11.6, 5.56 Hz, 1H), 6.29
(s, 1H), 6.83 (d, J = 11.6 Hz, 1H).
NCI-MS (M) (584).

[Synthesis Example 5]
Synthesis Synthesis Example 4 of Dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2,4-dimethyl-5,6,7,8-tetrahydro-4H-1-azurenyl)] hafnium Dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium (180 mg, 0.31 mmol) prepared in the above step was added to methylene chloride ( Dissolved in 30 mL), and platinum oxide (40 m
g) was added. The mixture was stirred under hydrogen (0.7 MPa) at 20 ° C. for 3 hours. The resulting suspension was filtered through celite, washed with dehydrated methylene chloride (15 mL), and the filtrate was concentrated. The crude product was washed three times with dehydrated hexane (20 mL) and dried under reduced pressure to obtain dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2,4-dimethyl-5,6 , 7,8-tetrahydro-4H-1-azulenyl)] hafnium (145 mg, 0.25 mmol, 80% yield).
¹ H-NMR (CDCl ₃ ): δ0.92 (s, 3H), 0.97 (s, 3H), 1.24 (d, J = 7.0 Hz, 3H), 1.93 (s,
3H), 2.03 (s, 3H), 2.07 (s, 3H), 2.08 (s, 3H), 2.24 (s, 3H), 1.08-2.27 (m, 7H),
2.81 (dd, J = 13.6, 6.33 Hz, 1H), 2.99-3.10 (m, 1H), 6.38 (s, 1H).
NCI-MS (M) (588).

[Synthesis Example 6]
Synthesis of dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] hafnium 2-ethylazulene (2.01 g, 12. 9 mmol) was dissolved in dehydrated hexane (50 mL), cooled to 0 ° C., and a cyclohexane / diethyl ether solution of phenyllithium (0.94 M, 14.0 mL, 13.2 mmol) was added dropwise at the same temperature. After completion of dropping, the reaction was allowed to proceed at room temperature for 2 hours. Thereafter, the mother liquor was extracted, and the precipitate was washed with dehydrated hexane (20 mL × 2). Dehydrated tetrahydrofuran (40 mL) was added to the suspension and cooled to 0 ° C. To this solution, a solution of dimethylsilyl (2,3,4,5-tetramethylcyclopentadienyl) chloride (2.76 g, 12.8 mmol) in dehydrated hexane (40 mL) and N-methylimidazole (30 μL) manufactured by Aldrich Was added. After stirring at room temperature for 2 hours, water was added and the desired compound was extracted with diethyl ether. The extracted solution was dehydrated with magnesium sulfate and then dried to obtain an unpurified product of the target ligand.
The ligand obtained above was dissolved in dehydrated tetrahydrofuran (65 mL) and cooled to 5 ° C. with an ice bath. At the same temperature, an n-hexane solution of n-butyllithium (2.44M, 10.6 mL, 25.9 mmol) was slowly added dropwise. After completion of dropping, the ice bath was removed and the mixture was stirred for 3 hours, and the solvent was distilled off under reduced pressure. Dehydrated toluene (60 mL) and dehydrated tetrahydrofuran (5 mL) were added to the residue obtained after evaporation, and then cooled to -78 ° C. To this was added hafnium tetrachloride (4.13 g, 12.9 mmol) slowly. Thereafter, the cooling bath was removed and the mixture was stirred overnight. After completion of stirring, the reaction solution was filtered. A brown powder was obtained by concentrating the filtrate. The target complex was extracted from this brown powder with dehydrated toluene / dehydrated hexane (50 mL / 150 mL). After the extraction solution was dried, the obtained solid was suspended and washed with dehydrated n-hexane (30 mL × 3 times), suspended and washed with dehydrated diethyl ether (20 mL × 3), and dried under reduced pressure. . Furthermore, dehydrated toluene / dehydrated hexane (50 mL / 150 mL) was added to the obtained powder, the precipitate was filtered off, and the filtrate was concentrated. The obtained powder was washed with dehydrated hexane (20 mL × 3) and dehydrated diethyl ether (20 mL × 3) to obtain the target complex (1.69 g, 2.55 mmol, yield 20%).
¹ H-NMR (CDCl ₃ ): δ0.96 (s, 3H), 1.00 (s, 3H), 1.03 (d, J = 7.3 Hz, 3H), 2.02 (s,
3H), 2.08 (s, 3H), 2.11 (s, 3H), 2.12 (s, 3H), 2.33 (dt, J = 7.3, 22.0 Hz, 1H),
2.59 (dt, J = 7.3, 22.0 Hz, 1H), 5.11 (d, J = 4.1 Hz, 1H), 5.77 (s, 1H), 5.85-5.97 (m, 2H), 6.07 (dd, J = 11.6, 5.5 Hz, 1H), 6.78 (d, J = 11.6 Hz, 1H), 7.26-7.
47 (m, 5H).
NCI-MS (M) (663).

[Synthesis Example 7]
Synthesis of dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-ethyl-4-methyl-4H-1-azulenyl)] hafnium 2-ethylazulene (2.00 g, 12. 8 mmol) was dissolved in dehydrated tetrahydrofuran (45 mL), cooled to 5 ° C., and then methyl lithium in diethyl ether (0.92 M, 14.3 mL, 13.2 mmol) was added dropwise at the same temperature. After completion of dropping, the reaction was allowed to proceed at room temperature for 2 hours. To this solution, a solution of dimethylsilyl (2,3,4,5-tetramethylcyclopentadienyl) chloride (2.75 g, 12.8 mmol) made by Aldrich and dehydrated tetrahydrofuran (45 mL) and N-methylimidazole (40 μL) were added. Was added. After stirring at room temperature for 2 hours, water was added and the desired compound was extracted with hexane. The extracted solution was dehydrated with magnesium sulfate and then dried to obtain an unpurified product of the target ligand.
The ligand obtained above was dissolved in dehydrated tetrahydrofuran (60 mL) and cooled to 5 ° C. with an ice bath. The n-hexane solution (1.58M, 15.8 mL, 25.0 mmol) of n-butyllithium was slowly dripped here at the same temperature. After completion of dropping, the ice bath was removed and the mixture was stirred for 3 hours, and the solvent was distilled off under reduced pressure. Dehydrated toluene (40 mL) and dehydrated tetrahydrofuran (4 mL) were added to the residue obtained after evaporation, and then cooled to -78 ° C. A suspension of dehydrated toluene (50 mL) of hafnium tetrachloride (4.55 g, 14.2 mmol) cooled to −78 ° C. was slowly added thereto. Thereafter, the cooling bath was removed and the mixture was stirred overnight. After completion of stirring, the reaction solution was filtered. A brown powder was obtained by concentrating the filtrate. The target complex was extracted from this brown powder with dehydrated toluene / dehydrated hexane (30 mL / 60 mL, 15 mL / 30 mL). After the extract solution was dried, the obtained solid was suspended and washed with dehydrated dehydrated n-hexane (10 mL × 5), suspended and washed with dehydrated diethyl ether (10 mL × 3), and dried under reduced pressure. . Furthermore, dehydrated toluene / dehydrated hexane (15 mL / 30 mL) was added to the obtained powder, the precipitate was filtered off, and the filtrate was concentrated. The obtained powder was washed with dehydrated hexane (20 mL × 3) and dehydrated diethyl ether (15 mL × 3) to obtain the target complex (0.25 g, 0.42 mmol, yield 3%).
¹ H-NMR (CDCl ₃ ): δ0.97 (s, 3H), 0.99 (s, 3H), 1.11 (t, J = 7.6 Hz, 3H), 1.49 (d,
J = 7.1 Hz, 3H), 2.05 (s, 3H), 2.07 (s, 3H), 2.08 (s, 3H), 2.12 (s, 3H), 2.50 (dt, J = 22.0, 7.6 Hz, 1H), 2.65 (dt, J = 22.0, 7.6 Hz, 1H), 3.52-3.64 (m, 1H), 5.44 (dd, J = 10.1, 4.6 Hz, 1H), 5.75-5.84 (m, 1H), 6.10 (dd, J = 11.6, 5.0 Hz,
1H), 6.32 (s, 1H), 6.83 (d, J = 11.6 Hz, 1H).
NCI-MS (M) (598).
[Example 1]
(1) Chemical treatment of clay mineral In a 300 mL round bottom flask, demineralized water (113.4 mL), lithium hydroxide (16.26 g) and sulfuric acid (66.40 g) were collected, stirred and dissolved. In this solution, commercially available granulated montmorillonite (Mizusawa Chemical Benclay SL) (41.58 g) was dispersed and refluxed for 140 minutes with stirring. Thereafter, desalted water (600 mL) was added and cooled, and the resulting slurry was centrifuged. The supernatant was decanted and the wet cake was recovered. The recovered cake was suspended in demineralized water (600 mL), and centrifuged and decanted in the same manner. This operation was repeated twice. The finally obtained cake was dried at 100 ° C. for 3 hours to obtain chemically treated montmorillonite (35.63 g).

The obtained chemically treated montmorillonite was dried under reduced pressure at 200 ° C. for 2 hours. To the dried chemically treated montmorillonite (1.04 g) was added a toluene solution of triethylaluminum (0.45 M, 4.6 mL, 2.0 mmol), and room temperature was added. For 30 minutes. To this suspension was added dehydrated toluene (30 mL), and after stirring, the supernatant was removed. This operation was repeated twice to obtain a clay slurry. Of the slurry, 2.6 mL of dehydrated toluene was present.
(2) Polymerization Triisobutylaluminum (0.02 mmol) manufactured by Nippon Alkyl Aluminum Co. was collected in a separate flask, and obtained in the clay slurry (1.9 mL) obtained in (1) and Synthesis Example 1- (10). A diluted solution of the obtained complex (4.0 mg, 5.7 μmol) with dehydrated toluene was added, and the mixture was stirred at room temperature for 20 minutes to obtain a catalyst slurry.
Next, triisobutylaluminum (0.35 mmol) (in terms of Al atoms) was introduced into a stirring autoclave having an internal volume of 2 L. on the other hand. The catalyst prepared above was introduced into a catalyst feeder with a rupturable plate. Thereafter, 1,400 mL of propylene was introduced into the autoclave, the rupture disc was cut at room temperature, heated to 80 ° C., and polymerized for 1 hour to obtain a polymer having a vinyl group at the terminal (95 g). Table 1 shows the physical properties of the polymer.
[Example 2]
Triisobutylaluminum (0.01 mmol) manufactured by Nippon Alkyl Aluminum Co. was collected in the flask, and the clay slurry (0.5 mL) obtained in Example 1- (1) and the complex (0. 9 mg, 1.5 μmol) of a diluted solution with toluene was added, and the mixture was stirred at room temperature for 20 minutes to obtain a catalyst slurry.
Next, triisobutylaluminum (0.35 mmol) (in terms of Al atoms) was introduced into a stirring autoclave having an internal volume of 2 L. on the other hand. The catalyst prepared above was introduced into a catalyst feeder with a rupturable plate. Thereafter, 1,400 mL of propylene was introduced into the autoclave, the rupturable plate was cut at room temperature, heated to 80 ° C., and polymerized for 1 hour to obtain a polymer having a vinyl group at the terminal (116 g). Table 1 shows the physical properties of the polymer.
[Examples 3 to 6]
The complex (0.9 mg, 1) obtained in Synthesis Example 7 (Example 3), Synthesis Example 4 (Example 4), Synthesis Example 2 (Example 5), and Synthesis Example 6 (Example 6) was used. Polymerization was carried out in the same manner as in Example 2 except that the amount was changed to 5 μmol), and a polymer having a vinyl group at the terminal was obtained. Table 1 shows the physical properties of the polymer.

From Table 1, it can be seen that when the C1-symmetric transition metal compound of the present invention is used as a catalyst component, a mmmm is high and a polypropylene containing 10% or more of terminal vinyl is obtained.

Claims (4)

A C1-symmetric transition metal compound represented by the following general formula (I):

(In general formula (I), R ^{1 to} R ⁴ are all the same hydrocarbon group, halogenated hydrocarbon group or silicon-containing hydrocarbon group, and R ⁹ is a hydrocarbon group, halogenated hydrocarbon group or A silicon-containing hydrocarbon group, or R ¹ and R ² and R ³ and R ⁴ are combined to form a divalent hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group, and R ⁹ is Aromatic hydrocarbon group:
R ⁵ represents a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group:
R ⁶ is a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group:
R ⁷ is a saturated or unsaturated divalent hydrocarbon group having 4 to 9 carbon atoms:
R ⁸ represents a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group:
n is 0 or an integer less than or equal to 2 times the carbon number of R ⁷ (however, when n is 2 or more, R ⁸ may be bonded to each other at any position to form a ring structure):
Q is a crosslinking group:
X and Y are each independently a ligand that forms a σ bond with M:
M represents a transition metal of Groups 4 to 6 in the periodic table. ) An olefin polymerization catalyst component comprising the C1-symmetric transition metal compound according to claim 1. An α-olefin polymerization catalyst comprising the following components (A) and (D) and optionally a component (E).
Component (A): C1-symmetric transition metal compound according to claim 1 Component (D): Compound component (E) selected from the group consisting of ion-exchange layered compounds excluding silicates and inorganic silicates: Organoaluminum Compound A method for producing a propylene-based polymer, comprising polymerizing or copolymerizing the olefin polymerization catalyst according to claim 3 and an α-olefin in contact with each other.