JP2015157924A - Method of producing olefin polymer and cross-linked metallocene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of efficiently producing an olefin polymer high in molecular weight or melting point even under industrially advantageous high-temperature conditions.SOLUTION: A method of producing an olefin polymer comprises polymerizing 2-20C α-olefins under a polymerization temperature condition of 50-200°C in the presence of an olefin polymerization catalyst containing a cross-linked metallocene compound of a group 4 transition metal including a fluorenyl group having a 2,7-diphenyl substituent group and a tetrahydropentalenyl group having a tertiary hydrocarbon group.

Description

  The present invention relates to a method for producing an olefin polymer and a bridged metallocene compound.

  In recent years, metallocene compounds are well known as homogeneous catalysts for olefin polymerization. Regarding the method for polymerizing olefins using metallocene compounds (particularly, the method for polymerizing α-olefins), W.W. Since the report of isotactic polymerization by Kaminsky et al., Many improvement studies have been conducted from the viewpoint of further improving stereoregularity and polymerization activity (Non-patent Document 1).

  In the polymerization of α-olefin using a metallocene compound, it can be obtained by introducing a substituent into the cyclopentadienyl ring of the ligand of the metallocene compound or by crosslinking two cyclopentadienyl rings. It is known that the stereoregularity and molecular weight of olefin polymers vary greatly.

  For example, when a metallocene compound having a ligand in which a cyclopentadienyl ring and a fluorenyl ring are bridged is used as a catalyst for propylene polymerization, from the viewpoint of the stereoregularity of the polymer, dimethylmethylene (cyclopentadiene) In the case of (enyl) (fluorenyl) zirconium dichloride, syndiotactic polypropylene (Non-Patent Document 2) is dimethylmethylene (3-methylcyclopentadienyl) (fluorenyl) zirconium dichloride in which a methyl group is introduced at the 3-position of the cyclopentadienyl ring. Then, hemiisotactic polypropylene is obtained (Patent Document 1), and similarly, dimethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride into which tert-butyl group is introduced gives isotactic polypropylene ( Patent Literature ).

  From attempts to improve these metallocene compounds, it has become possible to obtain a relatively high melting point, which is an index of the stereoregularity of the polymer, and a sufficiently high molecular weight of the polymer. It is supposed to be.

Japanese Patent Laid-Open No. 3-19396 JP-A-6-122718

Angew. Chem. Int. Ed. Engl., 24, 507 (1985) J. Am. Chem. Soc., 110, 6255 (1988)

  Although the above-described development has been carried out as an olefin polymerization catalyst, the development of a polymerization catalyst for producing a high molecular weight or high melting point polymer with high polymerization activity is still not sufficient. Therefore, a production method for obtaining a high molecular weight or high melting point polymer with high productivity has been strongly desired.

  Furthermore, in order to enable industrial production of these olefin polymers, it is desired that the olefin polymer having the above characteristics can be produced at a temperature higher than normal temperature, preferably higher than normal temperature.

  The present invention has been made to solve the above-mentioned problems, and its object is to provide a method for efficiently producing a high-molecular-weight or high-melting-point olefin polymer even under high-temperature conditions advantageous in an industrial production process. There is to do.

  The present inventor has intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by a method for producing an olefin polymer using an olefin polymerization catalyst containing a useful and novel metallocene compound having a specific structure, and completed the present invention.

The present invention relates to the following [1] to [17], for example.
[1] (A) a bridged metallocene compound represented by the general formula [1], (B) (b-1) an organoaluminum oxy compound, and (b-2) a bridged metallocene compound (A) to react with an ion pair In the presence of a catalyst for olefin polymerization comprising at least one compound selected from (b-3) an organoaluminum compound and a polymerization temperature condition of 50 ° C. or higher and 200 ° C. or lower. A method for producing an olefin polymer, wherein at least one monomer selected from α-olefins of 20 or less is polymerized.

[In the formula [1], R ¹ is a tertiary hydrocarbon group, R ² and R ⁷ are groups represented by the general formula [2], and R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different, and R ³ and R ⁶ are a hydrocarbon group, Selected from silicon-containing groups, halogen atoms, and halogen-containing hydrocarbon groups, which may be the same or different, and adjacent substituents other than R ² and R ⁷ may combine with each other to form a ring; Is a Group 4 transition metal and Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons And when there are multiple Qs, they may be the same or different, Is an integer of 1 to 4. ]

[In the formula [2], R ^{13 to} R ¹⁷ are selected from a hydrogen atom, a hydrocarbon group, an oxygen-containing group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different, and adjacent to each other. The substituted groups may be bonded to each other to form a ring. ]

[2] The method for producing an olefin polymer according to [1], wherein in the general formula [1], R ¹ is a tert-butyl group or a 1-adamantyl group.
[3] The method for producing an olefin polymer as described in [1] or [2], wherein in the general formula [1], R ⁴ and R ⁵ are hydrogen atoms.
[4] The production of the olefin polymer as described in any one of [1] to [3], wherein in the general formula [1], R ¹² is a hydrocarbon group having 1 to 20 carbon atoms. Method.

[5] In the general formula [1], R ^{8 to} R ¹¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and adjacent substituents of R ^{8 to} R ¹¹ are bonded to each other. The method for producing an olefin polymer according to any one of the above [1] to [4], wherein a ring may be formed.

[6] In the general formula [2], R ^{13 to} R ¹⁷ are each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a fluorine atom, or a chlorine atom. The method for producing an olefin polymer according to any one of [1] to [5].

[7] The method for producing an olefin polymer according to any one of [1] to [6], wherein the olefin polymerization catalyst further contains a carrier (C).
[8] The method for producing an olefin polymer according to any one of [1] to [7], wherein at least one of the monomers is propylene.

[9] The method for producing an olefin polymer according to [8], wherein the obtained olefin polymer satisfies the following requirements (ia) to (iia) at the same time.
(Ia) Propylene-derived structural unit (P) is 50 mol% ≦ P ≦ 100 mol%
(Iia) The intrinsic viscosity [η] in decalin at 135 ° C. is 0.5 dl / g ≦ [η] ≦ 20 dl / g

[10] The method for producing an olefin polymer according to [8], wherein the obtained olefin polymer satisfies the following requirements (ib) to (iib) at the same time.
(Ib) The ethylene-derived structural unit (E) is 0 mol% ≦ E ≦ 50 mol%, and the propylene-derived structural unit (P) is 50 mol% ≦ P ≦ 100 mol%.
(Iib) The intrinsic viscosity [η] in 135 ° C. decalin is 0.5 dl / g ≦ [η] ≦ 20 dl / g

[11] The method for producing an olefin polymer according to [8], wherein the obtained olefin polymer satisfies the following requirements (ic) to (iic) at the same time.
(Ic) The melting point peak (Tm) determined by a differential scanning calorimeter (DSC) is 150 ° C. ≦ Tm ≦ 170 ° C.
(Iic) Intrinsic viscosity [η] in decalin at 135 ° C. is 0.5 dl / g ≦ [η] ≦ 20 dl / g

  [12] A bridged metallocene compound represented by the general formula [1].

[In the formula [1], R ¹ is a tertiary hydrocarbon group, R ² and R ⁷ are groups represented by the general formula [2], and R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different, and R ³ and R ⁶ are a hydrocarbon group, Selected from silicon-containing groups, halogen atoms, and halogen-containing hydrocarbon groups, which may be the same or different, and adjacent substituents other than R ² and R ⁷ may combine with each other to form a ring; Is a Group 4 transition metal and Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons And when there are multiple Qs, they may be the same or different, Is an integer of 1 to 4. ]

[In the formula [2], R ^{13 to} R ¹⁷ are selected from a hydrogen atom, a hydrocarbon group, an oxygen-containing group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different, and adjacent to each other. The substituted groups may be bonded to each other to form a ring. ]

[13] The bridged metallocene compound according to [12], wherein in general formula [1], R ¹ is a tert-butyl group or a 1-adamantyl group.
[14] The bridged metallocene compound according to [12] or [13], wherein in general formula [1], R ⁴ and R ⁵ are hydrogen atoms.
[15] The bridged metallocene compound according to any one of [12] to [14], wherein in the general formula [1], R ¹² is a hydrocarbon group having 1 to 20 carbon atoms.

[16] In the general formula [1], R ^{8 to} R ¹¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and adjacent substituents of R ^{8 to} R ¹¹ are bonded to each other. The bridged metallocene compound according to any one of [12] to [15] above, which may form a ring.

[17] In the general formula [2], R ^{13 to} R ¹⁷ are each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a fluorine atom, or a chlorine atom. The bridged metallocene compound according to any one of [12] to [16].

  According to the present invention, a high molecular weight or high melting point olefin polymer can be produced efficiently by using an olefin polymerization catalyst containing a useful and novel metallocene compound having a specific structure.

  Hereinafter, the manufacturing method of the olefin polymer of this invention and the bridge | crosslinking metallocene compound which can be used suitably by the said method are demonstrated. After describing the bridged metallocene compound of the present invention (hereinafter also referred to as “metallocene compound (A)”), an olefin polymerization catalyst and an olefin polymer production method will be described.

In the following description, N ¹ or more and N ² or less (N ¹ and N ² respectively indicate a lower limit value and an upper limit value of a numerical range) may be simply referred to as “N ^{1 to} N ² ”. For example, an α-olefin having 2 to 20 carbon atoms may be referred to as an “α-olefin having 2 to 20 carbon atoms”.

[Metalocene Compound (A)]
The metallocene compound (A) of the present invention is represented by the general formula [1].

In the formula [1], R ¹ is a tertiary hydrocarbon group, R ² and R ⁷ are groups represented by the general formula [2], and R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different, and R ³ and R ⁶ are a hydrocarbon group, silicon Selected from a containing group, a halogen atom, and a halogen-containing hydrocarbon group, which may be the same or different, and adjacent substituents other than R ² and R ⁷ may be bonded to each other to form a ring; Group 4 transition metal, Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair Yes, when there are multiple Qs, they may be the same or different, j An integer of 1 to 4.

In the formula [2], R ^{13 to} R ¹⁷ are selected from a hydrogen atom, a hydrocarbon group, an oxygen-containing group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different and adjacent to each other. The substituents may be bonded to each other to form a ring.

  By using the olefin polymerization catalyst containing the metallocene compound (A) of the present invention, for example, when polymerizing an α-olefin such as propylene, a high molecular weight or high melting point olefin polymer can be produced efficiently. That is, the metallocene compound (A) of the present invention can be suitably used as a catalyst component for olefin polymerization for producing an olefin polymer, particularly a propylene polymer.

  Hereinafter, specific examples and preferred examples of the groups in the formula [1] and the formula [2] will be described for the metallocene compound (A), but a compound comprising any combination of the preferred groups described for each group, It can be mentioned as a preferred metallocene compound (A).

<For R ¹ ~R ^17>
The following describes each group according to R ¹ to R ¹⁷ in the formula [1] and the formula [2]. Unless otherwise specified, for each group (hydrocarbon group, oxygen-containing group, silicon-containing group, halogen atom, halogen-containing hydrocarbon group) listed as R ^{1 to} R ¹⁷ in formula [1] and formula [2], The following groups can be exemplified.

  Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a saturated alicyclic group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Twenty hydrocarbon groups are exemplified.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. Group, a linear alkyl group such as n-decanyl group; iso-propyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1 -Branched alkyl groups such as methyl-1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl Is done. The alkyl group preferably has 1 to 4 carbon atoms.

  Examples of the saturated alicyclic group having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; alicyclic polycyclic groups such as norbornyl group and adamantyl group. . The carbon number of the saturated alicyclic group is preferably 5-11.

  Examples of the aryl group having 6 to 20 carbon atoms include unsubstituted aryl groups such as a phenyl group, a naphthyl group, a phenanthryl group, an anthracenyl group, and a biphenyl group; an o-tolyl group, an m-tolyl group, a p-tolyl group, and an ethylphenyl group. And alkylaryl groups such as n-propylphenyl group, iso-propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, xylyl group, 2,4,6-trimethylphenyl group, etc. Is done. The aryl group preferably has 6 to 10 carbon atoms.

  Examples of the aralkyl group having 7 to 20 carbon atoms include unsubstituted aralkyl groups such as benzyl group, cumyl group, α-phenethyl group, β-phenethyl group, diphenylmethyl group, naphthylmethyl group, and neophyll group; o-methylbenzyl group, alkylaralkyl groups such as m-methylbenzyl group, p-methylbenzyl group, ethylbenzyl group, n-propylbenzyl group, iso-propylbenzyl group, n-butylbenzyl group, sec-butylbenzyl group, tert-butylbenzyl group, etc. Is exemplified. The carbon number of the aralkyl group is preferably 7-10.

  Examples of the oxygen-containing group include alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group. As for carbon number of an alkoxy group, 1-4 are preferable. As for carbon number of an aryloxy group, 6-10 are preferable.

  Examples of the silicon-containing group include methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group and the like; dimethylphenylsilyl group, diphenylmethylsilyl group, trimethyl group An arylsilyl group such as a phenylsilyl group is exemplified. The alkylsilyl group preferably has 1 to 10 carbon atoms. The arylsilyl group preferably has 6 to 18 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the halogen-containing hydrocarbon group include groups formed by substituting at least one hydrogen atom of the hydrocarbon group with a halogen atom. Specifically, halogen substitution such as a fluoroalkyl group such as a trifluoromethyl group Alkyl group; fluoroaryl group such as pentafluorophenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, chloroaryl group such as chloronaphthyl group, o-bromophenyl group, m-bromophenyl group, p -Halogen substitution of the above-mentioned unsubstituted aryl groups such as iodoaryl groups such as bromoaryl groups such as bromophenyl group and bromonaphthyl group, o-iodophenyl group, m-iodophenyl group, p-iodophenyl group and iodonaphthyl group A group; a fluoroalkylaryl group such as a trifluoromethylphenyl group, Halogen substituted aryl groups such as bromoalkylaryl groups such as lomomethylphenyl group and dibromomethylphenyl group, halogen substituents of the above alkylaryl groups such as iodoalkylaryl groups such as iodomethylphenyl group and diiodomethylphenyl group; chloroaralkyl groups such as o-chlorobenzyl group, m-chlorobenzyl group, p-chlorobenzyl group, chlorophenethyl group, o-bromobenzyl group, m-bromobenzyl group, p-bromobenzyl group, bromophenethyl group, etc. A halogen-substituted aralkyl group such as a halogen substituent of the above-mentioned unsubstituted aralkyl group such as a bromoaralkyl group, an o-iodobenzyl group, an m-iodobenzyl group, a p-iodobenzyl group and an iodophenethyl group; Illustrated.

In formula [1] and formula [2], ^two adjacent substituents excluding R ² and R ⁷ (eg, R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰⁾ R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ ) are bonded to each other, and these substituents are bonded. The ring carbon may form a ring and the ring formation may exist in two or more places in the molecule.

  In this specification, examples of the ring (additional ring) formed by bonding two substituents to each other include an alicyclic ring, an aromatic ring, and a heterocyclic ring. Specific examples include a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; a hetero ring such as a furan ring and a thiophene ring and a corresponding hydrogenated hetero ring, and preferably a cyclohexane ring, a benzene ring, and hydrogen. Benzene ring. Such a ring structure may further have a substituent such as an alkyl group on the ring.

R ¹ is a tertiary hydrocarbon group, preferably having 4 to 20 carbon atoms, more preferably 4 to 12 carbon atoms. Specific examples of the tertiary hydrocarbon group include tertiary alkyl groups such as tert-butyl group, tert-pentyl group and tert-amyl group, tertiary cycloalkyl groups such as 1-methylcyclohexyl group, and 1-adamantyl. And tertiary alicyclic polycyclic groups such as a group, tert-butyl group, tert-pentyl group, 1-methylcyclohexyl group and 1-adamantyl group are preferable, and tert-butyl group and 1-adamantyl group are particularly preferable. . The reason why R ¹ is preferably the group is that it contributes to the stabilization of the catalyst structure and is thought to lead to an improvement in the stereoregularity of the olefin polymer to be produced.

R ² and R ⁷ are each independently a group represented by the above formula [2]. The reason why these groups are preferably the above groups is that if the fluorene ring has a substituent having a conjugated electron, it is thought that it contributes to stabilization of the catalyst structure and contributes to improvement of the melting point of the resulting olefin polymer. is there.

R ⁴ and R ⁵ are preferably hydrogen atoms. The reason why R ⁴ and R ⁵ are preferably hydrogen atoms is that the olefin polymer to be produced can be efficiently obtained.

As an embodiment of R ³ and R ^6, for example, are each independently a hydrocarbon group. As a hydrocarbon group, the C1-C20 alkyl group, the C3-C20 saturated alicyclic group, and the C6-C20 aryl group which were enumerated above are preferable, and the said alkyl group is more preferable.

R ^{8 to} R ¹¹ are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. As a hydrocarbon group, the C1-C20 alkyl group enumerated above is preferable. In addition, adjacent substituents among R ^{8 to} R ¹¹ may be bonded to each other to form a ring. For example, R ⁹ and R ¹⁰ may be bonded to each other to form the ring described above. And alicyclic rings.

R ¹² is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group include the alkyl groups having 1 to 20 carbon atoms, saturated alicyclic groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. Examples thereof are preferably the alkyl group and the aryl group, more preferably the alkyl group, and particularly preferably an alkyl group having 1 to 10 carbon atoms. The reason why R ¹² is preferably the group is that the catalyst structure is stabilized, and it is considered that the molecular weight of the resulting olefin polymer is improved.

R ^{13 to} R ¹⁷ are preferably each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, or a halogen atom, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen atom, more preferably a hydrogen atom, an alkyl group or a halogen atom, and particularly preferably a hydrogen atom, a methyl group, an ethyl group, n -Propyl group, iso-propyl group, fluorine atom or chlorine atom. The group represented by the formula [2] is particularly preferably a phenyl group, or an o-substituted product or a p-substituted product. The reason why these groups are preferably the above groups is that they contribute to the stability of the olefin polymer and are thought to contribute to the improvement of the molecular weight of the resulting olefin polymer.

<About M, Q and j>
M is a Group 4 transition metal, that is, Ti, Zr or Hf, preferably Zr or Hf, particularly preferably Zr.

  Q can be coordinated by a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), hydrocarbon group, neutral conjugated or nonconjugated diene having 10 or less carbon atoms, anionic ligand, or lone electron pair A neutral ligand.

  As a hydrocarbon group in Q, a C1-C10 alkyl group and a C3-C10 cycloalkyl group are preferable. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1 , 1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1, Examples include a 1,3-trimethylbutyl group and a neopentyl group; examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclohexylmethyl group, a cyclohexyl group, and a 1-methyl-1-cyclohexyl group. The number of carbon atoms of the hydrocarbon group in Q is more preferably 5 or less.

Neutral conjugated or nonconjugated dienes having 10 or less carbon atoms include s-cis- or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4- Diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1, 3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s- cis - or s- trans eta ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

  Examples of the anionic ligand include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate.

Neutral ligands that can be coordinated by lone electron pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran (THF), diethyl ether, dioxane, 1,2-dimethoxy Examples are ethers such as ethane.
A preferred embodiment of Q is a halogen atom or an alkyl group having 1 to 5 carbon atoms.
j is an integer of 1 to 4, preferably 2.

<Example of metallocene compound (A)>
Although the specific example of the metallocene compound (A) of this invention is shown, the range of this invention is not specifically limited by this. In the present invention, the metallocene compound (A) may be used alone or in combination of two or more.

For the convenience of explanation, the ligand structure excluding MQ _j (metal part) of the metallocene compound (A) is represented by the substituent R ² / R on the cyclopentadienyl derivative part (α), fluorenyl part (β) and fluorenyl. Divided into ⁷ parts (γ). Specific examples of each partial structure are shown in Tables 1 to 3. “Flu” in the table refers to the fluorenyl moiety, and “Cp” refers to the cyclopentadienyl derivative moiety.

According to the above table, a ligand structure comprising a combination of α7, β3 and γ1, γ1, and when the metal part MQ _j is ZrCl ₂ , the following metallocene compound 1 is represented by a ligand structure comprising a combination of α9, β3 and γ1, γ1. In the case where the metal part MQ _j is ZrCl ₂ , the following metallocene compound 2 has a ligand structure comprising a combination of α9, β3 and γ9, γ9, and in the case where the metal part MQ _j is ZrCl ₂ , the following metallocene compound 3 is , Β3 and a combination of γ4, γ4, and the metal part MQ _j is ZrCl ₂ , the following metallocene compound 4 is formed, and the ligand structure is a combination of α9, β3, γ2, γ2, and the metal part MQ _j is In the case of ZrCl _2, the following metallocene compounds 5 are exemplified.

Specific examples of MQ _j include ZrCl ₂ , ZrBr ₂ , ZrMe ₂ , Zr (Me) (Et), Zr (OTs) ₂ , Zr (OMs) ₂ , Zr (OTf) ₂ , TiCl ₂ , TiBr _{2. , TiMe 2, Ti (Me)} (Et), Ti (OTs) 2, Ti (OMs) 2, Ti (OTf) 2, HfCl 2, HfBr 2, HfMe 2, Hf (Me) (Et), Hf (OTs ) ₂ , Hf (OMs) ₂ , Hf (OTf) _{2 and the} like. Me represents a methyl group, Et represents an ethyl group, Ts represents a p-toluenesulfonyl group, Ms represents a methanesulfonyl group, and Tf represents a trifluoromethanesulfonyl group.

<Synthesis of Metallocene Compound (A)>
The metallocene compound (A) of the present invention can be synthesized, for example, according to the method described in the following patent publication. Specifically, JP 2000-212194 A, JP 2004-168744 A, JP 2004-189666 A, JP 2004-161957 A, JP 2007-302854 A, and JP 2007-302853 A. No. publication, WO 01/027124 pamphlet, and the like.

Below, an example of the manufacturing method of the metallocene compound (A) of this invention is demonstrated.
For example, the following pentalene compound (1a) and the following fluorene derivative (2a) are reacted to obtain a precursor compound (3a) of the metallocene compound (A), and from the precursor compound (3a), the metallocene compound ( A) can be obtained.

In the above reaction, R ^{1 to} R ¹² are each synonymous with the same symbol in the general formula [1], and L is an alkali metal or an alkaline earth metal. Examples of the alkali metal include lithium, sodium, and potassium, and examples of the alkaline earth metal include magnesium and calcium. The pentalene compound (1a) and the fluorene derivative (2a) can be obtained by a conventionally known method.

  Examples of the organic solvent that can be used in the above reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin; aromatic hydrocarbons such as benzene, toluene, and xylene; tetrahydrofuran, diethyl ether, dioxane, 1 , 2-dimethoxyethane, tert-butyl methyl ether, cyclopentyl methyl ether and other ethers; dichloromethane, chloroform and other halogenated hydrocarbons; or solvents obtained by mixing two or more of these.

  The reaction between the pentalene compound (1a) and the fluorene derivative (2a) is preferably a molar ratio of 10: 1 to 1:10, more preferably 2: 1 to 1: 2, particularly preferably 1.2: 1 to 1. : Performed in 1.2. The reaction temperature is preferably −100 to 150 ° C., more preferably −40 to 120 ° C.

  An example of producing the metallocene compound (A) of the present invention from the precursor compound (3a) is shown below. This does not limit the scope of the present invention, and the metallocene compound (A) of the present invention may be produced by any known method.

  By bringing the precursor compound (3a) into contact with at least one metal component selected from an alkali metal, an alkali metal hydrogen atom, an alkali metal alkoxide, an organic alkali metal and an organic alkaline earth metal in an organic solvent. To obtain a dialkali metal salt.

  Examples of the alkali metal that can be used in the above reaction include lithium, sodium, and potassium; examples of the hydrogen atom alkali metal include sodium hydrogen atom and potassium hydrogen atom; and examples of the alkali metal alkoxide include Examples include sodium methoxide, potassium ethoxide, sodium ethoxide, potassium tert-butoxide, etc .; examples of the organic alkali metal include methyl lithium, butyl lithium, and phenyl lithium; examples of the organic alkaline earth metal include methyl Examples thereof include magnesium halide, butyl magnesium halide, and phenyl magnesium halide; or two or more of these may be used in combination.

  Examples of the organic solvent used in the above reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin; aromatic hydrocarbons such as benzene, toluene, and xylene; tetrahydrofuran, diethyl ether, dioxane, 1, 2, and the like. -Ethers such as dimethoxyethane, tert-butyl methyl ether and cyclopentyl methyl ether; halogenated hydrocarbons such as dichloromethane and chloroform; or solvents obtained by mixing two or more of these.

  The reaction between the precursor compound (3a) and the metal component is preferably a molar ratio (precursor compound (3a): metal component) = 1: 1 to 1:20, more preferably 1: 1.5 to 1: 4, particularly preferably 1: 1.8 to 1: 2.5. The reaction temperature is preferably −100 to 200 ° C., more preferably −80 to 120 ° C.

  In order to promote the reaction, Lewis bases typified by tetramethylethylenediamine and the like, α-methylstyrene and the like as described in International Publication No. 2009/072505 pamphlet can also be used.

The metallocene compound (A) of the present invention is synthesized by reacting the dialkali metal salt obtained by the above reaction with the compound represented by the general formula (4a) in an organic solvent.
MZ _k (4a)
In formula (4a), M is a Group 4 transition metal, and a plurality of Zs are each independently a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or an isolated group. It is a neutral ligand capable of coordinating with an electron pair, and k is an integer of 3 to 6. The atoms or groups listed as M and Z are the same as M and Q described in the section of the general formula [1], respectively.

  Examples of the compound (4a) include trivalent or tetravalent titanium fluoride, chloride, bromide and iodide; tetravalent zirconium fluoride, chloride, bromide and iodide; tetravalent hafnium fluoride, chloride. Products, bromides and iodides; or complexes thereof with ethers such as tetrahydrofuran, diethyl ether, dioxane or 1,2-dimethoxyethane.

  Examples of the organic solvent used in the above reaction include the organic solvents described in the synthesis of the dialkali metal salt. The reaction between the dialkali metal salt and the compound (4a) is preferably a molar ratio of 10: 1 to 1:10, more preferably 2: 1 to 1: 2, particularly preferably 1.2: 1 to 1: 1. Perform in step 2. The reaction temperature is preferably -80 to 200 ° C, more preferably -75 to 120 ° C.

  As another method, the precursor compound (3a) is converted into an organometallic reagent such as tetrabenzyl titanium, tetrabenzyl zirconium, tetrabenzyl hafnium, tetrakis (trimethylsilylmethylene) titanium, tetrakis (trimethylsilylmethylene) zirconium, tetrakis (trimethylsilylmethylene) hafnium. Dibenzyldichlorotitanium, dibenzyldichlorozirconium, dibenzyldichlorohafnium, and titanium, zirconium, or hafnium amide salts may be reacted directly.

The metallocene compound (A) obtained by the above reaction can be isolated and purified by methods such as extraction, recrystallization and sublimation. The metallocene compound (A) of the present invention obtained by such a method is identified by using analytical techniques such as proton nuclear magnetic resonance spectrum, ¹³ C-nuclear magnetic resonance spectrum, mass spectrometry, and elemental analysis.

[Olefin polymerization catalyst]
The olefin polymerization catalyst used in the method for producing an olefin polymer of the present invention preferably contains the components described below in addition to the metallocene compound (A) described above.

[Compound (B)]
In the present invention, it is preferable to use the compound (B) as a component of the olefin polymerization catalyst. The compound (B) is selected from (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with the metallocene compound (A) to form an ion pair, and (b-3) an organoaluminum compound. At least one. In these, it is preferable to use an organoaluminum oxy compound (b-1) at least. The organoaluminum oxy compound (b-1) is preferable from the viewpoint of efficiently obtaining the produced olefin polymer.

<Organic aluminum oxy compound (b-1)>
As the organoaluminum oxy compound (b-1), a conventionally represented aluminoxane such as a compound represented by the general formula [B1] and a compound represented by the general formula [B2], a structure represented by the general formula [B3] And a modified methylaluminoxane having boron, and a boron-containing organoaluminum oxy compound represented by the general formula [B4].

In the formulas [B1] and [B2], R is a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group, and n is an integer of 2 or more, preferably 3 or more, more preferably 10 or more. In the present invention, methylaluminoxane in which R is a methyl group (Me) in formulas [B1] and [B2] is preferably used.

In the formula [B3], R is a hydrocarbon group having 2 to 10 carbon atoms, and m and n are each independently an integer of 2 or more. A plurality of R may be the same or different from each other. The modified methylaluminoxane [B3] can be prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such modified methylaluminoxane [B3] is generally called MMAO (modified methyl aluminoxane). MMAO can be specifically prepared by the methods mentioned in US Pat. No. 4,960,878 and US Pat. No. 5,041,584.

  In addition, modified methylaluminoxanes prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem Co., Ltd. (that is, R is an isobutyl group in the general formula [B3]) are trade names such as MMAO and TMAO. Is produced commercially.

  MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, unlike a compound that is insoluble or hardly soluble in benzene such as a compound represented by the general formula [B1] or [B2], MMAO is an aliphatic hydrocarbon, alicyclic hydrocarbon, and aromatic. It is soluble in group hydrocarbons.

In the formula [B4], R ^c is a hydrocarbon group having 1 to 10 carbon atoms. A plurality of R ^d are each independently a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms. In the present invention, an olefin polymer can be produced even at a high temperature as described later. Accordingly, one of the features of the present invention is that a benzene-insoluble or hardly soluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can also be used. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxane having two or more alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like are also included. It can be suitably used.

The above-mentioned “benzene insoluble or hardly soluble” organoaluminum oxy compound means that the amount of the compound dissolved in benzene at 60 ° C. is usually 10% by weight or less, preferably 5% by weight or less in terms of Al atom. In particular, the organoaluminum oxy compound is preferably 2% by weight or less.
In the present invention, the organoaluminum oxy compound (b-1) exemplified above may be used alone or in combination of two or more.

<Compound (b-2) which forms an ion pair by reacting with the metallocene compound (A)>
As the compound (b-2) (hereinafter also referred to as “ionic compound (b-2)”) that reacts with the metallocene compound (A) to form an ion pair, JP-A-1-501950 and JP-A-1- No. 502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, JP-A-2004-51676, US Pat. No. 5,321,106, etc. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in (1). Furthermore, heteropoly compounds and isopoly compounds are also exemplified. In these, as an ionic compound (b-2), the compound represented by general formula [B5] is preferable.

In the formula [B5], R ^{e +} is exemplified by H ⁺ , oxonium cation, carbenium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^f , R ^g , R ^h and R ⁱ each independently represents an organic group, preferably an aryl group or a halogen-substituted aryl group.

  Examples of the carbenium cation include trisubstituted carbenium cations such as a triphenyl carbenium cation, a tris (methylphenyl) carbenium cation, and a tris (dimethylphenyl) carbenium cation.

  Examples of ammonium cations include trialkylammonium cations, triethylammonium cations, tri (n-propyl) ammonium cations, triisopropylammonium cations, tri (n-butyl) ammonium cations, triisobutylammonium cations, and the like; N, N -N, N-dialkylanilinium cations such as dimethylanilinium cation, N, N-diethylanilinium cation, N, N, 2,4,6-pentamethylanilinium cation; diisopropylammonium cation, dicyclohexylammonium cation, etc. Examples include dialkylammonium cations.

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

In the above examples, R ^{e +} is preferably a carbenium cation or an ammonium cation, and particularly preferably a triphenylcarbenium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

1. When R ^{e +} is a carbenium cation (carbenium salt)
Examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methylphenyl) carbe. Examples thereof include nium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

2. When R ^{e +} is an ammonium cation (ammonium salt)
Examples of ammonium salts include trialkylammonium salts, N, N-dialkylanilinium salts, and dialkylammonium salts.

  Specific examples of the trialkylammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis ( o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4 -Dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) bore Tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o -Tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, di Octadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate , Dioctadecyl methyl ammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecyl methyl ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, dioctadecyl methyl ammonium and the like.

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

Specific examples of the dialkylammonium salt include diisopropylammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.
An ionic compound (b-2) may be used independently and may be used in combination of 2 or more type.

<Organic aluminum compound (b-3)>
Examples of the organoaluminum compound (b-3) include an organoaluminum compound represented by the general formula [B6] and a complex alkylated product of a group 1 metal of the periodic table represented by the general formula [B7] and aluminum. The

R ^a _m Al (OR ^b ) _n H _p X _q ... [B6]
In the formula [B6], R ^a and R ^b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m is 0 <m ≦ 3, and n is 0 ≦ n <3, p is a number 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3.

M ² AlR ^a ₄ [B7]
In the formula [B7], M ² is Li, Na or K, and a plurality of R ^a are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

Examples of the organoaluminum compound [B6] include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, and trioctylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, Tri-branched alkylaluminum such as tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triphenyl Triaryl aluminum such as aluminum and tolyl aluminum; diisopropyl aluminum Idoraido, diisobutylaluminum hydride, etc. dialkylaluminum hydride; formula (i-C ₄ H ₉₎ in _{x Al y (C 5 H 10} ) z ( wherein, x, y and z are positive numbers, z ≦ 2x Alkenyl aluminum alkoxides such as isoprenylaluminum and the like; alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide Alkyl aluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; general formula R ^a _2.5 Al (OR ^b ) _0.5 , wherein R ^a and R ^b are the formula [B 6] partially alkoxylated alkylaluminum having an average composition represented by: R ^a and R ^b ; diethylaluminum phenoxide, diethylaluminum (2,6-ditert-butyl-4 Alkyl aluminum aryloxides such as -methylphenoxide); Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquichloride Alkyl aluminum sesquihalides such as bromide; partially halogenated alkyl aluminum dihalides such as ethylaluminum dichloride Alkylated alkylaluminum; Dialkylaluminum hydride such as diethylaluminum hydride and dibutylaluminum hydride; Partially hydrogenated alkylaluminum such as alkylaluminum dihydride such as ethylaluminum dihydride and propylaluminum dihydride; Ethylaluminum ethoxy Illustrative examples include partially alkoxylated and halogenated alkylaluminums such as chloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, and the like.

Examples of the complex alkylated product [B7] include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . A compound similar to the complex alkylated product [B7] can also be used, and an organic aluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom is exemplified. An example of such a compound is (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

  As the organoaluminum compound (b-3), trimethylaluminum and triisobutylaluminum are preferable because they are easily available. Moreover, an organoaluminum compound (b-3) may be used by 1 type, and may use 2 or more types together.

[Carrier (C)]
In the present invention, the carrier (C) may be used as a component of the olefin polymerization catalyst. The carrier (C) is an inorganic compound or an organic compound, and is a granular or particulate solid.

<Inorganic compounds>
Inorganic compounds include porous oxides, inorganic halides, clay minerals, clay (usually composed of the clay mineral as a main component), ion-exchange layered compounds (most clay minerals are ion-exchange layered) A compound)). Examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ ; a composite or a mixture containing these oxides. . The composite or mixture includes natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —. An example is TiO ₂ —MgO. Among these, porous oxides containing as a main component one or both of SiO ₂ and Al ₂ O ₃ are preferable.

The properties of the porous oxide vary depending on the type and production method, but the particle size is preferably 10 to 300 μm, more preferably 20 to 200 μm; the specific surface area is preferably 50 to 1000 m ² / g, more preferably. Is in the range of 100 to 700 m ² / g; the pore volume is preferably in the range of 0.3 to 3.0 cm ³ / g. Such a porous oxide is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary. Examples of inorganic halides include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Moreover, after dissolving the said inorganic halide in solvents, such as alcohol, the component made to deposit into a fine particle form with a depositing agent can also be used.

  The clay, clay mineral, and ion-exchange layered compound are not limited to natural products, and artificial synthetic products can also be used. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak binding force, and the contained ions can be exchanged.

Specifically, as clay and clay minerals, kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, synthetic mica and other ummo groups, montmorillonite group, vermiculite, ryokdeite group, palygorskite, Examples include kaolinite, nacrite, dickite, hectorite, teniolite, halloysite; examples of ion-exchangeable layered compounds include ions having a layered crystal structure such as hexagonal close-packed type, antimony type, CdCl ₂ type, and CdI ₂ type Examples include crystalline compounds. Specifically, as the ion exchange layered compound, α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α- Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ And crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

  It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.

  In addition, the ion-exchangeable layered compound may be a layered compound in which the interlayer is expanded by exchanging the exchangeable ions between the layers with another large bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. For example, an oxide column (pillar) can be formed between layers by intercalating the following metal hydroxide ions between layers of the layered compound and then heat-dehydrating. The introduction of another substance between the layers of the layered compound is called intercalation.

Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ ; metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ and B (OR) ₃ ( R is a hydrocarbon group); metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Is exemplified. These guest compounds may be used alone or in combination of two or more.

In addition, when intercalating a guest compound, it is obtained by hydrolysis and polycondensation of a metal alkoxide (R is a hydrocarbon group, etc.) such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) _4. In addition, a polymer, a colloidal inorganic compound such as SiO ₂ can be coexisted.
Among inorganic compounds, clay minerals and clays are preferable, and montmorillonite group, vermiculite, hectorite, teniolite and synthetic mica are particularly preferable.

<Organic compounds>
Examples of the organic compound include a granular or particulate solid having a particle size in the range of 10 to 300 μm. Specifically, a polymer synthesized mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene; synthesized from vinylcyclohexane and styrene as main components Examples of such polymers are modified products of these polymers.

[Organic compound component (D)]
In the present invention, the organic compound component (D) may be used as a component of the olefin polymerization catalyst. The organic compound component (D) is used for the purpose of improving the polymerization performance in the polymerization reaction of α-olefin and the physical properties of the olefin polymer, if necessary. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

[Usage and order of addition of each component]
In the case of olefin polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified. Hereinafter, the metallocene compound (A), the compound (B), the carrier (C) and the organic compound component (D) are also referred to as “component (A)” to “component (D)”, respectively.
(1) A method of adding the component (A) alone to the polymerization vessel.
(2) A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.
(3) a catalyst component having component (A) supported on component (C);
A method of adding the component (B) to the polymerization vessel in an arbitrary order.
(4) a catalyst component carrying component (B) on component (C);
A method of adding the component (A) to the polymerization vessel in an arbitrary order.
(5) A method in which a catalyst component in which component (A) and component (B) are supported on component (C) is added to a polymerization vessel.
(6) A method of adding the component (A), the component (B) and the component (D) to the polymerization vessel in an arbitrary order.

  In each of the above methods (2) to (6), at least two of the catalyst components may be contacted in advance. In the above methods (4) and (5) in which the component (B) is supported, the component (B) that is not supported may be added in any order as necessary. In this case, the component (B) may be the same or different. Further, the solid catalyst component in which the component (C) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) In addition, a catalyst component may be further supported on the prepolymerized solid catalyst component.

[Olefin polymer production method]
The method for producing an olefin polymer of the present invention is at least one selected from α-olefins having 2 to 20 carbon atoms under the polymerization temperature conditions of 50 ° C. or more and 200 ° C. or less in the presence of the olefin polymerization catalyst. A step of polymerizing seed monomers. Here, “polymerization” is used as a generic term for homopolymerization and copolymerization. In addition, “polymerize monomers in the presence of an olefin polymerization catalyst” means that each component of the olefin polymerization catalyst is added to the polymerization vessel by any method as in the above methods (1) to (6). And an embodiment in which the monomer is polymerized.

  For example, by polymerizing at least propylene in the presence of the olefin polymerization catalyst, the structural unit derived from propylene is 50 to 100 mol%, preferably 55 to 100 mol%, more preferably 80 to 100 mol%, particularly Preferably, an olefin polymer containing 90 mol% to 100 mol% or less is produced. However, the total of the content of structural units derived from propylene and the content of structural units derived from α-olefins having 2 to 20 carbon atoms other than propylene is 100 mol%.

  Further, when copolymerizing propylene and an α-olefin having 2 to 20 carbon atoms other than propylene, the constituent unit derived from propylene is preferably 50 to 95 mol%, more preferably 55 to 95 mol%, particularly preferably. Is contained in the range of 55 to 90 mol%, and the total of structural units derived from α-olefins having 2 to 20 carbon atoms other than propylene are preferably 5 to 50 mol%, more preferably 5 to 45 mol%, particularly preferably. An olefin polymer containing in the range of 10 to 45 mol% is produced. However, the total of the content of structural units derived from propylene and the content of structural units derived from α-olefins having 2 to 20 carbon atoms other than propylene is 100 mol%.

  In addition to the above, for example, by polymerizing at least 4-methyl-1-pentene, the structural unit derived from 4-methyl-1-pentene is 50 to 100 mol%, preferably 55 to 100 mol%, more preferably 80. An olefin polymer containing -100 mol%, particularly preferably more than 90 mol% and not more than 100 mol% is produced. However, the total of the content of structural units derived from 4-methyl-1-pentene and the content of structural units derived from α-olefins having 2 to 20 carbon atoms other than 4-methyl-1-pentene is 100 mol%.

  In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. An inert hydrocarbon medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. In addition, a so-called bulk polymerization method in which liquefied olefin itself that can be supplied to the polymerization is used as a solvent can also be used.

  When the monomer is polymerized using the olefin polymerization catalyst, the amount of each component that can constitute the olefin polymerization catalyst is as follows. In the olefin polymerization catalyst, the content of each component can be set as follows.

(1) When a monomer is polymerized using an olefin polymerization catalyst, the metallocene compound (A) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻ , per liter of reaction volume. It is used in such an amount that it becomes ² mol.

  (2) When the organoaluminum oxy compound (b-1) is used as a component of the olefin polymerization catalyst, the compound (b-1) is composed of an aluminum atom (Al) in the compound (b-1) and a metallocene compound ( The molar ratio [Al / M] to all transition metal atoms (M) in A) is usually 0.01 to 5000, preferably 0.05 to 2000.

  (3) When the ionic compound (b-2) is used as a component of the olefin polymerization catalyst, the compound (b-2) is composed of all transition metal atoms in the compound (b-2) and the metallocene compound (A). The molar ratio [(b-2) / M] to (M) is usually 1 to 10, preferably 1 to 5.

  (4) When the organoaluminum compound (b-3) is used as a component of the olefin polymerization catalyst, the compound (b-3) is composed of all transition metal atoms in the compound (b-3) and the metallocene compound (A). The molar ratio [(b-3) / M] to (M) is usually 10 to 5000, preferably 20 to 2000.

  (5) When the organic compound component (D) is used as a component of the olefin polymerization catalyst, when the compound (B) is the organoaluminum oxy compound (b-1), the organic compound component (D) and the compound ( the molar ratio [(D) / (b-1)] to b-1) is usually 0.01 to 10, preferably 0.1 to 5; compound (B) is ionic. When it is the compound (b-2), the molar ratio [(D) / (b-2)] of the organic compound component (D) and the compound (b-2) is usually 0.01 to 10, preferably Is an amount such that 0.1 to 5; when the compound (B) is an organoaluminum compound (b-3), the molar ratio of the organic compound component (D) to the compound (b-3) [( D) / (b-3)] is usually used in such an amount that it is 0.01 to 2, preferably 0.005 to 1.

  In the production method of the present invention, the polymerization temperature of the monomer is usually 50 to 200 ° C., preferably 50 to 180 ° C., particularly preferably 50 to 150 ° C. (in other words, particularly preferably an industrializable temperature. ); The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen or the like to exist in the polymerization system, changing the polymerization temperature, or using the component (B).

  The production method of the present invention produces an olefin polymer such as a propylene polymer having a high stereoregularity and a high molecular weight while maintaining a high catalytic activity even under high temperature conditions advantageous in an industrial production method. Is possible.

  In particular, hydrogen can be said to be a preferable additive because it can improve the polymerization activity of the catalyst and increase or decrease the molecular weight of the polymer. When hydrogen is added to the system, the amount is suitably about 0.00001 to 100 NL per mole of monomer. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system is not limited to the method of generating or consuming hydrogen in the system, the method of separating hydrogen using a membrane, It can also be adjusted by releasing the gas out of the system.

  For the olefin polymer obtained by the production method of the present invention, after synthesis by the above method, a post-treatment step such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step is performed as necessary. It's okay.

<monomer>
In the production method of the present invention, the monomer supplied to the polymerization reaction is, for example, at least one olefin selected from α-olefins having 2 to 20 carbon atoms.

  Examples of the α-olefin having 2 to 20 carbon atoms include linear or branched α-olefins. Examples of linear or branched α-olefins include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl. Examples include -1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-icocene. At least one selected from α-olefins having 2 to 10 carbon atoms is preferable, and propylene is particularly preferable. The α-olefin may be used alone or in combination of two or more.

  When using propylene as the α-olefin, at least one olefin A selected from ethylene and an α-olefin having 4 to 20 carbon atoms can be used in combination as necessary. The olefin A that can be used together with propylene is preferably at least one selected from ethylene and an α-olefin having 4 to 10 carbon atoms. For example, ethylene, 1-butene, 1-pentene, 3-methyl-1- Examples include butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene and 1-decene. Among these, at least one selected from ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene is more preferable, and ethylene is more preferable. In the case of copolymerization, the copolymerization of propylene and ethylene is most preferred.

  When propylene is used as the α-olefin and the olefin A is used, the amount ratio of propylene to the olefin A is propylene: olefin A (molar ratio), usually 1:10 to 5000: 1, preferably 1: 5 to 1000: 1.

  Further, at least one selected from a cyclic olefin, a polar group-containing monomer, a terminal hydroxylated vinyl compound, and an aromatic vinyl compound can be allowed to coexist in the reaction system to proceed the polymerization. It is also possible to use polyene in combination. Further, other components such as vinylcyclohexane may be copolymerized without departing from the spirit of the present invention. The other monomer can be used in an amount of, for example, 50 parts by mass or less, preferably 40 parts by mass or less with respect to 100 parts by mass of the α-olefin having 2 to 20 carbon atoms.

  Examples of the cyclic olefin include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

Examples of polar group-containing monomers include:
Α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride Acids and their metal salts such as sodium, potassium, lithium, zinc, magnesium, calcium, and aluminum salts;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid α, β-unsaturated carboxylic acid esters such as n-propyl, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; unsaturated glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. Glycidyl;
Is mentioned.

  Examples of the terminal hydroxylated vinyl compound include hydroxyl-1-butene, hydroxyl-1-pentene, hydroxyl-1-hexene, hydroxyl-1-octene, hydroxyl-1-decene, hydroxyl-1- Linear terminal hydroxylated vinyl compounds such as undecene, hydroxylated 1-dodecene, hydroxylated 1-tetradecene, hydroxylated 1-hexadecene, hydroxylated 1-octadecene, hydroxylated 1-eicocene; -3-methyl-1-butene, hydroxyl-3-methyl-1-pentene, hydroxyl-4-methyl-1-pentene, hydroxyl-3-ethyl-1-pentene, hydroxyl-4,4-dimethyl -1-pentene, hydroxyl-4-methyl-1-hexene, hydroxyl-4,4-dimethyl-1-hexene, hydroxyl-4-ethyl-1-hexene, hydroxyl-3-ethyl-1-hexene Branched terminal hydroxyl acid such as Vinyl compounds.

  Examples of the aromatic vinyl compound include styrene; o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, and the like. Or polyalkylstyrene; methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, and other functional group-containing styrene derivatives; 3-phenyl Examples include propylene, 4-phenylpropylene, and α-methylstyrene.

  The polyene is preferably selected from diene and triene. It is also a preferred embodiment that polyene is used in the range of 0.0001 to 1 mol% with respect to the total olefin supplied to the polymerization reaction.

  Examples of the dienes include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1, Α, ω-non-conjugated dienes such as 9-decadiene; non-conjugated such as ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene Diene; conjugated dienes such as butadiene and isoprene are exemplified. Among these, α, ω-nonconjugated dienes and dienes having a norbornene skeleton are preferable.

  Examples of the triene include 6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene, 5,9-dimethyl-1,4,8-decatriene, 6,9-dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, 4- Ethylidene-1,6, -octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene (EMND), 7-methyl-4-ethylidene-1, 6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylidene-1,7- Nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecane Nonconjugated trienes such as ene; include trienes such as 1,3,5-hexatriene. Among these, non-conjugated triene having a double bond at the terminal, 4,8-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene (EMND) is preferable.

  Each of the diene or triene may be used alone or in combination of two or more. A combination of diene and triene may also be used. Among the polyenes, α, ω-nonconjugated dienes and polyenes having a norbornene skeleton are particularly preferable.

[Olefin polymer]
According to the present invention, in the presence of an olefin polymerization catalyst containing a useful and novel metallocene compound (A) having the above-described specific structure, one or more α-olefins having 2 to 20 carbon atoms are obtained. By polymerization; preferably by polymerizing propylene and optionally at least one olefin A selected from ethylene and an α-olefin having 4 to 20 carbon atoms; -An olefin polymer is efficiently produced by polymerizing pentene and, if necessary, at least one olefin B selected from α-olefins having 2 to 20 carbon atoms other than 4-methyl-1-pentene. can do.

  As one aspect 1 of the olefin polymer of the present invention, the constituent unit derived from propylene is 50 to 100 mol%, preferably 55 to 100 mol%, more preferably 80 to 100 mol%, particularly preferably more than 90 mol%. And a propylene polymer contained in a range of 100 mol% or less. However, the total of the content of the structural unit derived from propylene and the content of the structural unit derived from olefin A is 100 mol%.

  In the olefin polymer of the above aspect 1, the melting point peak (Tm) determined by a differential scanning calorimeter (DSC) is preferably 150 to 170 ° C, more preferably 155 to 170 ° C.

  Moreover, as one aspect 2 of the olefin polymer of this invention, the structural unit derived from propylene becomes like this. Preferably it contains 50-95 mol%, More preferably, it is 55-95 mol%, Most preferably, it is 55-90 mol%. A propylene polymer is mentioned. The propylene polymer preferably contains 5 to 50 mol%, more preferably 5 to 45 mol%, and particularly preferably 10 to 45 mol% of the structural units derived from the olefin A in total. However, the total of the content of the structural unit derived from propylene and the content of the structural unit derived from olefin A is 100 mol%. The propylene polymer in which the structural unit derived from the olefin A is in the above range is excellent in molding processability.

  In addition to the above, as an embodiment 3 of the olefin polymer of the present invention, the structural unit derived from 4-methyl-1-pentene is 50 to 100 mol%, preferably 55 to 100 mol%, more preferably 80 to 100 mol. %, Particularly preferably a 4-methyl-1-pentene polymer contained in the range of more than 90 mol% and not more than 100 mol%. However, the total of the content of structural units derived from 4-methyl-1-pentene and the content of structural units derived from olefin B is 100 mol%.

  Moreover, the said olefin polymer may contain the other structural unit in the range which does not deviate from the meaning of this invention. These contents can be measured by nuclear magnetic resonance spectroscopy or, if there is a reference substance, infrared spectroscopy.

  Among these polymers, propylene homopolymer, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer, propylene / 1-octene polymer, propylene / 1 -Hexene polymer, propylene / 4-methyl-1-pentene polymer, propylene / ethylene / 1-octene polymer, propylene / ethylene / 1-hexene polymer, propylene / ethylene / 4-methyl-1-pentene polymer 4-methyl-1-pentene homopolymer is particularly preferred. Moreover, what is called a block copolymer (impact copolymer) obtained by mixing or manufacturing continuously 2 or more types selected from these polymers may be sufficient.

  Among the polymers having the structural units described above, the olefin polymer of the present invention is preferably an α-olefin polymer consisting essentially of structural units derived from an α-olefin having 2 to 20 carbon atoms. A propylene polymer consisting of only a propylene-derived constituent unit, a propylene / ethylene copolymer consisting essentially of a propylene-derived constituent unit and an ethylene-derived constituent unit, substantially derived from 4-methyl-1-pentene. A 4-methyl-1-pentene polymer consisting only of structural units is most preferred. “Substantially” means that in the α-olefin polymer, the proportion of the structural unit derived from the α-olefin having 2 to 20 carbon atoms is 95% by weight or more with respect to all the structural units, and in the propylene polymer, The proportion of propylene-derived structural units is 95% by weight or more, and in the propylene / ethylene copolymer, the total proportion of propylene-derived structural units and ethylene-derived structural units is 95% by weight or more, and the 4-methyl In a -1-pentene polymer, it means that the proportion of structural units derived from 4-methyl-1-pentene is 95% by weight or more.

  In the olefin polymer of the present invention, the weight average molecular weight measured by a gel permeation chromatography (GPC) method is preferably 10,000 to 1,000,000, more preferably 80,000 to 500,000, particularly preferably 90,000 to 40. Ten thousand. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is preferably 1.0 to 8.0, more preferably 1.5 to 8.0, particularly preferably. Is 1.8 to 7.0.

  In the olefin polymer of the present invention, the intrinsic viscosity [η] in 135 ° C. decalin is preferably 0.5 to 20 dl / g, more preferably 1.0 to 20 dl / g, and particularly preferably 1.0 to 5. 0 dl / g.

  In the olefin polymer of the present invention, the melt mass flow rate (MFR; unit is g / 10 minutes) measured according to ASTM D1238 (230 ° C., load 2.16 kg) is preferably in the range of 0.1 ≦ MFR ≦ 150, more preferably Is in the range of 0.1 ≦ MFR ≦ 100. The olefin polymer in the above range is excellent in molding processability.

Details of the measurement conditions of the above physical property values are as described in the examples.
In the method for producing an olefin polymer according to the present invention, the obtained olefin polymer preferably satisfies the following requirements (ia) to (iia) at the same time. The reason why the following range is preferable is that the molding processability of the resulting olefin polymer is improved.
(Ia) Propylene-derived structural unit (P) is 50 mol% ≦ P ≦ 100 mol%
(Iia) The intrinsic viscosity [η] in decalin at 135 ° C. is 0.5 dl / g ≦ [η] ≦ 20 dl / g
Moreover, it is more preferable that the obtained olefin polymer simultaneously satisfies the following requirements (ib) to (iib). The reason why the following range is preferable is that the molding processability of the resulting olefin polymer is improved.
(Ib) The ethylene-derived structural unit (E) is 0 mol% ≦ E ≦ 50 mol%, and the propylene-derived structural unit (P) is 50 mol% ≦ P ≦ 100 mol%.
(Iib) The intrinsic viscosity [η] in 135 ° C. decalin is 0.5 dl / g ≦ [η] ≦ 20 dl / g
It is further preferable that the obtained olefin polymer satisfies the following requirements (ic) to (iic) at the same time. The reason why the following range is preferable is that the molding processability of the resulting olefin polymer is improved.
(Ic) The melting point peak (Tm) determined by a differential scanning calorimeter (DSC) is 150 ° C. ≦ Tm ≦ 170 ° C.
(Iic) Intrinsic viscosity [η] in decalin at 135 ° C. is 0.5 dl / g ≦ [η] ≦ 20 dl / g

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. First, a method for measuring physical properties and properties of an olefin polymer will be described.

[Melting point (Tm), crystallization temperature (Tc)]
The melting point (Tm) and crystallization temperature (Tc) of the olefin polymer were measured as follows using DSC Pyris 1 or DSC 7 manufactured by PerkinElmer. Under a nitrogen atmosphere (20 mL / min), the sample (about 5 mg) was (1) heated to 230 ° C. and held at 230 ° C. for 10 minutes, and (2) cooled to 30 ° C. at 10 ° C./min at 30 ° C. After holding for 1 minute, (3) the temperature was raised to 230 ° C. at 10 ° C./min. The melting point (Tm) was calculated from the peak vertex of the crystal melting peak in the temperature raising process (3), and the crystallization temperature (Tc) was calculated from the peak vertex of the crystallization peak in the temperature lowering process (2). In the olefin polymers described in Examples and Comparative Examples, when a plurality of crystal melting peaks are observed (for example, the low temperature side peak Tm1 and the high temperature side peak Tm2), the high temperature side peak is regarded as the melting point of the olefin polymer. (Tm).

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the olefin polymer is a value measured at 135 ° C. using a decalin solvent. That is, granulated pellets (about 20 mg) of an olefin polymer are dissolved in a decalin solvent (15 mL), and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After the decalin solution (5 mL) is added to the decalin solution for dilution, the specific viscosity ηsp is measured in the same manner as described above. This dilution operation is further repeated twice, and the value of ηsp / C when the concentration (C) of the olefin polymer is extrapolated to 0 is defined as the intrinsic viscosity [η] of the olefin polymer.
Intrinsic viscosity [η] = lim (ηsp / C) (C → 0)

[Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. The separation columns were TSKgel GNH6-HT: 2 and TSKgel GNH6-HTL: 2; both column sizes were 7.5 mm in diameter and 300 mm in length, the column temperature was 140 ° C., and the mobile phase was o- Using dichlorobenzene (Wako Pure Chemical Industries) and 0.025% by weight of BHT (Takeda Pharmaceutical) as an antioxidant, the mobile phase was moved at 1.0 mL / min, the sample concentration was 15 mg / 10 mL, and sample injection The amount was 500 microliters, and a differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ . The molecular weight distribution and various average molecular weights were calculated in terms of polypropylene molecular weight according to the general calibration procedure.

[Measurement of ethylene content (E) and propylene content (P)]
The ethylene content (E) and the propylene content (P) were measured by using a Fourier transform infrared spectrophotometer FT / IR-610 manufactured by JASCO Corporation, and an area near a rolling vibration of 1155 cm ⁻¹ based on the methyl group of propylene and C− Absorbance in the vicinity of overtone absorption 4325 cm ⁻¹ due to H stretching vibration was determined, and calculated from the ratio by a calibration curve (prepared using a standard sample standardized by ¹³ C-NMR).

(Identification of target)
The structure of the metallocene compound obtained in the synthesis example was determined using 270 MHz ¹ H-NMR (JEOL GSH-270) and FD-MS (JEOL SX-102A).

(Synthesis of metallocene compounds)
[Synthesis Example 1] Catalyst (a): 1- (4- (2,7-diphenyl-3,6-di-tert-butylfluorenyl) (4,6,6-trimethyl-3a, 4,5, Synthesis of 6-tetrahydropentalenyl) adamantane) zirconium dichloride

[Synthesis Example 1-1] Ligand 1A: 1- (4- (9H-2,7-diphenyl-3,6-di-tert-butylfluorenyl) -4,6,6-trimethyl-3a, Synthesis of 4,5,6-tetrahydropentalen-2-yl) adamantane 2,7-diphenyl-3,6-di-tert-butylfluorene (1.28 g, 2.97 mmol) was tert-butyl methyl ether (150 mL) ) And cooled to -10 ° C. A 1.6M n-butyllithium hexane solution (1.9 mL, 3.1 mmol) was slowly added thereto, and the temperature was gradually raised to 50 ° C., followed by stirring for 2 hours. Cool to −10 ° C., add (4,4,6-trimethyl-4,5-dihydropentalen-2-yl) adamantane (1.0 g, 3.56 mmol) and follow the reaction at 50 ° C. Stir for 4 hours. The reaction vessel was cooled to 0 ° C., saturated aqueous ammonium chloride solution was added to stop the reaction, and the organic layer was extracted twice with hexane. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and filtered. The organic layer was concentrated, 10 ml of methylene chloride was added, and this was added dropwise to 250 ml of stirred methanol. The resulting precipitate was collected by filtration with a Kiriyama filter, and the filtered product was washed with methanol. The obtained powder was dried under reduced pressure to obtain 1.9 g (yield 90%) of the ligand 1A. Formation of the target product was confirmed by FD-MS measurement.
FD-MS: m / Z = 710 (M ⁺ )

[Synthesis Example 1-2] Synthesis of catalyst (a) Under a nitrogen atmosphere, the previously obtained ligand 1A (0.71 g, 1.0 mmol), α-methylstyrene (0.28 mL), cyclopentylmethyl ether ( 1.7 mL) and hexane (25 ml) were added and cooled to −78 ° C. A 1.63 M n-butyllithium hexane solution (1.3 mL, 2.2 mmol) was slowly added thereto, and the mixture was stirred at 50 ° C. for 4 hours. After concentration under reduced pressure, diethyl ether (40 ml) was added and the mixture was cooled to -78 ° C. Zirconium tetrachloride (0.23 g, 1 mmol) was added, the temperature was gradually raised to room temperature, and the mixture was stirred for 24 hours. The solvent was distilled off under reduced pressure, hexane (200 mL) was added, filtration was performed, and the organic layer was concentrated under reduced pressure. After washing with hexane and drying the precipitate, 650 mg (yield 75%) of the target catalyst (a) was obtained. Formation of the target product was confirmed by ¹ H-NMR (CDCl ₃ ) and FD-MS measurement.
¹ H-NMR (ppm, CDCl ₃ ): 8.1-7.8 (2H), 7.3-7.1 (12H), 6.0-5.3 (2H), 4.0-3. 9 (1H), 2.2-1.0 (44H)
FD-MS: m / Z = 868 (M ⁺ )

  [Synthesis Example 2] Catalyst (b): [1- (8- (3,6-di-tert-butyl-2,7-diphenyl-fluorenyl) -8-methyl-3b, 4,5,6,7, 7a, 8,8a-Octahydrocyclopentaindenyl) adamantane] zirconium dichloride

[Synthesis Example 2-1] Ligand 1B: 1- (8- (3,6-di-tert-butyl-2,7-diphenyl-fluorenyl) -8-methyl-3b, 4,5,6,7 , 7a, 8,8a-Octahydrocyclopentaindenyl) adamantane (4,4,6-trimethyl-4,5-dihydropentalen-2-yl) adamantane used in Synthesis Example 1-1 was (8-Methyl-3b, 4,5,6,7,7a-hexahydrocyclopenta [a] inden-2-yl) Except that it was changed to adamantane, it was carried out in the same manner as in Synthesis Example 1-1 and was the target product 3.0 g (yield 82%) of the ligand 1B was obtained. Formation of the target product was confirmed by ¹ H-NMR (CDCl ₃ ) and FD-MS measurement.
¹ H-NMR (ppm, CDCl ₃ ): 7.9-7.8 (2H), 7.3-7.1 (12H), 6.5-5.8 (2H), 4.0-3. 9 (1H), 2.8-1.0 (47H)
FD-MS: m / Z = 737 (M ⁺ )

[Synthesis Example 2-2] Synthesis of Catalyst (b) Synthesis Example 1-2 except that the ligand 1A used in Synthesis Example 1-2 was changed to the ligand 1B obtained in Synthesis Example 2-1. Then, 500 mg (yield 27%) of the target catalyst (b) was obtained. Formation of the target product was confirmed by ¹ H-NMR (CDCl ₃ ) and FD-MS measurement.
¹ H-NMR (ppm, CDCl ₃ ): 8.2-8.0 (2H), 7.5-7.0 (12H), 6.2 (1H), 5.2 (1H), 3.5 -3.3 (2H), 2.1-1.0 (44H)
FD-MS: m / Z = 894 (M ⁺ )

  Synthesis Example 3 Catalyst (c): [1- (8- (3,6-di-tert-butyl-2,7-di-p-chlorophenyl-fluorenyl) -8-methyl-3b, 4,5, Synthesis of 6,7,7a, 8,8a-octahydrocyclopentaindenyl) adamantane] zirconium dichloride

[Synthesis Example 3-1] Ligand 1C: 1- (8- (3,6-di-tert-butyl-2,7-di-p-chlorophenyl-fluorenyl) -8-methyl-3b, 4,5 , 6,7,7a, 8,8a-Octahydrocyclopentaindenyl) adamantane 2,7-diphenyl-3,6-di-tert-butylfluorene used in Synthesis Example 2-1 Except for changing to di-p-chlorophenyl-3,6-di-tert-butylfluorene, the same procedure as in Synthesis Example 2-1 was performed to obtain 1.6 g (yield 40%) of the target ligand 1C. It was. Formation of the target product was confirmed by ¹ H-NMR (CDCl ₃ ) and FD-MS measurement.
¹ H-NMR (ppm, CDCl ₃ ): 7.9-7.8 (2H), 7.3-7.1 (10H), 6.5-5.8 (2H), 4.0-3. 9 (1H), 2.8-1.0 (47H)
FD-MS: m / Z = 804 (M ⁺ )

[Synthesis Example 3-2] Synthesis of Catalyst (c) Synthesis Example 2-2 except that the ligand 1B used in Synthesis Example 2-2 was changed to the ligand 1C obtained in Synthesis Example 3-1. In the same manner as above, 250 mg (yield 13%) of the target catalyst (c) was obtained. Formation of the target product was confirmed by ¹ H-NMR (CDCl ₃ ) and FD-MS measurement.
¹ H-NMR (ppm, CDCl ₃ ): 8.0-7.8 (2H), 7.5-7.0 (12H), 6.5-5.8 (2H), 3.9-1. 0 (44H)
FD-MS: m / Z = 962 (M ⁺ )

  Synthesis Example 4 Catalyst (d): [1- (8- (3,6-di-tert-butyl-2,7-di-o-methylphenyl-fluorenyl) -8-methyl-3b, 4,5 , 6,7,7a, 8,8a-octahydrocyclopentaindenyl) adamantane] zirconium dichloride

[Synthesis Example 4-1] Ligand 1D: 1- (8- (3,6-di-tert-butyl-2,7-di-o-methylphenyl-fluorenyl) -8-methyl-3b, 4 Synthesis of 5,6,7,7a, 8,8a-octahydrocyclopentaindenyl) adamantane 2,7-diphenyl-3,6-di-tert-butylfluorene used in Synthesis Example 2-1 was replaced with 3,6 The same procedure as in Synthesis Example 2-1 except that the compound was changed to -di-tert-butyl-2,7-di-o-methylphenyl-fluorene, and 1.6 g (yield 42) of the target ligand 1D was obtained. %)Obtained. Formation of the target product was confirmed by ¹ H-NMR (CDCl ₃ ) and FD-MS measurement.
¹ H-NMR (ppm, CDCl ₃ ): 7.9-7.8 (2H), 7.3-7.1 (10H), 6.5-5.8 (2H), 4.0-3. 9 (1H), 2.8-1.0 (53H)
FD-MS: m / Z = 765 (M ⁺ )

[Synthesis Example 4-2] Synthesis of Catalyst (d) Synthesis Example 2-2 except that the ligand 1B used in Synthesis Example 2-2 was changed to the ligand 1D obtained in Synthesis Example 4-1. In the same manner as above, 250 mg (yield: 13%) of the target catalyst (d) was obtained. Formation of the target product was confirmed by ¹ H-NMR (CDCl ₃ ) and FD-MS measurement.
¹ H-NMR (ppm, CDCl ₃ ): 7.9-7.8 (2H), 7.3-7.1 (10H), 6.5-5.8 (2H), 4.0-3. 9 (1H), 2.8-1.0 (51H)
FD-MS: m / Z = 922 (M ⁺ )

  Synthesis Example 5 Catalyst (e): [1- (8- (3,6-di-tert-butyl-2,7-di-p-methylphenyl-fluorenyl) -8-methyl-3b, 4,5 , 6,7,7a, 8,8a-octahydrocyclopentaindenyl) adamantane] zirconium dichloride

[Synthesis Example 5-1] Ligand 1E: 1- (8- (3,6-di-tert-butyl-2,7-di-p-methylphenyl-fluorenyl) -8-methyl-3b, 4 Synthesis of 5,6,7,7a, 8,8a-octahydrocyclopentaindenyl) adamantane 2,7-diphenyl-3,6-di-tert-butylfluorene used in Synthesis Example 2-1 was replaced with 3,6 Except that it was changed to -di-tert-butyl-2,7-di-p-methylphenyl-fluorene, it was carried out in the same manner as in Synthesis Example 2-1, and 2.0 g (yield 80) of the target ligand 1E was obtained. %)Obtained. Formation of the target product was confirmed by FD-MS measurement.
FD-MS: m / Z = 765 (M ⁺ )

[Synthesis Example 5-2] Synthesis of Catalyst (e) Synthesis Example 2-2 except that the ligand 1B used in Synthesis Example 2-2 was changed to the ligand 1E obtained in Synthesis Example 5-1. 280 mg (yield 15%) of the target catalyst (e) was obtained. Formation of the target product was confirmed by ¹ H-NMR (CDCl ₃ ) and FD-MS measurement.
¹ H-NMR (ppm, CDCl ₃ ): 8.2-8.0 (2H), 7.3-7.1 (10H), 6.2-5.4 (2H), 3.6-3. 3 (1H), 2.4-1.0 (51H)
FD-MS: m / Z = 922 (M ⁺ )

  [Synthesis Example 6] Catalyst (f): Synthesis of 1- (4- (fluorenyl) (4,6,6-trimethyl-3a, 4,5,6-tetrahydropentalenyl) adamantane) zirconium dichloride

Synthesis Example 6-1 Synthesis of Ligand 1F: 1- (4-Fluorenyl-4,6,6-trimethyl-3a, 4,5,6-tetrahydropentalen-2-yl) adamantane Under a nitrogen atmosphere, A 100 mL three-necked flask was charged with 1.73 g of fluorene and 150 mL of tert-butyl methyl ether. In an ice-water bath, 4.0 mL of a 1.63 M n-butyllithium hexane solution was added dropwise over 5 minutes, and the mixture was stirred at 50 ° C. for 30 minutes. After returning to room temperature, 2.00 g of 5-adamantyl-1,1-dimethyl-3-methyl-1,2-dihydropentalene was added in an ice water bath. After stirring at 50 ° C. for 7 hours, a saturated aqueous ammonium chloride solution was added, the organic layer was separated, and the aqueous layer was extracted with diethyl ether. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution, water, and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. The obtained solid was washed with methanol and acetone to obtain 1.58 g of the target ligand 1F. Formation of the target product was confirmed by FD-MS measurement.
FD-MS: M / Z = 446 (M ⁺ )

[Synthesis Example 6-2] Synthesis of Catalyst (f) Under a nitrogen atmosphere, 750 mg of ligand 1F, toluene 40 mL, and THF 1 mL were charged into a 100 mL Schlenk flask. 2.16 mL of 1.63 M n-butyllithium hexane solution was added dropwise over 5 minutes in an ice water bath. The mixture was stirred at 50 ° C. for 4 hours. The solvent was distilled off and 50 mL of hexane was inserted. In a dry ice-methanol bath, 336 mg of ZrCl ₄ was charged and stirred for 16 hours while gradually returning to room temperature. The solvent was distilled off, and the soluble component was extracted with hexane and dichloromethane. The resulting solution was concentrated and the soluble component was extracted with cyclohexane. The target product was obtained by distilling off the solvent and drying under reduced pressure. Yield 213.5 mg, yield 21%. Formation of the target product was confirmed by ¹ H-NMR (CDCl ₃ ) and FD-MS measurement.
¹ H-NMR (ppm, CDCl ₃ ): 8.1-7.2 (8H), 6.1 (1H), 5.3 (1H), 4.0 (1H), 2.7 (1H), 2.4 (3H), 2.1-1.6 (15H), 1.5-1.4 (6H)
FD-MS: m / Z = 604 (M ⁺ )

  Synthesis Example 7 Catalyst (g): 1- (4- (2,7-diphenyl-3,6-di-tert-butylfluorenyl) (4-methyl-6-isopropyl-3a, 4,5, Synthesis of 6-tetrahydropentalenyl) adamantane) zirconium dichloride

[Synthesis Example 7-1] Ligand 1G: 1- (4- (9H-2,7-diphenyl-3,6-di-tert-butylfluorenyl) -4-methyl-6-isopropyl-3a, Synthesis of 4,5,6-tetrahydropentalen-2-yl) adamantane 2,7-diphenyl-3,6-di-tert-butylfluorene (0.84 g, 1.95 mmol) was tert-butyl methyl ether (150 mL) ) And cooled to -10 ° C. A 1.6 M n-butyllithium hexane solution (1.28 mL, 2.04 mmol) was slowly added thereto, and the temperature was gradually raised to 50 ° C., followed by stirring for 2 hours. Cool to −10 ° C., add (4-methyl-6-isopropyl-4,5-dihydropentalen-2-yl) adamantane (0.57 g, 1.95 mmol) and follow the reaction at 50 ° C. Stir for 4 hours. The reaction vessel was cooled to 0 ° C., saturated aqueous ammonium chloride solution was added to stop the reaction, and the organic layer was extracted twice with hexane. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and filtered. The organic layer was concentrated, 10 ml of methylene chloride was added, and this was added dropwise to 250 ml of stirred methanol. The resulting precipitate was collected by filtration with a Kiriyama filter, and the filtered product was washed with methanol. The obtained powder was dried under reduced pressure to obtain 1.0 g of ligand 1G (yield: 70.7%). Formation of the target product was confirmed by FD-MS measurement.
FD-MS: m / Z = 725 (M ⁺ )

[Synthesis Example 7-2] Synthesis of Catalyst (g) Under a nitrogen atmosphere, the previously obtained ligand 1G (1.0 g, 1.38 mmol), α-methylstyrene (0.43 mL), cyclopentylmethyl ether ( 2.73 mL) and hexane (50 ml) were added and cooled to −78 ° C. A 1.58 M n-butyllithium hexane solution (2.09 mL, 3.3 mmol) was slowly added thereto, followed by stirring at 50 ° C. for 4 hours. After concentration under reduced pressure, diethyl ether (40 ml) was added and the mixture was cooled to -78 ° C. Zirconium tetrachloride (0.32 g, 1.38 mmol) was added, the temperature was gradually raised to room temperature, and the mixture was stirred for 24 hours. The solvent was distilled off under reduced pressure, hexane (200 mL) was added, filtration was performed, and the organic layer was concentrated under reduced pressure. After washing with hexane and drying the precipitate, 300 mg (yield 25%) of the target catalyst (g) was obtained. Formation of the target product was confirmed by ¹ H-NMR (CDCl ₃ ) and FD-MS measurement.
¹ H-NMR (ppm, CDCl ₃ ): 8.1-7.9 (2H), 7.4-7.0 (12H), 6.2-5.0 (2H), 3.4-3. 0 (2H), 2.9-1.0 (44H)
FD-MS: m / Z = 882 (M ⁺ )

[Propylene homopolymerization]
[Example 1]
Under a nitrogen atmosphere, 4.2 μmol of catalyst (a) as a metallocene compound was placed in a Schlenk tube and dissolved in 7.8 mL of dehydrated toluene, and then a suspension of modified methylaluminoxane (trade name: TMAO341, manufactured by Tosoh Finechem Co., Ltd.) 0.72 mL of a liquid (n-hexane solvent, 2.96 M in terms of aluminum atom, 2.13 mmol) was added, and the mixture was stirred at room temperature for 1 hour to prepare a catalyst solution having a catalyst (a) concentration of 0.0005 M.

  In a SUS autoclave with an internal volume of 15 mL sufficiently purged with nitrogen, 0.2 mL (0.05 M, 10 μmol) of an n-heptane solution of triisobutylaluminum and 3.0 mL of n-heptane as a polymerization solvent were put at 600 rpm. And stirred. The solution was heated to 60 ° C. and then pressurized with propylene until the total pressure was 7 bar.

  To the autoclave, 0.1 mL of the catalyst solution (catalyst (a) 0.05 μmol) and 0.7 mL of n-heptane were added to initiate polymerization. After polymerization at 60 ° C. for 10 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. 50 mL of methanol and a small amount of aqueous hydrochloric acid solution were added to the resulting slurry containing the propylene homopolymer, and the mixture was stirred at room temperature for 1 hour. Thereafter, the propylene homopolymer recovered by filtration was dried under reduced pressure to obtain 0.21 g of propylene homopolymer.

  The polymerization activity was 26 kg-PP / mmol-Zr · hr. The melting point (Tm) of the obtained polymer was 151.0 ° C., the crystallization temperature (Tc) was 111.7 ° C., and [η] was 2.69 dl / g.

[Examples 2 to 6, Comparative Example 1]
Examples 2 to 6 and Comparative Example 1 were carried out in the same manner as in Example 1 except that the metallocene compound used and the polymerization time were changed as shown in Table 4. The results are shown in Table 4.

[Propylene / ethylene copolymer]
[Example 7]
Under a nitrogen atmosphere, a suspension of a modified methylaluminoxane (trade name: TMAO341, manufactured by Tosoh Finechem Co., Ltd.) (n-hexane solvent, 2.96 M in terms of aluminum atom, 500 eq / catalyst (b)) on catalyst (b). And then diluted with toluene to a catalyst (b) concentration of 0.25 mmol / L. Stirring was performed at room temperature for 1 hour to obtain a catalyst solution.

  A glass pressure-resistant container with a volume of 15 mL that has been sufficiently purged with nitrogen is charged with n-heptane solution of triisobutylaluminum (0.05 M, 200 eq / catalyst (b)) and 2.5 mL of n-heptane as a polymerization solvent, and 600 revolutions Stirring was performed at / min. After pressurizing with propylene until the total pressure reached 4 bar, the solution was heated to 60 ° C. and then pressurized with ethylene until the total pressure reached 7 bar.

To the glass pressure vessel, 0.4 mL of the catalyst solution (catalyst (b) 0.10 μmol) and 0.7 mL of n-heptane were added to initiate polymerization. After polymerization for 10 minutes while maintaining the total pressure at 7 bar with ethylene throughout the polymerization time, a small amount of isobutyl alcohol was added to terminate the polymerization. 50 mL of methanol and a small amount of hydrochloric acid aqueous solution were added to the obtained slurry containing propylene / ethylene copolymer, and the mixture was stirred at room temperature for 1 hour. Thereafter, the propylene / ethylene copolymer recovered by filtration was dried under reduced pressure to obtain 0.94 g of a propylene / ethylene copolymer.
The polymerization activity was 56.5 kg / mmol-Zr · hr, [η] of the obtained polymer was 1.02 dl / g, and the ethylene content (C2 content) was 42 mol%.

[Examples 8 to 11]
Example 8 was carried out in the same manner as in Example 7 except that the catalyst (d) was used as the metallocene compound and the initial total pressure was changed to 3 bar with propylene. In Example 9, it implemented like Example 7 except having used catalyst (e) as a metallocene compound and having made reaction time into 20 minutes. Example 10 was carried out in the same manner as in Example 7 except that the catalyst (g) was used as the metallocene compound and the initial total pressure was changed to 3 bar with propylene. In Example 11, it implemented like Example 7 except having used the catalyst (g) as a metallocene compound. The results are shown in Table 5.

  By the method for producing an olefin polymer of the present invention, a useful olefin polymer having a high molecular weight or a high melting point can be economically produced, and the production method of the present invention is extremely valuable industrially.

Claims (17)

(A) a bridged metallocene compound represented by the general formula [1];
(B) (b-1) an organoaluminum oxy compound,
(B-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair,
(B-3) An α having 2 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising at least one compound selected from organoaluminum compounds under polymerization temperature conditions of 50 ° C. or higher and 200 ° C. or lower. -A method for producing an olefin polymer, wherein at least one monomer selected from olefins is polymerized.
[In the formula [1], R ¹ is a tertiary hydrocarbon group, R ² and R ⁷ are groups represented by the general formula [2], and R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different, and R ³ and R ⁶ are a hydrocarbon group, Selected from silicon-containing groups, halogen atoms, and halogen-containing hydrocarbon groups, which may be the same or different, and adjacent substituents other than R ² and R ⁷ may combine with each other to form a ring; Is a Group 4 transition metal and Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons And when there are multiple Qs, they may be the same or different, Is an integer of 1 to 4. ]
[In the formula [2], R ^{13 to} R ¹⁷ are selected from a hydrogen atom, a hydrocarbon group, an oxygen-containing group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different, and adjacent to each other. The substituted groups may be bonded to each other to form a ring. ] The method for producing an olefin polymer according to claim 1, wherein in the general formula [1], R ¹ is a tert-butyl group or a 1-adamantyl group. In the general formula [1], R ⁴ and R ⁵ are hydrogen atoms, The method for producing an olefin polymer according to claim 1 or 2. The method for producing an olefin polymer according to any one of claims 1 to 3, wherein in the general formula [1], R ¹² is a hydrocarbon group having 1 to 20 carbon atoms. In General Formula [1], R ^{8 to} R ¹¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and adjacent substituents among R ^{8 to} R ¹¹ are bonded to each other to form a ring. The method for producing an olefin polymer according to any one of claims 1 to 4, which may be used. In the general formula [2], R ^{13 to} R ¹⁷ are each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a fluorine atom or a chlorine atom. The manufacturing method of the olefin polymer of any one of -5.   The method for producing an olefin polymer according to any one of claims 1 to 6, wherein the olefin polymerization catalyst further contains a carrier (C).   The method for producing an olefin polymer according to any one of claims 1 to 7, wherein at least one of the monomers is propylene. It is a manufacturing method of the olefin polymer of Claim 8, Comprising: The olefin polymer obtained satisfy | fills the following requirements (ia)-(iia) simultaneously, The manufacturing method of the olefin polymer characterized by the above-mentioned.
(Ia) Propylene-derived structural unit (P) is 50 mol% ≦ P ≦ 100 mol%
(Iia) The intrinsic viscosity [η] in decalin at 135 ° C. is 0.5 dl / g ≦ [η] ≦ 20 dl / g It is a manufacturing method of the olefin polymer of Claim 8, Comprising: The olefin polymer obtained satisfy | fills the following requirements (ib)-(iib) simultaneously, The manufacturing method of the olefin polymer characterized by the above-mentioned.
(Ib) The ethylene-derived structural unit (E) is 0 mol% ≦ E ≦ 50 mol%, and the propylene-derived structural unit (P) is 50 mol% ≦ P ≦ 100 mol%.
(Iib) The intrinsic viscosity [η] in 135 ° C. decalin is 0.5 dl / g ≦ [η] ≦ 20 dl / g The method for producing an olefin polymer according to claim 8, wherein the obtained olefin polymer satisfies the following requirements (ic) to (iic) simultaneously.
(Ic) The melting point peak (Tm) determined by a differential scanning calorimeter (DSC) is 150 ° C. ≦ Tm ≦ 170 ° C.
(Iic) Intrinsic viscosity [η] in decalin at 135 ° C. is 0.5 dl / g ≦ [η] ≦ 20 dl / g A bridged metallocene compound represented by the general formula [1].
[In the formula [1], R ¹ is a tertiary hydrocarbon group, R ² and R ⁷ are groups represented by the general formula [2], and R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different, and R ³ and R ⁶ are a hydrocarbon group, Selected from silicon-containing groups, halogen atoms, and halogen-containing hydrocarbon groups, which may be the same or different, and adjacent substituents other than R ² and R ⁷ may combine with each other to form a ring; Is a Group 4 transition metal and Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons And when there are multiple Qs, they may be the same or different, Is an integer of 1 to 4. ]
[In the formula [2], R ^{13 to} R ¹⁷ are selected from a hydrogen atom, a hydrocarbon group, an oxygen-containing group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different, and adjacent to each other. The substituted groups may be bonded to each other to form a ring. ] The bridged metallocene compound according to claim 12, wherein in the general formula [1], R ¹ is a tert-butyl group or a 1-adamantyl group. The bridged metallocene compound according to claim 12 or 13, wherein in the general formula [1], R ⁴ and R ⁵ are hydrogen atoms. In general formula [1], R < ¹² > is a C1-C20 hydrocarbon group, The bridge | crosslinking metallocene compound of any one of Claims 12-14 characterized by the above-mentioned. In General Formula [1], R ^{8 to} R ¹¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and adjacent substituents among R ^{8 to} R ¹¹ are bonded to each other to form a ring. The bridged metallocene compound according to any one of claims 12 to 15, which may be used. In the general formula [2], R ^{13 to} R ¹⁷ are each independently a hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, fluorine atom or chlorine atom. The bridged metallocene compound according to any one of -16.