JP2013060518A - Method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an olefin polymer having high molecular weight, and a high melting point.SOLUTION: The method comprises: polymerizing ≥2C α-olefin under a condition of 40°C or higher temperature in the presence of an olefin polymerization catalyst containing (A) a specific crosslinked metallocene compound in which a cyclopentadienyl group and a fluorenyl group are crosslinked, and (B) at least one compound selected from an organic aluminumoxy compound and organic aluminum compound.

Description

  The present invention relates to a method for producing an olefin polymer using an olefin polymerization catalyst containing a crosslinked metallocene compound having a specific structure, and particularly relates to a method for producing a high molecular weight and high melting point olefin polymer.

  As a homogeneous catalyst for olefin polymerization, a so-called metallocene compound is well known. Regarding the method of polymerizing olefins using metallocene compounds (particularly the method of 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).

  As a part of such research, it is known that as a result of polymerizing propylene in the presence of a specific catalyst, a polypropylene having a high tacticity such that the syndiotactic pentad fraction exceeds 0.7 is obtained. A. Reported by Ewen (Non-Patent Document 2). Here, the specific catalyst includes a metallocene compound having a ligand obtained by crosslinking a cyclopentadienyl group and a fluorenyl group with isopropylidene, and an aluminoxane.

  As an improvement of the metallocene compound, an attempt has been made to improve stereoregularity by changing the fluorenyl group to a 2,7-ditert-butylfluorenyl group (Patent Document 1). In addition, an attempt to improve stereoregularity by changing the fluorenyl group to a 3,6-ditert-butylfluorenyl group (Patent Document 2), or a combination of a cyclopentadienyl group and a fluorenyl group Attempts to improve stereoregularity by converting the cross-linked part (Patent Documents 3 and 4) have been reported.

  On the other hand, as compared with dimethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene (3-tert-butyl-5-5-methylmethyl) introduced with a methyl group also at the 5-position of the cyclopentadienyl ring. It has also been reported that methylcyclopentadienyl) (fluorenyl) zirconium dichloride can obtain high molecular weight isotactic polypropylene (Patent Document 5).

  Further, as a metallocene compound capable of polymerizing at a high temperature and capable of producing a high molecular weight polymer, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- (Butylfluorenyl) zirconium dichloride has also been reported (Patent Document 6).

  Thus, by improving the metallocene compound, (1) an olefin polymer having a high melting point, which is an index of stereoregularity, and (2) an olefin polymer having a high molecular weight are obtained. However, even the above-described metallocene compound still has insufficient polymerization performance for synthesizing an olefin polymer having a high molecular weight and a sufficiently high melting point. For this reason, the efficient manufacture of the olefin polymer which has the said characteristic is desired.

  Furthermore, in order to enable industrial production of these olefin polymers, it is desired to produce olefin polymers having the above characteristics at temperatures higher than room temperature, preferably higher than room temperature. .

Japanese Patent Laid-Open No. 04-069394 JP 2000-212194 A JP 2004-189666 A JP 2004-189667 A Special table 2001-526730 gazette JP 2007-302853 A

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

  The problem to be solved by the present invention is to produce an olefin polymer having a high molecular weight and a sufficiently high melting point, even under high temperature conditions that can be industrialized, when polymerizing olefins such as propylene. Is to provide a method.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using an olefin polymerization catalyst containing a crosslinked metallocene compound having a specific structure, and the present invention has been completed.

That is, the present invention relates to the following [1] to [6].
[1] (A) ion reacts with a bridged metallocene compound represented by the following general formula [1], (B) (b-1) an organoaluminum oxy compound, and (b-2) a bridged metallocene compound (A) In the presence of an olefin polymerization catalyst comprising a compound that forms a pair, and (b-3) at least one compound selected from organoaluminum compounds, α- A method for producing an olefin polymer comprising polymerizing at least one monomer selected from olefins:

〔式［１］において、Ｒ¹〜Ｒ⁴はそれぞれ独立に炭化水素基、ハロゲン置換炭化水素基、窒素含有基、酸素含有基またはケイ素含有基を示し、相互に隣り合う２つの基が結合して環を形成していてもよい。Ｒ⁵は水素原子、ハロゲン原子、炭化水素基、ハロゲン置換炭化水素基、窒素含有基、酸素含有基またはケイ素含有基を示し；Ｙは炭素原子またはケイ素原子を示し；ＭはＴｉ、ＺｒまたはＨｆを示し；Ｑはハロゲン原子、炭化水素基、炭素数が１０以下の中性の共役もしくは非共役ジエン、アニオン配位子または孤立電子対で配位可能な中性配位子を示す。ｊは１〜４の整数を示し、ｊが２以上のときは、複数あるＱは相互に同一でも異なっていてもよい。〕

[In the formula [1], R ^{1 to} R ⁴ each independently represents a hydrocarbon group, a halogen-substituted hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group, and two groups adjacent to each other are bonded to each other. May form a ring. R ⁵ represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-substituted hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group; Y represents a carbon atom or a silicon atom; M represents Ti, Zr or Hf Q represents 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 coordination with a lone electron pair. j represents an integer of 1 to 4, and when j is 2 or more, a plurality of Qs may be the same or different from each other. ]

[2] In the general formula [1], R ¹ and R ⁴ are the same group selected from a hydrocarbon group having 1 to 40 carbon atoms, a halogen-substituted hydrocarbon group, an oxygen-containing group and a silicon-containing group, The method for producing an olefin polymer according to the above [1], wherein both or one of R ² and R ³ is a hydrocarbon group having 1 to 40 carbon atoms or a silicon-containing group.

[3] The olefin polymer as described in [1] or [2], wherein in the general formula [1], R ⁵ is a hydrocarbon group having 6 to 20 carbon atoms or a halogen-substituted hydrocarbon group. Manufacturing method.

[4] The method for producing an olefin polymer according to any one of [1] to [3], wherein the olefin polymerization catalyst further contains a carrier (C).
[5] The method for producing an olefin polymer according to any one of [1] to [4], wherein at least a part of the monomer is propylene.

  [6] In the above [5], an olefin polymer having a weight average molecular weight distribution (Mw) determined by gel permeation chromatography (GPC) of 80,000 or more and a melting point of 150 ° C. or more is produced. The manufacturing method of the olefin polymer of description.

  According to the present invention, there is provided a method for producing an olefin polymer having a high molecular weight and a sufficiently high melting point even under high temperature conditions that can be industrialized when polymerizing olefins such as propylene. be able to.

  The method for producing an olefin polymer according to the present invention comprises (A) a bridged metallocene compound described below and (B) a catalyst for olefin polymerization containing a compound described below under the condition of 40 ° C. or higher. It is characterized by polymerizing at least one monomer selected from two or more α-olefins.

  Hereinafter, the olefin polymerization catalyst containing the bridged metallocene compound (A) and the compound (B) used in the present invention, and a method for polymerizing an α-olefin having 2 or more carbon atoms in the presence of the olefin polymerization catalyst, The best mode for carrying out the invention will be described sequentially.

[Olefin polymerization catalyst]
The catalyst for olefin polymerization used in the present invention reacts with the bridged metallocene compound (A), (B) (b-1) an organoaluminum oxy compound, and (b-2) the bridged metallocene compound (A) to form an ion pair. And (b-3) at least one compound selected from organoaluminum compounds as essential components. Further, the carrier (C) and the organic compound component (D) may be included as optional components.

<< Bridged metallocene compound (A) >>
The bridged metallocene compound (A) used in the present invention is represented by the following general formula [1].

〔式［１］において、Ｒ¹〜Ｒ⁴はそれぞれ独立に炭化水素基、ハロゲン置換炭化水素基、窒素含有基、酸素含有基またはケイ素含有基を示し、相互に隣り合う２つの基が結合して環を形成していてもよい。

[In the formula [1], R ^{1 to} R ⁴ each independently represents a hydrocarbon group, a halogen-substituted hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group, and two groups adjacent to each other are bonded to each other. May form a ring.

R ⁵ represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-substituted hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group; Y represents a carbon atom or a silicon atom; M represents Ti, Zr or Hf Q represents 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 coordination with a lone electron pair. j represents an integer of 1 to 4, and when j is 2 or more, a plurality of Qs may be the same or different from each other. ]
Hereinafter, atoms and groups constituting the bridged metallocene compound (A) will be described.

−About R ^{1 to} R ⁵⁻
As a hydrocarbon group, a C1-C40 hydrocarbon group is preferable and a C1-C20 hydrocarbon group is more preferable. 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.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Linear alkyl groups such as octyl group, n-nonyl group, n-decanyl group; iso-propyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1 -Dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, etc. Examples are branched alkyl groups.

  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. .

  Examples of the aryl group having 6 to 20 carbon atoms include unsubstituted aryl groups such as phenyl group, naphthyl group, phenanthryl group, anthracenyl group, biphenyl group and pyrenyl group; o-tolyl group, m-tolyl group, p-tolyl group, Examples thereof include alkylaryl groups such as ethylphenyl group, n-propylphenyl group, iso-propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group and xylyl group.

  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, neophyll group, and benzhydryl group; o-methyl Benzyl group, m-methylbenzyl group, p-methylbenzyl group, ethylbenzyl group, n-propylbenzyl group, iso-propylbenzyl group, n-butylbenzyl group, sec-butylbenzyl group, tert-butylbenzyl group, etc. An alkylaralkyl group is exemplified.

Examples of the halogen-substituted hydrocarbon group include groups in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom. Specifically, a halogen-substituted alkyl group such as a fluoroalkyl group such as a trifluoromethyl 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-bromophenyl A halogen substituent of the above-mentioned unsubstituted aryl group such as an iodoaryl group such as a bromoaryl group such as a bromonaphthyl group, an o-iodophenyl group, an m-iodophenyl group, a p-iodophenyl group and an iodonaphthyl group; Fluoroalkylaryl group such as fluoromethylphenyl group, bromoalkylaryl group such as bromomethylphenyl group and dibromomethylphenyl group, iodoalkylaryl group such as iodomethylphenyl group and diiodomethylphenyl group Haloge Substituents; a halogen-substituted aryl group such as;
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. Illustrative are halogen-substituted aralkyl groups such as halogen substituents of the above-mentioned unsubstituted aralkyl groups such as bromoaralkyl groups, o-iodobenzyl groups, m-iodobenzyl groups, p-iodobenzyl groups, iodophenethyl groups, etc. The

Examples of the nitrogen-containing group include a nitro group, a cyano group, an N-methylamino group, an N, N-dimethylamino group, and an N-phenylamino group.
Examples of the oxygen-containing group include a methoxy group, an ethoxy group, and a phenoxy group.

  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, Examples include arylsilyl groups such as phenylsilyl groups.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Further, at least one pair selected from R ^{1 to} R ⁴ may be bonded to each other to form a ring. Examples of the ring structure include 1-methyl-2-naphthalenyl group, 3-methyl-2-naphthalenyl group, 1-methyl-2- (5,6,7,8-tetrahydro) naphthalenyl group, 3-methyl-2- (5,6,7,8-tetrahydro) naphthalenyl group, 7-methyl-1H-6-indenyl group, 6-methyl-1H-5-indenyl group, 7-methyl-6-benzofuranyl group, 6-methyl-5 -A benzofuranyl group, 7-methyl-6-benzothiophenyl group, 6-methyl-5-benzothiophenyl group is illustrated.

R ¹ and R ⁴ are preferably each independently the hydrocarbon group, halogen-substituted hydrocarbon group, oxygen-containing group or silicon-containing group, more preferably the hydrocarbon group or halogen-substituted hydrocarbon group, The aryl group or the halogen-substituted aryl group is more preferable, and the phenyl group, the alkylphenyl group, or a halogen substituent thereof is particularly preferable. R ¹ and R ⁴ are preferably the same group.

One or more groups selected from R ² and R ³ are preferably the above hydrocarbon group or silicon-containing group. Further, R ² and R ³ are preferably each independently the hydrocarbon group or silicon-containing group, more preferably the hydrocarbon group, and particularly preferably the alkyl group. R ² and R ³ are preferably the same group.

R ⁵ is preferably the hydrocarbon group or the halogen-substituted hydrocarbon group, more preferably the aryl group, the halogen-substituted aryl group, the aralkyl group or the halogen-substituted aralkyl group, the aryl group, the unsubstituted aryl group. More preferably, it is a halogen substituent of the group or a halogen substituent of the alkylaryl group.

-About M, Y, Q and j-
M represents Ti, Zr or Hf, preferably Zr or Hf, particularly preferably Zr. Y represents a carbon atom or a silicon atom, preferably a carbon atom. By using the cross-linked metallocene compound (A) having the central metal and the cross-linking part, a high molecular weight and high melting point olefin polymer can be efficiently produced.

Q represents a halogen atom (Q), a hydrocarbon group (Q), 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.
Examples of the halogen atom (Q) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  As a hydrocarbon group (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. More preferably, the hydrocarbon group (Q) has 5 or less carbon atoms.

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, tert-butoxy and phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate.

  Neutral ligands that can be coordinated by lone 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.

<Examples of bridged metallocene compounds>
Specific examples of the bridged metallocene compound (A) represented by the general formula [1] are shown below, but the scope of the present invention is not particularly limited thereby. In the present invention, the crosslinked metallocene compound (A) may be used alone or in combination of two or more.

As the bridged metallocene compound (A),
Benzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
Benzylmethylene (cyclopentadienyl) (2,7-di (2,4,6-trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,
Benzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
Benzylmethylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,
Benzylmethylene (cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,
Benzylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
Benzylmethylene (cyclopentadienyl) (2,7-di (4-tert-butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,
(Cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
Phenethylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
(Benzhydryl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
(N-octyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
(1-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
(2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
(1-pyrenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
(P-Chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride is exemplified.

  In the above exemplified compounds, the compounds in which “zirconium” is replaced with “hafnium” or “titanium”, and the metallocene compounds in which “dichloride” is replaced with “dimethyl” or “methylethyl” are also used in the present invention. Included in the metallocene compound (A).

  The bridged metallocene compound (A) represented by the general formula [1] used in the present invention can be produced by a known method, and the production method is not particularly limited. Examples of known production methods include those described in the pamphlet of WO 2001/027124 and WO 2004/087775 by the applicant.

<< Compound (B) >>
In the present invention, the compound (B) is used as a component of the olefin polymerization catalyst. Compound (B) is selected from (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with a bridged metallocene compound (A) to form an ion pair, and (b-3) an organoaluminum compound. At least one kind. In these, combined use with an organoaluminum oxy compound (b-1) and an organoaluminum compound (b-3) is preferable.

-Organoaluminum oxy compound (b-1)-
As the organoaluminum oxy compound (b-1), a conventionally known aluminoxane such as a compound represented by the following general formula [3] and a compound represented by the following general formula [4], represented by the following general formula [5]: Examples thereof include a modified methylaluminoxane having a structure represented by the following formula, and a boron-containing organoaluminum oxy compound represented by the following general formula [6].

式［３］および［４］において、Ｒは炭素数１〜１０の炭化水素基、好ましくはメチル基を示し、ｎは２以上、好ましくは３以上、より好ましくは１０以上の整数を示す。本発明では、式［３］および［４］において、Ｒがメチル基であるメチルアルミノキサンが好適に使用される。

In the formulas [3] and [4], R represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group, and n represents 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 in formulas [3] and [4] is preferably used.

式［５］において、Ｒは炭素数２〜１０の炭化水素基を示し、ｍおよびｎはそれぞれ独立に２以上の整数を示す。複数あるＲは相互に同一でも異なっていてもよい。

In the formula [5], R represents a hydrocarbon group having 2 to 10 carbon atoms, and m and n each independently represents an integer of 2 or more. A plurality of R may be the same or different from each other.

  The modified methylaluminoxane [5] can be prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such modified methylaluminoxane [5] is generally called MMAO (modified methyl aluminoxane). MMAO can be prepared specifically by the methods listed in US4960878 and US5041584.

  In addition, modified methylaluminoxane prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem Co., Ltd. (namely, R in the above general formula [5] is an isobutyl group) is named MMAO or 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 above general formula [3] or [4], MMAO is an aliphatic hydrocarbon, an alicyclic hydrocarbon, and It is soluble in aromatic hydrocarbons.

式［６］において、Ｒ^cは炭素数１〜１０の炭化水素基を示す。複数あるＲ^dはそれぞれ独立に水素原子、ハロゲン原子または炭素数１〜１０の炭化水素基を示す。

In the formula [6], R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. Plural R ^{d s} each independently represent 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 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 used suitably.

  The “benzene-insoluble” 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, particularly preferably in terms of Al atom. An organoaluminum oxy compound that is 2% by weight or less and is insoluble or hardly soluble in benzene.

In the present invention, the organic aluminum oxy compound (b-1) exemplified above may be used alone or in combination of two or more.
—Compound (b-2) that reacts with the bridged metallocene compound (A) to form an ion pair—
As the compound (b-2) that reacts with the bridged metallocene compound (A) to form an ion pair (hereinafter sometimes abbreviated as “ionic compound (b-2)”), JP-A-1-501950 is disclosed. JP, 1-502036, JP 3-179005, JP 3-179006, JP 3-207703, JP 3-207704, JP 2004-51676. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in U.S. Pat. No. 5,321,106. Furthermore, heteropoly compounds and isopoly compounds are also exemplified. In these, as an ionic compound (b-2), the compound represented by following General formula [7] is preferable.

式［７］において、Ｒ^e+としては、Ｈ⁺、オキソニウムカチオン、カルベニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンが例示される。Ｒ^f、Ｒ^g、Ｒ^hおよびＲⁱはそれぞれ独立に有機基、好ましくはアリール基、ハロゲン置換アリール基を示す。

In the formula [7], 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 triphenyl carbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

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

  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.

  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 individually by 1 type, and may use 2 or more types together.
-Organoaluminum compound (b-3)-
Examples of the organoaluminum compound (b-3) include an organoaluminum compound represented by the following general formula [8] and a complex alkylated product of a group 1 metal of the periodic table represented by the following general formula [9] and aluminum. Illustrated.

R ^a _m Al (OR ^b ) _n H _p X _q [8]
In the formula [8], R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m represents 0 <m ≦ 3, and n represents 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 ... [9]
In the formula [9], M ² represents Li, Na or K, and a plurality of R ^a each independently represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

As organoaluminum compound [8], tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum;
Tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tritolylaluminum;
Dialkylaluminum hydrides such as diisopropylaluminum hydride, diisobutylaluminum hydride;
Formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y and z are each a positive number, and z ≦ 2x.) Isoprenyl represented by like Alkenyl aluminum such as aluminum;
Alkyl aluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide ;
(Wherein, R ^a and R ^b are. Synonymous with R ^a and R ^b in the formula [8]) formula R ^a _2.5 Al (OR ^b) _0.5 partially alkoxy having an average composition represented by Alkyl aluminum; alkyl aluminum aryloxides such as diethyl aluminum phenoxide and diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide); dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum Dialkylaluminum halides such as bromide and diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride Illustrative are partially partially alkylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycyclyl, ethylaluminum ethoxybromide.

Examples of the complex alkylated product [9] include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . A compound similar to the complex alkylated product [9] can also be used, and an organic aluminum compound in which two or more aluminum compounds are bonded via 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 individually 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-
Examples of the inorganic compound include porous oxides, inorganic halides, clay minerals, clay (usually composed of the clay mineral as a main component), ion-exchangeable layered compounds (most clay minerals are ion-exchangeable). A layered 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 mixture containing these oxides. The Examples of the composite or mixture include 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. -TiO ₂ -MgO and the like. Among these, porous oxides containing as a main component one or both of SiO ₂ and Al ₂ O ₃ are preferable.

The porous oxide has different properties 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, Preferably it is in the range of 100-700 m ² / g; the pore volume is preferably in the range of 0.3-3.0 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 the inorganic halide 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. In addition, it is possible to use a component that is dissolved in a fine particle by a precipitating agent after the inorganic halide is dissolved in a solvent such as alcohol.

  The clay, clay mineral, and ion-exchange layered compound are not limited to natural products, and artificial synthetic products can also be used. In addition, the said ion exchange layered compound is a compound which has the crystal structure where the surface comprised by an ionic bond etc. was piled up in parallel with weak mutual bond force, and is a compound which can contain the ion contained.

Specifically, the clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, synthetic mica, etc. And kaolinite, nacrite, dickite, hectorite, teniolite and halloysite; examples of the ion-exchangeable layered compound have a layered crystal structure such as hexagonal close-packed packing type, antimony type, CdCl ₂ type, CdI ₂ type Examples are ionic 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.

  The clay and clay mineral are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.

  Moreover, the said ion exchange layered compound is good also as a layered compound which the interlayer expanded by exchanging the exchangeable ion of an interlayer for another big bulky ion using the ion exchange property. 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 the guest compound is intercalated, a metal alkoxide (R is a hydrocarbon group, etc.) such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ is hydrolyzed and polycondensed. The obtained polymer, a colloidal inorganic compound such as SiO _2, etc. can also coexist.
Among the 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 granular or particulate solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer synthesized mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene; mainly vinylcyclohexane and styrene. (Co) polymers synthesized as components; modified examples of these (co) polymers are exemplified.

<< 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.

[Α-olefin]
In the method for producing an olefin polymer according to the present invention, an α-olefin having 2 or more carbon atoms is used as a raw material for the olefin polymer. The α-olefin may be used alone or in combination of two or more.

The α-olefin has 2 or more carbon atoms, preferably 3 to 20, and more preferably 3 to 10. Moreover, it is preferable that it is a linear or branched alpha olefin.
Examples of the α-olefin include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1-pentene. 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene. Of these, propylene is particularly preferred.

In the present invention, as the raw material for the olefin polymer, together with the α-olefin, a cyclic olefin having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene. Tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene;
Polar monomers, for example, α, such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride β-unsaturated carboxylic acid; metal salt such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt of α, β-unsaturated carboxylic acid; methyl acrylate, n-butyl acrylate, acrylic N-propyl acid, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-n-butylhexyl acrylate, methyl methacrylate, n-butyl methacrylate, n-propyl methacrylate, Α, β-unsaturation such as isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Vinyl esters such as rubonic acid ester; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate Unsaturated glycidyl etc. may be used.

  Vinyl cyclohexane, diene, polyene; aromatic vinyl compounds such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, on-butyl styrene, mn Mono- or polyalkyl styrenes such as butyl styrene, pn-butyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chlorostyrene, p-chlorostyrene, Polymerization can also proceed by coexisting a functional group-containing styrene derivative such as divinylbenzene; 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like in the reaction system.

  In a preferred embodiment of the present invention, propylene is used as at least a part of the monomer (α-olefin). For example, the proportion of propylene used is preferably 51 to 100 mol% and more preferably 61 to 100 mol% with respect to 100 mol% of the α-olefin.

[Olefin polymer production conditions]
In the method for producing an olefin polymer according to the present invention, the polymerization temperature is 40 ° C. or higher, preferably 40 to 200 ° C., more preferably 45 to 150 ° C., particularly preferably 50 to 150 ° C. (in other words, particularly preferably It is a temperature that can be industrialized. The polymerization pressure is usually in the range of normal pressure to 10 MPa-G (gauge pressure), preferably normal pressure to 5 MPa-G. When at least a part of the monomer is propylene, the polymerization temperature is preferably 45 ° C. or higher, and particularly preferably 50 to 180 ° C., from the viewpoint of enabling industrialization.

The polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.
The melting point of the olefin polymer can be adjusted by the presence of hydrogen in the polymerization reaction system or by changing the polymerization temperature. The molecular weight of the olefin polymer can be adjusted by allowing hydrogen to exist in the polymerization reaction system or changing the polymerization temperature. Furthermore, the molecular weight of the olefin polymer can be adjusted by the amount of the compound (B) used as a component of the olefin polymerization catalyst. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of α-olefin.

  In the method for producing an olefin polymer according to the present invention, at the time of polymerization, the usage and order of addition of each component of the olefin polymerization catalyst such as the crosslinked metallocene compound (A) and the compound (B) are arbitrarily selected. The following method is exemplified.

  (1) A method in which the bridged metallocene compound (A) and the compound (B) are added to the polymerization vessel in an arbitrary order; (2) a catalyst component in which the bridged metallocene compound (A) is supported on the carrier (C), and a compound ( A method of adding B) to the polymerization vessel in an arbitrary order; (3) a catalyst component in which the compound (B) is supported on the carrier (C), and the bridged metallocene compound (A) are added to the polymerization vessel in an arbitrary order. Method; (4) A method in which a catalyst component in which a bridged metallocene compound (A) and a compound (B) are supported on a carrier (C) is added to a polymerization vessel.

  In each of the above methods (1) to (4), at least two of the catalyst components may be contacted in advance. In each of the above methods (3) and (4) in which the compound (B) is supported on the carrier (C), the unsupported compound (B) is added to the polymerization vessel in any order as necessary. May be. In this case, the compound (B) supported on the carrier (C) and the compound (B) not supported may be the same or different.

  The solid catalyst component in which the crosslinked metallocene compound (A) is supported on the support (C) and the solid catalyst component in which the crosslinked metallocene compound (A) and the compound (B) are supported on the support (C) It may be polymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

  In the method for producing an olefin polymer according to the present invention, an olefin polymer is obtained by homopolymerizing or copolymerizing one or more of the α-olefins in the presence of the olefin polymerization catalyst. In the present invention, the polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization; and gas phase polymerization methods.

  Examples of the inert hydrocarbon solvent used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; fats such as cyclopentane, cyclohexane, and methylcyclopentane. Examples include cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. Moreover, these inert hydrocarbon solvents may be used individually by 1 type, and may use 2 or more types together. Moreover, alpha-olefin itself used as a raw material of an olefin polymer can also be used as a solvent.

-Composition of olefin polymerization catalyst-
(1) When the olefin polymerization is performed using the olefin polymerization catalyst, the crosslinked metallocene compound (A) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 1 liter per reaction volume. It is used in such an amount that it becomes 10 ⁻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 contained in the compound (b-1) and the crosslinked metallocene compound (A). The molar ratio [(b-1) / M] with all transition metal atoms (M) 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 catalyst for olefin polymerization, the compound (b-2) is a mixture of the compound (b-2) and the bridged metallocene compound (A). The molar ratio [(b-2) / M] with the transition metal atom (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 crosslinked with the aluminum atom (Al) in the compound (b-3). The metallocene compound (A) is used in such an amount that the molar ratio [Al / M] to all transition metal atoms (M) in the metallocene compound (A) 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 an organoaluminum oxy compound (b-1), the organic compound component (D) and the compound In an amount such that the molar ratio [(D) / (b-1)] to (b-1) is usually 0.01 to 10, preferably 0.1 to 5; compound (B) is an ion When the organic compound (b-2) is used, the molar ratio [(D) / (b-2)] of the organic compound component (D) and the compound (b-2) is usually 0.01 to 10 , Preferably in an amount of 0.1 to 5; when the compound (B) is an organoaluminum compound (b-3), the moles of the organic compound component (D) and the compound (b-3) The ratio [(D) / (b-3)] is usually 0.01 to 2, preferably 0.005 to 1. It is.

[Olefin polymer]
According to the present invention described above, when an olefin such as propylene is polymerized, an olefin polymer having a high molecular weight and a sufficiently high melting point not only under a low polymerization temperature condition but also at a high polymerization temperature condition. Can be manufactured.

  Hereinafter, physical properties of a propylene polymer such as a propylene homopolymer or a copolymer of propylene and an α-olefin other than propylene (when at least a part of the monomer is propylene) will be described.

  The weight average molecular weight (Mw) calculated | required by the gel permeation chromatography (GPC) of the said propylene polymer is normally 80,000 or more, Preferably it is 85,000-1,000,000, More preferably, it is 100,000- 1,000,000. The weight average molecular weight (Mw) / number average molecular weight (Mn) of the propylene polymer is usually 1.5 to 5.0, preferably 1.5 to 4.0, more preferably 1.5 to 3.0. It is.

  The intrinsic viscosity [η] of the propylene polymer is preferably 0.7 dl / g or more, more preferably 0.8 dl / g or more, and further preferably 0.9 dl / g or more. The upper limit of the intrinsic viscosity [η] is usually about 10 dl / g.

A propylene polymer having an intrinsic viscosity [η] that is an index of weight average molecular weight (Mw) and molecular weight is in the above range is excellent in stability during melt extrusion.
The melting point (Tm) determined by DSC of the propylene polymer is usually 150 ° C. or higher, preferably 150.5 to 180 ° C., more preferably 151 to 180 ° C. A propylene polymer having a melting point (Tm) in the above range is excellent in moldability.

  The crystallization temperature (Tc) calculated | required by DSC of the said propylene polymer is 70 degreeC or more normally, More preferably, it is 80-150 degreeC, More preferably, it is 85-130 degreeC. A propylene polymer having a crystallization temperature (Tc) in the above range is excellent in moldability.

  In the present invention, the weight average molecular weight (Mw), number average molecular weight (Mn), intrinsic viscosity [η], melting point (Tm) and crystallization temperature (Tc) of the olefin polymer are as described in the examples. The value to be measured.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. 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) or crystallization temperature (Tc) of the olefin polymer was measured as follows using DSC Pyris 1 or DSC 7 manufactured by Perkin Elmer.

  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 the examples, when two crystal melting peaks are observed, Tm2 is the melting point of the olefin polymer when the low temperature side peak is Tm1 and the high temperature side peak is Tm2. 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 of olefin polymer (about 20 mg) are dissolved in decalin solvent (15 mL), and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After decalin solvent (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 was further repeated twice, and the value of ηsp / C when the concentration (C) of the olefin polymer was extrapolated to 0 was 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 using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters as follows. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is oji Chlorobenzene (Wako Pure Chemical Industries) and 0.025 wt% BHT (Takeda Pharmaceutical) as the antioxidant were used, the mobile phase was moved at 1.0 mL / min, the sample concentration was 15 mg / 10 mL, and the sample injection volume was 500 micron. 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 as polypropylene molecular weights according to the general calibration procedure.

[Bridged metallocene compound used in Examples]
The bridged metallocene compound used in the examples was synthesized by the method described in the following patent publication. JP2000-212194, JP2004-168744, JP2004-189666, JP2004-161957, JP2007-302854, JP2007-302853, WO01 / 027124 pamphlet.
Catalyst (a): (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

・触媒（ｂ）：（ピレニル）メチレン（シクロペンタジエニル）（２，７−ジフェニル−３，６−ジｔｅｒｔ−ブチルフルオレニル）ジルコニウムジクロリド

Catalyst (b): (pyrenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

［実施例１］
充分に窒素置換した内容積１５ｍｌのＳＵＳ製オートクレーブに、シクロヘキサンとヘキサンとを９：１（体積比）で混合した溶媒３．９ｍＬを入れ、６００回転／分にて攪拌した。溶液を５０℃に昇温し、次いでプロピレンで全圧が７ｂａｒになるまで加圧した。

[Example 1]
A SUS autoclave with an internal volume of 15 ml sufficiently purged with nitrogen was charged with 3.9 mL of a solvent prepared by mixing cyclohexane and hexane at a ratio of 9: 1 (volume ratio) and stirred at 600 rpm. The solution was warmed to 50 ° C. and then pressurized with propylene until the total pressure was 7 bar.

  Under a nitrogen atmosphere, 3.5 mg (molecular weight 779.39 g / mol) of the catalyst (a) as a metallocene complex was added to a Schlenk tube and dissolved in 9 mL of dehydrated toluene to prepare a 0.00050M metallocene solution. 0.55 mL of a suspension of modified methylaluminoxane (n-hexane solvent, 4.08 M in terms of aluminum atom, 2.24 mmol) was added and stirred at room temperature for 15 minutes to prepare a catalyst solution.

  In the autoclave, 0.2 mL (0.05 M, 10 μmol) of triisobutylaluminum, 0.2 mL (0.00050 M, 0.10 μmol) of the catalyst solution, and 9: 1 (volume ratio) of cyclohexane and hexane were mixed. 0.7 mL of solvent was added to initiate polymerization. After polymerization at 50 ° C. for 9 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. Methanol 50mL and a small amount of hydrochloric acid aqueous solution were added to the obtained polymer, and it stirred at room temperature for 1 hour. The polymer was filtered and dried under reduced pressure to obtain 1.24 g of polypropylene.

  The polymerization activity was 82.8 kg / mmol-Zr / hr. [Η] of the obtained polymer was 1.15 dl / g, weight average molecular weight (Mw) was 103,000, number average molecular weight (Mn) was 53,700, molecular weight distribution (Mw / Mn) was 1.92, crystals The conversion temperature (Tc) was 102.3 ° C., and the melting point (Tm) was 152.7 ° C.

[Example 2]
In a SUS autoclave with an internal volume of 15 ml sufficiently purged with nitrogen, 2.9 mL of a solvent in which 0.2 mL (0.05 M, 10 μmol) of triisobutylaluminum and 9: 1 (volume ratio) of cyclohexane and hexane were mixed, Stir at 600 rpm. The solution was warmed to 50 ° C. and then pressurized with propylene until the total pressure was 7 bar.

  Under a nitrogen atmosphere, 2.6 mg (molecular weight: 871.10 g / mol) of the catalyst (b) as a metallocene complex was added to a Schlenk tube, dissolved in 5.5 mL of dehydrated toluene, and then 0.36 mL of a suspension of modified methylaluminoxane ( n-Hexane solvent, 4.15 M in terms of aluminum atom, 1.49 mmol) was added, and the mixture was stirred at room temperature for 15 minutes to prepare a 0.00051 M catalyst solution.

  To the autoclave, 0.2 mL (0.00051 M, 0.10 μmol) of the catalyst solution and 0.7 mL of a solvent prepared by mixing 9: 1 (volume ratio) of cyclohexane and hexane were added to initiate polymerization. After 10 minutes of polymerization at 50 ° C., a small amount of isobutyl alcohol was added to terminate the polymerization. Methanol 50mL and a small amount of hydrochloric acid aqueous solution were added to the obtained polymer, and it stirred at room temperature for 1 hour. The polymer was filtered and dried under reduced pressure to obtain 0.71 g of polypropylene.

The polymerization activity was 42.7 kg / mmol-Zr / hr. [Η] of the obtained polymer was 1.38 dl / g, weight average molecular weight (Mw) was 114,000, number average molecular weight (Mn) was 60,400, molecular weight distribution (Mw / Mn) was 1.89, crystal The conversion temperature (Tc) was 103.4 ° C., and the melting point (Tm) was 156.7 ° C.
The results of Examples 1 and 2 are summarized in Table 1 below.

Claims (6)

(A) a bridged metallocene compound represented by the following 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) In the presence of an olefin polymerization catalyst comprising at least one compound selected from organoaluminum compounds,
A method for producing an olefin polymer comprising polymerizing at least one monomer selected from α-olefins having 2 or more carbon atoms under a condition of 40 ° C. or higher

[In the formula [1], R ^{1 to} R ⁴ each independently represents a hydrocarbon group, a halogen-substituted hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group, and two groups adjacent to each other are bonded to each other. May form a ring.
R ⁵ represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-substituted hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group; Y represents a carbon atom or a silicon atom; M represents Ti, Zr or Hf Q represents 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 coordination with a lone electron pair. j represents an integer of 1 to 4, and when j is 2 or more, a plurality of Qs may be the same or different from each other. ] In the general formula [1], R ¹ and R ⁴ are the same group selected from a hydrocarbon group having 1 to 40 carbon atoms, a halogen-substituted hydrocarbon group, an oxygen-containing group and a silicon-containing group, and R ² and The method for producing an olefin polymer according to claim 1, wherein both or one of R ³ is a hydrocarbon group having 1 to 40 carbon atoms or a silicon-containing group. In the said General formula [1], R < ⁵ > is a C6-C20 hydrocarbon group or a halogen-substituted hydrocarbon group, The manufacturing method of the olefin polymer of Claim 1 or 2 characterized by the above-mentioned.   The method for producing an olefin polymer according to any one of claims 1 to 3, 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 4, wherein at least a part of the monomer is propylene.   6. The olefin polymer according to claim 5, wherein an olefin polymer having a weight average molecular weight distribution (Mw) determined by gel permeation chromatography (GPC) of 80,000 or more and a melting point of 150 ° C. or more is produced. Manufacturing method of coalescence.