JP5979920B2 - Olefin polymerization catalyst and process for producing olefin polymer using the same - Google Patents

Description

  The present invention relates to an olefin polymerization catalyst containing a metallocene compound having a specific structure, and a method for producing an olefin polymer using the same, and more particularly to a metallocene having a specific structure capable of producing a syndiotactic olefin polymer. The present invention relates to an olefin polymerization catalyst containing a compound and a method for producing an olefin polymer using the same.

  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.

  Attempts have also been made to use metallocene compounds having two fluorenyl groups as ligands as ethylene (co) polymerization catalysts. For example, Patent Document 5 reports an attempt to use (1,2-difluorenylethane) zirconium dichloride as a polymerization catalyst in homopolymerization of ethylene and copolymerization with hexene.

  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, such improved bridged metallocene compounds generally tend to be expensive to manufacture. On the other hand, although it is considered that uncrosslinked metallocene compounds can generally be produced at a lower cost than crosslinked metallocene compounds, the polymerization performance of synthesizing olefin polymers having sufficiently high stereoregularity and high molecular weight is known. It is not done. For example, there is an example using bis (fluorenyl) zirconium dichloride, but only a polymerization example of ethylene has been reported (Non-patent Document 3). In addition, with regard to bis (2,7-di-tertbutyl-4-methylfluorenyl) zirconium dichloride, attempts have been made to apply it to a catalyst for propylene polymerization, but the production of a propylene polymer is extremely small. It has been reported that it stayed (Patent Document 5).

  Therefore, a metallocene compound that can be produced at lower cost and has good polymerization performance has been demanded.

Japanese Patent Laid-Open No. 04-069394 JP 2000-212194 A JP 2004-189666 A JP 2004-189667 A European Patent Application No. 0666267

Angew. Chem. Int. Ed. Engl., 24, 507 (1985) J. Am. Chem. Soc., 1988, 110, 6255 Chemical Reviews, 2000, Vol.100, No. 4, P.1209

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

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

That is, the present invention relates to the following [1] to [8].
[1]
(A) a metallocene compound (A) represented by the following general formula [1];
(B) (b-1) an organoaluminum oxy compound,
(B-2) a compound that reacts with the metallocene compound (A) to form an ion pair,
(B-3) Olefin polymerization catalyst comprising at least one compound (B) selected from organoaluminum compounds

[In the above formula (1),
R ¹ , R ⁶ , R ^{1 ′} and R ^{6 ′} each independently represent a hydrocarbon group having 6 to 20 carbon atoms, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group;
R ² , R ³ , R ⁴ , R ⁵ and R ⁷ , and R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} , and R ^{7 ′} are each independently a hydrogen atom, hydrocarbon group, or halogen-containing A hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group;
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 coordinating with a lone electron pair; and
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 , R ⁶ , R ^{1 ′} and R ^{6 ′} are a hydrocarbon group having 6 to 20 carbon atoms or a halogen-containing hydrocarbon group, The catalyst for olefin polymerization as described in 1].
[3] In the above general formula (1), R ² , R ⁵ , R ^{2 ′} and R ^{5 ′} are a hydrocarbon group having 4 to 10 carbon atoms or a halogen-containing hydrocarbon group. ] Or the catalyst for olefin polymerization according to [2].

[4] The olefin polymerization catalyst according to any one of [1] to [3], further comprising (C) a support.

[5] A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of [1] to [4].
[6] The method for producing an olefin polymer according to the above [5], wherein the olefin contains an α-olefin having 3 or more carbon atoms.

[7] The method for producing an olefin polymer as described in [5], wherein the olefin contains propylene.
[8] The method for producing an olefin polymer according to [6], wherein the obtained olefin polymer satisfies the following requirements (i) to (iii):
(I) The melting point (Tm) determined by DSC of the olefin polymer is 150 ° C. or higher.
(Ii) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 100,000 or more, and (iii) the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) and the number average The molecular weight (Mn) ratio (Mw / Mn) is 2.5 or more.

  According to the present invention, when an olefin such as propylene is polymerized, an olefin polymer having a sufficiently high stereoregularity and a high molecular weight can be produced even under high temperature conditions that can be industrialized, and industrially It is possible to provide an olefin polymerization catalyst that can be produced at a relatively low cost, and an olefin polymerization method using the olefin polymerization catalyst.

  The catalyst for olefin polymerization according to the present invention comprises a metallocene compound (A) having two specific fluorene ligands (hereinafter simply referred to as “metallocene compound (A)”), and a compound ( B) (hereinafter simply referred to as “compound (B)”).

  And the manufacturing method of the olefin polymer which concerns on this invention is characterized by superposing | polymerizing an olefin in presence of such a catalyst for olefin polymerization. The process for producing an olefin polymer according to the present invention is preferably carried out by polymerizing at least one monomer selected from olefins having 2 or more carbon atoms, preferably at 40 ° C. or higher.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an olefin polymerization catalyst containing a metallocene compound (A) and a compound (B) used in the present invention, and a method for polymerizing an olefin in the presence of the olefin polymerization catalyst are the best for carrying out the invention. The forms will be described sequentially.
[Olefin polymerization catalyst]
The olefin polymerization catalyst used in the present invention is:
A metallocene compound (A),
(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) at least one compound (B) selected from organoaluminum compounds are included as essential components. Further, the carrier (C) and the organic compound component (D) may be included as optional components.

<< Metalocene Compound (A) >>
The metallocene compound (A) used in the present invention is represented by the following general formula (1).

[In the above formula (1),
R ¹ , R ⁶ , R ^{1 ′} and R ^{6 ′} each independently represent a hydrocarbon group having 6 to 20 carbon atoms, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group;
R ² , R ³ , R ⁴ , R ⁵ and R ⁷ , and R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} , and R ^{7 ′} are each independently a hydrogen atom, a hydrocarbon group, or a halogen-containing group A hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group;
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 coordinating 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 metallocene compound (A) will be described.

-R ¹ to R ⁷ and the R ^{1 '~R 7'} -
In the metallocene compound (A) used in the present invention, R ¹ , R ⁶ , R ^{1 ′} and R ^{6 ′} are each independently a hydrocarbon group having 6 to 20 carbon atoms, a halogen-containing hydrocarbon group, a nitrogen-containing group, R ² , R ³ , R ⁴ , R ⁵ and R ⁷ , and R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} and R ^{7 ′} are each independently an oxygen-containing group or a silicon-containing group. And a hydrogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group.

The “hydrocarbon group” that the fluorenyl ligand of the hydrocarbon group metallocene compound (A) may have is preferably a hydrocarbon group having 1 to 40 carbon atoms, and more preferably a hydrocarbon group having 1 to 20 carbon atoms. 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 aryl groups in which aromatic ring groups such as a phenyl group, a naphthyl group, a phenanthryl group, an anthracenyl group, and a biphenyl group are all hydrogen (hereinafter referred to as an unsubstituted aryl group). O-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, n-propylphenyl group, iso-propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl And an alkylaryl group such as a xylyl group.

  Aralkyl groups having 7 to 20 carbon atoms include benzyl groups, cumyl groups, α-phenethyl groups, β-phenethyl groups, diphenylmethyl groups, naphthylmethyl groups, neophyll groups and the like; o-methylbenzyl groups, m- Examples include alkylaralkyl groups such as methylbenzyl group, p-methylbenzyl group, ethylbenzyl group, n-propylbenzyl group, iso-propylbenzyl group, n-butylbenzyl group, sec-butylbenzyl group, and tert-butylbenzyl group. Is done.

Among these “hydrocarbon groups”, R ¹ , R ⁶ , R ^{1 ′} and R ^{6 ′} are hydrocarbon groups having 6 to 20 carbon atoms, preferably hydrocarbon groups having 6 to 10 carbon atoms. be able to. R ² , R ³ , R ⁴ , R ⁵ and R ⁷ , and R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} and R ^{7 ′} are hydrocarbon groups having 1 to 10 carbon atoms. It is particularly preferred. Of these, R ² , R ⁵ , R ^{2 ′} and R ^{5 ′} are particularly preferably hydrocarbon groups having 4 to 10 carbon atoms.

The “halogen-containing hydrocarbon group” that the fluorenyl ligand of the halogen-containing hydrocarbon group metallocene compound (A) may have is a group in which at least one hydrogen atom of the “hydrocarbon group” is substituted with a halogen atom. Exemplified, specifically,
Halogen-containing alkyl groups such as fluoroalkyl groups such as trifluoromethyl groups;
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 part of the above-mentioned unsubstituted aryl 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, Substituted group: Fluoroalkylaryl group such as trifluoromethylphenyl group, bromoalkylaryl group such as bromomethylphenyl group and dibromomethylphenyl group, iodoalkylaryl group such as iodomethylphenyl group and diiodomethylphenyl group, etc. Of the above alkyl ants Halogen-containing aryl group such as; partially group substituted with a halogen alkyl structure Le 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-containing aralkyl group in which a hydrogen atom of the unsubstituted aralkyl group such as a bromoaralkyl group, an o-iodobenzyl group, an m-iodobenzyl group, a p-iodobenzyl group, or an iodophenethyl group is substituted with a halogen; Illustrated.

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among these “halogen-containing hydrocarbon groups”, R ¹ , R ⁶ , R ^{1 ′} and R ^{6 ′} are halogen-containing hydrocarbon groups having 6 to 20 carbon atoms, preferably halogens having 6 to 10 carbon atoms. A containing hydrocarbon group can be used. R ² , R ³ , R ⁴ , R ⁵ and R ⁷ , and R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} and R ^{7 ′} are halogen-containing hydrocarbons having 1 to 10 carbon atoms. Particularly preferred is a group. Among these, R ² , R ⁵ , R ^{2 ′} and R ^{5 ′} are particularly preferably a halogen-containing hydrocarbon group having 4 to 10 carbon atoms.

Nitrogen-containing group, oxygen-containing group, silicon-containing group As the “nitrogen-containing group” that the fluorenyl ligand of the metallocene compound (A) may have, nitro group, cyano group, N-methylamino group, N, N-dimethylamino Group, N-phenylamino group is exemplified.

Examples of the “oxygen-containing group” include a methoxy group, an ethoxy group, and a phenoxy group.
In addition, as the “silicon-containing group”, alkylsilyl groups such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group; dimethylphenylsilyl group, diphenylmethylsilyl And arylsilyl groups such as a triphenylsilyl group.

In the other structure metallocene compound (A) that the fluorenyl ligand may have, any two adjacent groups among R ^{1 to} R ⁶ may be bonded to form a ring, and R ^{1 ′} to R ^{1 ′} to R ⁶ Any two adjacent groups of R ^{6 ′} may be bonded to form a ring. That is, each of the two fluorenyl ligands constituting the metallocene compound (A) includes a fluorene ring as a basic component, and a benzene ring; a hydrogenated benzene ring; and a furan ring, a thiophene ring, etc. It may have a ring structure formed by further condensing an additional ring such as a heterocycle and a corresponding hydrogenated heterocycle. Such a ring structure may further have a substituent such as an alkyl group on the ring. Examples of such a ring structure include a benzofluorenyl group, a dibenzofluorenyl group, an octahydrodibenzofluorenyl group, an octamethyloctahydrodibenzofluorenyl group, and the like.

Preferred Embodiments for R ^{1 to} R ⁷ and R ^{1 ′ to} R ^{7 ′ In the} metallocene compound (A) used in the present invention, R ¹ , R ⁶ , R ^{1 ′} and R ^{6 ′} are each independently the above carbon number. 6-20 hydrocarbon groups or halogen-containing hydrocarbon groups are preferred, more preferably the above aryl groups or halogen-containing aryl groups, phenyl groups, alkylphenyl groups, halogen-containing phenyl groups or halogen-containing alkylphenyls. More preferably, it is a group.

R ¹ and R ⁶ are preferably the same group. R ^{1 ′} and R ^{6 ′} are preferably the same group.
One or more groups selected from R ² , R ⁵ , R ^{2 ′} , R ^{5 ′} , R ⁷ and R ^{7 ′} may be the above hydrocarbon group, halogenated hydrocarbon group or silicon-containing group. preferable. Further, R ² , R ⁵ , R ^{2 ′} and R ^{5 ′} are preferably each independently the hydrocarbon group, halogenated hydrocarbon group or silicon-containing group, and the hydrocarbon group or halogenated hydrocarbon group More preferably, the hydrocarbon group is more preferable, and the alkyl group is particularly preferable. R ² and R ⁵ are preferably the same group, and R ^{2 ′} and R ^{5 ′} are preferably the same group.

R ³ , R ⁴ , R ^{3 ′} , R ^{4 ′} , R ⁷ and R ^{7 ′} are preferably each independently a hydrogen atom, the above hydrocarbon group or a halogen-containing hydrocarbon group, and preferably a hydrogen atom, the above aryl group or A halogen-containing aryl group is more preferable, and a hydrogen atom, a phenyl group, an alkylphenyl group, a halogen-containing phenyl group, or a halogen-containing alkylphenyl group is further preferable. R ³ and R ⁴ are preferably the same group, and R ^{3 ′} and R ^{4 ′} are preferably the same group.

  In the present invention, an olefin polymer having a high melting point can be obtained by using the metallocene compound (A) having the structure as described above. This is because the metallocene compound (A) catalyzes the production of a highly stereoregular olefin polymer. For this reason, even an olefin polymer synthesized at a temperature higher than room temperature, preferably a temperature much higher than room temperature, can exhibit good moldability, increase the value of the product and industrially produce olefin polymers. The cost performance when doing so is improved.

  Further, by using the metallocene compound (A) having the above structure, an olefin polymer having a large molecular weight can be obtained. This is because the metallocene compound (A) catalyzes the production of a high molecular weight product. For this reason, it becomes possible to synthesize an olefin polymer at a temperature not lower than room temperature, preferably a temperature significantly higher than room temperature, and the cost performance when industrially producing the olefin polymer is improved.

  Furthermore, by using the metallocene compound (A) having the above structure, an olefin polymer having a wide molecular weight distribution may be obtained. This is because the metallocene compound (A) may catalyze the production of a wide molecular weight product. For this reason, it becomes possible to synthesize | combine the olefin polymer excellent in the moldability easily, and the cost performance at the time of producing an olefin polymer industrially can improve.

  The metallocene compound (A) used in the present invention is a polymer having a high stereoregularity while having a structure in which a plurality of fluorenyl ligands are not crosslinked, and a polymer having a high molecular weight and a relatively wide molecular weight distribution. The unexpected performance of giving. The reason for this is not clear at the present time, but the present inventors presume as follows.

  The metallocene compound (A) used in the present invention has a structure having a specific substituent at a specific position in the fluorenyl ligand. Due to the steric hindrance between the substituents, a steric configuration similar to that of a ligand having a crosslinked structure is formed during the polymerization reaction, so that it is presumed to give a polymer with high stereoregularity. In addition, because it is not a complete cross-linked structure, there is fluctuation in the above-mentioned configuration, so that the performance of the active species slightly changes over time, so that the molecular weight distribution is widened and chain transfer is suppressed. It is estimated that.

-About M, Q and j-
In the metallocene compound (A) used in the present invention, M represents Ti, Zr or Hf, preferably Zr or Hf, particularly preferably Zr.

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 pair of electrons. .
Here, examples of the halogen atom (Q) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Moreover, as a hydrocarbon group (Q), a C1-C10 alkyl group and a C3-C10 cycloalkyl group are preferable. Here, the alkyl group having 1 to 10 carbon atoms includes methyl group, ethyl group, n-propyl group, iso-propyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group. 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 1,1,3-trimethylbutyl group, and 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.

Examples of the neutral conjugated or nonconjugated diene 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 Examples include -η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene.

  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.

  Furthermore, as a neutral ligand that can be coordinated by a lone pair of electrons, organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran (THF), diethyl ether, dioxane, 1, 2, -Ethers such as dimethoxyethane are exemplified.

The preferable aspect of said Q is a halogen atom or a C1-C5 alkyl group.
J is an integer of 1 to 4, preferably 2.
In the present invention, the metallocene compound (A) is preferably a compound represented by the following general formula (2).

In the above formula (2),
The definitions of R ¹ , R ² , R ⁵ and R ⁶ and R ^{1 ′} , R ^{2 ′} , R ^{5 ′} and R ^{6 ′} are the same as those in the above formula (1),
The definitions of M, Q and j are the same as the definitions of M, Q and j in the above formula (1).

<Example of metallocene compound (A)>
Specific examples of the 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 metallocene compound (A) may be used alone or in combination of two or more.

Here, for the sake of convenience, the ligand structure excluding MQ _j (metal part) of the metallocene compound (A), that is, the ligand structure comprising the fluorenyl ligand is represented by Flu-A (fluorenyl part) and Flu-B (fluorenyl part). ). In the present specification, the Flu-A (fluorenyl moiety) and Flu-B (fluorenyl moiety) are not cross-linked with each other, and the ligand structure excluding MQ _j (metal moiety), ie, the two fluorenyl moieties. The structure consisting of is referred to as a non-crosslinked portion. Then, the structure of the non-crosslinked portion is divided into two in the notation, and specific examples of each partial structure (ie, Flu-A and Flu-B) constituting the non-crosslinked portion are shown in Table 1, Specific examples of the structure are shown in Table 2, respectively.

According to Tables 1 and 2 above, no. α1β2 means a combination of α1-β2; The metallocene compound (A) having an α1β2 non-crosslinked portion and having a metal portion MQ _j of ZrCl ₂ is represented as a metallocene compound represented by the following formula.

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

<< Synthesis Method of Metallocene Compound (A) >>
The metallocene compound (A) represented by the general formula (1) used in the present invention can be produced by the following method, but the production method is not particularly limited.

  First, a precursor compound (3a) and a precursor compound (3b) constituting Flu-A (fluorenyl moiety) and Flu-B (fluorenyl moiety) of the metallocene compound (A) represented by the general formula (1) are: Each can be produced by a known method.

In the above formula (3a), the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as those in the above formula (1).

In the above formula (3b), the definitions of R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} , R ^{6 ′} and R ^{7 ′} are the same as those in the above formula (1). .
Next, an example of producing the metallocene compound (A) from the precursor compounds represented by the general formulas (3a) and (3b) is shown below, but this does not limit the scope of the invention, and is known in the art. It may be manufactured by any method.

  First, the precursor compounds represented by the general formulas (3a) and (3b) are reacted with an alkali metal, an alkali metal hydride, or an organic alkali metal in an organic solvent at a reaction temperature of −80 ° C. to 200 ° C. By contacting, it converts to the corresponding dialkali metal salt. Examples of the organic solvent used in the above reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin, or aromatic hydrocarbons such as benzene, toluene, and xylene, or tetrahydrofuran, diethyl ether, dioxane, 1, 2, and the like. -Ethers such as dimethoxyethane, tert-butyl methyl ether and cyclopentyl methyl ether, or halogenated hydrocarbons such as dichloromethane and chloroform. Examples of the alkali metal used in the above reaction include lithium, sodium, and potassium. Examples of the alkali metal hydride include sodium hydride and potassium hydride. Examples of the organic alkali metal include methyl lithium, butyl lithium, and phenyl. Examples include lithium.

Next, the dialkali metal salt obtained above is represented by the general formula (4) in an organic solvent.
MZk (4)
(In the above formula (4), M is a metal selected from Group 4 of the periodic table, and Z is the same or different combination from a halogen, an anionic ligand, or a neutral ligand capable of coordination with a lone pair of electrons. And k is an integer of 3 to 6.) By reacting with the compound represented by (1), the metallocene compound (A) represented by the general formula (1) can be synthesized.

  Preferable specific examples of the compound represented by the general formula (4) include trivalent or tetravalent titanium fluoride, chloride, bromide and iodide, tetravalent zirconium fluoride, chloride, bromide and iodide, tetra Mention may be made of divalent hafnium fluorides, chlorides, bromides and iodides or their complexes with ethers such as tetrahydrofuran, diethyl ether, dioxane or 1,2-dimethoxyethane. Moreover, as an organic solvent used, the same thing as the above can be mentioned.

The reaction between the dialkali metal salt obtained above and the compound represented by the general formula (4) is preferably carried out by an equimolar reaction, and the reaction temperature is in the range of −80 ° C. to 200 ° C. in the organic solvent. Can be done. The metallocene compound obtained by the reaction can be isolated and purified by methods such as extraction, recrystallization and sublimation. The transition metal compound 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.

  The following scheme illustrates a method for synthesizing the metallocene compound (A) when zirconium tetrachloride is used as the compound represented by the general formula (4).

  As exemplified in the above scheme, a compound represented by the general formula (4) such as zirconium tetrachloride is obtained with respect to the alkali metal salt derived from the precursor compounds represented by the above formulas (3a) and (3b). By reacting, the metallocene compound (A) can be obtained. However, as long as the metallocene compound (A) can be obtained, the production method of the metallocene compound (A) is not limited to the production method exemplified in the above scheme, and may be other production methods.

Thus, since the metallocene compound (A) does not require a step of producing a crosslinked structure as compared with a general crosslinked metallocene compound, it can be produced at a relatively low cost.
<< Compound (B) >>
In the present invention, the compound (B) is used as a component constituting the promoter in 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, an organoaluminum oxy compound (b-1) 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 (5) and a compound represented by the following general formula (6), represented by the following general formula (7): Examples thereof include a modified methylaluminoxane having a structure as described above and a boron-containing organoaluminum oxy compound represented by the following general formula (8)

In the formulas (5) and (6), 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, in formulas (5) and (6), methylaluminoxane in which R is a methyl group is preferably used.

In the formula (7), 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.

In Formula (8), 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.
Among these organoaluminum oxy compounds (b-1), the modified methylaluminoxane represented by the above formula (7) can be prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such modified methylaluminoxane is generally called MMAO (modified methyl aluminoxane). MMAO can be prepared specifically by the methods listed in US Pat. No. 4,960,878 and US Pat. No. 5,041,584.

  In addition, modified methylaluminoxane prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem Co., Ltd. (that is, R is an isobutyl group in the above general formula (7)) 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 the compound represented by the above general formula (5) or (6), MMAO is an aliphatic hydrocarbon, an alicyclic hydrocarbon, and It is soluble in aromatic hydrocarbons.

  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. Here, 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. 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.

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 metallocene compound (A) to form an ion pair—
As a compound (b-2) that reacts with the metallocene compound (A) to form an ion pair (hereinafter sometimes abbreviated as “ionic compound (b-2)”), JP-A-1-501950 is disclosed. Gazette, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, JP-A-2004-51676, Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in US 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 (9) is preferable.

In the formula (9), 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-containing 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 (10) and a complex alkylated product of a group 1 metal of the periodic table represented by the following general formula (11) and aluminum. Illustrated.

R ^a _m Al (OR ^b ) _n H _p X _q (10)
In Formula (10), 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 (11)
In formula (11), 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.

Examples of the organoaluminum compound represented by the formula (10) include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, and 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 tolylaluminum
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 have the same meanings as R ^a and R ^b in the formula (10).) General 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.

Further, examples of the complex alkylated product represented by the above formula (11) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . Moreover, the compound similar to a complex alkylation thing (11) can also be used, and the organoaluminum compound which two or more aluminum compounds couple | bonded through the nitrogen atom is illustrated. 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) >>
The catalyst for olefin polymerization according to the present invention may further contain a carrier (C). 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 from olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene as main components; vinylcyclohexane and styrene as main components. Examples of synthesized (co) polymers; modified products of these (co) polymers.

<< Organic compound component (D) >>
The catalyst for olefin polymerization according to the present invention may further contain an organic compound component (D). The organic compound component (D) is used for the purpose of improving the polymerization performance in the olefin polymerization reaction 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.
[Olefin]
The method for producing an olefin polymer according to the present invention is characterized by polymerizing an olefin in the presence of an olefin polymerization catalyst, whereby an olefin (co) polymer is obtained.

Here, an olefin having 2 or more carbon atoms is used as a raw material for the olefin (co) polymer. This olefin may be used individually by 1 type, and may use 2 or more types together.
The olefin used in the present invention has 2 or more carbon atoms, preferably 3 or more, more preferably 3 to 20, and still more preferably 3 to 10 carbon atoms. Moreover, it is preferable that it is a linear or branched alpha olefin.

  Examples of the olefin include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1 -Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene are exemplified. Of these, propylene is particularly preferred.

In the present invention, as the raw material for the olefin polymer, together with the 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, tetra Cyclododecene, 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, an olefin containing propylene can be used as the olefin used as a monomer. That is, in this embodiment, propylene is used for at least a part of the olefin. For example, the proportion of propylene used is preferably 60 to 100 mol% and more preferably 70 to 100 mol% with respect to 100 mol% of the olefin. Moreover, in the obtained polymer, it is preferable that the ratio of the propylene measured using ¹³ CNMR is 60-100 mol%, and it is more preferable that it is 70-100 mol%.
[Olefin polymer production conditions]
In the method for producing an olefin polymer according to the present invention, the polymerization temperature is not particularly limited, and is usually −100 to 250 ° C., preferably 40 to 200 ° C., more preferably 45 to 150 ° C., and particularly preferably 50 to 50 ° C. It is 150 ° C. (in other words, it is particularly preferably 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, from the viewpoint of productivity, the polymerization temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and more preferably 60 to 150 ° C. Particularly preferred.

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 changing the polymerization temperature.

  The molecular weight of the olefin polymer can be adjusted, for example, 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 olefin.

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

  (1) A method in which the metallocene compound (A) and the compound (B) are added to the polymerization vessel in any order; (2) a catalyst component in which the metallocene compound (A) is supported on the carrier (C), and the compound (B) (3) A method in which the catalyst component in which the compound (B) is supported on the carrier (C) and a metallocene compound (A) are added to the polymerization vessel in an arbitrary order; 4) A method in which a catalyst component in which a 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 metallocene compound (A) is supported on the carrier (C) and the solid catalyst component in which the metallocene compound (A) and the compound (B) are supported on the carrier (C) are prepolymerized with olefin. The 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 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, the 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 carried out using the olefin polymerization catalyst, the metallocene compound (A) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 mol per liter of reaction volume. Used in such an amount as to be ^-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 the total of the compound (b-1) and the metallocene compound (A). The molar ratio [(b-1) / M] with the transition metal atom (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 olefin polymerization catalyst, the compound (b-2) is an all transition between the compound (b-2) and the metallocene compound (A). The molar ratio [(b-2) / M] with the 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 composed of an aluminum atom (Al) in the compound (b-3) and a metallocene. It is used in such an amount that the molar ratio [Al / M] to all transition metal atoms (M) in the 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 0.05 to 1. That.
[Olefin polymer]
According to the present invention described above, when an olefin such as propylene is polymerized, the olefin has a sufficiently high stereoregularity and a high molecular weight not only in a low polymerization temperature condition but also in a high polymerization temperature condition. A polymer can be produced.

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

  The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of the propylene polymer is usually 90,000 or more, preferably 97,000 or more, more preferably 100,000 or more, and even more preferably 100. , 1,000 to 1,000,000. The MWD (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the propylene polymer is usually 1.0 to 10, preferably 2.5 to 10, more preferably 2.6 to 10, and still more preferably. Is 2.8-10.

  The intrinsic viscosity [η] of the propylene polymer is preferably 1.20 dl / g or more, more preferably 1.25 dl / g or more, and further preferably 1.35 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 140 ° C. or higher, preferably 145 to 170 ° C., more preferably 150 to 170 ° C. A propylene polymer having a melting point (Tm) in the above range is excellent in moldability. In addition, it exhibits relatively high heat resistance.

  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, Most preferably, it is 100-130 degreeC. A propylene polymer having a crystallization temperature (Tc) in the above range is excellent in moldability. In addition, it exhibits relatively high heat resistance.

  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.

  Generally, when the polymerization temperature during olefin polymerization is increased, the melting point and molecular weight of the olefin polymer are lowered. According to the olefin polymerization catalyst, the melting point (Tm) is 150 ° C. or higher, the weight average molecular weight (Mw) is 100,000 or more, and the molecular weight distribution (Mw / Mn) is 2. An olefin polymer that is 5 or more can be produced.

  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 Examples and Comparative Examples, when a plurality of crystal melting peaks were observed, the peak on the highest temperature side was defined as the melting point (Tm) of the olefin polymer.

[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 of adding a decalin solvent (5 ml) 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. did.

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. As the standard polystyrene for preparing the calibration curve, those manufactured by Tosoh Corporation were used for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and those manufactured by Pressure Chemical Co. were used 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.

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

[Synthesis Example 1]
Synthesis of bis (3,6-di-tert-butyl-2,7-diphenylfluorenyl) zirconium dichloride 4.0 g (9 of 2,7-diphenyl-3,6-di-tert-butylfluorene under nitrogen flow ) .3 mmol) and 30 ml of diethyl ether were added to the reactor, and 5.6 mL (9.3 mmol) of a 1.65 M n-butyllithium hexane solution was added dropwise while the reactor was cooled to −45 ° C. and stirred. After dropping, the temperature was raised to room temperature in 1 hour and 30 minutes. While the reactor was again cooled to -45 ° C and stirred, 1.0 g (4.3 mmol) of zirconium tetrachloride was added and stirred for 24 hours while gradually raising the temperature. Concentration was performed under reduced pressure, hexane was added, filtration was performed, and the resulting organic layer was concentrated under reduced pressure. Recrystallization from pentane and diethyl ether and washing with pentane gave bis (3,6-di-tert-butyl-2,7-diphenylfluorenyl) zirconium dichloride (yield 0.5 g). The measured values of ¹ H NMR spectrum and FD-MS spectrum are shown below.

¹ H-NMR (CDCl ₃ , ppm); 1.2 (36H), 6.3 (2H), 6.7-7.3 (22H), 7.9 (4H)
FD-MS: 1021
[Example 1]
A SUS autoclave with an internal volume of 15 ml that had been sufficiently purged with nitrogen was charged with 2.9 mL of a solvent prepared by mixing 9: 1 cyclohexane and hexane, 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, was added a metallocene complex body 3.4mg obtained in Synthesis Example 1 in a Schlenk tube and dissolved in dehydrated toluene 7.3mL prepare metallocene solution 0.00050M. A suspension of modified methylalumoxane (0.47 mL, n-hexane solvent, 4.15 M in terms of aluminum atom, 1.95 mmol) was added, and the mixture was stirred at room temperature for 30 minutes to prepare a catalyst solution. Polymerization is started by adding 0.2 mL (0.05 M, 10 μmol) of triisobutylaluminum, 0.2 mL of catalyst solution (0.00050 M, 0.10 μmol), and 0.7 mL of a mixture of cyclohexane and hexane at 9: 1 to the autoclave. did. After 10 minutes of polymerization at 50 ° C., 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, and the mixture was stirred at room temperature for 1 hour. Filtration and drying under reduced pressure gave 42.3 mg of polymer. The polymerization activity was 2.54 kg / mmol-Zr / hr. [Η] of the obtained polymer was 3.88, weight average molecular weight (Mw) was 427,000, number average molecular weight (Mn) was 143000, molecular weight distribution (Mw / Mn) was 2.98, and crystallization temperature (Tc) was The temperature was 109.1 ° C. and the melting point (Tm) was 157.3 ° C.

[Example 2]
The same procedure as in Example 1 was carried out except that the polymerization temperature was changed to 65 ° C., to obtain 26.8 mg of a polymer. The polymerization activity was 1.61 kg / mmol-Zr / hr. [Η] of the obtained polymer was 2.56, the weight average molecular weight (Mw) was 261000, the number average molecular weight (Mn) was 61900, the molecular weight distribution (Mw / Mn) was 4.22, and the crystallization temperature (Tc) was 103.8 degreeC and melting | fusing point (Tm) were 150.1 degreeC.

[Comparative Example 1]
The same procedure as in Example 1 was conducted except that bis (cyclopentadienyl) zirconium dichloride was used as the complex, but no solid was obtained after filtration. This is probably because the polymer was not obtained, the molecular weight of the obtained polymer was extremely low, or the stereoregularity was low.

[Reference Example 1]
The same procedure as in Example 1 was conducted, except that dimethylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was used as a complex, to obtain 804 mg of a polymer. The polymerization activity was 32.2 kg / mmol-Zr / hr. [Η] of the obtained polymer was 1.64, weight average molecular weight (Mw) was 146000, number average molecular weight (Mn) was 73000, molecular weight distribution (Mw / Mn) was 2.0, and crystallization temperature (Tc) was The melting point (Tm) was 95 ° C. and 139 ° C.

  The results of Examples 1 and 2 and Comparative Example 1 are summarized in Table 3.

Claims (7)

(A) a metallocene compound (A) represented by the following general formula [1];
(B) (b-1) an organoaluminum oxy compound,
(B-2) a compound that reacts with the metallocene compound (A) to form an ion pair,
(B-3) Olefin polymerization catalyst comprising at least one compound (B) selected from organoaluminum compounds

[In the above formula (1),
R ¹ , R ⁶ , R ^{1 ′} and R ^{6 ′} each independently represent an aryl group having 6 to 20 carbon atoms or a halogen-containing aryl group ,
R ² , R ³ , R ⁴ , R ⁵ and R ⁷ , and R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} , and R ^{7 ′} are each independently a hydrogen atom, hydrocarbon group, or halogen-containing A hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group;
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 coordinating 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 Formula (1), according to claim 1, wherein ^{R 2, R 5, R 2} ' and R ^5' is a hydrocarbon group or halogen-containing hydrocarbon group having 4 to 10 carbon atoms Olefin polymerization catalyst. The catalyst for olefin polymerization according to claim 1 or 2 , further comprising (C) a carrier. The manufacturing method of the olefin polymer characterized by superposing | polymerizing an olefin in presence of the catalyst for olefin polymerization as described in any one of Claims 1-3 . The method for producing an olefin polymer according to claim 4 , wherein the olefin contains an α-olefin having 3 or more carbon atoms. The method for producing an olefin polymer according to claim 4 , wherein the olefin contains propylene. The method for producing an olefin polymer according to claim 5 , wherein the obtained olefin polymer satisfies the following requirements (i) to (iii):
(I) The melting point (Tm) determined by a differential scanning calorimeter (DSC) is 150 ° C. or higher,
(Ii) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 100,000 or more,
(Iii) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is 2.5 or more.