JP2013253149A - Method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an olefin polymer of a high molecular weight and a high melting point by polymerizing an olefin such as a propylene even under a hot condition that can be industrialized.SOLUTION: A method for producing an olefin polymer has a process for polymerizing an olefin under a condition of 40°C or higher in the presence of an olefin polymerization catalyst that contains (A) a crosslinked metallocene compound of titanium, zirconium, and hafnium which has a ligand in which non-substituted cyclopentadienyl group and 2,7-(substituted phenyl) fluorenyl group are crosslinked, (B) at least one compound selected from (b-1) an organoaluminum oxy compound, etc.

Description

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

  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.

  As described above, by improving the metallocene compound, (1) an olefin polymer having a certain melting point, which is an index of stereoregularity, and (2) an olefin polymer having a certain molecular weight are obtained. However, a method for synthesizing an olefin polymer having a higher molecular weight and a higher melting point 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

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

  An object of the present invention is to provide a method for producing an olefin polymer having a high molecular weight and a high melting point by polymerizing olefins such as propylene even under industrially high temperature conditions.

  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 [7].
[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, an olefin having 2 or more carbon atoms under conditions of 40 ° C. or higher A method for producing an olefin polymer, comprising a step of polymerizing at least one selected olefin.

[In the formula [1], R ^{1 to} R ¹⁴ are each independently a hydrogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group, and two adjacent groups are They may be bonded to form a ring; Z ¹ and Z ² are each independently a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group, and Z ¹ and R 2 ² may combine to form a ring, and Z ² and R ¹¹ may combine to form a ring; X ¹ and X ² each independently represent a hydrocarbon group, a halogen atom or a halogen-containing carbon A hydrogen group, R ² and X ¹ may combine to form a ring, R ¹¹ and X ² may combine to form a ring, and R ³ and X ¹ combine to form a ring; it may be formed, they may form a ring by bonding R ¹⁰ and X ^2; M is, Ti Z is Zr or Hf; Y is a carbon atom or a silicon atom; Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a lone electron pair A coordinateable neutral ligand; j is an integer of 1 to 4, and when j is 2 or more, a plurality of Qs may be the same or different. ]
[2] In the above [1], in the general formula [1], R ⁵ and R ⁸ are each independently a hydrocarbon group having 1 to 40 carbon atoms or a halogen-containing hydrocarbon group having 1 to 40 carbon atoms. The manufacturing method of the olefin polymer of description.

[3] In the general formula [1], X ¹ and X ² are each independently a hydrocarbon group having 1 to 10 carbon atoms, a fluorine atom, a chloro atom, a bromo atom, an iodo atom, or a halogen having 1 to 10 carbon atoms. The method for producing an olefin polymer according to the above [1] or [2], which is a containing hydrocarbon group.

[4] In the general formula [1], Z ¹ and Z ² are each independently a hydrocarbon group having 1 to 10 carbon atoms, or Z ¹ and R ² are bonded to form an aromatic ring. And the method for producing an olefin polymer according to any one of [1] to [3], wherein Z ² and R ¹¹ are bonded to form an aromatic ring.

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

  [7] The method for producing an olefin polymer according to [6], wherein the obtained olefin polymer satisfies the following requirements (i) to (iii): (i) Weight determined by GPC (gel permeation chromatography) Average molecular weight (Mw) is 100,000 or more. (Ii) The melting point (Tm) determined by DSC (differential scanning calorimetry) is 145 ° C. or higher. (Iii) The crystallization temperature (Tc) obtained by DSC (differential scanning calorimetry) is 90 ° C. or higher.

  According to the present invention, it is possible to provide a method for producing an olefin polymer having a high molecular weight and a high melting point by polymerizing an olefin such as propylene even under a high temperature condition that can be industrialized.

  The method for producing an olefin polymer according to the present invention comprises a metallocene compound (A) described later and a compound (B) described later in the presence of an olefin polymerization catalyst under a condition of 40 ° C. or higher and having 2 or more carbon atoms. Polymerizing at least one olefin selected from olefins.

1. Olefin Polymerization Catalyst The olefin polymerization catalyst used in the present invention includes (A) a bridged metallocene compound represented by the general formula [1] (hereinafter also referred to as “metallocene compound (A)”), and (B) ( 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 selected from organoaluminum compounds (hereinafter referred to as “a”). (Also referred to as “compound (B)”) as an essential component. The catalyst may contain at least one selected from the carrier (C) and the organic compound component (D) as an optional component.

1-1. Metallocene compound (A)
1-1-1. The constituent metallocene compound (A) of the metallocene compound (A) is represented by the general formula [1].

In the formula [1], the meaning of each symbol is as follows.
R ^{1 to} R ¹⁴ are each independently a hydrogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group, and two adjacent groups (eg, R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹³ and R ¹⁴ ) to form a ring You may do it.

Z ¹ and Z ² are each independently a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group, and Z ¹ and R ² may combine to form a ring. , Z ² and R ¹¹ may combine to form a ring.

X ¹ and X ² are each independently a hydrocarbon group, a halogen atom or a halogen-containing hydrocarbon group, R ² and X ¹ may be bonded to form a ring, and R ¹¹ and X ² are bonded. May form a ring, R ³ and X ¹ may combine to form a ring, or R ¹⁰ and X ² may combine to form a ring.

  M is Ti, Zr or Hf; Y is a carbon atom or a silicon atom; Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand Alternatively, it is a neutral ligand that can be coordinated by a lone pair of electrons. j is an integer of 1 to 4, and when j is 2 or more, a plurality of Qs may be the same or different.

  In the present specification, examples of the ring (additional ring) formed by combining two groups include an alicyclic ring, an aromatic ring, and a heterocyclic ring. Specific examples include a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; a hetero ring such as a furan ring and a thiophene ring and a corresponding hydrogenated hetero ring, and a benzene ring is preferred. Such a ring structure may further have a substituent such as an alkyl group on the ring.

This will be described in more detail below.
In the present specification, the term “group” is used to include atoms.
(1) Hydrocarbon groups R ^{1 to} R ¹⁴ , Z ¹ and Z ² , and hydrocarbon groups listed as X ¹ and X ² are exemplified by alkyl groups, saturated alicyclic groups, aryl groups, and aralkyl groups. Is done. Carbon number of a hydrocarbon group is 1-40 normally, Preferably it is 1-20, More preferably, it is 1-10.

  Examples of the alkyl group include alkyl groups having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms; specifically, methyl group, ethyl group, n-propyl group, n- Linear alkyl groups such as butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group; iso-propyl group, iso-butyl group, sec-butyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propyl Examples thereof include branched alkyl groups such as a butyl group, a 1,1-dimethyl-2-methylpropyl group, and a 1-methyl-1-isopropyl-2-methylpropyl group.

  Examples of the saturated alicyclic group include saturated alicyclic groups having 3 to 40 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms; specifically, cyclopentyl group, cyclohexyl group, 4 -Cycloalkyl groups such as methylcyclohexyl group, cycloheptyl group, cyclooctyl group; cycloaliphatic polycyclic groups such as norbornyl group, adamantyl group, methyladamantyl group; Illustrated.

  Examples of the aryl group include an aryl group having 6 to 40 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms; specifically, a phenyl group, a naphthyl group, a phenanthryl group, an anthracenyl group, and biphenyl. An aryl group in which all the groups bonded to the aromatic carbon such as a group are hydrogen atoms (hereinafter also referred to as “unsubstituted aryl group”); o-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, Examples thereof include alkylaryl groups such as n-propylphenyl group, iso-propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group and xylyl group.

  Examples of the aralkyl group include aralkyl groups having 7 to 40 carbon atoms, preferably 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms; specifically, benzyl group, cumyl group, α-phenethyl group, β- Aralkyl groups in which all groups bonded to aromatic carbon such as phenethyl group, diphenylmethyl group, naphthylmethyl group, neophyll group, biphenylmethyl group, 1,1,1-triphenylmethyl group are hydrogen atoms (hereinafter referred to as “unsubstituted”) Also referred to as an aralkyl group.); O-methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group, ethylbenzyl group, n-propylbenzyl group, iso-propylbenzyl group, n-butylbenzyl group, sec- Examples thereof include alkylaralkyl groups such as a butylbenzyl group and a tert-butylbenzyl group.

(2) Halogen-containing hydrocarbon groups R ^{1 to} R ¹⁴ , Z ¹ and Z ² , and halogen-containing hydrocarbon groups listed as X ¹ and X ² include at least one hydrogen atom possessed by the hydrocarbon group. Examples thereof include groups substituted with a halogen atom (eg, fluorine atom, chloro atom, bromo atom, iodo atom).

In particular,
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 or all of the above-mentioned unsubstituted aryl groups such as iodoaryl groups such as bromoaryl groups such as bromonaphthyl groups, o-iodophenyl groups, m-iodophenyl groups, p-iodophenyl groups, iodonaphthyl groups A group in which a hydrogen atom is substituted with a halogen atom; a fluoroalkylaryl group such as a trifluoromethylphenyl group, a bromoalkylaryl group such as a bromomethylphenyl group or a dibromomethylphenyl group, an iodomethylphenyl group, or a diiodomethylphenyl group The iodoalkyl aryl Halogen-containing aryl group such as; the part of the hydrogen atoms of the alkyl aryl group group substituted with a halogen atom such as;
Fluoroaralkyl groups such as o-fluorobenzyl group, m-fluorobenzyl group, p-fluorobenzyl group, fluorophenethyl group, o-chlorobenzyl group, m-chlorobenzyl group, p-chlorobenzyl group, chlorophenethyl group, etc. Bromoaralkyl groups such as chloroaralkyl group, o-bromobenzyl group, m-bromobenzyl group, p-bromobenzyl group, bromophenethyl group, o-iodobenzyl group, m-iodobenzyl group, p-iodobenzyl group, iodo A group in which a part of hydrogen atoms in the unsubstituted aralkyl group such as an iodoaralkyl group such as a phenethyl group is substituted with a halogen atom; a part of hydrogen atoms in the alkyl aralkyl group such as a trifluoromethylbenzyl group is a halogen atom Illustrative are halogen-containing aralkyl groups such as substituted groups

(3) Nitrogen-containing groups R ^{1 to} R ¹⁴ and the nitrogen-containing groups listed as Z ¹ and Z ² include nitro group, cyano group, N-methylamino group, N, N-dimethylamino group, N- A phenylamino group is exemplified.

(4) Examples of oxygen-containing groups listed as oxygen-containing groups R ^{1 to} R ¹⁴ and Z ¹ and Z ² include alkoxy groups such as methoxy and ethoxy groups; and aryloxy groups such as phenoxy groups.

(5) Silicon-containing groups R ^{1 to} R ¹⁴ and silicon-containing groups listed as Z ¹ and Z ² are methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethyl group Examples include alkylsilyl groups such as -tert-butylsilyl group; arylsilyl groups such as dimethylphenylsilyl group, diphenylmethylsilyl group and triphenylsilyl group.

(6) Examples of the halogen atom listed as the halogen atoms X ¹ and X ² include a fluorine atom, a chloro atom, a bromo atom and an iodo atom; a fluorine atom, a chloro atom and a bromo atom are preferred.

<For R ¹ ~R ^14>
R ^{1 to} R ¹⁴ are each independently preferably a hydrogen atom, the hydrocarbon group or the halogen-containing hydrocarbon group from the viewpoint of improving the melting point of the olefin polymer to be produced; a hydrogen atom, the alkyl group, and the above It is more preferably a halogen-containing alkyl group, the aryl group, the halogen-containing aryl group, the aralkyl group, the halogen-containing aralkyl group or the saturated alicyclic group; a hydrogen atom, the alkyl group having 1 to 10 carbon atoms. And more preferably a phenyl group, an alkylphenyl group, a benzyl group or a halogen substituent thereof. R ¹ and R ¹² are preferably the same group from the viewpoint of improving the molecular weight of the produced olefin polymer. R ⁵ and R ⁸ are preferably the same group.

A more preferred embodiment is as follows: R ¹ , R ⁶ , R ⁷ and R ¹² are each independently a hydrogen atom, the above alkyl group or the above aryl group, so that the melting point of the resulting olefin polymer is improved. From the viewpoint of R ⁵ and R ⁸ are each independently preferably the above hydrocarbon group having 1 to 40 carbon atoms or the above halogen-containing hydrocarbon group having 1 to 40 carbon atoms from the viewpoint of improving the melting point of the olefin polymer to be produced. It is more preferable that they are each independently the alkyl group, the saturated alicyclic group, or the aryl group. R ³ , R ⁴ , R ⁹ and R ¹⁰ are preferably each independently a hydrogen atom or the above alkyl group having 1 to 10 carbon atoms. R ² and R ¹¹ are each independently preferably a hydrogen atom or the above alkyl group having 1 to 10 carbon atoms from the viewpoint of improving the melting point of the resulting olefin polymer, or Z ¹ and R ² are bonded to each other. From the viewpoint of improving the melting point of the olefin polymer to be formed, an aromatic ring (eg, benzene ring) is formed and Z ² and R ¹¹ are bonded to form an aromatic ring (eg: benzene ring). preferable. R ¹³ and R ¹⁴ are preferably each independently a hydrogen atom, the hydrocarbon group or the halogen-containing hydrocarbon group, and include a hydrogen atom, the alkyl group, the saturated alicyclic group, the aryl group, and the aralkyl. It is more preferably a group or a halogen substituent thereof, and further preferably the above aralkyl group.

At least one set of two adjacent groups selected from R ^{1 to} R ¹⁴ may be bonded to form a ring. That is, the metallocene compound (A) has a ring structure in which the additional ring is further condensed with the fluorenyl moiety in the formula [1] or the aryl group moiety at the 2,7-position of the fluorenyl. May be.

<For Z ¹ and Z ^2>
Z ¹ and Z ² are each independently preferably the hydrocarbon group or the halogen-containing hydrocarbon group from the viewpoint of improving the molecular weight of the olefin polymer to be produced, and the hydrocarbon group having 1 to 10 carbon atoms. More preferably, the alkyl group having 1 to 10 carbon atoms, the saturated alicyclic group having 3 to 10 carbon atoms, a phenyl group, or an alkylphenyl group is more preferable. Z ¹ and Z ² are preferably the same group.

Z ¹ and R ² may be combined to form a ring, or Z ² and R ¹¹ may be combined to form a ring. For example, it is also preferred that Z ¹ and R ² are bonded to form an aromatic ring (eg, benzene ring), and Z ² and R ¹¹ are bonded to form an aromatic ring (eg, benzene ring). That is, in the metallocene compound (A), at least one pair of Z ¹ and R ² , Z ² and R ¹¹ is bonded to the aryl group portion at the 2,7-position of fluorenyl in the formula [1], and the addition It may have a ring structure in which a typical ring is further condensed.

<For X ¹ and X ^2>
X ¹ and X ² are olefins produced by being the above hydrocarbon group having 1 to 10 carbon atoms, a fluorine atom, a chloro atom, a bromo atom, an iodo atom, or the above halogen-containing hydrocarbon group having 1 to 10 carbon atoms. More preferable from the viewpoint of improving the melting point of the polymer, the above alkyl group having 1 to 10 carbon atoms, the above aryl group having 6 to 10 carbon atoms, a fluorine atom, a chloro atom, a bromo atom, an iodo atom, or the above 1 to 10 carbon atoms. A halogen-containing alkyl group is more preferred, and a methyl group, ethyl group, propyl group, fluorine atom or chloro atom is still more preferred. X ¹ and X ² are preferably the same group from the viewpoint of improving the melting point of the resulting olefin polymer.

R ² and X ¹ may combine to form a ring, R ¹¹ and X ² may combine to form a ring, or R ³ and X ¹ combine to form a ring. R ¹⁰ and X ² may combine to form a ring. That is, the metallocene compound (A) has R ² and X ¹ , R ¹¹ and X ² , R ³ and X ¹ , R ¹⁰ and X in the aryl group moiety at the 2,7-position of fluorenyl in the formula [1]. ^At least one pair of ² may be bonded to each other to have a ring structure formed by further condensing the additional ring.

<About Y, M, Q and j>
Y is preferably a carbon atom.
M is preferably Zr or Hf, and particularly preferably Zr. By using the metallocene compound (A) having the central metal and the cross-linking part, it is possible to efficiently produce a high molecular weight and high melting point olefin polymer.

  Q is coordinated by a halogen atom (eg, fluorine atom, chloro atom, bromo atom, iodo atom), hydrocarbon group, neutral conjugated or nonconjugated diene having 10 or less carbon atoms, anionic ligand, or lone electron pair It is a possible neutral ligand.

  As a hydrocarbon group enumerated as 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, A 1,3-trimethylbutyl group and a neopentyl group are exemplified, and an alkyl group having 1 to 5 carbon atoms is more preferable; a cycloalkyl group having 3 to 10 carbon atoms includes a cyclohexylmethyl group, a cyclohexyl group, and 1-methyl-1 -A cyclohexyl group is illustrated.

Neutral conjugated or non-conjugated dienes having 10 or less carbon atoms listed as Q 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 Examples are s-trans-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 listed as Q include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate.

  Neutral ligands that can be coordinated with lone pairs enumerated as Q include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran (THF), diethyl ether, dioxane, Examples include ethers such as 1,2-dimethoxyethane.

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.
1-1-2. Physical properties of metallocene compound (A) By using the metallocene compound (A) having the above substituent, an olefin polymer having a high melting point can be obtained. 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 normal temperature, can exhibit good moldability, increase the value of the product, and industrially use an olefin polymer. Cost performance when producing is improved.

  Moreover, an olefin polymer with a large molecular weight is obtained by using the metallocene compound (A) having the above substituent. This is because the metallocene compound (A) catalyzes the production of a high molecular weight olefin polymer. 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.

1-1-3. Examples of metallocene compound (A) Specific examples of the metallocene compound (A) 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.

For convenience, the ligand structure of the metallocene compound, excluding MQ _j (metal moiety), is represented by a bridging moiety, a fluorenyl moiety excluding the 2,7-position, an aryl group moiety at the 2,7-position of fluorenyl, and a cyclopentadienyl moiety. Divide into four. Among the structures of the bridging moiety, Y is composed of δ1 or δ2 in the table, and R ¹³ and R ¹⁴ are each composed of a combination selected from γ1 to γ23 in the table. Further, the fluorenyl portion excluding the 2,7-position is composed of β1 to β9 in the table, and the aryl group portion at the 2,7-position of fluorenyl is composed of a combination selected from α1 to α45 in the table.

According to the above notation, of crosslinking moiety, Y is δ1 in Table, R ¹³ and R ¹⁴ are each in the table Ganma19, also fluorenyl portion excluding the 2,7-position β1 in the table, fluorenyl When the 2,7-position aryl group moiety is composed of a combination of α1 in the table, and the MQ _{j of} the metal moiety is ZrCl ₂ , the following metallocene compounds are exemplified.

Of the bridging moieties, Y is δ1, R ¹³ and R ¹⁴ in the table are γ19 in the table, and the fluorenyl portion excluding the 2,7-position is β1, and the 2,7-position of fluorenyl in the table. In the case where each of the aryl group parts is composed of a combination of α3 in the table and MQ _{j of} the metal part is ZrCl ₂ , the following metallocene compounds are exemplified.

Of the bridging moieties, Y is δ1, R ¹³ and R ¹⁴ in the table are γ19 in the table, and the fluorenyl portion excluding the 2,7-position is β1, and the 2,7-position of fluorenyl in the table. In the case where each of the aryl group parts is composed of a combination of α2 in the table and MQ _{j of} the metal part is ZrCl ₂ , the following metallocene compounds are exemplified.

Furthermore, among the bridging moieties, Y is δ1, R ¹³ and R ¹⁴ in the table are γ19 in the table, respectively, and the fluorenyl portion excluding the 2,7-position is β1, and the 2,7-position of fluorenyl in the table In the case where each of the aryl group parts is composed of a combination of α31 in the table and the MQ _{j of} the metal part is ZrCl ₂ , the following metallocene compounds are exemplified.

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. Ts is a p-toluenesulfonyl group, Ms is a methanesulfonyl group, and Tf is a trifluoromethanesulfonyl group.

  Similarly, the compounds exemplified above, in which “zirconium” is replaced with “hafnium” or “titanium”, or 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 metallocene compound (A) 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 the methods described in WO 2001/027124 and WO 2004/087775 by the present applicant.

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

<Organic aluminum 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].

  In the formulas [3] and [4], R is a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group, and n is an integer of 2 or more, preferably 3 or more, more preferably 10 or more. In the present invention, methylaluminoxane in which R is a methyl group in formulas [3] and [4] is preferably used.

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

In the formula [6], R ^c is a hydrocarbon group having 1 to 10 carbon atoms. A plurality of R ^d are each independently a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
In the present invention, an olefin polymer can be produced even at a high temperature as described later. Accordingly, one of the features of the present invention is that a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can also be used. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxane having two or more alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like are also included. It can be suitably used.

  The “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) which forms an ion pair by reacting with the metallocene compound (A)>
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 [7] is preferable.

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 are each independently 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, dioctadecyl methyl ammonium and the like.

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

  Specific examples of the dialkylammonium salt include diisopropylammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

An ionic compound (b-2) may be used individually by 1 type, and may use 2 or more types together.
<Organic aluminum 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 are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m is 0 <m ≦ 3, and n is 0 ≦ n <3, p is a number 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3.

M ² AlR ^a ₄ ... [9]
In the formula [9], M ² is Li, Na or K, and a plurality of R ^a are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

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.

1-3. 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 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.

1-4. 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 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.

2. Olefin In the method for producing an olefin polymer of the present invention, an olefin having 2 or more carbon atoms is used as a raw material for the olefin polymer. The said olefin may be used individually by 1 type, and may use 2 or more types together.

  The olefin is an olefin having 2 or more carbon atoms, preferably an olefin having 3 to 20 carbon atoms, more preferably an olefin having 3 to 10 carbon atoms. The olefin is preferably an α-olefin, more preferably a linear or branched α-olefin.

  Examples of olefins include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1- Examples include α-olefins such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene. Of these, propylene is particularly preferred.

In the present invention, as a 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, tetracyclodone. Decene, 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 invention, propylene is used for at least a portion 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 olefin. Moreover, in the obtained polymer, it is preferable that the ratio of the structural unit derived from propylene measured using < ¹³ > C-NMR is 60-100 mol%, and it is more preferable that it is 70-100 mol%.

3. Olefin Polymer Production Conditions In the method for producing an olefin polymer of 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, In particular, it is a temperature at which industrialization is possible. 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 olefin is propylene, from the viewpoint of productivity, the polymerization temperature is preferably 50 ° C. or higher, and particularly preferably 60 to 150 ° C.

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 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 of the present invention, during 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. Such a method is 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 of the present invention, an olefin polymer is obtained by homopolymerizing or copolymerizing one or more 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 polymerization solvent used in the liquid phase polymerization method include inert hydrocarbon solvents, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Examples include alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and 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 polymerization solvent.

  The catalyst for olefin polymerization used in the present invention can be used by dissolving the metallocene compound (A) and the compound (B), which are catalyst components, in a solvent. That is, the olefin polymerization catalyst may be supplied to the polymerization system as a catalyst solution.

  Generally as said solvent, the said polymerization solvent can be used. From the viewpoint of polymerization activity, it is preferable to supply a catalyst solution having a metallocene compound (A) concentration of 0.01 mmol / L to 2.00 mol / L to the polymerization system, more preferably 0.03 mmol / L to 1.50 mol. / L.

<Configuration 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 0.005 to 1. It is.

5. According to the present invention described above olefin polymer, if the polymerization of olefins such as propylene, even at high polymerization temperature not only in low polymerization temperature, to produce an olefin polymer having a high molecular weight and high melting point Can do.

  Below, the physical property 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 olefin is propylene) will be described.

  The weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) of the propylene polymer is usually 100,000 or more, preferably 110,000 to 1,000,000, more preferably 120,000 to 1,000,000. The propylene polymer has an MWD (weight average molecular weight (Mw) / number average molecular weight (Mn)) of usually 1 to 3, preferably 1 to 2.9, and more preferably 1 to 2.8.

  The metallocene compound (A) used in the present invention exhibits properties as a so-called single site catalyst and is advantageous for obtaining a polymer having a narrow molecular weight distribution as described above. Of course, a polymer having a wide molecular weight distribution can be obtained by adopting a so-called multistage polymerization method in which polymerization reactions under different conditions are sequentially performed.

  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 (differential scanning calorimetry) of the propylene polymer is usually 145 ° C. or higher, preferably 145 to 170 ° C., more preferably 148 to 170 ° 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 (differential scanning calorimetry) of the said propylene polymer is 90 degreeC or more normally, More preferably, it is 92-150 degreeC, More preferably, it is 94-130 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.

  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, even at a temperature that can be industrialized, (i) the weight average molecular weight (Mw) is 100,000 or more, (ii) the melting point (Tm) is 145 ° C. or more, and (iii) An olefin polymer having a crystallization temperature (Tc) of 90 ° C. or higher 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 are observed (for example, the low temperature side peak Tm1 and the high temperature side peak Tm2), the high temperature side peak is regarded as the melting point of the olefin polymer. (Tm).

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the olefin polymer is a value measured at 135 ° C. using a decalin solvent. That is, granulated pellets 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 is further repeated twice, and the value of ηsp / C when the concentration (C) of the olefin polymer is extrapolated to 0 is defined as the intrinsic viscosity [η] of the olefin polymer.

Intrinsic viscosity [η] = lim (ηsp / C) (C → 0)
[Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were measured using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters as follows. The separation columns are TSKgel GNH6-HT: 2 and TSKgel GNH6-HTL: 2, 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 o- Using dichlorobenzene (Wako Pure Chemical Industries) and 0.025% by weight of BHT (Takeda Pharmaceutical) as an antioxidant, the mobile phase was moved at 1.0 mL / min, the sample concentration was 15 mg / 10 mL, and sample injection The amount was 500 microliters, and a differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ . The molecular weight distribution and various average molecular weights were calculated in terms of polypropylene molecular weight according to the general calibration procedure.

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

[Synthesis examples of metallocene compounds]
Synthesis Example 1 Catalyst (a): Dibenzylmethylene (cyclopentadienyl) (2,7-di (o-methyl-p-chloro) phenyl-3,6-ditert-butylfluorenyl) zirconium dichloride (1) Synthesis of 3,6-ditert-butyl-2,7-bis (4-chloro-2-methylphenyl) -9H-fluorene:
2,7-dibromo-3,6-ditert-butylfluorene 4.36 g (10 mmol), palladium acetate 0.5 mmol, tripotassium phosphate 60 mmol, tetrahydrofuran 240 ml, H ₂ O 60 ml, and 4-chloro-2-methylphenylboron 40 mmol of acid was mixed. The resulting solution was stirred at 50 ° C. for 4 hours. The target product was extracted with diethyl ether. The organic layer was dried with magnesium sulfate. The organic layer was separated by filtration and concentrated under reduced pressure, and washed with methanol and methylene chloride to obtain the desired product (yield 90%).

(2) Synthesis of dibenzylmethylene (cyclopentadienyl) (2,7-di (4-chloro-2-methylphenyl) -3,6-ditert-butylfluorenine):
200 ml of tetrahydrofuran was added to 5.64 g (5.0 mmol) of 3,6-ditert-butyl-2,7-bis (4-chloro-2-methylphenyl) -9H-fluorene. The obtained solution was cooled to 0 ° C., and 5.5 mmol of n-butyllithium (1.65 M hexane solution) was added dropwise with stirring. After confirming the reaction progress of the reaction solution, it was cooled again to 0 ° C., 6.0 mmol of 6,6-dibenzylfulvene was added, and the reaction progress of the reaction solution was confirmed while gradually raising the temperature. 1N-hydrochloric acid was added to stop the reaction. The target product was extracted with diethyl ether. The organic layer was dried with magnesium sulfate. The organic layer was separated by filtration and concentrated under reduced pressure, and washed with methanol and methylene chloride to obtain the desired product (yield 80%).

(3) Synthesis of catalyst (a):
To 786 mg (1 mmol) of dibenzylmethylene (cyclopentadienyl) (2,7-di (4-chloro-2-methylphenyl) -3,6-ditert-butylfluorenine) was added 40 ml of diethyl ether. The obtained solution was cooled to 0 ° C., and 2.1 mmol of n-butyllithium (1.65 M hexane solution) was added dropwise with stirring. After confirming the reaction progress of the reaction solution, it was cooled again to 0 ° C., and 0.95 mmol of zirconium tetrachloride was added to proceed the reaction. The obtained reaction solution was concentrated under reduced pressure, dissolved in hexane, and insolubles were removed by filtration. The reaction mixture was concentrated again under reduced pressure, and the resulting crude product was washed with diethyl ether and hexane to obtain the desired product (yield 36%).

¹ H-NMR (CDCl ₃ ); 8.4 (2H), 7.5-6.9 (18H), 6.5 (2H), 5.8 (2H), 4.4-3.8 (4H), 2.2-1.5 (6H), 1.3-1.1 (18H ) .FD-MS; 942
[Synthesis Example 2] Catalyst (b): Synthesis of dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-bis (4-methylnaphthalen-1-yl) fluorenyl) zirconium dichloride In Synthesis Example 1, the reaction was performed in the same manner as in Synthesis Example 1 except that the boronic acid used was changed to 4-methylnaphthalen-1-ylboronic acid to obtain the target product. ¹ H-NMR (CDCl ₃ ); 8.4 (2H), 7.5-6.9 (24H), 6.5 (2H), 5.8 (2H), 4.4-3.8 (4H), 2.2-1.5 (6H), 1.3-1.1 (18H ) .FD-MS; 974
[Synthesis Example 3] Catalyst (c): Synthesis of dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-bis (2,4-dimethylphenyl) fluorenyl) zirconium dichloride Synthesis Example In Example 1, the reaction was carried out in the same manner as in Synthesis Example 1 except that the boronic acid used was changed to 2,4-dimethylphenylboronic acid to obtain the desired product. ¹ H-NMR (CDCl ₃ ); 8.4 (2H), 7.5-6.9 (16H), 6.5 (2H), 5.8 (2H), 4.4-3.8 (4H), 2.2-1.5 (12H), 1.3-1.1 (18H ) .FD-MS; 902
[Synthesis Example 4] Catalyst (d): Synthesis of dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-bis (2,4,5-trimethylphenyl) fluorenyl) zirconium dichloride In Synthesis Example 1, the reaction was performed in the same manner as in Synthesis Example 1 except that the boronic acid used was changed to 2,4,5-trimethylphenylboronic acid to obtain the desired product. ¹ H-NMR (CDCl ₃ ); 8.4 (2H), 7.5-6.9 (14H), 6.5 (2H), 5.8 (2H), 4.4-3.8 (4H), 2.2-1.5 (18H), 1.3-1.1 (18H ) .FD-MS; 930
[Synthesis Example 5] Catalyst (f): Synthesis of dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl-fluorenyl) zirconium dichloride The catalyst (f) is a method described in the following patent publications: Was synthesized. JP 2000-212194 A, JP 2004-168744 A, JP 2004-189666 A, JP 2004-161957 A, JP 2007-302854 A, JP 2007-302853 A, International Publication. 01/027124 pamphlet.

[Example 1]
In a 15 mL SUS autoclave sufficiently purged with nitrogen, 3.1 mL of a solvent prepared by mixing cyclohexane and hexane as a polymerization solvent in a ratio of cyclohexane: hexane = 9: 1 (volume ratio) was added and stirred at 600 rpm. Went. The solution was heated to 50 ° C. and then pressurized with propylene until the total pressure was 7 bar.

  Under a nitrogen atmosphere, 5.2 mg (946.04 g / mol, 5.5 μmol) of the catalyst (a) as a metallocene compound was placed in a Schlenk tube, dissolved in 10.2 mL of dehydrated toluene, and then modified methylaluminoxane (trade name: TMAO341). , Tosoh Finechem Co., Ltd.) 0.72 mL (n-hexane solvent, 3.83 M in terms of aluminum atom, 2.76 mmol) was added, and the mixture was stirred at room temperature for 15 minutes to give a 0.0005 M catalyst solution. Was prepared.

  In the autoclave, 0.2 mL (0.05 M, 10 μmol) of triisobutylaluminum, 0.2 mL (0.10 μmol) of the catalyst solution, and cyclohexane and hexane as polymerization solvents, cyclohexane: hexane = 9: 1 (volume ratio) 0.7 mL of the solvent mixed in (1) was added to initiate polymerization. After polymerization at 65 ° C. for 10 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. Thereafter, the polymer was filtered and dried under reduced pressure to obtain 0.69 g of syndiotactic polypropylene.

  The polymerization activity was 41.4 kg-PP / mmol-Zr · hr. The obtained polymer had a melting point (Tm) of 152.7 ° C., a crystallization temperature (Tc) of 101.2 ° C., and [η] of 1. 87 dl / g, the weight average molecular weight (Mw) was 175,000, and the molecular weight distribution (Mw / Mn) was 2.33.

[Examples 2-6, Comparative Examples 1-2]
In Example 1, it carried out like Example 1 except having changed the used metallocene compound, polymerization temperature, and the polymerization solvent as shown in Table 3. The results are shown in Table 3. “Mixed” in Table 3 refers to a solvent in which cyclohexane and hexane are mixed in cyclohexane: hexane = 9: 1 (volume ratio).

Claims (7)

(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 a step of polymerizing at least one olefin selected from olefins having 2 or more carbon atoms under conditions of 40 ° C or higher.

[In Formula [1],
R ^{1 to} R ¹⁴ are each independently a hydrogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group, or a silicon-containing group, and two adjacent groups are bonded to form a ring. May be;
Z ¹ and Z ² are each independently a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group, and Z ¹ and R ² may combine to form a ring. , Z ² and R ¹¹ may combine to form a ring;
X ¹ and X ² are each independently a hydrocarbon group, a halogen atom or a halogen-containing hydrocarbon group, R ² and X ¹ may be bonded to form a ring, and R ¹¹ and X ² are bonded. May form a ring, R ³ and X ¹ may combine to form a ring, or R ¹⁰ and X ² may combine to form a ring;
M is Ti, Zr or Hf; Y is a carbon atom or a silicon atom; Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand Or a neutral ligand capable of coordinating with a pair of lone electrons; j is an integer of 1 to 4, and when j is 2 or more, a plurality of Qs may be the same or different. ] In the general formula [1], R ⁵ and R ⁸ are each independently a hydrocarbon group having 1 to 40 carbon atoms or a halogen-containing hydrocarbon group having 1 to 40 carbon atoms. Manufacturing method of coalescence. In the general formula [1], X ¹ and X ² are each independently a hydrocarbon group having 1 to 10 carbon atoms, a fluorine atom, a chloro atom, a bromo atom, an iodo atom, or a halogen-containing hydrocarbon having 1 to 10 carbon atoms. The manufacturing method of the olefin polymer of Claim 1 or 2 which is group. In the general formula [1], Z ¹ and Z ² are each independently a hydrocarbon group having 1 to 10 carbon atoms, or Z ¹ and R ² are bonded to form an aromatic ring, and Z ^The method for producing an olefin polymer according to any one of claims 1 to 3, wherein ² and R ¹¹ are bonded to form an aromatic ring.   The method for producing an olefin polymer according to any one of claims 1 to 4, wherein the olefin polymerization catalyst further comprises a carrier (C).   The method for producing an olefin polymer according to any one of claims 1 to 5, wherein at least a part of the olefin is propylene. The method for producing an olefin polymer according to claim 6, wherein the obtained olefin polymer satisfies the following requirements (i) to (iii).
(I) The weight average molecular weight (Mw) obtained by GPC (gel permeation chromatography) is 100,000 or more.
(Ii) The melting point (Tm) determined by DSC (differential scanning calorimetry) is 145 ° C. or higher.
(Iii) The crystallization temperature (Tc) determined by DSC (differential scanning calorimetry) is 90 ° C. or higher.