JP2014177508A - Method of producing catalyst containing novel fluorene derivative and method of producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an advantageous production method with high productivity which provides a polypropylene having a low melting point and a high molecular weight.SOLUTION: An olefin is polymerized at 40°C or higher in the presence of catalyst which contains a crosslinked metallocene compound of formula [1] and an organic aluminum oxy compound. In the formula [1], Rand Rare 6-20C aryl group optionally containing a halogen; Rand Rare derivatives of the phenyl group; Y is a crosslinking group; and M is Zr.

Description

  The present invention relates to a method for producing an olefin polymer using an olefin polymerization catalyst containing a metallocene compound having a specific structure, and particularly relates to a method for producing an olefin polymer having a high molecular weight and a low 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 isotactic polymerization was reported by Kaminsky et al., Many improvements have been conducted from the viewpoint of further improving stereoregularity and polymerization activity (Non-Patent Document 1: Angew. Chem. Int. Ed. Engl., 24, 507 (1985)).

  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. Ewen (Non-Patent Document 2: J. Am. Chem. Soc., 1988, 110, 6255). 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: Japanese Patent Application Laid-Open No. 04-069394). ). In addition, attempts to improve stereoregularity by changing the fluorenyl group to a 3,6-ditert-butylfluorenyl group (Patent Document 2: JP 2000-212194 A), cyclopentadienyl group Reported attempts to improve stereoregularity by converting the cross-linked portion where fluorenyl group and fluorenyl group are bonded (Patent Document 3: Japanese Patent Application Laid-Open No. 2004-189666, Patent Document 4: Japanese Patent Application Laid-Open No. 2004-189667) Has been.

  Thus, by improving the metallocene compound, (1) an olefin polymer having a controlled melting point, which is an index of stereoregularity, and (2) an olefin polymer having a controlled molecular weight can be obtained. ing. However, even the above-mentioned metallocene compound still has insufficient polymerization performance for synthesizing an olefin polymer that is freely controlled by a combination of melting point and molecular weight.

  In particular, in applications requiring a buffering action and slidability as typified by shock absorbing materials, the polymerization performance of synthesizing an olefin polymer having a low melting point and a high molecular weight is still insufficient.

For this reason, the efficient manufacture of the olefin polymer which has the said characteristic is desired.
Furthermore, in order to enable industrial production of these olefin polymers, it is desired to produce olefin polymers having the above characteristics at temperatures higher than room temperature, preferably higher than room temperature. .

Japanese Patent Laid-Open No. 04-069394 JP 2000-212194 A JP 2004-189666 A JP 2004-189667 A Angew. Chem. Int. Ed. Engl., 24, 507 (1985) J. Am. Chem. Soc., 1988, 110, 6255

  The problem to be solved by the present invention is to produce an olefin polymer having a low melting point and a high molecular weight by polymerizing an olefin such as propylene, which is advantageous in an industrial production method and has a high productivity. Is to provide.

  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 [4].
[1]
(A) a bridged metallocene compound represented by the following general formula [1];
(B) (b-1) an organoaluminum oxy compound,
(B-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair,
(B-3) In the presence of an olefin polymerization catalyst comprising at least one compound selected from organoaluminum compounds,
A method for producing an olefin polymer, comprising polymerizing at least one olefin selected from olefins containing 2 or more carbon atoms under conditions of 40 ° C. or higher:

〔式［１］において、Ｒ¹およびＲ⁴はそれぞれ独立に水素原子、炭化水素基、ハロゲン含有炭化水素基、窒素含有基、酸素含有基またはケイ素含有基から選ばれる基を示し；
Ｒ²およびＲ³はそれぞれ独立に水素原子、炭化水素基、ハロゲン含有炭化水素基、炭素数６〜２０のアリール基または炭素数６〜２０のハロゲン含有アリール基から選ばれる基を示し；
Ｒ²およびＲ³の少なくとも一方は炭素数６〜２０のアリール基または炭素数６〜２０のハロゲン含有アリール基であり；
Ｒ⁵、Ｒ⁶はそれぞれ独立にフェニル基誘導体であり；
Ｙは炭素原子またはケイ素原子であり；
ＭはＴｉ、ＺｒまたはＨｆであり；
Ｑはハロゲン原子、炭化水素基、炭素数１０以下の中性の共役もしくは非共役ジエン、アニオン配位子または孤立電子対で配位可能な中性配位子であり；ｊは１〜４の整数をであり；ｊが２以上のときは、複数のＱは同一でも異なっていてもよい。〕
［２］前記オレフィン重合用触媒が、さらに担体（Ｃ）を含むことを特徴とする［１］に記載のオレフィン重合体の製造方法。
［３］前記オレフィンの少なくとも１種が、プロピレンであることを特徴とする［１］または［２］に記載のオレフィン重合体の製造方法。
［４］得られるオレフィン重合体が下記要件（i）〜（iii）を満たすことを特徴とする、［１］〜［３］の何れかに記載のオレフィン重合体の製造方法。
（i）ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により求められる重量平均分子量（Ｍｗ）が２００，０００以上
（ii）ＤＳＣ（示差走査熱量分析）により求められる融点（Ｔｍ）が１４５℃以下
（iii）ＤＳＣ（示差走査熱量分析）により求められる結晶化温度（Ｔｃ）が１００℃以下

[In the formula [1], R ¹ and R ⁴ each independently represents a group selected from a hydrogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group;
R ² and R ³ each independently represent a group selected from a hydrogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, an aryl group having 6 to 20 carbon atoms, or a halogen-containing aryl group having 6 to 20 carbon atoms;
At least one of R ² and R ³ is an aryl group having 6 to 20 carbon atoms or a halogen-containing aryl group having 6 to 20 carbon atoms;
R ⁵ and R ⁶ are each independently a phenyl group derivative;
Y is a carbon atom or a silicon atom;
M is Ti, Zr or Hf;
Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair; An integer; when j is 2 or more, multiple Qs may be the same or different. ]
[2] The method for producing an olefin polymer according to [1], wherein the catalyst for olefin polymerization further contains a carrier (C).
[3] The method for producing an olefin polymer according to [1] or [2], wherein at least one of the olefins is propylene.
[4] The method for producing an olefin polymer according to any one of [1] to [3], 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 200,000 or more. (Ii) The melting point (Tm) obtained by DSC (differential scanning calorimetry) is 145 ° C. or less. (Iii) DSC The crystallization temperature (Tc) obtained by (differential scanning calorimetry) is 100 ° C. or less.

  According to the present invention, when an olefin polymer such as propylene is polymerized to produce an olefin polymer having a controlled low melting point and a high molecular weight, it is advantageous in an industrial production method and has a high productivity. Can do.

  The method for producing an olefin polymer of the present invention comprises an olefin polymerization catalyst containing a metallocene compound (A) described later and a compound (B) described later, containing an olefin having 3 or more carbon atoms, and having 2 or more carbon atoms. A step of 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].

式［１］において、各記号の意味は以下のとおりである。
Ｒ¹およびＲ⁴はそれぞれ独立に水素原子、炭化水素基、ハロゲン含有炭化水素基、窒素含有基、酸素含有基またはケイ素含有基から選ばれる基であり；
Ｒ²およびＲ³はそれぞれ独立に水素原子、炭化水素基、ハロゲン含有炭化水素基、炭素数６〜２０のアリール基または炭素数６〜２０のハロゲン含有アリール基から選ばれる基であり；
Ｒ²およびＲ³の少なくとも一方は炭素数６〜２０のアリール基または炭素数６〜２０のハロゲン含有アリール基であり；
Ｒ⁵、Ｒ⁶はそれぞれ独立にフェニル基誘導体であり;
Ｙは炭素原子またはケイ素原子であり；
ＭはＴｉ、ＺｒまたはＨｆであり；
Ｑはハロゲン原子、炭化水素基、炭素数１０以下の中性の共役もしくは非共役ジエン、アニオン配位子または孤立電子対で配位可能な中性配位子であり；ｊは１〜４の整数であり；ｊが２以上のときは、複数のＱは同一でも異なっていてもよい。〕
以下、さらに詳細に説明する。
なお、本明細書において、基とは原子を含む意味で用いる。

In the formula [1], the meaning of each symbol is as follows.
R ¹ and R ⁴ are each independently a group selected from a hydrogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group;
R ² and R ³ are each independently a hydrogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, an aryl group having 6 to 20 carbon atoms or a halogen-containing aryl group having 6 to 20 carbon atoms;
At least one of R ² and R ³ is an aryl group having 6 to 20 carbon atoms or a halogen-containing aryl group having 6 to 20 carbon atoms;
R ⁵ and R ⁶ are each independently a phenyl group derivative;
Y is a carbon atom or a silicon atom;
M is Ti, Zr or Hf;
Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair; An integer; when j is 2 or more, multiple Qs may be the same or different. ]
This will be described in more detail below.
In the present specification, the term “group” is used to include atoms.

(1) Examples of hydrocarbon groups listed as hydrocarbon groups R ^{1 to} R ⁶ include alkyl groups, saturated alicyclic groups, aryl groups, and aralkyl groups. 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; and other groups such as cyclopentylmethyl group, cyclohexylmethyl group, and cyclooctylmethyl 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) As the halogen-containing hydrocarbon groups listed as halogen-containing hydrocarbon groups R ^{1 to} R ⁶ , at least one hydrogen atom of the hydrocarbon group is a halogen atom (eg, fluorine atom, chloro atom, bromo atom) And a group substituted with an 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 by a halogen atom;
Fluoroalkylaryl groups such as trifluoromethylphenyl groups, bromoalkylaryl groups such as bromomethylphenyl groups and dibromomethylphenyl groups, and the above alkylaryl groups such as iodoalkylaryl groups such as iodomethylphenyl groups and diiodomethylphenyl groups A halogen-containing aryl group such as a group in which a part of hydrogen atoms are substituted with a halogen atom;
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 listed as nitrogen-containing groups R ¹ and R ⁴ are exemplified by nitro groups, cyano groups, N-methylamino groups, N, N-dimethylamino groups, and N-phenylamino groups. .

(4) Examples of oxygen-containing groups listed as oxygen-containing groups R ¹ and R ⁴ include alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group.

(5) Silicon-containing groups listed as silicon-containing groups R ¹ and R ⁴ include methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group, etc. Examples thereof include alkylsilyl groups; arylsilyl groups such as dimethylphenylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group.

(6) Examples of the halogen atom listed as the halogen atom Q 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 ^6>
R ¹ and R ⁴ are each independently preferably a hydrogen atom, the hydrocarbon group, the halogen-containing hydrocarbon group or a halogen atom from the viewpoint of controlling the melting point of the olefin polymer to be produced; More preferably a group, the halogen-containing alkyl group, the aryl group, the halogen-containing aryl group, the aralkyl group, the halogen-containing aralkyl group, the saturated alicyclic group, or a halogen atom; hydrogen atom, carbon number 1 It is more preferable that they are 10 to 10 alkyl groups, phenyl groups, alkylphenyl groups, benzyl groups, their halogen substituents or halogen atoms. R ¹ and R ⁴ are preferably the same group from the viewpoint of controlling the molecular weight of the olefin polymer to be produced.

R ² and R ³ are each independently preferably a hydrogen atom, the above hydrocarbon group or the above halogen-containing hydrocarbon group from the viewpoint of controlling the melting point of the olefin polymer to be produced; a hydrogen atom, the above alkyl group, 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. , A phenyl group, an alkylphenyl group, a benzyl group, a halogen substituent or a halogen atom thereof; more preferably a hydrogen atom, a phenyl group, an alkylphenyl group or a halogen substituent thereof. Also it one of R ² and R ³ is not a hydrogen atom is preferable from the viewpoint of molecular weight control of olefin polymer produced.
R ⁵ and R ⁶ are preferably each independently a phenyl group derivative from the viewpoint of increasing the molecular weight of the olefin polymer to be produced.

<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 bridging part, an olefin polymer having a controlled melting point and a controlled molecular weight can be efficiently produced.

  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 controlled melting point can be obtained. This is because the metallocene compound (A) catalyzes the production of an olefin polymer having appropriate stereoregularity. 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 high 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 because it is relatively less likely to cause chain transfer than the polymerization growth reaction. For this reason, it becomes possible to synthesize a high-molecular-weight olefin polymer even at a temperature higher than room temperature, preferably a temperature much higher than room temperature, and the cost performance when industrially producing the olefin polymer is improved.

  Furthermore, since it is possible to synthesize a high molecular weight olefin polymer at a temperature higher than room temperature, preferably a temperature significantly higher than room temperature, by adding an appropriate amount of chain transfer agent (usually using hydrogen) Therefore, it is possible to control the molecular weight to a desired value, and the cost performance when industrially producing an 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 excluding MQ _j (metal part) of the metallocene compound is divided into two parts, a cyclopentadienyl derivative part and a fluorenyl derivative part. The cyclopentadienyl derivative portion is composed of α1 to α5 in the table, and the fluorenyl derivative portion is composed of a combination selected from β1 to β12 in the table.

  The melting point of the produced polymer is an index of the stereoregularity of the polymer, and a polymer having high stereoregularity has a high melting point. The stereoregularity of the polymer is generated from the regularity of the polymerization reaction (growth reaction), which is regulated by the ligand structure.

  In the metallocene compound of the present invention, the 3,6-position of the fluorenyl derivative is relatively bulky and the 2,7-position is a relatively small substituent, so that the polymer in the polymerization reaction (growth reaction) It is considered that the stereoregularity is controlled to be moderately low, and thus an olefin polymer having a desired melting point is produced.

Since R ⁵ and R ⁶ are phenyl derivatives, the angle at which the ligand structure sandwiches the central metal (in formula [1], the angle formed by the cyclopentadienyl derivative portion and the fluorenyl derivative portion; the coordination angle (bite angle) ), See the following formula) is increased, and the chain transfer reaction in the polymerization reaction is promoted, and thus the molecular weight of the produced polymer is considered to be reduced.

According to the above table, no. The ligand structure of 1 means a combination of α1 and β1. The ligand structure of 8 means a combination of α1 and β8. When MQ _{j of} the metal moiety is ZrCl ₂ , the following metallocene compounds are exemplified.

ＭＱ_jの具体的な例示としては、ＺｒＣｌ₂、ＺｒＢｒ₂、ＺｒＭｅ₂、Ｚｒ（ＯＴｓ）₂、Ｚｒ（ＯＭｓ）₂、Ｚｒ（ＯＴｆ）₂、ＴｉＣｌ₂、ＴｉＢｒ₂、ＴｉＭｅ₂、Ｔｉ（ＯＴｓ）₂、Ｔｉ（ＯＭｓ）₂、Ｔｉ（ＯＴｆ）₂、ＨｆＣｌ₂、ＨｆＢｒ₂、ＨｆＭｅ₂、Ｈｆ（ＯＴｓ）₂、Ｈｆ（ＯＭｓ）₂、Ｈｆ（ＯＴｆ）₂などが挙げられる。Ｔｓはｐ−トルエンスルホニル基、Ｍｓはメタンスルホニル基、Ｔｆはトリフルオロメタンスルホニル基である。

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].

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

In the formulas [3] and [4], R 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.

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

In the formula [5], R 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.

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

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 used suitably.

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

<Compound (b-2) 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.

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

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 alkylaluminum such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; , Tricycloalkyl aluminum such as tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tolyl aluminum;
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 Partially having an average composition represented by the general formula R ^a _2.5 Al (OR ^b ) _0.5 (wherein R ^a and R ^b are synonymous with R ^a and R ^b in formula [8]); Alkoxylated alkylaluminum; alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide) Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides such as dichloride; moieties such as dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride Hydrogenation Alkyl aluminum; ethylaluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride, partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide are exemplified.

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 and other ummo groups, montmorillonite group, vermiculite, ryokdeite group, palygorskite. 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. Although the said olefin may be used individually by 1 type and may use 2 or more types together, it contains C3 or more olefins.

  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 such as acrylic acid, methacrylic acid, fumaric acid, Α, β-unsaturated carboxylic acids such as maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride; the α, β-unsaturated Metal salts such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt of carboxylic acid; methyl acrylate, acrylic acid n -Butyl, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-n-butylhexyl acrylate, methyl methacrylate, n-butyl methacrylate, methacrylic acid α, β-unsaturated carboxylic acid esters such as n-propyl, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, stearic acid Vinyl esters such as vinyl and vinyl trifluoroacetate; unsaturated glycidyl such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate may also 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, lower at high polymerization temperature not only in the polymerization temperature, the melting point is controlled low and high molecular weight olefin polymer Can be manufactured.

  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) determined by gel permeation chromatography (GPC) of the propylene polymer is usually 100,000 or more, preferably 150,000 to 1,000,000, more preferably 250,000 to 1,000,000. The molecular weight distribution (Mw / Mn) of the propylene polymer is usually 1 to 3.2, preferably 1 to 3.0, 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 1.30 dl / g or more, more preferably 1.70 dl / g or more, and further preferably 2.50 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 after molding.
The melting point (Tm) determined by DSC (differential scanning calorimetry) of the propylene polymer is usually 160 ° C. or less, preferably 100 to 150 ° C., more preferably 110 to 145 ° C. A propylene polymer having a melting point (Tm) in the above range is excellent in fluidity when heated and melted.

  The crystallization temperature (Tc) calculated | required by DSC (differential scanning calorimetry) of the said propylene polymer is 120 degrees C or less normally, More preferably, it is 40-115 degreeC, More preferably, it is 50-100 degreeC. A propylene polymer having a crystallization temperature (Tc) in the above range is excellent in stability during heating and melting.

  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 200,000 or more, (ii) the melting point (Tm) is 145 ° C. or less, and (iii) An olefin polymer having a crystallization temperature (Tc) of 100 ° C. or lower 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 the examples, when two crystal melting peaks are observed, Tm2 is the melting point of the olefin polymer when the low temperature side peak is Tm1 and the high temperature side peak is Tm2. Tm).

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

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

(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 diphenylmethylene (cyclopentadienyl) (3,6-diphenylfluorenyl) zirconium dichloride

［合成例１−１］
ジフェニルメチレン-（シクロペンタジエニル）-(3,6-ジフェニルフルオレン)の合成

[Synthesis Example 1-1]
Synthesis of diphenylmethylene- (cyclopentadienyl)-(3,6-diphenylfluorene)

窒素雰囲気下、50 mLナス型フラスコに３、６−ジフェニルフルオレン（0.40 g、1.26 mmol）、tBuOMe（7 mL）を加え、氷浴で冷却、攪拌した（無色透明溶液）。これに市販のnBuLi（1.65Mヘキサン溶液、0.84 mL、1.38 mmol）をゆっくり加え（褐色〜濃緑色溶液）。さらに、反応容器をドライアイス-MeOHバスで-78℃に冷却した。(2-(シクロペンタ -2,4-ジエニリデン)プロパン-1,3-ジイル)ジベンゼン、0.50 g、1.51 mmol）のtBuOMe（7 mL）溶液を滴下した。反応容器を徐々に室温まで昇温し終夜攪拌した（黄色ベージュ懸濁液）。反応溶液にEt2O（10 mL）、1N-HClaq.（5 mL）を加え、反応を停止し、Et2Oで抽出し、水洗、飽和食塩水洗後、無水硫酸マグネシウムで乾燥し、濃縮した。濃縮残渣をシリカゲルクロマトグラフィー（展開溶媒：ヘキサン-ジクロロメタン）で精製し、目的物含有フラクションを集め、濃縮した。収量89.8 mg、収率13%
GC−MS；549

Under a nitrogen atmosphere, 3,6-diphenylfluorene (0.40 g, 1.26 mmol) and tBuOMe (7 mL) were added to a 50 mL eggplant-shaped flask, and the mixture was cooled and stirred in an ice bath (colorless transparent solution). To this, commercially available nBuLi (1.65 M hexane solution, 0.84 mL, 1.38 mmol) was slowly added (brown to dark green solution). Furthermore, the reaction vessel was cooled to −78 ° C. with a dry ice-MeOH bath. A solution of (2- (cyclopenta-2,4-dienylidene) propane-1,3-diyl) dibenzene, 0.50 g, 1.51 mmol) in tBuOMe (7 mL) was added dropwise. The reaction vessel was gradually warmed to room temperature and stirred overnight (yellow beige suspension). Et2O (10 mL) and 1N-HClaq. (5 mL) were added to the reaction solution to stop the reaction, extracted with Et2O, washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated. The concentrated residue was purified by silica gel chromatography (developing solvent: hexane-dichloromethane), and fractions containing the desired product were collected and concentrated. Yield 89.8 mg, Yield 13%
GC-MS; 549

[Synthesis Example 1-2]
Diphenylmethylene (cyclopentadienyl) (3,6-diphenyl-9H-fluorenyl) zirconium dichloride

窒素雰囲気下、20 mLナス型フラスコにジフェニルメチレン-（シクロペンタジエニル）-(3,6-ジフェニルフルオレン)（0.09 g、0.16 mmol）、Et2O（10 mL）を加え、氷浴で冷却、攪拌し（オレンジ懸濁液）、市販のnBuLi（1.65Mヘキサン溶液、0.22 mL、0.36 mmol）をゆっくり加え（濃赤褐色溶液）、3時間攪拌した。ドライアイス-MeOHバスで-78℃に冷却後、ZrCl4のTHF錯体（0.06 g、0.16 mmol）を粉末で加え、徐々に室温まで昇温し終夜攪拌した（赤色懸濁液）。減圧攪拌下、反応溶媒を留去、残渣をクローブボックスに移し、残渣にヘキサンを加えセライトろ過を行い、Et2Oで洗浄、ジクロロメタンで溶解、ろ液を濃縮、残渣をヘキサン、Et2Oでデカントし残渣を減圧乾燥した。収量99.4 mg、収率86%（270MHz NMR(CDCl3溶媒)、FD/MS測定）
¹Ｈ−ＮＭＲ （２７０ ＭＨｚ, ＣＤＣｌ₃) :δ３．４２ (ｂｒｓ, １Ｈ) ，５．６９ (ｂｒｓ, １Ｈ), ６．２５(ｂｒｓ, １Ｈ), ６．２２(ｍ, １Ｈ), ７．１０−７．７０(ｍ, ２６Ｈ), FD-MS;７０８

In a nitrogen atmosphere, add diphenylmethylene- (cyclopentadienyl)-(3,6-diphenylfluorene) (0.09 g, 0.16 mmol) and Et2O (10 mL) to a 20 mL eggplant-shaped flask, cool in an ice bath, and stir (Orange suspension), commercially available nBuLi (1.65 M hexane solution, 0.22 mL, 0.36 mmol) was slowly added (dark reddish brown solution) and stirred for 3 hours. After cooling to −78 ° C. with a dry ice-MeOH bath, a ZrCl 4 THF complex (0.06 g, 0.16 mmol) was added as a powder, and the mixture was gradually warmed to room temperature and stirred overnight (red suspension). While stirring under reduced pressure, the reaction solvent was distilled off, the residue was transferred to a clove box, hexane was added to the residue, filtered through Celite, washed with Et2O, dissolved in dichloromethane, the filtrate was concentrated, the residue was decanted with hexane and Et2O, and the residue was removed. It was dried under reduced pressure. Yield 99.4 mg, 86% yield (270 MHz NMR (CDCl3 solvent), FD / MS measurement)
¹ H-NMR (270 MHz, CDCl ₃ ): δ 3.42 (brs, 1H), 5.69 (brs, 1H), 6.25 (brs, 1H), 6.22 (m, 1H), 7. 10-7.70 (m, 26H), FD-MS; 708

[Example 1]
Under a nitrogen atmosphere, 2.2 mg (3.1 μmol) of the catalyst (a) as a metallocene complex was added to a Schlenk tube, dissolved in 5.8 mL of dehydrated toluene, and then 1.57 mmol (3.83 M) of a suspension of modified methylaluminoxane. n-hexane solvent) was added and stirred at room temperature for 30 minutes to prepare a 0.0005 M catalyst solution.

  A 0.2 mL solution of triisobutylaluminum diluted with a solvent (hereinafter referred to as a mixed solvent) prepared by mixing 9: 1 (volume ratio) of cyclohexane and hexane into a 15 mL SUS autoclave sufficiently purged with nitrogen. 0.05M, 10 μmol) and 2.7 mL of a mixed solvent as a polymerization solvent were added and stirred at 600 rpm. The solution was heated to 65 ° C. and then pressurized with propylene until the total pressure was 7 bar.

  To the autoclave, 0.2 mL of the catalyst solution (0.00051 M, 0.101 μmol) and 0.7 mL of a mixed solvent were 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 syndiotactic polypropylene.

[Examples 2 to 5]
In Example 1, it carried out like Example 1 except having changed the metallocene complex catalyst used, the polymerization solvent, and the polymerization temperature as described in Table 4. The results are shown in Table 4.

Claims (4)

(A) a bridged metallocene compound represented by the following general formula [1];
(B) (b-1) an organoaluminum oxy compound,
(B-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair,
(B-3) In the presence of an olefin polymerization catalyst comprising at least one compound selected from organoaluminum compounds,
A method for producing an olefin polymer, comprising polymerizing at least one olefin selected from olefins containing 2 or more carbon atoms under conditions of 40 ° C. or higher:

[In the formula [1], R ¹ and R ⁴ each independently represents a group selected from a hydrogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group or a silicon-containing group;
R ² and R ³ each independently represents a group selected from a hydrogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, an aryl group having 6 to 20 carbon atoms, or a halogen-containing aryl group having 6 to 20 carbon atoms;
At least one of R ² and R ³ is an aryl group having 6 to 20 carbon atoms or a halogen-containing aryl group having 6 to 20 carbon atoms;
R ⁵ and R ⁶ are each independently a phenyl group derivative;
Y is a carbon atom or a silicon atom;
M is Ti, Zr or Hf;
Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair; An integer; when j is 2 or more, a plurality of Qs may be the same or different. ]   The method for producing an olefin polymer according to claim 1, wherein the olefin polymerization catalyst further contains a carrier (C).   The method for producing an olefin polymer according to any one of claims 1 and 2, wherein at least one of the olefins is propylene. The method for producing an olefin polymer according to any one of claims 1 to 3, wherein the obtained olefin polymer satisfies the following requirements (i) to (iii).
(I) The weight average molecular weight (Mw) calculated | required by GPC (gel permeation chromatography) is 200,000 or more,
(Ii) Melting point (Tm) determined by DSC (Differential Scanning Calorimetry) is 145 ° C. or less (iii) Crystallization temperature (Tc) determined by DSC (Differential Scanning Calorimetry) is 100 ° C. or less