JP6260128B2 - Catalyst for producing ethylene polymer and method for producing ethylene polymer using the same - Google Patents

Description

  The present invention relates to a catalyst for producing an ethylene polymer comprising a transition metal compound having a specific structure, an organically modified clay modified with an aliphatic salt having a specific structure, and a metallocene catalyst obtained from an organoaluminum compound. The present invention relates to a method for producing an ethylene-based polymer to be used. More specifically, the method is applicable to a slurry process, and has an intrinsic viscosity (dL / g) of 9.0 or more or a viscosity-converted molecular weight (Mv) of 100. An ultrahigh molecular weight ethylene polymer having a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (molecular weight distribution: Mw / Mn) of more than 3.0 and less than 5.0. (Ultra high molecular weight) ethylene polymer production catalyst that can be efficiently produced, (ultra high molecular weight) ethylene polymer production method using the same, and (ultra high molecular weight) ) It relates to ethylene polymer.

  Conventionally, ultra-high molecular weight ethylene polymers have a viscosity average molecular weight (Mv) of 1,000,000 to 7,000,000, so impact resistance, self-lubricity, chemical resistance, dimensions not found in ordinary ethylene polymers. Because it has the effect of being excellent in stability, light weight, food stability, etc., it has a physical property comparable to engineering plastic, and is molded by various molding methods such as injection molding, extrusion molding, compression molding, lining material, Used in food industry line parts, machine parts, sports equipment, etc.

  However, the ultra-high molecular weight ethylene polymer produced by a normal Ziegler catalyst has a ratio (molecular weight distribution) of weight average molecular weight (Mw) to number average molecular weight (Mn) of more than 5, and an ultra high molecular weight component and a low molecular weight component. The molecular weight distribution with a large amount of molecular weight components was very large. The ultrahigh molecular weight component has an adverse effect of reducing the molding processability when forming a molded body. On the other hand, the low molecular weight component decreases the mechanical properties such as abrasion resistance or increases the number of molecular chain ends when it is made into a fiber, which causes a decrease in fiber strength by inhibiting crystallization, This was a factor that deteriorated the characteristics of the ultrahigh molecular weight ethylene polymer.

  As means for solving these problems, an ultrahigh molecular weight ethylene (co) polymer having a molecular weight distribution of 3.0 or less by using a metallocene catalyst has been proposed (for example, see Patent Document 1).

Japanese Unexamined Patent Publication No. 09-291112 (for example, refer to the claims)

  However, in the ultra-high molecular weight ethylene-based (co) polymer proposed in Patent Document 1, as a result of making the molecular weight distribution too small, the low molecular weight component contributing to molding processability is excessively reduced, and the molded article is formed. There existed a subject that molding processability fell. Moreover, it had the subject that it was inferior to a solution dispersibility in the solution dispersion process to the solvent in the spinning process at the time of making it into a fiber.

  An ultra-high molecular weight ethylene polymer having both a physical property comparable to engineering plastics and processability by having an appropriate molecular weight distribution has not been found.

  Therefore, the present invention has an intrinsic viscosity (dL / g) of 9.0 or more or a viscosity-converted molecular weight (Mv) of 1 million or more, and a ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) (molecular weight). It was found that an ultra high molecular weight ethylene polymer having a distribution (Mw / Mn) of more than 3.0 and less than 5.0 has both moldability and physical properties comparable to engineering plastics. The present invention provides a catalyst for producing an ethylene polymer that can efficiently produce a polymer and a method for producing an ethylene polymer using the same.

  As a result of intensive investigations to solve the above problems, the present inventors have found that at least a transition metal compound having a specific structure, an organically modified clay modified with an aliphatic salt having a specific structure, and a metallocene obtained from an organoaluminum compound. When a novel ethylene polymer production catalyst comprising a catalyst is applied to a slurry process or the like, the intrinsic viscosity (dL / g) is 9.0 or more, or Mv is 1 million or more, and Mw / Mn is 3 The inventors have found that it is possible to efficiently produce an ultra high molecular weight ethylene polymer having a value exceeding 0.0 and less than 5.0, and has completed the present invention.

  That is, the present invention provides at least a transition metal compound (A) represented by the following general formula (1),

［式中、Ｍ^１はチタン原子またはジルコニウム原子であり、Ｘは各々独立して水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルアミノ基、炭素数１〜２０のアルキルシリル基、炭素数１〜２０の炭化水素基の炭素と炭素の結合間に酸素を導入した置換基、炭素数１〜２０の炭化水素基の一部を炭素数１〜２０のアルキルアミノ基に置換した置換基、炭素数１〜２０の炭化水素基の一部の炭素をケイ素に置換した置換基であり、Ｒ¹は下記一般式（２）で示されるシクロペンタジエニル基であり、

[Wherein, M ¹ is a titanium atom or a zirconium atom, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 alkylamino groups, alkyl silyl groups having 1 to 20 carbon atoms, substituents having oxygen introduced between carbon-carbon bonds of hydrocarbon groups having 1 to 20 carbon atoms, hydrocarbon groups having 1 to 20 carbon atoms R ¹ is a substituent obtained by substituting a part of the hydrocarbon group having 1 to 20 carbon atoms with silicon, and R ¹ is represented by the following general formula (2). And a cyclopentadienyl group represented by

（式中、Ｒ⁴は各々独立して水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、炭素数１〜２０のアルキルアミノ基、炭素数１〜２０のアルキルシリル基、炭素数１〜２０の炭化水素基の炭素と炭素の結合間に酸素を導入した置換基、炭素数１〜２０の炭化水素基の一部を炭素数１〜２０のアルキルアミノ基に置換した置換基、炭素数１〜２０の炭化水素基の一部の炭素をケイ素に置換した置換基である。）
Ｒ^２は下記一般式（３）で示されるアミノ基を１つ有するフルオレニル基であり、

(In the formula, each R ⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or 1 carbon atom. A substituent in which oxygen is introduced between the carbon-carbon bonds of a hydrocarbon group having ˜20, a substituent in which a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms, carbon (This is a substituent obtained by substituting a part of carbons of the hydrocarbon group of 1 to 20 with silicon.)
R ² is a fluorenyl group having one amino group represented by the following general formula (3),

（式中、Ｒ^５は各々独立して水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、炭素数１〜２０のアルキルアミノ基、炭素数６〜３０のアリールアミノ基、炭素数７〜３０のアリールアルキルアミノ基、炭素数１〜２０のアルキルシリル基、炭素数１〜２０の炭化水素基の炭素と炭素の結合間に酸素を導入した置換基、炭素数１〜２０の炭化水素基の一部を炭素数１〜２０のアルキルアミノ基に置換した置換基、炭素数１〜２０の炭化水素基の一部の炭素をケイ素に置換した置換基であり、Ｒ^５の１つが炭素数１〜２０のアルキルアミノ基、炭素数６〜３０のアリールアミノ基又は炭素数７〜３０のアリールアルキルアミノ基である。）
Ｒ^３は、下記一般式（４）または下記一般式（５）で示されるＲ^１とＲ^２の架橋単位であり、

(In the formula, each R ⁵ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 30 carbon atoms, or 7 carbon atoms. -30 arylalkylamino group, C1-C20 alkylsilyl group, C1-C20 hydrocarbon group substituted with oxygen introduced between carbon-carbon bonds, C1-C20 hydrocarbon A substituent obtained by substituting a part of the group with an alkylamino group having 1 to 20 carbon atoms, a substituent obtained by substituting a part of the carbon of the hydrocarbon group having 1 to 20 carbons with silicon, and one of R ⁵ is carbon It is an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 30 carbon atoms, or an arylalkylamino group having 7 to 30 carbon atoms.)
R ³ is a crosslinking unit of R ¹ and R ² represented by the following general formula (4) or the following general formula (5),

（式中、Ｒ^６は各々独立して水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルアミノ基、炭素数１〜２０のアルキルシリル基、炭素数１〜２０の炭化水素基の炭素と炭素の結合間に酸素を導入した置換基、炭素数１〜２０の炭化水素基の一部を炭素数１〜２０のアルキルアミノ基に置換した置換基、炭素数１〜２０の炭化水素基の一部の炭素をケイ素に置換した置換基であり、Ｍ^２はケイ素原子、ゲルマニウム原子または錫原子である。）
ｎは１〜５の整数である。］
下記一般式（６）で表される脂肪族塩にて変性した有機変性粘土（Ｂ）、

(In the formula, each R ⁶ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 alkylsilyl groups, substituents in which oxygen is introduced between the carbon-carbon bonds of hydrocarbon groups having 1 to 20 carbon atoms, and some of the hydrocarbon groups having 1 to 20 carbon atoms are alkyl groups having 1 to 20 carbon atoms. A substituent substituted with an amino group, a substituent obtained by substituting a part of carbons of a hydrocarbon group having 1 to 20 carbon atoms with silicon, and M ² is a silicon atom, a germanium atom or a tin atom.)
n is an integer of 1-5. ]
Organically modified clay (B) modified with an aliphatic salt represented by the following general formula (6),

（式中、Ｒ^７〜Ｒ^９は各々独立して炭素数１〜３０のアルキル基、炭素数１〜３０のアルキルアルコキシ基、炭素数１〜３０のアルキルアミノ基、炭素数１〜３０のアルキルシリル基、上記炭素数１〜３０のアルキル基の炭素と炭素の結合間に酸素を導入した置換基、上記炭素数１〜３０のアルキル基の一部を炭素数１〜３０のアルキルアミノ基に置換した置換基、上記炭素数１〜３０のアルキル基の一部の炭素をケイ素に置換した置換基であり、かつＲ^７〜Ｒ^９のうち少なくとも１つが炭素数１０以上のアルキル基であり、Ｍ^３は周期表第１５族の原子であり、［Ａ⁻］はアニオンである。）
及び、有機アルミニウム化合物（Ｃ）より得られるメタロセン系触媒からなることを特徴とするエチレン系重合体製造用触媒、それを用いてなるエチレン系重合体の製造方法に関するものである。

(In the formula, R ^{7 to} R ⁹ are each independently an alkyl group having 1 to 30 carbon atoms, an alkyl alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and an alkyl having 1 to 30 carbon atoms. A silyl group, a substituent in which oxygen is introduced between carbon-carbon bonds of the alkyl group having 1 to 30 carbon atoms, and a part of the alkyl group having 1 to 30 carbon atoms to an alkylamino group having 1 to 30 carbon atoms. A substituted substituent, a substituent obtained by substituting a part of carbons of the alkyl group having 1 to 30 carbon atoms with silicon, and at least one of R ^{7 to} R ⁹ is an alkyl group having 10 or more carbon atoms; M ³ is an atom of Group 15 of the periodic table, and [A ⁻ ] is an anion.)
The present invention also relates to an ethylene polymer production catalyst comprising a metallocene catalyst obtained from an organoaluminum compound (C), and an ethylene polymer production method using the same.

  The present invention is described in detail below.

  The catalyst for producing an ethylene-based polymer of the present invention comprises an organically modified clay modified with at least a transition metal compound (A) represented by the general formula (1) and an aliphatic salt represented by the general formula (6) ( B) and a metallocene catalyst obtained from the organoaluminum compound (C).

The transition metal compound constituting the ethylene polymer production catalyst of the present invention (A) is a transition metal compound represented by the general formula (1), cyclopentadienyl group and R ² is R ¹ It has a structure in which M ¹ is sandwiched by a fluorenyl group having one amino group and a structure in which R ¹ and R ² are bridged by R ³ .

Here, M ¹ is a titanium atom or a zirconium atom, and these specific metal atoms make it possible to efficiently produce an ethylene polymer having a high molecular weight. Zirconium atoms are preferable because it becomes a catalyst for producing an ethylene-based polymer that can be produced with high production efficiency.

  X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms. Group, a substituent in which oxygen is introduced between carbon-carbon bonds of a hydrocarbon group having 1 to 20 carbon atoms, and a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms It is possible to produce an ethylene-based polymer having a high molecular weight by substituting a part of carbon of a hydrocarbon group having 1 to 20 carbon atoms with silicon, and these specific substituents. It becomes. Specific examples of X include, for example, halogen atoms such as hydrogen atom, chlorine atom, bromine atom and iodine atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and isomer substituents thereof. C1-C30 alkyl group, such as a phenyl group, an indenyl group, a naphthyl group, a fluorenyl group, a biphenylenyl group, a C6-C30 aryl group, a benzyl group, a phenylethyl group, a diphenylmethyl group, a diphenylethyl group And an arylalkyl group having 7 to 30 carbon atoms, such as an alkylaryl group having 7 to 30 carbon atoms such as a methylphenyl group, an ethylphenyl group, and a methylnaphthyl group, and an alkylsilyl group such as a trimethylsilyl group.

R ¹ is a cyclopentadienyl group represented by the general formula (2), and each R ⁴ is independently a hydrogen atom, a halogen atom, a C 1-30 hydrocarbon group, or a C 1-20 carbon atom. Alkylamino group, alkylsilyl group having 1 to 20 carbon atoms, substituent having oxygen introduced between carbon-carbon bonds of hydrocarbon group having 1 to 20 carbon atoms, part of hydrocarbon group having 1 to 20 carbon atoms Is a substituent obtained by substituting an alkylamino group having 1 to 20 carbon atoms, and a substituent obtained by substituting a part of carbons of the hydrocarbon group having 1 to 20 carbon atoms with silicon. An ethylene polymer having a high molecular weight can be produced. Specific examples of R ⁴ can be the same as those of X described above. Specific examples of R ¹ include, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, ethyl Cyclopentadienyl group, n-butyl-cyclopentadienyl group, dimethylcyclopentadienyl group, diethylcyclopentadienyl group, methoxycyclopentadienyl group, dimethylamino-cyclopentadienyl group, trimethylsilyl-cyclopenta A dienyl group etc. are mentioned.

R ² is a fluorenyl group having one amino group represented by the general formula (3), and each R ⁵ is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a carbon number of 1 Carbon of -20 alkylamino group, arylamino group having 6-30 carbon atoms, arylalkylamino group having 7-30 carbon atoms, alkylsilyl group having 1-20 carbon atoms, hydrocarbon group having 1-20 carbon atoms, and A substituent in which oxygen is introduced between carbon bonds, a substituent in which part of a hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms It is a substituent in which a part of carbon is substituted with silicon, and one of R ⁵ is an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 30 carbon atoms, or an arylalkylamino group having 7 to 30 carbon atoms Especially having 1 to 20 carbon atoms Alkylamino group, or a diarylamino alkylamino group diarylamino group, or a C7-30 having 6 to 30 carbon atoms. By using these specific substituents, it becomes possible to produce an ethylene polymer having a high molecular weight. Specific examples of R ⁵ are the same as those described above for X, and further include a diphenylamino group, a dibenzylamino group, and the like. Specific examples of R ² include 2- ( Dimethylamino) -fluorenyl group, 2- (diethylamino) -fluorenyl group, 2- (diisopropylamino) -fluorenyl group, 2- (di-n-propylamino) -fluorenyl group, 2- (di-n-butylamino) -Fluorenyl group, 2- (dibenzylamino) -fluorenyl group, 3- (dimethylamino) -fluorenyl group, 3- (diethylamino) -fluorenyl group, 3- (diisopropylamino) -fluorenyl group, 3- (di-n -Propylamino) -fluorenyl group, 3- (di-n-butylamino) -fluorenyl group, 3- (dibenzylamino)- Luenyl group, 4- (dimethylamino) -fluorenyl group, 4- (diethylamino) -fluorenyl group, 4- (diisopropylamino) -fluorenyl group, 4- (di-n-propylamino) -fluorenyl group, 4- (di -N-butylamino) -fluorenyl group, 4- (dibenzylamino) -fluorenyl group and the like. Here, when none of R ⁵ is an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 30 carbon atoms, or an arylalkylamino group having 7 to 30 carbon atoms, the obtained catalyst is treated with an ethylene-based polymer. Even if it uses for manufacture of a coalescence, an ethylene-type polymer with a high molecular weight cannot be manufactured efficiently.

R ³ is a bridging unit of R ¹ and R ² and is a bridging unit represented by the general formula (4) or the general formula (5). R ⁶ is independently a hydrogen atom, halogen Atom, hydrocarbon group having 1 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkylamino group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, hydrocarbon group having 1 to 20 carbon atoms A substituent in which oxygen is introduced between the carbon-carbon bonds, a substituent in which part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms, and carbonization having 1 to 20 carbon atoms It is a substituent obtained by substituting a part of carbon of a hydrogen group with silicon, and these specific substituents make it possible to produce an ethylene polymer having a high molecular weight. As specific examples of R ^6, the same examples as those of X described above can be given. M ² is a silicon atom, a germanium atom, or a tin atom.

  And n is an integer of 1-5.

  The transition metal compound (A) is a transition metal compound having a ligand having a structure in which a cyclopentadienyl group (or a substituted cyclopentadienyl group) and a fluorenyl group having one amino group are combined. Examples include, for example, diphenylsilanediyl (cyclopentadienyl) (2- (dimethylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2- (diethylamino) -9-fluorenyl) zirconium dichloride. Diphenylsilanediyl (cyclopentadienyl) (2- (diisopropylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2- (di-n-propyl-amino) -9-fluorenyl )zirconium Chloride, diphenylsilanediyl (cyclopentadienyl) (2- (di-n-butyl-amino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2- (dibenzylamino) -9 -Fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (3- (dimethylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (3- (diethylamino) -9-fluorenyl) Zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (3- (diisopropylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (3- (di n-propyl-amino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (3- (di-n-butyl-amino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadi) Enyl) (3- (dibenzylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4- (dimethylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) ) (4- (diethylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4- (diisopropylamino) -9-fluorenyl) zirconium dichloride, di Phenylsilanediyl (cyclopentadienyl) (4- (di-n-propyl-amino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4- (di-n-butyl-amino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4- (dibenzylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2- (dimethylamino) -9 -Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2- (diethylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2- (diisopropylamino) -9 Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2- (di-n-propyl-amino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2- (di-n-butyl) -Amino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2- (dibenzylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3- (dimethylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3- (diethylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) ( -(Diisopropylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3- (di-n-propyl-amino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) ( 3- (di-n-butyl-amino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3- (dibenzylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) ) (4- (dimethylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4- (diethylamino) -9-fluorenyl) zirconium dichloride, diphenylmethy Len (cyclopentadienyl) (4- (diisopropylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4- (di-n-propyl-amino) -9-fluorenyl) zirconium dichloride, Diphenylmethylene (cyclopentadienyl) (4- (di-n-butyl-amino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4- (dibenzylamino) -9-fluorenyl) zirconium Examples include zirconium compounds such as dichloride, compounds in which zirconium atoms are changed to titanium atoms, and compounds in which the dichloro form of the transition metal compound is changed to dimethyl, diethyl, dihydro, diphenyl, and dibenzyl. That But, it is preferable that zirconium compounds from becoming the ultrahigh molecular weight ethylene polymer production efficiency that can be produced ethylene polymer produced catalyst.

  The organic modified clay (B) constituting the catalyst for producing an ethylene polymer of the present invention is an organic modified clay modified with an aliphatic salt represented by the general formula (6).

Here, R ^{7 to} R ⁹ are each independently an alkyl group having 1 to 30 carbon atoms, an alkyl alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and an alkyl having 1 to 30 carbon atoms. A silyl group, a substituent in which oxygen is introduced between carbon-carbon bonds of the alkyl group having 1 to 30 carbon atoms, and a part of the alkyl group having 1 to 30 carbon atoms to an alkylamino group having 1 to 30 carbon atoms. A substituted substituent, a substituent obtained by substituting a part of carbons of the alkyl group having 1 to 30 carbon atoms with silicon, and at least one of R ^{7 to} R ⁹ is an alkyl group having 10 or more carbon atoms. . When any of R ^{7 to} R ⁹ is an alkyl group having less than 10 carbon atoms or a substituent other than an alkyl group, it is difficult to efficiently produce an ethylene polymer having a high molecular weight. Become.

Specific examples of R ^{7 to} R ⁹ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, 1-ethylpropyl group, neopentyl group, tert-pentyl group, n-hexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group Group, oleyl group, behenyl group and other alkyl groups having 1 to 30 carbon atoms; methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group and other alkyl alkoxy groups having 1 to 30 carbon atoms; dimethylamino group, diethylamino group Group, dipropylamino group, dibutylamino group, diisopropylamino group, etc. 0 alkylamino group; trimethylsilyl group, tritert-butylsilyl group, ditert-butylmethylsilyl group, tert-butyldimethylsilyl group and other alkylsilyl groups having 1 to 30 carbon atoms; carbon such as methoxymethylene group and ethoxymethylene group A substituent in which oxygen is introduced between the carbon-carbon bond of the alkyl group having 1 to 30; Examples include a substituent substituted with an alkylamino group; a substituent obtained by substituting a part of carbons of an alkyl group having 1 to 30 carbon atoms such as trimethylsilylmethylene group and tert-butyldimethylsilylmethylene group with silicon.

At least one substituent among the R ^{7 to} R ⁹ is an alkyl group having 10 or more carbon atoms, and examples thereof include a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an oleyl group, and a behenyl group. be able to.

The M ³ is an atom belonging to Group 15 of the periodic table, and when it is an atom other than Group 15 of the periodic table, it is difficult for the resulting catalyst to efficiently produce an ethylene-based polymer having a high molecular weight. It becomes. Examples of M ³ include a nitrogen atom and a phosphorus atom.

The [A ⁻ ] is an anion and may be any as long as it belongs to the category of anions. For example, fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchloric acid Examples include ions, oxalate ions, citrate ions, succinate ions, tetrafluoroborate ions, hexafluorophosphate ions, and the like.

  Specific examples of the aliphatic salt include, for example, N, N-dimethyl-behenylamine hydrochloride, N-methyl-N-ethyl-behenylamine hydrochloride, N-methyl-Nn-propyl-behenylamine hydrochloride Salt, N, N-dioleyl-methylamine hydrochloride, N, N-dimethyl-behenylamine hydrofluoride, N-methyl-N-ethyl-behenylamine hydrofluoride, N-methyl-Nn -Propyl-behenylamine hydrofluoride, N, N-dioleyl-methylamine hydrofluoride, N, N-dimethyl-behenylamine hydrobromide, N-methyl-N-ethyl-behenylamine odor Hydrobromide, N-methyl-Nn-propyl-behenylamine hydrobromide, N, N-dioleyl-methylamine hydrobromide, N, N-dimethyl-behenylamine Hydroiodide, N-methyl-N-ethyl-behenylamine hydroiodide, N-methyl-Nn-propyl-behenylamine hydroiodide, N, N-dioleyl-methylamine hydrogen iodide Acid salt, N, N-dimethyl-behenylamine sulfate, N-methyl-N-ethyl-behenylamine sulfate, N-methyl-Nn-propyl-behenylamine sulfate, N, N-dioleoyl-methylamine Aliphatic amine salts such as sulfate; P, P-dimethyl-behenylphosphine hydrochloride, P, P-diethyl-behenylphosphine hydrochloride, P, P-dipropyl-behenylphosphine hydrochloride, P, P-dimethyl-behenylphosphine Hydrofluoride, P, P-diethyl-behenylphosphine hydrofluoride, P, P-dipropyl-behenylphosphine hydrofluoride, P P-dimethyl-behenylphosphine hydrobromide, P, P-diethyl-behenylphosphine hydrobromide, P, P-dipropyl-behenylphosphine hydrobromide, P, P-dimethyl-behenylphosphine iodide Hydronate, P, P-diethyl-behenylphosphine hydroiodide, P, P-dipropyl-behenylphosphine hydroiodide, P, P-dimethyl-behenylphosphine sulfate, P, P-diethyl-behenyl And aliphatic phosphonium salts such as phosphine sulfate and P, P-dipropyl-behenylphosphine sulfate.

Further, the clay compound constituting the organically modified clay (B) may be any clay compound as long as it belongs to the category of clay compounds, and generally a tetrahedron in which a silica tetrahedron is two-dimensionally continuous. A layer called a silicate layer formed by combining a sheet and an octahedron sheet in which an alumina octahedron, a magnesia octahedron, etc. are two-dimensionally continuous in a 1: 1 or 2: 1 layer is formed to overlap. Some of the silica tetrahedrons are replaced with the same type of Si by Al, alumina octahedron Al by Mg, magnesia octahedron Mg by Li, etc. It is known that cations such as Na ⁺ and Ca ²⁺ exist between the layers in order to compensate for this negative charge. As the clay compound, kaolinite, talc, smectite, vermiculite, mica, brittle mica, curdstone and the like as natural products or synthetic products exist, and these can be used. Smectite is preferable from the viewpoint of easiness of modification and organic modification, and hectorite or montmorillonite is more preferable among smectites.

  The organically modified clay (B) can be obtained by introducing the aliphatic salt between layers of the clay compound to form an ionic complex. In preparing the organically modified clay (B), it is preferable to carry out the treatment by selecting conditions of a clay compound concentration of 0.1 to 30% by weight and a treatment temperature of 0 to 150 ° C. The aliphatic salt may be prepared as a solid and dissolved in a solvent for use, or a solution of the aliphatic salt may be prepared by a chemical reaction in the solvent and used as it is. Regarding the reaction amount ratio between the clay compound and the aliphatic salt, it is preferable to use an aliphatic salt having an equivalent amount or more with respect to exchangeable cations of the clay compound. Examples of the processing solvent include aliphatic hydrocarbons such as pentane, hexane and heptane; aromatic hydrocarbons such as benzene and toluene; alcohols such as ethyl alcohol and methyl alcohol; ethers such as ethyl ether and n-butyl ether. Halogenated hydrocarbons such as methylene chloride and chloroform; acetone; 1,4-dioxane; tetrahydrofuran; water; Preferably, alcohols or water is used alone or as one component of a solvent.

  Moreover, there is no restriction | limiting in the particle size of the organic modified clay (B) which comprises the catalyst for ethylene-type polymer manufacture of this invention, Among them, it becomes excellent in the efficiency at the time of catalyst preparation, and the efficiency at the time of ethylene-type polymer manufacture. Therefore, it is preferably 1 to 100 μm. There is no limitation on the method of adjusting the particle size at that time, and large particles may be pulverized to an appropriate particle size, small particles may be granulated to an appropriate particle size, or pulverization and granulation May be combined. The particle size may be adjusted on the clay before organic modification or on the organic modified clay after modification.

  There is no limitation on the method of pulverization and granulation when controlling the particle size of the organically modified clay (B). Examples of the pulverization include impact mill, rotary mill, cascade mill, cutter mill, cage mill, impact pulverizer, and conical mill. , Colloid mill, compound mill, jet mill, vibration mill, stamp mill, tube mill, disk mill, tower mill, medium agitator mill, hammer mill, pin mill, fret mill, pebble mill, ball mill, attritor, planetary mill, ring ball mill, ring Examples of the granulation include roll mill, rod mill, roller mill, roll crusher and the like. Examples of granulation include rolling granulation, fluidized bed granulation, stirring granulation, compression granulation, extrusion granulation, crush granulation. Examples of the method include granulation, melt granulation, and spray granulation.

  As the organoaluminum compound (C) constituting the catalyst for producing an ethylene-based polymer of the present invention, any organoaluminum compound (C) can be used as long as it belongs to a category called an organoaluminum compound, and among them, particularly an ultrahigh molecular weight compound. An organoaluminum compound represented by the following general formula (7) is preferable because it becomes a catalyst for producing an ethylene polymer capable of producing an ethylene polymer with high production efficiency. Here, when a compound other than the organoaluminum compound, such as a boron compound or a methylalumoxane compound, is used, the ethylene polymer obtained by the catalyst has a low molecular weight or is inferior in moldability. It has a problem.

（式中、Ｒ^１０は炭素数１〜２０の炭化水素基であり、Ｒ^１１は各々独立して炭素数１〜２０の炭化水素基、水素原子または塩素原子である。）
該有機アルミニウム化合物としては、特に遷移金属化合物（Ａ）を容易にアルキル化することが可能となることから、例えばトリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウムなどのアルキルアルミニウムなどを挙げることができる。

(Wherein R ¹⁰ is a hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ is each independently a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a chlorine atom.)
Examples of the organoaluminum compound include alkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum because the transition metal compound (A) can be easily alkylated.

  The transition metal compound (A) (hereinafter also referred to as component (A)) constituting the catalyst for producing an ethylene-based polymer of the present invention, the organically modified clay (B) (hereinafter also referred to as component (B)). And the organoaluminum compound (C) (hereinafter sometimes referred to as component (C)) are subject to any restrictions as long as they can be used as catalysts for the production of ethylene-based polymers. Among them, among them, since it becomes a catalyst for producing an ethylene polymer capable of producing an ultra-high molecular weight ethylene polymer with a high production efficiency, it is suitable for the metal atoms of the components (A) and (C). Is preferably in the range of (A component) :( C component) = 100: 1 to 1: 100000, and more preferably in the range of 1: 1 to 1: 10000. The weight ratio of the component (A) to the component (B) is preferably (component A) :( component B) = 10: 1 to 1: 10000, particularly in the range of 3: 1 to 1: 1000. It is preferable.

  Regarding the method for preparing an ethylene polymer production catalyst of the present invention, it is possible to prepare an ethylene polymer production catalyst obtained from at least the component (A), the component (B) and the component (C). Any method may be used as long as it includes, for example, a method in which each of the components (A), (B), and (C) is mixed in an inert solvent or a monomer that performs polymerization as a solvent. . Moreover, there is no restriction | limiting also about the order which makes these components react, and the temperature and processing time which perform this process also have no restriction | limiting. It is also possible to prepare an ethylene polymer production catalyst by using two or more of each of the component (A), the component (B), and the component (C).

  The ethylene polymer obtained using the catalyst for producing an ethylene polymer of the present invention may be not only ethylene homopolymerization but also copolymerization with other olefins. The term “copolymer” is used to mean not only a homopolymer but also a copolymer.

  Examples of the production method for producing an ethylene polymer using the ethylene polymer production catalyst of the present invention include a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, and a slurry polymerization method. Among them, a slurry polymerization method is preferable because an ethylene-based polymer having a particularly uniform particle shape can be produced efficiently and stably. The solvent used in the slurry polymerization method may be any organic solvent that is generally used, and examples thereof include benzene, toluene, xylene, pentane, hexane, heptane, and the like. Propylene, 1-butene, 1- Olefins such as octene and 1-hexene can also be used as a solvent.

  Other olefins used for copolymerization with ethylene when an ethylene polymer is used as a copolymer include, for example, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. Styrene, styrene derivatives; butadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, etc. Conjugated and non-conjugated dienes; cyclic olefins such as cyclobutene; and the like. Further, a copolymer using three or more components such as ethylene, propylene and styrene, ethylene, 1-hexene and styrene, ethylene, propylene, and ethylidene norbornene can be used.

  Polymerization conditions such as a polymerization temperature, a polymerization time, a polymerization pressure, and a monomer concentration when producing an ethylene polymer with the catalyst for producing an ethylene polymer of the present invention can be arbitrarily selected. It is preferable to carry out in the range of ˜90 ° C., polymerization time of 10 seconds to 20 hours, and polymerization pressure of normal pressure to 100 MPa. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. The ethylene polymer obtained after the completion of the polymerization can be obtained by separating and recovering from the polymerization solvent by a conventionally known method and drying.

  The catalyst for producing an ethylene-based polymer of the present invention is particularly suitable for producing an ultra-high-molecular-weight ethylene polymer, and the obtained ethylene-based polymer includes ethylene having excellent mechanical properties such as wear resistance. Intrinsic viscosity (dL / g) of 9.0 or more or Mv is preferably 1,000,000 or more, and further, intrinsic viscosity (dL / g) of 13 or more and less than 19 or Mv is 2,000,000 or more and 400. Preferably, it is less than 10,000. Further, Mw / Mn is preferably more than 3.0 and less than 5.0, and more preferably more than 3.0 and more preferably less than 5.0, because an ethylene polymer having an excellent balance between moldability and mechanical properties is obtained. It is preferably less than 0.

  An ethylene-based catalyst comprising a transition metal compound (A) having a specific structure of the present invention, an organically modified clay (B) modified with an aliphatic salt having a specific structure, and a metallocene catalyst obtained from an organoaluminum compound (C) The catalyst for polymer production can efficiently and stably produce an ethylene polymer having excellent mechanical properties, wear resistance, and moldability (ultra high molecular weight).

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise noted, the reagents used were commercially available products or those synthesized according to known methods.

  For the pulverization of the organically modified clay, a jet mill (manufactured by Seishin Enterprise Co., Ltd., (trade name) CO-JET SYSTEM α MARK III) is used. Name) MT3000) and ethanol as a dispersant.

  Preparation of the ethylene polymer production catalyst, production of the ethylene polymer and solvent purification were all carried out under an inert gas atmosphere. A hexane solution (20 wt%) of triisobutylaluminum manufactured by Tosoh Finechem Co., Ltd. was used.

  Furthermore, various physical properties of the ethylene-based polymer in the examples were measured by the following methods.

~ Measurement of Mw, Mn and Mw / Mn ~
Using a GPC device (manufactured by Tosoh Corporation, (trade name) HLC-8121GPC / HT) and a column (manufactured by Tosoh Corporation, (trade name) TSKgel GMHhr-H (20) HT), the column temperature was set to 140 ° C. Set and measured using 1,2,4-trichlorobenzene as eluent. A measurement sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected and measured. The calibration curve of molecular weight was calibrated using a polystyrene sample having a known molecular weight. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion.

~ Measurement of intrinsic viscosity ~
Using an Ubbelohde viscometer, ODCB (orthodichlorobenzene) was used as a solvent at 135 ° C. with an ultrahigh molecular weight ethylene polymer concentration of 0.005 wt% to 0.01 wt%.

~ Viscosity conversion molecular weight ~
It calculated based on the following relational expression of intrinsic viscosity ([η] (dL / g)) and viscosity conversion molecular weight (Mv).
[Η] = 5.05 × 10 ⁻⁴ × (Mv) ^0.693
Example 1
(1) Preparation of organically modified clay 300 ml of industrial alcohol (manufactured by Nippon Alcohol Sales Co., Ltd., (trade name) Echinen F-3) and 300 ml of distilled water were placed in a 1 liter flask, and 15.0 g of concentrated hydrochloric acid and dioleylmethylamine were added. (Lion Corporation, (trade name) Armin M20) 64.2 g (120 mmol) was added and heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives, (trade name) Laponite RDS). Thereafter, the mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 600 ml of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 160 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.

(2) Preparation of suspension of catalyst for production of ethylene polymer After replacing 300 ml flask equipped with thermometer and reflux tube with nitrogen, 25.0 g of organically modified clay obtained in (1) and 108 ml of hexane were obtained. Then, 0.600 g of diphenylmethylene (cyclopentadienyl) (2- (dimethylamino) -9-fluorenyl) zirconium dichloride and 142 ml of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed twice with 200 ml of hexane, and then 200 ml of hexane was added to obtain a suspension of the ethylene polymer production catalyst (solid weight: 11.3 wt%). .

(3) Production of ethylene polymer 1.2 l of hexane, 1.0 ml of 20% triisobutylaluminum in a 2 liter autoclave, and the suspension of the ethylene polymer production catalyst obtained in (2) 372.6 mg (equivalent to a solid content of 42.1 mg) was added, and after the temperature was raised to 60 ° C., ethylene was continuously supplied so that the partial pressure became 0.87 MPa, and ethylene slurry polymerization was performed. After 90 minutes, the pressure was released, the slurry was filtered, and dried to obtain 59.3 g of an ethylene homopolymer (activity: 1410 g / g catalyst). Table 1 shows the physical properties of the obtained ethylene homopolymer.

Example 2
(1) Preparation of organically modified clay and (2) Preparation of suspension of ethylene polymer production catalyst were carried out in the same manner as in Example 1.

(3) Production of ethylene polymer 1.2 l of hexane, 1.0 ml of 20% triisobutylaluminum in a 2 liter autoclave, and the suspension of the ethylene polymer production catalyst obtained in (2) 225.7 mg (corresponding to a solid content of 25.5 mg) was added, and after the temperature was raised to 70 ° C., ethylene was continuously supplied so that the partial pressure became 1.0 MPa, and slurry polymerization of ethylene was performed. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 61.1 g of an ethylene homopolymer (activity: 2400 g / g catalyst). Table 1 shows the physical properties of the obtained ethylene homopolymer.

Example 3
(1) Preparation of organically modified clay Into a 1 liter flask was placed 300 ml of industrial alcohol (manufactured by Nippon Alcohol Sales Co., Ltd., (trade name) Echinen F-3) and 300 ml of distilled water, and 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine ( After adding 42.4 g (120 mmol) of (trade name) Armin DM22D, manufactured by Lion Corporation and heating to 45 ° C., 100 g of synthetic hectorite (Rockwood Additives, (trade name) Laponite RDS) was dispersed. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 600 ml of 60 ° C. water, and dried in an oven at 85 ° C. for 12 hours to obtain 125 g of an organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.

(2) Preparation of suspension of catalyst for production of ethylene polymer After replacing 300 ml flask equipped with thermometer and reflux tube with nitrogen, 25.0 g of organically modified clay obtained in (1) and 108 ml of hexane were obtained. Then, 0.600 g of diphenylmethylene (cyclopentadienyl) (2- (dimethylamino) -9-fluorenyl) zirconium dichloride and 142 ml of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed twice with 200 ml of hexane, and then 200 ml of hexane was added to obtain a suspension of an ethylene polymer production catalyst (solid weight: 13.2 wt%). .

(3) Production of ethylene polymer 1.2 l of hexane, 1.0 ml of 20% triisobutylaluminum in a 2 liter autoclave, and the suspension of the ethylene polymer production catalyst obtained in (2) 320.5 mg (equivalent to a solid content of 42.3 mg) was added, and after the temperature was raised to 60 ° C., ethylene was continuously supplied so that the partial pressure became 0.87 MPa, and slurry polymerization of ethylene was performed. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 212 g of an ethylene homopolymer (activity: 5010 g / g catalyst). Table 1 shows the physical properties of the obtained ethylene homopolymer.

Example 4
(1) Preparation of organically modified clay and (2) Preparation of suspension of catalyst for ethylene polymer production were carried out in the same manner as in Example 3.

(3) Polymerization 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum in a 2 liter autoclave, and 233.3 mg (solid) of the suspension of the catalyst for producing an ethylene polymer obtained in (2) After adding the temperature to 60 ° C., ethylene was continuously supplied so that the partial pressure became 0.5 MPa, and slurry polymerization of ethylene was performed. After 300 minutes, the pressure was released, and the slurry was filtered and dried to obtain 267 g of an ethylene homopolymer (activity: 8660 g / g catalyst). Table 1 shows the physical properties of the obtained ethylene homopolymer.

Example 5
(1) Preparation of organically modified clay and (2) Preparation of suspension of catalyst for ethylene polymer production were carried out in the same manner as in Example 3.

(3) Polymerization 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum in a 2 liter autoclave, 189.4 mg of solid suspension of the ethylene polymer production catalyst obtained in (2) (solid After adding a temperature of 70 ° C., ethylene was continuously supplied so that the partial pressure became 1.0 MPa, and slurry polymerization of ethylene was performed. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 213 g of an ethylene homopolymer (activity: 8500 g / g catalyst). Table 1 shows the physical properties of the obtained ethylene homopolymer.

Example 6
(1) Preparation of organically modified clay The same procedure as in Example 1 was performed.

(2) Preparation of suspension of catalyst for production of ethylene polymer After replacing 300 ml flask equipped with thermometer and reflux tube with nitrogen, 25.0 g of organically modified clay obtained in (1) and 108 ml of hexane were obtained. Then, 0.628 g of diphenylmethylene (cyclopentadienyl) (2- (diethylamino) -9-fluorenyl) zirconium dichloride and 142 ml of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed twice with 200 ml of hexane, and then 200 ml of hexane was added to obtain a suspension of an ethylene polymer production catalyst (solid weight: 12.0 wt%). .

(3) Production of ethylene polymer 1.2 l of hexane, 1.0 ml of 20% triisobutylaluminum in a 2 liter autoclave, and the suspension of the ethylene polymer production catalyst obtained in (2) 333.3 mg (equivalent to a solid content of 40.0 mg) was added, and after the temperature was raised to 60 ° C., ethylene was continuously supplied so that the partial pressure became 0.87 MPa, and ethylene slurry polymerization was performed. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 56.0 g of an ethylene homopolymer (activity: 1400 g / g catalyst). Table 1 shows the physical properties of the obtained ethylene homopolymer.

Example 7
(1) Preparation of organically modified clay and (2) Preparation of suspension of ethylene polymer production catalyst were carried out in the same manner as in Example 5.

(3) Production of ethylene polymer 1.2 l of hexane, 1.0 ml of 20% triisobutylaluminum in a 2 liter autoclave, and the suspension of the ethylene polymer production catalyst obtained in (2) 258.3 mg (corresponding to a solid content of 31.0 mg) was added, and after the temperature was raised to 70 ° C., ethylene was continuously supplied so that the partial pressure became 1.0 MPa, and slurry polymerization of ethylene was performed. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 76.0 g of an ethylene homopolymer (activity: 2450 g / g catalyst). Table 1 shows the physical properties of the obtained ethylene homopolymer.

Example 8
(1) Preparation of organically modified clay The same procedure as in Example 1 was performed.

(2) Preparation of suspension of catalyst for production of ethylene polymer After replacing 300 ml flask equipped with thermometer and reflux tube with nitrogen, 25.0 g of organically modified clay obtained in (1) and 108 ml of hexane were obtained. Then, 0.752 g of diphenylmethylene (cyclopentadienyl) (2- (dibenzylamino) -9-fluorenyl) zirconium dichloride and 142 ml of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed twice with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.5 wt%).
(3) Polymerization 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum in a 2 liter autoclave, and 336 mg (corresponding to a solid content of 42.0 mg) of the catalyst suspension obtained in (2) were added. After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.87 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 58.8 g of polymer (activity: 1400 g / g catalyst). The physical properties of the obtained polymer are shown in Table 1.

Comparative Example 1
(1) Preparation of organically modified clay The same procedure as in Example 1 was performed.

(2) Preparation of catalyst suspension After replacing a nitrogen flask in a 300 ml flask equipped with a thermometer and a reflux tube, 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane were added, and then diphenylmethylene (cyclohexane) 0.557 g of pentadienyl) (9-fluorenyl) zirconium dichloride and 142 ml of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed twice with 200 ml of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 11.0 wt%).

(3) Production of ethylene polymer In a 2 liter autoclave, 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum, and 368.1 mg (solid content of 40%) of the catalyst suspension obtained in (2) Then, ethylene was continuously supplied so that the partial pressure became 0.87 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 22.3 g of polymer (activity: 550 g / g catalyst). The physical properties of the obtained polymer are shown in Table 1.

  The obtained catalyst had a low polymerization activity of ethylene and a low molecular weight of the polymer.

Comparative Example 2
(1) Preparation of organically modified clay and (2) Preparation of catalyst suspension were carried out in the same manner as in Comparative Example 1.

(3) Production of ethylene polymer In a 2 liter autoclave, 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum, and 277.3 mg (solid content 30) of the catalyst suspension obtained in (2) Then, ethylene was continuously supplied to raise the partial pressure to 1.0 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 37.2 g of polymer (activity: 1220 g / g catalyst). The physical properties of the obtained polymer are shown in Table 1.

  The obtained polymer had a low molecular weight.

Comparative Example 3
(1) Preparation of organically modified clay The same procedure as in Example 3 was performed.

(2) Preparation of catalyst suspension After replacing a nitrogen flask in a 300 ml flask equipped with a thermometer and a reflux tube, 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane were added, and then diphenylmethylene (cyclohexane) 0.557 g of pentadienyl) (9-fluorenyl) zirconium dichloride and 142 ml of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed twice with 200 ml of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 11.5 wt%).

(3) Production of ethylene polymer In a 2 liter autoclave, 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum, and 356.5 mg (solid content 41) of the catalyst suspension obtained in (2) Then, ethylene was continuously supplied to raise the partial pressure to 0.87 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 32.8 g of polymer (activity: 800 g / g catalyst). The physical properties of the obtained polymer are shown in Table 1.

  The obtained catalyst had a low polymerization activity of ethylene and a low molecular weight of the polymer.

Comparative Example 4
(1) Preparation of organically modified clay and (2) Preparation of catalyst suspension were carried out in the same manner as in Comparative Example 3.

(3) Polymerization 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum in a 2 liter autoclave, and 260.9 mg of catalyst suspension obtained in (2) (corresponding to solid content of 30.0 mg) were added. After raising the temperature to 70 ° C., ethylene was continuously supplied so that the partial pressure became 1.0 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 46.2 g of polymer (activity: 1540 g / g catalyst). The physical properties of the obtained polymer are shown in Table 1.

  The obtained polymer had a low molecular weight.

Comparative Example 5
(1) Preparation of organically modified clay The same procedure as in Example 1 was performed.

(2) Preparation of catalyst suspension After replacing a nitrogen flask in a 300 ml flask equipped with a thermometer and a reflux tube, 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane were added, and then diphenylmethylene (cyclohexane) 0.669 g of pentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride and 142 ml of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed twice with 200 ml of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).

(3) Production of ethylene polymer 1.2 liters of hexane, 1.0 ml of 20% triisobutylaluminum in a 2 liter autoclave, 333.3 mg (solid content 40) of the catalyst suspension obtained in (2) Then, ethylene was continuously supplied to raise the partial pressure to 0.87 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 40.0 g of polymer (activity: 970 g / g catalyst). The physical properties of the obtained polymer are shown in Table 1.

  The obtained catalyst had low polymerization activity of ethylene, and the molecular weight of the obtained polymer was relatively low.

Comparative Example 6
(1) Preparation of organically modified clay In a 1 liter flask, 300 ml of industrial alcohol (manufactured by Nippon Alcohol Sales Co., Ltd., (trade name) Echinen F-3) and 300 ml of distilled water were placed, and 15.0 g of concentrated hydrochloric acid and trioctylamine ( 42.4 g (120 mmol) manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives, (trade name) Laponite RDS), and then to 60 ° C. The mixture was heated up and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 600 ml of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 160 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.

(2) Preparation of suspension of catalyst for production of ethylene polymer After replacing 300 ml flask equipped with thermometer and reflux tube with nitrogen, 25.0 g of organically modified clay obtained in (1) and 108 ml of hexane were obtained. Then, 0.600 g of diphenylmethylene (cyclopentadienyl) (2- (dimethylamino) -9-fluorenyl) zirconium dichloride and 142 ml of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed twice with 200 ml of hexane, and then 200 ml of hexane was added to obtain a suspension of an ethylene polymer production catalyst (solid weight: 12.0 wt%). .

(3) Production of ethylene polymer 1.2 l of hexane, 1.0 ml of 20% triisobutylaluminum in a 2 liter autoclave, and the suspension of the ethylene polymer production catalyst obtained in (2) 500 mg (corresponding to a solid content of 60 mg) was added, and after raising the temperature to 60 ° C., ethylene was continuously supplied so that the partial pressure became 0.87 MPa, and slurry polymerization of ethylene was performed. After 90 minutes, the pressure was released and filtration was performed, but almost no ethylene homopolymer was obtained.

Comparative Example 7
The physical properties of the commercially available polyethylene (trade name Hi-Zex Million Grade 030S manufactured by Mitsui Chemicals) were measured in the same manner as in the Examples. The results are shown in Table 1.

  The polyethylene had a very large Mw / Mn.

  The ethylene polymer production catalyst of the present invention is excellent in mechanical properties, wear resistance, and moldability (ultra high molecular weight) ethylene useful for applications such as lining materials, food industry line parts, machine parts, and sporting goods. Since the polymer can be efficiently and stably produced, its industrial applicability is extremely high.

Claims (4)

At least a transition metal compound (A) represented by the following general formula (1),

[Wherein, M ¹ is a titanium atom or a zirconium atom, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 alkylamino groups, alkyl silyl groups having 1 to 20 carbon atoms, substituents having oxygen introduced between carbon-carbon bonds of hydrocarbon groups having 1 to 20 carbon atoms, hydrocarbon groups having 1 to 20 carbon atoms R ¹ is a substituent obtained by substituting a part of the hydrocarbon group having 1 to 20 carbon atoms with silicon, and R ¹ is represented by the following general formula (2). And a cyclopentadienyl group represented by

(In the formula, each R ⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or 1 carbon atom. A substituent in which oxygen is introduced between the carbon-carbon bonds of a hydrocarbon group having ˜20, a substituent in which a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms, carbon (This is a substituent obtained by substituting a part of carbons of the hydrocarbon group of 1 to 20 with silicon.)
R ² is a fluorenyl group having one amino group represented by the following general formula (3),

(In the formula, each R ⁵ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 30 carbon atoms, or 7 carbon atoms. -30 arylalkylamino group, C1-C20 alkylsilyl group, C1-C20 hydrocarbon group substituted with oxygen introduced between carbon-carbon bonds, C1-C20 hydrocarbon A substituent obtained by substituting a part of the group with an alkylamino group having 1 to 20 carbon atoms, a substituent obtained by substituting a part of the carbon of the hydrocarbon group having 1 to 20 carbons with silicon, and one of R ⁵ is carbon It is an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 30 carbon atoms, or an arylalkylamino group having 7 to 30 carbon atoms.)
R ³ is a crosslinking unit of R ¹ and R ² represented by the following general formula (4) or the following general formula (5),

(In the formula, each R ⁶ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 alkylsilyl groups, substituents in which oxygen is introduced between the carbon-carbon bonds of hydrocarbon groups having 1 to 20 carbon atoms, and some of the hydrocarbon groups having 1 to 20 carbon atoms are alkyl groups having 1 to 20 carbon atoms. A substituent substituted with an amino group, a substituent obtained by substituting a part of carbons of a hydrocarbon group having 1 to 20 carbon atoms with silicon, and M ² is a silicon atom, a germanium atom or a tin atom.)
n is an integer of 1-5. The broken lines between R ¹ and M ¹ and R ² and M ¹ indicate coordination bonds. ]
Organically modified clay (B) modified with an aliphatic salt represented by the following general formula (6),

(In the formula, R ^{7 to} R ⁹ are each independently an alkyl group having 1 to 30 carbon atoms, an alkyl alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and an alkyl having 1 to 30 carbon atoms. A silyl group, a substituent in which oxygen is introduced between carbon-carbon bonds of the alkyl group having 1 to 30 carbon atoms, and a part of the alkyl group having 1 to 30 carbon atoms to an alkylamino group having 1 to 30 carbon atoms. A substituted substituent, a substituent obtained by substituting a part of carbons of the alkyl group having 1 to 30 carbon atoms with silicon, and at least one of R ^{7 to} R ⁹ is an alkyl group having 10 or more carbon atoms; M ³ is an atom of Group 15 of the periodic table, and [A ⁻ ] is an anion.)
And an ethylene polymer production catalyst comprising a metallocene catalyst obtained from the organoaluminum compound (C). Transition metal compound (A), the ethylene-based polymer production catalyst according to claim 1, characterized in that the transition metal compound is a zirconium atom M ^1. The catalyst for producing an ethylene-based polymer according to claim 1 or 2, wherein the organoaluminum compound (C) is an organoaluminum represented by the following general formula (7).

(Wherein R ¹⁰ is a hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ is each independently a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a chlorine atom.) Polymerization of an ethylene monomer is performed by a slurry process using the catalyst for producing an ethylene polymer according to any one of claims 1 to 3, and an intrinsic viscosity (dL / g) is 9.0 or more or a viscosity The conversion molecular weight (Mv) is 1 million or more, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (molecular weight distribution: Mw / Mn) is more than 3.0 and less than 5.0 A method for producing an ethylene polymer, which comprises producing a high molecular weight ethylene polymer.