JP2017155133A - Manufacturing method of ultrahigh molecular weight ethylenic polymer powder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of efficiently manufacturing an ultrahigh molecular weight ethylenic polymer powder that has less static electricity, does not cause powder attachment to a silo or a hopper of a processor, and has high fluidity.SOLUTION: In a manufacturing method of an ultrahigh molecular weight ethylenic polymer powder, when a slurry polymerization of ethylene alone or ethylene and alpha-olefin is performed by a metallocene catalyst obtained from a transition metal compound (A) having a specific structure, organic modified clay (B) modified by an aliphatic salt having a specific structure, and an organoaluminum compound (C) in a polymerization solvent, a polymer solvent containing the organoaluminum compound (C) and calcium stearate (D) is used.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an ultra high molecular weight ethylene polymer powder containing calcium stearate, and more particularly to a method for producing an ultra high molecular weight ethylene polymer powder excellent in fluidity.

  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 lowers 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. It 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).

  Ethylene polymers are produced by a slurry method, a gas phase method, a solution method, etc., but since an ultra-high molecular weight ethylene polymer has low solubility in a solvent, a slurry method or a gas phase method may be employed. Many. In the slurry method or the gas phase method, the ethylene polymer is obtained as a powder, but in the case of a normal ethylene polymer, the powder is once melted and shipped as pellets from the viewpoints of ease of handling, storage, and transportability. There are many cases. On the other hand, when an ultra-high molecular weight ethylene polymer is made into a pellet, the processability is remarkably deteriorated, so that it is generally shipped as a powder.

  However, the powder containing an ethylene polymer generally has a problem that the smaller the particle size, the lower the fluidity due to an increase in the frictional force accompanying an increase in the apparent specific surface area or charging due to static electricity.

JP 09-291112 A

  Additives such as antistatic agents, slip agents, antiblocking agents or antioxidants may be added to the ethylene polymer pellets as necessary, but these are added to the powdered ethylene polymer. Since it is difficult to mix uniformly, it is generally added during processing.

  However, in the case of ultra high molecular weight ethylene polymer powder, from the viewpoint of processability, the maximum particle size is 300 to 400 μm or less, and the median diameter is often about several tens to several tens of μm. As a result of problems such as powder adhering to the hopper of a processing machine due to a decrease in fluidity accompanying the development of a high-molecular-weight ethylene polymer powder, development of a method for containing an antistatic agent has been desired. .

  Therefore, the present invention provides a method for efficiently producing ultrahigh molecular weight ethylene polymer powder having excellent fluidity.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a metallocene system obtained from a transition metal compound having a specific structure, an organically modified clay modified with an aliphatic salt having a specific structure, and an organoaluminum compound When producing ultra high molecular weight ethylene polymer powder with a catalyst, the ultra high molecular weight ethylene polymer powder containing calcium stearate is efficiently produced by producing it in a polymerization solvent containing calcium stearate and an organoaluminum compound. The inventors have found that it is possible to manufacture well, and have completed the present invention.

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

［式中、Ｍ^１はチタン原子、ジルコニウム原子またはハフニウム原子であり、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, a zirconium atom or a hafnium 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, carbon An alkylamino group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a substituent having oxygen introduced between carbon-carbon bonds of a hydrocarbon group having 1 to 20 carbon atoms, carbonization having 1 to 20 carbon atoms A substituent in which a part of the hydrogen group is substituted with an alkylamino group having 1 to 20 carbon atoms, a substituent in which a part of carbons in the hydrocarbon group having 1 to 20 carbon atoms is substituted with silicon, and R ¹ is A cyclopentadienyl group represented by formula (2);

（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 an amino group represented by the following general formula (3),

（式中、Ｒ^５および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もの置換基であり、Ｒ^５および／またはＲ^６の少なくとも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、

(Wherein R ⁵ and R ⁶ are each independently 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, C1-C20 arylalkylamino group, C1-C20 alkyl silyl group, C1-C20 hydrocarbon group, the substituent which introduce | transduced oxygen between the carbon-carbon bonds, C1-C20 A substituent obtained by substituting a part of the hydrocarbon group with an alkylamino group having 1 to 20 carbon atoms, a substituent obtained by substituting part of the carbons of the hydrocarbon group having 1 to 20 carbons with silicon, R ⁵ and (At least one of R ⁶ 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^７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 ⁷ 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^８〜Ｒ^１０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^８〜Ｒ^１０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）から得られるメタロセン系触媒により、エチレン単独又はエチレンとα−オレフィンとのスラリー重合を行うに際し、有機アルミニウム化合物（Ｃ）及びステアリン酸カルシウム（Ｄ）を含む重合溶媒を用いること特徴とする超高分子量エチレン系重合体パウダーの製造方法に関するものである。

(Wherein R ^{8 to} R ¹⁰ 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 ^{8 to} R ¹⁰ 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 using a polymerization solvent containing organoaluminum compound (C) and calcium stearate (D) when carrying out slurry polymerization of ethylene alone or ethylene and α-olefin with a metallocene catalyst obtained from organoaluminum compound (C) The present invention relates to a method for producing a featured ultrahigh molecular weight ethylene polymer powder.

  The present invention is described in detail below.

  The production method of the ultrahigh molecular weight ethylene polymer powder of the present invention is an organic material modified with a transition metal compound (A) represented by the general formula (1) and an aliphatic salt represented by the general formula (6). When slurry polymerization is performed using a metallocene catalyst obtained from the modified clay (B) and the organoaluminum compound (C), a polymerization solvent containing calcium stearate (D) and the organoaluminum compound (C) is used.

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

Here, M ¹ is a titanium atom, a zirconium atom or a hafnium atom, and by using these specific metal atoms, it becomes possible to efficiently produce an ultrahigh molecular weight ethylene polymer powder having a very high molecular weight, In particular, a zirconium atom or a hafnium atom is preferable because it becomes an ethylene polymer production catalyst capable of producing an ultrahigh molecular weight ethylene polymer powder 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 And an ultra high molecular weight ethylene polymer powder having a very high molecular weight due to the substitution of a part of carbon of the hydrocarbon group having 1 to 20 carbon atoms with silicon. Can be manufactured. 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 a C 1-20 alkylamino group, a part of the C 1-20 hydrocarbon group with silicon substituted by silicon, and the molecular weight is determined by these specific substituents. It is possible to produce an ultra-high molecular weight ethylene polymer powder having a very high density. 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 an amino group represented by the general formula (3), and R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a carbon number Carbon of 1-20 alkylamino group, C6-C30 arylamino group, C7-C30 arylalkylamino group, C1-C20 alkylsilyl group, C1-C20 hydrocarbon group A substituent in which oxygen is introduced between the carbon and 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, or a hydrocarbon group having 1 to 20 carbon atoms In which at least one of R ⁵ and / or R ⁶ is an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 30 carbon atoms, or a carbon number. 7-30 arylalkyls An amino group, in particular a dialkylamino group having 1 to 20 carbon atoms is preferably a diarylamino alkylamino group diarylamino group, or a C7-30 having 6 to 30 carbon atoms. These specific substituents make it possible to produce an ethylene polymer having a very high molecular weight. Specific examples of R ⁵ and R ⁶ are the same as those described above for X, and further include a diphenylamino group, a dibenzylamino group, etc. Specific examples of R ² include 2-dimethylaminofluorenyl group, 2-diethylaminofluorenyl group, 2-diisopropylaminofluorenyl group, 2- (di-n-propylamino) fluorenyl group, 2- (di-n-butylamino) fluorenyl Group, 2-dibenzylaminofluorenyl group, 3-dimethylaminofluorenyl group, 3-diethylaminofluorenyl group, 3-diisopropylaminofluorenyl group, 3- (di-n-propylamino) fluorenyl group , 3- (di-n-butylamino) fluorenyl group, 3-dibenzylaminofluorenyl group, 2-dimethylaminofluorenyl 2-diethylaminofluorenyl group, 2-diisopropylaminofluorenyl group, 2- (di-n-propylamino) fluorenyl group, 2- (di-n-butylamino) fluorenyl group, 2-dibenzylaminofluoride Olenyl group, 2,7-bis (dimethylamino) -fluorenyl group, 2,7-bis (diethylamino) -fluorenyl group, 2,7-bis (diisopropylamino) -fluorenyl group, 2,7-bis (di-) n-propylamino) -fluorenyl group, 2,7-bis (di-n-butylamino) -fluorenyl group, 2,7-bis (dibenzylamino) -fluorenyl group, 3,6-bis (dimethylamino)- Fluorenyl group, 3,6-bis (diethylamino) -fluorenyl group, 3,6-bis (diisopropylamino) -fluorenyl group, 3 6-bis (di-n-propylamino) -fluorenyl group, 3,6-bis (di-n-butylamino) -fluorenyl group, 3,6-bis (dibenzylamino) -fluorenyl group, 2,5- Bis (dimethylamino) -fluorenyl group, 2,5-bis (diethylamino) -fluorenyl group, 2,5-bis (diisopropylamino) -fluorenyl group, 2,5-bis (di-n-propylamino) -fluorenyl group 2,5-bis (di-n-butylamino) -fluorenyl group, 2,5-bis (dibenzylamino) -fluorenyl group, and the like. Here, when neither R ⁵ nor R ⁶ 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 used. Even if it uses for manufacture of an ethylene-type polymer, an extremely high molecular weight ethylene-type polymer 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 ⁷ 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 by using these specific substituents, it becomes possible to produce an ultra high molecular weight ethylene polymer powder having a high molecular weight. As specific examples of R ^7, 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 an amino group are combined. For example, diphenylsilanediyl (cyclopentadienyl) (2- (dimethylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2- (diethylamino) -9-fluorenyl) zirconium dichloride, diphenyl Silanediyl (cyclopentadienyl) (2- (diisopropylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2- (di-n-propyl-amino) -9-fluorenyl) zirconium Jiku , 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 (cyclopentadienyl) (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, diphe Nylsilanediyl (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-fur Oleenyl) 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) (3- 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, diphenylmethylene (Cyclopentadienyl) (4- (diisopropylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4- (di-n-propyl-amino) -9-fluorenyl) zirconium dichloride, diphenyl Methylene (cyclopentadienyl) (4- (di-n-butyl-amino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4- (dibenzylamino) -9-fluorenyl) zirconium dichloride Diphenylsilanediyl (cyclopentadienyl) (2,7-bis (dimethylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7-bis (diethylamino) -9-fur Oleenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7-bis (diisopropylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7-bis (di-)) n-propyl-amino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7-bis (di-n-butyl-amino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl ( Cyclopentadienyl) (2,7-bis (dibenzylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (3,6-bis (dimethylamino) -9-fluorenyl) zirconi Mudichloride, diphenylsilanediyl (cyclopentadienyl) (3,6-bis (diethylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (3,6-bis (diisopropylamino) -9 -Fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (3,6-bis (di-n-propyl-amino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (3, 6-bis (di-n-butyl-amino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (3,6-bis (dibenzylamino) -9-fluorenyl) zirconium dichloride, diph Phenylsilanediyl (cyclopentadienyl) (2,5-bis (dimethylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,5-bis (diethylamino) -9-fluorenyl) Zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,5-bis (diisopropylamino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,5-bis (di-n- Propyl-amino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,5-bis (di-n-butyl-amino) -9-fluorenyl) zirconium dichloride, diphenylsilanediyl Lopentadienyl) (2,5-bis (dibenzylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-bis (dimethylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene ( Cyclopentadienyl) (2,7-bis (diethylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-bis (diisopropylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl) (2,7-bis (di-n-propyl-amino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-bis (di-n-butyl) -Amino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-bis (dibenzylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6 -Bis (dimethylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-bis (diethylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3, 6-bis (diisopropylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-bis (di-n-propyl-amino) -9-fluorenyl) zirconium dichloride , Diphenylmethylene (cyclopentadienyl) (3,6-bis (di-n-butyl-amino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-bis (dibenzyl) Amino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,5-bis (dimethylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,5-bis (Diethylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,5-bis (diisopropylamino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) 2,5-bis (di-n-propyl-amino) -9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,5-bis (di-n-butyl-amino) -9-fluorenyl) Zirconium compounds such as zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,5-bis (dibenzylamino) -9-fluorenyl) zirconium dichloride, compounds in which the zirconium atom is changed to a titanium atom or a hafnium atom, and the above transition metals Examples thereof include compounds in which the dichloro form of the compound is changed to a dimethyl form, a diethyl form, a dihydro form, a diphenyl form, and a dibenzyl form. Among them, an ultrahigh molecular weight ethylene polymer powder can be produced with high production efficiency. Possible ethylene polymer production catalyst It is preferably a zirconium compound or a hafnium compound from becoming a.

  The organic modified clay (B) constituting the metallocene catalyst is an organic modified clay modified with an aliphatic salt represented by the general formula (6).

Here, R ^{8 to} R ¹⁰ 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 ^{8 to} R ¹⁰ is an alkyl group having 10 or more carbon atoms. . When any of R ^{8 to} R ¹⁰ 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 ultrahigh molecular weight ethylene polymer. Become.

Specific examples of R ^{8 to} R ¹⁰ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, aryl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, neopentyl, tert-pentyl, n-hexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl 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. An alkylamino group having ˜30; a trimethylsilyl group, a tri-tert-butylsilyl group, a ditert-butylmethylsilyl group, a tert-butyldimethylsilyl group, etc., an alkylsilyl group having 1 to 30 carbon atoms; a methoxymethylene group, an ethoxymethylene group, etc. A substituent in which oxygen is introduced between the carbon-carbon bond of the alkyl group having 1 to 30 carbon atoms; a part of the alkyl group having 1 to 30 carbon atoms such as a dimethylaminomethylene group and a diethylaminomethylene group; A substituent in which a part of the carbon atoms of the alkyl group having 1 to 30 carbon atoms such as a trimethylsilylmethylene group and a tert-butyldimethylsilylmethylene group are substituted with silicon, and the like. .

At least one substituent among the R ^{8 to} R ¹⁰ 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 a group 15 atom in the periodic table, and when it is an atom other than group 15 in the periodic table, the resulting catalyst can efficiently produce an ultrahigh molecular weight ethylene polymer powder. It becomes difficult. 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, fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, phosphate ion, Examples include perchlorate 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 induces | guides | derives the catalyst system for ethylene polymer manufacture of this invention, Among them, it is excellent in the efficiency at the time of catalyst preparation, and the efficiency at the time of ethylene 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 composition of the metallocene catalyst and the organoaluminum compound (C) contained in the polymerization solvent, any compound belonging to the category referred to as an organoaluminum compound can be used. An organoaluminum compound represented by the following general formula (7) is preferred because it becomes a catalyst system for producing an ethylene polymer capable of producing ethylene polymer powder 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 the subject of.

（式中、Ｒ^１１は炭素数１〜２０の炭化水素基であり、Ｒ^１２及びＲ^１３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。

(In the formula, R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² and R ¹³ are 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.

  Calcium stearate (D) may be any commercially available calcium stearate and may be of any shape, but is preferably in the form of powder, and in particular, ultrahigh molecular weight ethylene having excellent fluidity. The median diameter is more preferably 10 μm or less because it becomes a polymer powder.

  When calcium stearate and a hydrophobic plastic such as an ethylene polymer are mixed, the hydrophobic group of calcium stearate adsorbs to the plastic, and the hydrophilic group adsorbs moisture in the air, so the apparent conductivity of the plastic increases. Plastics are less likely to be charged with static electricity. That is, calcium stearate acts as an antistatic agent. Furthermore, when ethylene homopolymerization or copolymerization of ethylene and α-olefin is carried out in the presence of calcium stearate to obtain an ultrahigh molecular weight ethylene polymer powder, calcium stearate is uniformly dispersed in the powder. High antistatic effect can be expressed with calcium stearate. Therefore, the ultra-high molecular weight ethylene polymer powder obtained by the present invention is less likely to cause powder adhesion to static silos and processing machine hoppers, and calcium stearate itself acts as a lubricant. Have.

  The transition metal compound (A) constituting the metallocene catalyst (hereinafter also referred to as component (A)), the organically modified clay (B) (hereinafter also referred to as component (B)) and the organic Regarding the usage ratio of the aluminum compound (C) (hereinafter also referred to as the component (C)), the component (A), the component (B), and the component (C) are metallocenes that are catalysts for producing ethylene-based polymers. As long as it can be used as a system catalyst, it is not subject to any restrictions, and among them, since it becomes a catalyst capable of producing an ultrahigh molecular weight ethylene polymer with high production efficiency, The molar ratio of the component (C) per metal atom is preferably in the range of (component (A)) :( component (C)) = 100: 1 to 1: 100000, particularly 1: 1 to 1: 10000. This is a range It is preferred. The weight ratio of the component (A) to the component (B) is preferably ((A) component): ((B) component) = 10: 1 to 1: 10000, particularly 3: 1 to 1: 1000. It is preferable that it is the range of these.

  The use ratio of calcium stearate (D) (hereinafter also referred to as component (D)) is excellent in antistatic action and polymerization activity, and therefore the weight ratio of component (B) to component (D) is ((B ) Component): ((D) component) = 1: 0.0001-1: 100 is preferable. Particularly, ((B) component): ((D) component) = 1: 0.01-20. It is preferable that it is the range of these.

  As for the method for preparing the metallocene catalyst, any method may be used as long as it can be prepared from the component (A), the component (B) and the component (C). For example, there can be mentioned a method in which each of the components (A), (B) and (C) is mixed in an inert solvent or using a monomer for polymerization as a solvent. The order of reacting these components is not limited. However, since the polymerization activity is particularly excellent, after contacting the (B) component and the (C) component, the ultra-high height in which the (A) component is contacted. A catalyst for producing a molecular weight ethylene polymer is preferred. There is no limitation on the temperature and processing time for performing the treatment at this time. It is also possible to prepare a catalyst system for producing an ultrahigh molecular weight ethylene polymer by using two or more of each of the component (A), the component (B), and the component (C).

  The ultra high molecular weight ethylene polymer powder obtained by the present invention may be not only an ethylene homopolymer powder but also a copolymer powder with another α-olefin, and the ultra high molecular weight obtained by these polymerizations. The ethylene polymer powder is used to mean not only a homopolymer powder but also a copolymer powder.

  The production method of the ultrahigh molecular weight ethylene polymer powder of the present invention is based on a slurry polymerization method. 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. The organic solvent contains the organoaluminum compound (C) and calcium stearate (D), and the mixing method is not particularly limited.

  Examples of the α-olefin used for copolymerization with ethylene when the ethylene polymer is used as a copolymer include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. Of the α-olefin.

  Polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration in producing the ultrahigh molecular weight ethylene polymer powder of the present invention can be arbitrarily selected. Since it becomes possible to produce polymer powder, it is preferable to carry out in the range of polymerization temperature of 30 to 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 present invention is particularly suitable for efficiently producing an ultrahigh molecular weight ethylene polymer powder having an excellent powder morphology, and the obtained ultrahigh molecular weight ethylene polymer powder is particularly easy to handle. It is preferable that the median diameter is 50 μm or more and 500 μm or less because of excellent molding processability. It is preferable that the standard deviation of a particle size of 0.4 or less, it is preferable bulk density is 600Kgm ³ or less 200 kg / ^{m 3} or more. And, since it becomes an ultra-high molecular weight ethylene polymer powder excellent in mechanical properties such as abrasion resistance, the viscosity average molecular weight is 1 million or more, and preferably 1 million to 7.5 million. . In addition, since the ultra-high molecular weight ethylene polymer powder has an excellent balance between moldability and mechanical properties, Mw / Mn, which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 2.0. Is more preferably less than 5.0, more preferably more than 2.0 and less than 4.0.

  The production method of the ultra high molecular weight ethylene polymer powder of the present invention is excellent in fluidity and does not adhere to the wall surface during transfer from a silo or hopper. It is possible to stabilize, fouling during the production of ethylene polymer can be suppressed, and has excellent powder morphology, mechanical properties, wear resistance, moldability, ultra-high The molecular weight ethylene polymer powder can be produced efficiently and stably.

  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.

  The preparation of the metallocene catalyst, the production of the ultrahigh molecular weight ethylene polymer powder and the 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 ultrahigh molecular weight ethylene polymer powder 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, decalin was used as a solvent, and the measurement was performed at 135 ° C. at an ultrahigh molecular weight polyethylene 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).
Mv = [η] / (6.2 × 10 ⁴ ) × (1 / 0.7) / 10 ⁴
~ Median diameter and standard deviation of ultra high molecular weight ethylene polymer powder ~
The average particle diameter is obtained when classifying 100 g of particles using nine types of sieves (openings: 710 μm, 500 μm, 425 μm, 300 μm, 212 μm, 150 μm, 106 μm, 75 μm, 53 μm) defined by JIS Z8801. This is a value obtained by measuring the particle diameter at 50% weight in an integral curve obtained by integrating the weight of the particles remaining on each sieve obtained from the side having a larger mesh size.

~The bulk density~
It measured according to JIS K-6721: 1997.

~ Powder fluidity ~
50 g of powder was put into a funnel for measuring the bulk density, and the time until dropping was measured.

~ Chargeability of powder ~
50g of powder is put into a No. 14 plastic bag that has been neutralized, and the bag mouth is tied and shaken 10 times with a width of 30cm. When the powder is naturally dropped from the plastic bag, it does not fall due to static electricity. The amount of powder (charged adhesion amount) was measured.

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 are placed in a 1 liter flask, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine; 42.4 g (120 mmol) of C ₂₂ H ₄₅ (CH ₃ ) ₂ N (manufactured by Lion Corporation, (trade name) Armin DM22D) was added, heated to 45 ° C. and synthesized hectorite (manufactured by Rockwood Additives, Inc. Name) Laponite RDS) was dispersed in 100 g, and then 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 140 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 metallocene catalyst suspension A 300 ml flask equipped with a thermometer and a reflux tube was purged with nitrogen, and 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane were added, and then diphenylmethylene 0.600 g of (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 at 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 the metallocene catalyst (solid weight: 11.3 wt%).

(3) Production of ultrahigh molecular weight ethylene polymer powder 1.2 mg of hexane in a 2 liter autoclave, 16 mg of powdered calcium stearate (manufactured by Sakai Chemical Co., Ltd.) having a median diameter of 8.0 μm and 20% triisobutyl Add 1.1 ml of aluminum and stir at 80 ° C. for 30 minutes, and then add 168 mg (corresponding to 19.0 mg of solid content) of the metallocene catalyst suspension obtained in (2), resulting in a partial pressure of 0.85 MPa. Thus, ethylene was continuously supplied to carry out slurry polymerization of ethylene. After 180 minutes, depressurization and cooling were performed, and the slurry was filtered and dried to obtain 93.7 g of ultrahigh molecular weight ethylene homopolymer powder. Table 1 shows the physical properties of the resulting ultrahigh molecular weight ethylene homopolymer powder. Moreover, no powder adhesion was observed on each testing machine after the physical property measurement.

Example 2
(1) Preparation of organically modified clay was carried out in the same manner as in Example 1.

(2) Preparation of suspension of metallocene catalyst 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 diphenyl 0.629 g of methylene (cyclopentadienyl) (2-dimethylamino-9-fluorenyl) hafnium 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 metallocene catalyst suspension (solid weight: 12.1 wt%).

(3) Production of ultrahigh molecular weight ethylene copolymer powder 1.2 liters of hexane, 16 mg of calcium stearate and 1.1 ml of 20% triisobutylaluminum were added to a 2 liter autoclave and stirred at 60 ° C. for 30 minutes. The suspension of the metallocene catalyst obtained in (2) was added with 2.31 g (equivalent to 280.4 mg of solid content) and 4.5 g of 1-butene, and ethylene was continuously added so that the partial pressure became 0.38 MPa. The slurry copolymerization of ethylene and 1-butene was performed. After 240 minutes, depressurization and cooling were performed, and the slurry was filtered and dried to obtain 201.2 g of ultrahigh molecular weight ethylene-1-butene copolymer powder. Table 1 shows the physical properties of the obtained ultrahigh molecular weight ethylene-1-butene copolymer powder. Moreover, no powder adhesion was observed on each testing machine after the physical property measurement.

Example 3
(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 are placed in a 1 liter flask, 15.0 g of concentrated hydrochloric acid and methyldioleylamine; 63.7 g (120 mmol) of (C ₁₈ H ₃₅ ) ₂ CH ₃ N (manufactured by Lion Corporation, (trade name) Armin M2O) was added, heated to 45 ° C., and synthetic hectorite (manufactured by Rockwood Additives, Inc., (product) Name) Laponite RDS) was dispersed in 100 g, and then heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was filtered, washed twice with 600 ml of water at 60 ° C., and dried in a dryer at 85 ° C. for 12 hours to obtain 152 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 metallocene catalyst After replacing 300 ml flask equipped with thermometer and reflux tube with nitrogen, 25.0 g of organically modified clay obtained in (2) and 108 ml of hexane were added, and then diphenyl 0.630 g of methylene (cyclopentadienyl) (2-dimethylamino) -9-fluorenyl) hafnium 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 the metallocene catalyst (solid weight: 14.1 wt%).

(3) Production of ultrahigh molecular weight ethylene copolymer powder 1.2 liters of hexane, 25 mg of calcium stearate, 1.1 ml of 20% triisobutylaluminum in a 2 liter autoclave, metallocene system obtained in (2) 1.86 g (corresponding to a solid content of 262 mg) of the catalyst suspension was added, and after the temperature was raised to 60 ° C., ethylene was continuously supplied so that the partial pressure became 0.38 MPa to carry out homopolymerization of ethylene. After 180 minutes, depressurization and cooling were performed, and the slurry was filtered and dried to obtain 166.6 g of ultrahigh molecular weight ethylene homopolymer powder. Table 1 shows the physical properties of the resulting ultrahigh molecular weight ethylene homopolymer powder. Moreover, no powder adhesion was observed on each testing machine after the physical property measurement.

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

(2) Preparation of suspension of metallocene catalyst The same procedure as in (2) of Example 1 was performed.

(3) Production of ethylene polymer In a 2 liter autoclave, 1.2 liters of hexane, 1.1 ml of 20% triisobutylaluminum, 160 mg of a suspension of the metallocene catalyst obtained in (2) (solid content) 18.1 mg equivalent) was added, and after the temperature was raised to 60 ° C., ethylene was continuously supplied so that the partial pressure became 0.87 MPa. After 180 minutes, depressurization and cooling were performed, and the slurry was filtered and dried to obtain 87.4 g of ethylene homopolymer particles. Table 1 shows the physical properties of the resulting ethylene homopolymer powder. Moreover, many powder adhesion to each testing machine after a physical-property measurement was seen.

Comparative Example 2
Preparation of organically modified clay The same procedure as in Example 1 (1) was performed.

(2) Preparation of suspension of metallocene catalyst The same procedure as in (2) of Example 2 was performed.

(3) Production of ethylene polymer In a 2 liter autoclave, 1.2 liters of hexane, 1.1 ml of 20% triisobutylaluminum, and 2.35 g of a suspension of the metallocene catalyst obtained in (2) ( (Solid content equivalent to 284.3 mg), and after raising the temperature to 60 ° C., 4.5 g of 1-butene is added, and ethylene is continuously supplied so that the partial pressure becomes 0.38 MPa, and a slurry of ethylene and 1-butene Copolymerization was performed. After 240 minutes, depressurization and cooling were performed, and the slurry was filtered and dried to obtain 200.3 g of ethylene-1-butene copolymer powder. Table 1 shows the physical properties of the obtained ethylene-1-butene copolymer powder. Table 1 shows the physical properties of the resulting ethylene homopolymer powder. Moreover, many powder adhesion to each testing machine after a physical-property measurement was seen.

  The method for producing ultra-high molecular weight ethylene polymer powder of the present invention is excellent in fluidity and efficiently stabilizes ultra-high molecular weight ethylene polymer powder having excellent powder morphology, mechanical properties, abrasion resistance and moldability. Can be manufactured automatically.

Claims (5)

In a polymerization solvent, a transition metal compound (A) represented by the following general formula (1),

[Wherein, M ¹ is a titanium atom, a zirconium atom or a hafnium 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, carbon An alkylamino group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a substituent having oxygen introduced between carbon-carbon bonds of a hydrocarbon group having 1 to 20 carbon atoms, carbonization having 1 to 20 carbon atoms A substituent in which a part of the hydrogen group is substituted with an alkylamino group having 1 to 20 carbon atoms, a substituent in which a part of carbons in the hydrocarbon group having 1 to 20 carbon atoms is substituted with silicon, and R ¹ is A cyclopentadienyl group represented by formula (2);

(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 an amino group represented by the following general formula (3),

(Wherein R ⁵ and R ⁶ are each independently 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, C1-C20 arylalkylamino group, C1-C20 alkyl silyl group, C1-C20 hydrocarbon group, the substituent which introduce | transduced oxygen between the carbon-carbon bonds, C1-C20 A substituent obtained by substituting a part of the hydrocarbon group with an alkylamino group having 1 to 20 carbon atoms, a substituent obtained by substituting part of the carbons of the hydrocarbon group having 1 to 20 carbons with silicon, R ⁵ and (At least one of R ⁶ 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 ⁷ 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),

(Wherein R ^{8 to} R ¹⁰ 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 ^{8 to} R ¹⁰ 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 using a polymerization solvent containing organoaluminum compound (C) and calcium stearate (D) when carrying out slurry polymerization of ethylene alone or ethylene and α-olefin with a metallocene catalyst obtained from organoaluminum compound (C) A process for producing an ultra-high molecular weight ethylene polymer powder characterized by The method for producing an ultrahigh molecular weight ethylene polymer powder according to claim 1, wherein the organoaluminum compound (C) is an organoaluminum represented by the following general formula (7).

(In the formula, R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² is each independently a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a chlorine atom.) The method for producing an ultrahigh molecular weight ethylene polymer powder according to claim 1 or 2, wherein the calcium stearate (D) is in a powder form and the median diameter is 10 µm or less. The ultra high molecular weight ethylene polymer powder has a median diameter of 50 μm to 500 μm, a standard deviation of particle diameter of 0.4 or less, a bulk density of 200 kg / m ^{3 to} 600 kgm ³ and an intrinsic viscosity (dL / g) of 9 The method for producing an ultrahigh molecular weight ethylene polymer powder according to any one of claims 1 to 3, wherein the ultrahigh molecular weight ethylene polymer powder is 0.0 or more. Ultra high molecular weight ethylene polymer powder has an ultra high molecular weight in which 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 It consists of polyethylene, The manufacturing method of the ultra high molecular weight ethylene polymer powder in any one of Claims 1-4 characterized by the above-mentioned.