JP2005314544A - Ultra-high-molecular-weight polyethylene resin composition and molded article made thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultra-high-molecular-weight polyethylene composition having highly balanced abrasion property, mechanical properties and moldability and excellent drawability enabling the melt-drawing at a high temperature compared with conventional ultra-high-molecular-weight polyethylene. <P>SOLUTION: The ultra-high-molecular-weight polyethylene resin composition is composed of (A) an ultra-high-molecular-weight polyethylene resin and (B) a polyethylene resin and having at least two different viscosity-average molecular weights (Mv). The viscosity-average molecular weight of the ultra-high-molecular-weight polyethylene resin A is ≥6,000,000, the ratio of the viscosity-average molecular weight of A and B [Mv(A)/Mv(B)] is >1 and the viscosity-average molecular weight of the ultra-high-molecular-weight polyethylene resin composition is ≥1,000,000. The invention further provides a molded article of the composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ultra-high molecular weight polyethylene molded article obtained by a melt drawing method, and the obtained ultra-high molecular weight polyethylene has an excellent balance of mechanical properties and can be applied to various fields. And a molded body obtained therefrom.

Ultra high molecular weight polyethylene is classified as a kind of engineering plastic, and it has excellent mechanical properties due to its extremely high molecular weight (viscosity average molecular weight: Mv) of 1 million or more compared to high-density polyethylene, which is a general-purpose plastic. Are known. In addition, it has excellent characteristics such as weather resistance, chemical resistance, and insulation, and is widely used as a sliding member for gears and artificial joints because of its particularly high friction and wear resistance.
However, ultrahigh molecular weight polyethylene has an extremely high melt viscosity and is difficult to knead itself, so that molding with kneading is very difficult.
According to Non-Patent Document 1, in the case of a polymer material, various properties such as mechanical properties can be generally improved by a treatment (orientation treatment) for aligning the directions of polymer chains. There are various orientation treatments depending on the shape of the molded product, but in the case of a film or a sheet, the most effective one is said to be tensile stretching. Generally used high-density polyethylene can be given molecular orientation relatively easily because molecular chains are entangled even in the solid state, but in the case of ultra-high molecular weight polyethylene, Due to the length, the molecular chain entanglement density becomes high, and it is difficult to improve the physical properties by performing an alignment treatment.

In the case of ultra high molecular weight polyethylene, as described above, by further increasing the molecular weight to improve physical properties, on the contrary, the moldability tends to be inferior, so the ultimate physical properties by further polymerizing ultra high molecular weight polyethylene It has not reached expression.
In recent years, Non-Patent Document 2 reports research results on inflation molding technology using ultrahigh molecular weight polyethylene. As for the physical properties of the film obtained by this method, it has been confirmed that a high-strength film can be obtained as compared with the skive method in which the film is cut from compression molding, which is a typical molding method of ultrahigh molecular weight polyethylene. Ultra-high molecular weight polyethylene, which was previously difficult to mold and difficult to obtain physical properties as molded products, can now be improved by processing technology, and exhibits very high physical properties that could not be found before. Potential has been found.

In the above-mentioned blown film, the level of the viscosity average molecular weight is about 1 million, so there is still enough room for improving the physical properties, but the ultrahigh molecular weight polyethylene having a viscosity average molecular weight higher than this is also the same. When trying to mold, the motor load is too high for extrusion, or if forced extrusion occurs, degradation due to molecular chain breakage occurs during melt kneading, and the original physical properties can be expressed due to the decrease in molecular weight. Therefore, many problems still remain in molding ultra-high molecular weight polyethylene of 1 million or more.
As a method of obtaining ultra-high molecular weight polyethylene material having high physical properties by high orientation, there is a method of super-stretching by reducing molecular chain entanglement. Some examples include a surface growth fiber stretching method, a single crystal mat stretching method, a gel stretching method, and a polymerized powder stretching method.

On the other hand, there is a melt-stretching method that stretches in a molten state by utilizing entanglement of molecular chains. This is a drawing method that utilizes the feature that rubber chains are entangled with a lot of molecular chains like ultra high molecular weight polyethylene and show rubber elasticity even in a molten state. In this case, since the entanglement point transmits the stretching stress, the molecular chain can be oriented. In general high-density polyethylene with little entanglement of molecular chains, such melt drawing cannot be used. In order to obtain a stretched molded body having high strength by the melt stretching method, it is necessary to efficiently transmit the stretching stress to the entire film in a molten state.
The reason why ultra-high molecular weight polyethylene can be stretched to a high magnification at a temperature equal to or higher than the melting point is thought to be because some of the molecular chain entanglement is unraveled during the melt stretching process.

  However, the strength of the stretch-molded product obtained in the prior art is 155 ° C. with respect to ultrahigh molecular weight polyethylene having a molecular weight of 6 million or more, which has been difficult to mold until now when compared with the same ultrahigh molecular weight polyethylene. The (100) h reflection derived from the hexagonal crystal at the time of melt drawing in the above has not been reported. Moreover, although it can extend | stretch about molecular weight less than 6 million, since the extending | stretching temperature is low, sufficient extending | stretching cannot be performed but the high intensity | strength stretch molded object is not obtained. Ultra-high molecular weight polyethylene is known to have more molecular chain entanglement than ordinary high-density polyethylene, but as the molecular weight of ultra-high molecular weight polyethylene increases, the molecular chain entanglement increases and stretches uniformly. I couldn't. In Patent Document 1, a film formed by an inflation production method is used as a molded body. However, the molecular weight of ultra-high molecular weight polyethylene is about 1,000,000, and it can be extruded when the molecular weight of ultra-high molecular weight polyethylene is increased to further improve the physical properties. Disappear. On the other hand, with such ultra-high molecular weight polyethylene, the film is not sufficiently melted in an extruder and a film by uniform stretching cannot be obtained.

  In addition, there is a method to obtain a stretched molded article by melt stretching method using entanglement. However, when trying to stretch ultrahigh molecular weight polyethylene at a higher temperature, conventional ultrahigh molecular weight polyethylene is not sufficiently entangled and has a melting point. At the above stretching temperature, sufficient stretching stress is not applied, or during the conditioning of the stretching temperature, it was not possible to stretch due to large fluid deformation, so it was possible to obtain a stretched product of ultra high molecular weight polyethylene showing high physical properties. There wasn't. Although it is possible to increase the molecular weight of ultra-high molecular weight polyethylene to increase molecular chain entanglement with conventional techniques, the draw ratio is low, so the draw ratio is increased to achieve higher orientation and higher strength. There has never been an ultra-high molecular weight having sufficient characteristics for producing a molded body. Patent Documents 2 and 3 describe ultra-high molecular weight polyethylene compositions, but in both compositions having a molecular weight that can be called an ultra-high molecular weight polyethylene resin composition that has a large amount of low molecular weight components and strong entanglement at the time of melting. In addition, melt drawing under a high temperature condition of 155 ° C. could not be achieved.

Kyoritsu Publishing Co., Ltd. 1993, arranging polymer processed One Point-4 polymers Molding Volume 15 Issue 8 2003 “Inflation molding technology of ultra-high molecular weight polyethylene” Japanese Patent Laid-Open No. 9-183156 JP 60-240748 A Japanese Patent Publication No. 6-92457

  The present invention uses an ultra-high molecular weight polyethylene resin composition, and can be stably stretched even at a temperature exceeding the melting point, and further can be stretched at a high magnification at the time of melting, and then It aims at providing the molded object obtained.

As a result of intensive studies to solve the above problems, the inventors of the present invention can achieve good melt stretching at a specific temperature higher than the melting point in a polyethylene resin composition having at least two different specific viscosity-average molecular weights. It was found that a polyethylene resin composition having excellent performance capable of being drawn to a specific draw ratio can be obtained.
That is, the present invention is the inventions 1) to 6) below.
1) In an ultrahigh molecular weight polyethylene resin composition having a viscosity average molecular weight of 1 million or more, comprising an ultrahigh molecular weight polyethylene resin (A) polymerized with a metallocene catalyst and a polyethylene resin (B), the ultrahigh molecular weight The polyethylene resin (A) is an ultra high molecular weight polyethylene resin having a viscosity average molecular weight (Mv) of 6 million to 12 million determined from the following formula (1) from the intrinsic viscosity in decalin at 135 ° C., and the polyethylene resin (B) However, the ratio of the viscosity average molecular weight of the polyethylene resin (B) to the viscosity average molecular weight of the ultra high molecular weight polyethylene resin (A) satisfies the following formula (2), and the ultra high molecular polyethylene resin (A): Ultra high molecular weight polymer, characterized in that the mass ratio with polyethylene resin (B) is in the range of 5:95 to 95: 5 parts by mass. Ethylene resin composition.
Mv = 5.34 × 10 ⁴ [η] ^-1.49 formula (1)
Mv (A) / Mv (B)> 1 Formula (2)
2) The ultrahigh molecular weight polyethylene resin composition as described in 1) above, wherein the polyethylene resin (B) has a viscosity average molecular weight of 135 million ° C. and an intrinsic viscosity in decalin of 1 million or more.
3) After uniformly dissolving the liquid organic compound compatible with the ultrahigh molecular weight polyethylene resin composition, a dry mat is prepared from the obtained suspension, and a sheet-like molded body is further prepared by melt press molding. The ultrahigh molecular weight polyethylene resin composition according to 1) to 2) above, which can be melt-drawn in an atmosphere at a temperature of 155 ° C. or higher.
4) Said 1) thru | or 3) characterized by passing through the hexagonal crystal form which is one of the crystal forms of polyethylene during melt-drawing of this sheet-like molded object in high temperature atmosphere of 155 degreeC or more. Ultra high molecular weight polyethylene resin composition.
5) The ultrahigh molecular weight polyethylene resin composition according to any one of 1) to 4) above, wherein when the sheet-like molded body is melt-drawn in a high temperature atmosphere of 155 ° C. or higher, the draw ratio is 11 times or more. .
6) An ultrahigh molecular weight polyethylene molded article comprising the ultrahigh molecular weight polyethylene resin composition according to 1) to 5).

  Since the ultrahigh molecular weight resin composition of the present invention has a high molecular weight and a high draw ratio is possible, it has excellent strength and elastic modulus unprecedented.

Hereinafter, the present invention will be described in detail.
The ultra high molecular weight polyethylene used in the present invention is a resin composition comprising an ultra high molecular weight polyethylene resin (A) having at least two different molecular weights and a polyethylene resin (B), and the ultra high molecular weight polyethylene resin (A). Is an ultrahigh molecular weight polyethylene having a viscosity average molecular weight (Mv) of 6 million to 12 million determined from the following formula (1) from the intrinsic viscosity in decalin at 135 ° C., preferably 7 million to 11 million, more preferably 8 million to 11 million.
When the viscosity average molecular weight is 6 million or less, there is little entanglement of molecular chains at the time of melting, and it cannot be stably melt-stretched at a specific high temperature. When the viscosity average molecular weight is 12 million or more, it is difficult to uniformly dissolve the other low molecular weight component, and thus it cannot be stably melt-stretched.

The ratio of the viscosity average molecular weight of the polyethylene resin (B) to the viscosity average molecular weight of the ultrahigh molecular weight polyethylene resin (A) satisfies the following formula (2), and the ratio of the viscosity average molecular weight consisting of the following formula (2) is 1 or more, preferably 2 or more, more preferably 5 or more, and still more preferably 10 or more. The mass ratio of the ultrahigh molecular weight polyethylene resin (A) and the polyethylene resin (B) is in the range of 5:95 to 95: 5 parts by mass, preferably 15:85 to 85:15 parts by mass, and more preferably It is desirable that there be 25:75 to 75:25 parts by mass.
As the resin (A) or the resin (B), two or more resins having different viscosity average molecular weights may be used.

When the mass ratio of the ultrahigh molecular weight polyethylene resin (A) is lower than 5%, sufficient entanglement of molecular chains cannot be imparted at the time of melting, and melt stretching cannot be performed at a high temperature. On the other hand, if it is higher than 95%, the molecular chains are entangled at the time of melting and cannot be melt-stretched at a high magnification. The ultrahigh molecular weight polyethylene resin composition has a viscosity average molecular weight of 1 million or more, preferably 3 million or more, more preferably 5 million or more, and further preferably 7 million or more. It consists of things.
Mv = 5.34 × 10 ⁴ [η] ^-1.49 formula (1)
Mv (A) / Mv (B)> 1 Formula (2)
When the viscosity average molecular weight of the ultrahigh molecular weight polyethylene resin composition is 1,000,000 or less, it cannot be stably melt-stretched.

Furthermore, the polyethylene resin (B) of the present invention has a viscosity average molecular weight determined from the intrinsic viscosity in decalin of 135 ° C. of 1 million or more, preferably 2 million or more, more preferably 3 million or more. preferable. If it is 1,000,000 or less, it becomes difficult to stretch at a higher temperature, and it becomes difficult to express high-strength physical properties.
The method for obtaining the ultrahigh molecular weight polyethylene used in the present invention is not particularly limited. For example, ethylene alone or ethylene and other α-olefins are used as polymerization monomers, so-called Ziegler catalyst, chromium catalyst. And obtained by polymerization using a metallocene catalyst. Among these, it is particularly preferable to use ultrahigh molecular weight polyethylene that can be polymerized using a metallocene catalyst.

The ultrahigh molecular weight polyethylene resin (A) preferably used in the present invention comprises, for example, a metallocene catalyst used for polymerization at least a) a transition metal compound having a cyclic η-bonding anion ligand, and b) the transition metal compound It is composed of two catalytic components of an activator that can form a complex that reacts to express catalytic activity.
The transition metal compound having a cyclic η-bonding anion ligand used in the present invention can be represented, for example, by the following general formula (3).

L _j W _k MX _p X ′ _q (3)
(In the formula, each L is independently a η bond selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group. A cyclic anionic ligand, which optionally has 1 to 8 substituents, each of which is independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, carbon A halogen-substituted hydrocarbon group having 1 to 12 carbon atoms, an aminohydrocarbyl group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a dihydrocarbylamino group having 1 to 12 carbon atoms, and a hydrocarbyl phosphor having 1 to 12 carbon atoms Selected from the group consisting of a fino group, a silyl group, an aminosilyl group, a hydrocarbyloxysilyl group having 1 to 12 carbon atoms, and a halosilyl group, Is a substituent having a hydrogen atom,
M represents a transition metal selected from the group of transition metals belonging to Group 4 of the periodic table having a formal oxidation number of +2, +3, or +4, and represents a transition metal bonded to at least one ligand L by η ^5. ,
W is a divalent substituent having up to 50 non-hydrogen atoms, and binds to L and M with a valence of 1 each, thereby synergizing with L and M to perform a metallocycle. Represents a divalent substituent to be formed,
X is each independently a monovalent anionic σ-bonded ligand, a divalent anionic σ-bonded ligand that binds to M bivalently, and L and M each monovalently Represents an anionic σ-bonded ligand having up to 60 non-hydrogen atoms selected from the group consisting of divalent anionic σ-bonded ligands bonded by valence;
X ′ each independently represents a neutral Lewis base coordinating compound having up to 40 non-hydrogen atoms, j is 1 or 2, provided that when j is 2, Two ligands L are bonded to each other through a divalent group having up to 20 non-hydrogen atoms, and the divalent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, 1 to 12 carbon atoms A halohydrocarbadiyl group, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, a hydrocarbyleneamino group having 1 to 12 carbon atoms, a silanediyl group, a halosilanediyl group, and a silyleneamino group,
k is 0 or 1,
p is 0, 1 or 2, provided that X is a monovalent anionic σ-bonded ligand or a divalent anionic σ-bonded ligand bonded to L and M , P is an integer 1 or more smaller than the formal oxidation number of M, and when X is a divalent anionic σ-bonded ligand bonded only to M, p is smaller than the formal oxidation number of M ( j + 1) an integer smaller than or equal to q and q is 0, 1 or 2)

Examples of the ligand X in the compound of the above formula (3) include a halide, a hydrocarbon group having 1 to 60 carbon atoms, a hydrocarbyloxy group having 1 to 60 carbon atoms, a hydrocarbylamide group having 1 to 60 carbon atoms, Examples thereof include a hydrocarbyl phosphido group having 1 to 60 carbon atoms, a hydrocarbyl sulfide group having 1 to 60 carbon atoms, a silyl group, and a composite group thereof.
Examples of the neutral Lewis base coordination compound X ′ in the compound of the above formula (3) include phosphine, ether, amine, olefin having 2 to 40 carbon atoms, diene having 1 to 40 carbon atoms, and these compounds. Examples thereof include a derived divalent group.
In the present invention, the transition metal compound having a cyclic η-bonding anion ligand is preferably a transition metal compound represented by the formula (3) (where j = 1).
Preferable examples of the compound represented by the formula (3) (where j = 1) include a compound represented by the following formula (4).

(Wherein, M represents a transition metal selected from the group consisting of titanium, zirconium and hafnium, and represents a transition metal having a formal oxidation number of +2, +3 or +4,
Each R ⁵ is independently selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a composite group thereof; Represents a substituent having a hydrogen atom, provided that when the substituent R ⁵ is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group or a germyl group, in some cases, two adjacent substituents R ⁵ are bonded to each other. To form a ring by cooperating with a bond between two carbon atoms of the cyclopentadienyl ring bonded to each of the two adjacent substituents R ⁵ .
X ″ each independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, or a group having 1 to 18 carbon atoms. Represents a substituent having up to 20 non-hydrogen atoms selected from the group consisting of a hydrocarbylamide group, a hydrocarbyl phosphide group having 1 to 18 carbon atoms, a hydrocarbyl sulfide group having 1 to 18 carbon atoms, and a composite group thereof; However, in some cases, two substituents X ″ may cooperate to form a neutral conjugated diene having 4 to 30 carbon atoms or a divalent group,
Y ′ represents —O—, —S—, —NR ^* — or —PR ^* —, wherein R ^* is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbyl having 1 to 8 carbon atoms. An oxy group, a silyl group, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, or a composite group thereof;
Z represents SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ or GeR ^* ₂ , where R ^* is As defined,
n is 1, 2 or 3.

Specific examples of the transition metal compound having a cyclic η-bonding anion ligand used in the present invention include the following compounds.
Bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl,
(Pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl,

Bis (fluorenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4-methyl-1-indenyl) zirconium dimethyl, ethylene Bis (5-methyl-1-indenyl) zirconium dimethyl,
Ethylene bis (6-methyl-1-indenyl) zirconium dimethyl, ethylene bis (7-methyl-1-indenyl) zirconium dimethyl, ethylene bis (5-methoxy-1-indenyl) zirconium dimethyl, ethylene bis (2,3-dimethyl) -1-indenyl) zirconium dimethyl, ethylenebis (4,7-dimethyl-1-indenyl) zirconium dimethyl, ethylenebis- (4,7-dimethoxy-1-indenyl) zirconium dimethyl, methylenebis (cyclopentadienyl) zirconium dimethyl ,

Isopropylidene (cyclopentadienyl) zirconium dimethyl, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dimethyl,
Silylene bis (cyclopentadienyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) zirconium dimethyl, [(Nt-butyramide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl , [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl,
[(N-methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-phenylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, (N-benzylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(Nt-butylamido) (η ⁵ -cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl ,

[(Nt-butylamide) (η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-methylamido) (η ⁵ -cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [( N-methylamide) (η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(Nt-butylamide) (η ⁵ -indenyl) dimethylsilane] titanium dimethyl, [(N-benzylamide) (η ⁵ − Indenyl) dimethylsilane] titanium dimethyl,

  Dibromobistriphenylphosphine nickel, dichlorobistriphenylphosphine nickel, dibromodiacetonitrile nickel, dibromodibenzonitrile nickel, dibromo (1,2-bisdiphenylphosphinoethane) nickel, dibromo (1,3-bisdiphenylphosphinopropane) nickel, Dibromo (1,1′-diphenylbisphosphinoferrocene) nickel, dimethylbisdiphenylphosphinenickel, dimethyl (1,2-bisdiphenylphosphinoethane) nickel, methyl (1,2-bisdiphenylphosphinoethane) nickeltetrafluoro Borate, (2-diphenylphosphino-1-phenylethyleneoxy) phenylpyridine nickel, dichlorobistriphenylphosphine palladium, dichlorodibe Zone nitrile palladium, dichloro-di acetonitrile palladium, dichloro (1,2-bis-diphenylphosphino ethane) palladium, bis (triphenylphosphine) palladium bistetrafluoroborate, bis (2,2'-bipyridine) methyl iron tetrafluoroborate etherate, and the like.

  Specific examples of the transition metal compound having a cyclic η-bonding anion ligand used in the present invention include “dimethyl” in the names of the zirconium and titanium compounds listed above (this is the The last part of the name, that is, the part appearing immediately after the part of “zirconium” or “titanium”, which is the name corresponding to the part of X ″ in the above formula (4), is any of the following The compound which has a name made in place of a thing is also mentioned.

“Dichloro”, “Dibromo”, “Diiodo”, “Diethyl”, “Dibutyl”, “Diphenyl”, “Dibenzyl”, “2- (N, N-dimethylamino) benzyl”, “2-butene-1,4” -Diyl "," s-trans-η ⁴ -1,4-diphenyl-1,3-butadiene "," s-trans-η ⁴ -3-methyl-1,3-pentadiene "," s-trans-η ⁴ -1,4-dibenzyl-1,3-butadiene, "" s- trans eta ^{4-2,4-hexadiene,} "" s- trans eta ⁴ -1,3-pentadiene "," s- trans - eta ^{4-1,4-ditolyl-1,3-butadiene,} "" s- trans eta ^4-1,4-bis (trimethylsilyl) -1,3-butadiene "
“S-cis-η ⁴ -1,4-diphenyl-1,3-butadiene”, “s-cis-η ⁴ -3-methyl-1,3-pentadiene”, “s-cis-η ⁴ -1, 4-dibenzyl-1,3-butadiene ”,“ s-cis-η ⁴ -2,4-hexadiene ”,“ s-cis-η ⁴ -1,3-pentadiene ”,“ s-cis-η ⁴ −1 ” , 4-ditolyl-1,3-butadiene ”,“ s-cis-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene ”and the like.

The transition metal compound having a cyclic η-bonding anion ligand used in the present invention can be generally synthesized by a known method.
In the present invention, these transition metal compounds may be used alone or in combination.
Next, an activator capable of reacting with the transition metal compound used in the present invention to form a complex exhibiting catalytic activity (hereinafter sometimes referred to simply as “activator” in the present invention) will be described.
Examples of the activator in the present invention include compounds defined by the following general formula (5).

[L−H] ^{d +} [M _m Q _p ] ^d− (5)
(Wherein [L-H] ^{d +} represents a proton-donating Bronsted acid, wherein L represents a neutral Lewis base, d is an integer of 1 to 7; [M _m Q _p ] ^{d -} represents a non-coordinating anion of compatibility, where, M represents a metal or metalloid belonging to any of the fifth to group 15 of the periodic table, Q is each independently hydride, halide, Selected from the group consisting of a dihydrocarbylamide group having 2 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms, and a substituted hydrocarbon group having 1 to 40 carbon atoms. However, the number of Q which is a halide is 1 or less, m is an integer of 1-7, p is an integer of 2-14, d is as defined above, and pm = d .)

  Specific examples of the non-coordinating anion include, for example, tetrakisphenyl borate, tri (p-tolyl) (phenyl) borate, tris (pentafluorophenyl) (phenyl) borate, tris (2,4-dimethylphenyl) (hydrphenyl) ) Borate, tris (3,5-dimethylphenyl) (phenyl) borate, tris (3,5-di-trifluoromethylphenyl) (phenyl) borate, tris (pentafluorophenyl) (cyclohexyl) borate, tris (pentafluoro) Phenyl) (naphthyl) borate, tetrakis (pentafluorophenyl) borate, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) borate, tri (p-to) Ru) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (hydroxyphenyl) borate, Tris (3,5-di-trifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) borate, tris (penta Fluorophenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4′-hydroxyphenyl) phenyl) borate, tris (pentafluorophenyl) (6-hydroxy-2-naphtho) Le) borate, and the like.

Examples of other preferable non-coordinating anions include borates in which the hydroxy group of the borate exemplified above is replaced with an NHR group. Here, R is preferably a methyl group, an ethyl group or a tert-butyl group.
Specific examples of proton-providing Bronsted acids include triethylammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, tributylammonium, tri (n-octyl) ammonium and the like. An alkyl group-substituted ammonium cation,
Also, N, N-dialkyl such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium, N, N-dimethylbenzylanilinium, etc. Anilinium cations are also suitable.

Furthermore, dialkylammonium cations such as di- (i-propyl) ammonium and dicyclohexylammonium are also suitable, such as triphenylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium and the like. Such triarylphosphonium cations, dimethylsulfonium, diethylfuronium, diphenylsulfonium and the like are also suitable.
In the present invention, an organometallic oxy compound having a unit represented by the following formula (6) can also be used as an activator.

(Wherein M ² is a metal or metalloid of Groups 13 to 15 of the periodic table, R is each independently a hydrocarbon group or substituted hydrocarbon group having 1 to 12 carbon atoms, and n is a metal M ^2. And m is an integer of 2 or more.)
A preferred example of the activator of the present invention is an organoaluminum oxy compound containing a unit represented by the following formula (7), for example.

(However, R is an alkyl group having 1 to 8 carbon atoms, and m is an integer of 2 to 60.)
A further preferred example of the activator of the present invention is, for example, methylalumoxane containing a unit represented by the following formula (8).

(However, m is an integer of 2 to 60.)

In the present invention, the activator components may be used alone or in combination.
In the present invention, these catalyst components can be supported on a solid component and used as a supported catalyst. Examples of such a solid component include porous polymer materials such as polyethylene, polypropylene, and copolymers of styrene divinylbenzene, or silica, alumina, magnesia, magnesium chloride, zirconia, titania, boron oxide, calcium oxide, zinc oxide, and the like. Selected from inorganic solid materials of Group 2, 3, 4, 13 and 14 elements of periodic table such as barium oxide, vanadium pentoxide, chromium oxide and thorium oxide, and mixtures thereof, and their double oxides At least one inorganic solid material.

  Examples of the composite oxide of silica include composite oxides of silica such as silica magnesia, silica alumina and the like, and Group 2 or Group 13 elements of the periodic table. In the present invention, in addition to the above two catalyst components, an organoaluminum compound can be used as a catalyst component as required. The organoaluminum compound that can be used in the present invention is, for example, a compound represented by the following formula (9).

(However, R is an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 20 carbon atoms, X is a halogen, hydrogen or alkoxyl group, and the alkyl group is linear, branched or cyclic. , N is an integer from 1 to 3.)

The organoaluminum compound of the present invention may be a mixture of compounds represented by the general formula (9).
Examples of the organoaluminum compound that can be used in the present invention include, for example, the above general formula, wherein R represents a methyl group, an ethyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, and a tolyl group. X includes methoxy, ethoxy, butoxy, chloro and the like.

  Specific examples of the organoaluminum compound that can be used in the present invention include trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and the like, or these organoaluminums. And reaction products of alcohols such as methyl alcohol, ethyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol and decyl alcohol, such as dimethylmethoxyaluminum, diethylethoxyaluminum and dibutylbutoxyaluminum.

Next, the hydrogenating agent used in the present invention will be described.
The hydrogenating agent such as _hydrogen, in _{R r-n (Mt) α} H n ( wherein, Mt is an atom belonging to Group 1-3 and 14, 15 periodic table, R represents C 1 -C A group consisting of an alkyl group having 4 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms And a hydrocarbon group selected from the group consisting of n> 0, rn ≧ 0, and r is the valence of Mt).
Among these, preferred are hydrogen or R _n SiH _4-n (wherein 0 ≦ n ≦ 1, R is an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, a carbon atom) A hydrocarbon group selected from the group consisting of an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms, Hydrogen is preferred.

Specific examples of the hydrogenating agent include, for example, hydrogen, sodium hydride, calcium hydride, lithium aluminum hydride, SiH ₄ , methylsilane, ethylsilane, n-butylsilane, octylsilane, octadecylsilane, phenylsilane, benzylsilane, dimethylsilane, Diethylsilane, di-n-butylsilane, dioctylsilane, dioctadecylsilane, diphenylsilane, dibenzylsilane, ethenylsilane, 3-butenylsilane, 5-hexenylsilane, cyclohexenylsilane, 7-octenylsilane, 17-octadecenylsilane, etc. And preferably hydrogen, octylsilane or phenylsilane.

In the present invention, the metallocene catalyst is used for the polymerization after contacting with a hydrogenating agent in advance.
Examples of the method of bringing the metallocene catalyst into contact with the hydrogenating agent before introducing the metallocene catalyst into the polymerization reactor include, for example, 1) adding a hydrogenating agent to the catalyst transfer medium and transferring the catalyst to the polymerization reactor during transfer to the polymerization reactor. Examples include a method of bringing a hydrogenating agent into contact, and 2) a step before transferring the catalyst, for example, a method in which a hydrogenating agent is introduced into a catalyst storage tank and the catalyst is brought into contact with the hydrogenating agent.
Examples of a method for adding a hydrogenating agent to a catalyst transfer medium include, for example, connecting a hydrogenating agent supply line to a catalyst transfer line provided for introducing a catalyst into a polymerization reactor, and By supplying to the line, a method for causing the medium to contain a hydrogenating agent, or a supply line for the hydrogenating agent is provided in a catalyst supply nozzle provided in the polymerization reactor for introducing the catalyst into the polymerization reactor. Examples thereof include a method in which a hydrogenating agent is contained in the medium by connecting and supplying the hydrogenating agent to the line. In addition, a method may be mentioned in which a hydrogenating agent is previously contained in a medium for transferring the catalyst to the polymerization reactor, and the catalyst is transferred to the polymerization reactor using the hydrogenating agent-containing catalyst transfer medium.

When the hydrogenating agent and the metallocene catalyst are contacted in advance, the contact time is not particularly limited, but is preferably within 10 minutes, more preferably within 5 minutes, even more preferably within 1 minute, still more preferably. Is within 30 seconds, most preferably within 20 seconds.
In the present invention, the amount of the hydrogenating agent to be brought into contact with the metallocene catalyst is 0.5 to 5 000 mol of the transition metal compound contained in the catalyst. When the amount of the hydrogenating agent is less than 0.5 times mol, a massive polymer is produced and stable operation becomes difficult. On the other hand, if the amount of the hydrogenating agent is more than 50000 times mol, the polymerization activity and the molecular weight are reduced.
In the present invention, the amount of the hydrogenating agent to be brought into contact with the catalyst is preferably 1-fold mole and 30,000-fold mole, more preferably 10-fold mole and 1000-fold mole.

Next, the [B] compound having hydrogenation ability used in the present invention will be described. The compound having hydrogenation ability is a compound that reacts with hydrogen and hydrogenates ethylene or α-olefin in the system, and as a result, can reduce the hydrogen concentration in the polymerization reaction reactor, and is preferably polymerized. Any compound that does not decrease the catalytic activity may be used, and a metallocene compound or a compound containing platinum, palladium, palladium-chromium, nickel, or ruthenium can be used. Among them, a metallocene compound having a high hydrogenation activity is preferable, and a titanocene compound or a half titanocene compound that can exhibit a hydrogenation activity near the polymerization temperature is particularly preferable.

These titanocene compounds or half titanocene compounds alone are capable of hydrogenation activity, but are preferred because they can increase the hydrogenation activity ability by mixing and reacting with an organometallic compound such as organolithium, organomagnesium, and organoaluminum.
The mixing and reaction of the organometallic compound with the titanocene compound or the half titanocene compound may be performed before feeding into the polymerization reactor, or may be performed separately in the polymerization reactor and performed in the polymerization reactor system. .
The titanocene compound or the half titanocene compound used in the present invention can be represented by, for example, the following general formula (10).

L _j W _k TiX _p X ′ _q (10)
(In the formula, each L is independently a η bond selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group. A cyclic anionic ligand, which optionally has 1 to 8 substituents, each of which is independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, carbon A halogen-substituted hydrocarbon group having 1 to 12 carbon atoms, an aminohydrocarbyl group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a dihydrocarbylamino group having 1 to 12 carbon atoms, and a hydrocarbyl phosphor having 1 to 12 carbon atoms Selected from the group consisting of a fino group, a silyl group, an aminosilyl group, a hydrocarbyloxysilyl group having 1 to 12 carbon atoms, and a halosilyl group, Is a substituent having a hydrogen atom,
Ti represents titanium having a formal oxidation number of +2, +3 or +4 and η ⁵ bonded to at least one ligand L;
W is a divalent substituent having up to 50 non-hydrogen atoms, and binds to L and Ti at a valence of 1 each, thereby synergizing with L and Ti to perform a metallacycle. Represents a divalent substituent to be formed;
X and X ′ are each independently a monovalent ligand, a divalent ligand that binds divalently to Ti, and a divalent bond that binds to L and Ti each with a monovalent valence. A ligand selected from the group consisting of: a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-substituted hydrocarbon group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms. Aminohydrocarbyl group, C 1-12 hydrocarbyloxy group, C 1-12 dihydrocarbylamino group, C 1-12 hydrocarbyl phosphino group, silyl group, aminosilyl group, C 1-12 hydrocarbyl Represents a ligand having up to 20 non-hydrogen atoms selected from the group consisting of an oxysilyl group and a halosilyl group;
j is 1 or 2, provided that when j is 2, in some cases two ligands L are bonded to each other via a divalent group having up to 20 non-hydrogen atoms, The valent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, or a hydrocarbyleneamino group having 1 to 12 carbon atoms. A group selected from the group consisting of a silanediyl group, a halosilanediyl group, and a silyleneamino group,
k is 0 or 1,
p is 0, 1 or 2, provided that when X is a monovalent ligand or a divalent ligand bonded to L and Ti, p is 1 from the formal oxidation number of Ti. When X is a divalent anionic σ-bonded ligand bonded only to Ti, p is an integer smaller than (j + 1) or more than the formal oxidation number of Ti, and q is 0, 1 or 2)
Specific examples of the titanocene compound used in the present invention include the following compounds when the η-bonding cyclic anion ligand is a cyclopentadienyl group.

  Bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diethyl, bis (cyclopentadienyl) titanium diisopropyl, bis (cyclopentadienyl) titanium di-n-butyl, bis (cyclopentadienyl) ) Titanium di-sec-butyl, bis (cyclopentadienyl) titanium dihexyl, bis (cyclopentadienyl) titanium dioctyl, bis (cyclopentadienyl) titanium dimethoxide, bis (cyclopentadienyl) titanium diethoxide Bis (cyclopentadienyl) titanium diisopropoxide, bis (cyclopentadienyl) titanium dibutoxide, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) titanium di -M-tolyl, bis (cyclopentadienyl) titanium di-p-tolyl, bis (cyclopentadienyl) titanium di-m, p-xylyl,

  Bis (cyclopentadienyl) titanium di-4-ethylphenyl, bis (cyclopentadienyl) titanium di-4-hexylphenyl, bis (cyclopentadienyl) titanium di-4-methoxyphenyl, bis (cyclopentadi) Enyl) titanium di-4-ethoxyphenyl, bis (cyclopentadienyl) titanium diphenoxide, bis (cyclopentadienyl) titanium difluoride, bis (cyclopentadienyl) titanium dibromide, bis (cyclopentadienyl) ) Titanium dichloride, bis (cyclopentadienyl) titanium dibromide, bis (cyclopentadienyl) titanium diiodide, bis (cyclopentadienyl) titanium chloride methyl, bis (cyclopentadienyl) titanium Loride etoxide, bis (cyclopentadienyl) titanium chloride phenoxide, bis (cyclopentadienyl) titanium dibenzyl, bis (cyclopentadienyl) titanium di-dimethylamide, bis (cyclopentadienyl) titanium di- Diethylamide, bis (cyclopentadienyl) titanium di-diisopropylamide, bis (cyclopentadienyl) titanium di-di-sec-butyramide, bis (cyclopentadienyl) titanium di-di-tert-butyramide, bis (cyclo Pentadienyl) titanium di-ditrimethylsilylamide and the like.

As specific examples of the titanocene compound used in the present invention, a compound having a name formed by replacing the above-mentioned “cyclopentadienyl” part with any of the following η-bonding cyclic anion ligands Also mentioned.
“Methylcyclopentadienyl”, “n-butylcyclopentadienyl”, “1,3-dimethylcyclopentadienyl”, “pentamethylcyclopentadienyl”, “tetramethylcyclopentadienyl”, “trimethylsilyl” “Cyclopentadienyl”, “1,3-bistrimethylsilylcyclopentadienyl”, “indenyl”, “4,5,6,7-tetrahydro-1-indenyl”, “5-methyl-1-indenyl”, “ 6-methyl-1-indenyl, 7-methyl-1-indenyl, 5-methoxy-1-indenyl, 2,3-dimethyl-1-indenyl, 4,7-dimethyl-1- Indenyl "," 4,7-dimethoxy-1-indenyl "," fluorenyl "and the like.

  Further, the two η-bonding cyclic anionic ligands constituting the titanocene compound can be arbitrarily combined from the ligands shown above. Specific examples of arbitrary combinations include (pentamethylcyclopentadienyl) (cyclopentadienyl) titanium dichloride, (fluorenyl) (cyclopentadienyl) titanium dichloride, and (fluorenyl) (pentamethylcyclopentadienyl) titanium. Dichloride, (indenyl) (cyclopentadienyl) titanium dichloride, (indenyl) (pentamethylcyclopentadienyl) titanium dichloride, (indenyl) (fluorenyl) titanium dichloride, (tetrahydroindenyl) (cyclopentadienyl) titanium dichloride , (Tetrahydroindenyl) (pentamethylcyclopentadienyl) titanium dichloride, (tetrahydroindenyl) (fluorenyl) titanium dichloride Ido,

  (Cyclopentadienyl) (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride, (pentamethylcyclopentadienyl) (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride, (fluorenyl) (1, 3-bistrimethylsilylcyclopentadienyl) titanium dichloride, (indenyl) (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride, (tetrahydroindenyl) (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride, etc. Is mentioned. In addition, compounds having names obtained by replacing the “dichloride” portion of these compounds with any of those listed below are also included.

"Dibromide", "Diiodide", "Methyl chloride", "Methyl bromide", "Dimethyl", "Diethyl", "Dibutyl", "Diphenyl", "Dibenzyl", "Dimethoxy", "Methoxy chloride", "Bis -2- (N, N-dimethylamino) benzyl ”,“ 2-butene-1,4-diyl ”,“ s-trans-η ⁴ -1,4-diphenyl-1,3-butadiene ”,“ s- trans eta ^{4-3-methyl-1,3-pentadiene} "," s- trans eta ^{4-1,4-dibenzyl-1,3-butadiene,} "" s- trans eta ^{4-2,4-hexadiene} ”,“ S-trans-η ⁴ -1,3-pentadiene ”,“ s-trans-η ⁴ -1,4-ditolyl-1,3-butadiene ”,“ s-trans-η ⁴ -1,4- Bis (trimethi Rusilyl) -1,3-butadiene ”,“ s-cis-η ⁴ -1,4-diphenyl-1,3-butadiene ”,“ s-cis-η ⁴ -3-methyl-1,3-pentadiene ”, “S-cis-η ⁴ -1,4-dibenzyl-1,3-butadiene”, “s-cis-η ⁴ -2,4-hexadiene”, “s-cis-η ⁴ -1,3-pentadiene” , “S-cis-η ⁴ -1,4-ditolyl-1,3-butadiene”, “s-cis-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene” and the like.

These two η-bonding cyclic anionic ligands may be bonded by the following groups.
_{^{-SiR * 2 -, - CR *}} 2 -, - SiR * 2 SiR * 2 -, - CR * 2 CR * 2 -, - CR * = CR * -, - CR * 2 SiR * 2 -, - GeR * ₂ -etc. R ^* is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 8 carbon atoms, a silyl group, a halogenated alkyl group having 1 to 8 carbon atoms, or a halogen having 6 to 20 carbon atoms. Represents an aryl group or a composite group thereof.
Specific examples of bonding of two η-bonding cyclic anion ligands include, for example, ethylene bis (cyclopentadienyl) titanium dichloride, ethylene bis (tetramethylcyclopentadienyl) titanium dichloride, ethylene bis (indenyl). ) Titanium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) titanium dichloride, ethylenebis (4-methyl-1-indenyl) titanium dichloride, ethylenebis (5-methyl-1-indenyl) titanium Dichloride, ethylenebis (6-methyl-1-indenyl) titanium dichloride, ethylenebis (7-methyl-1-indenyl) titanium dichloride, ethylenebis (5-methoxy-1-indenyl) titanium dichloride Ethylenebis (2,3-dimethyl-1-indenyl) titanium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) titanium dichloride,

  Ethylenebis (4,7-dimethoxy-1-indenyl) titanium dichloride, methylenebis (cyclopentadienyl) titanium dichloride, isopropylidenebis (cyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) titanium Dichloride, silylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (methylcyclopentadienyl) titanium dichloride , Dimethylsilylene bis (trimethylsilylcyclopentadienyl) titanium dichloride, dimethylsilylene ( Cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride,

  Dimethylsilylene (tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (cyclopentadienyl) titanium dichloride , Dimethylsilylene (fluorenyl) (indenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (trimethylsilylcyclopentadienyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-bistrimethylsilylcyclo Pentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylsilylcyclopentadi) Yl) titanium dichloride,

  Dimethylsilylene (tetramethylcyclopentadienyl) (3,5-bistrimethylsilylcyclopentadienyl) titanium dichloride, dimethylsilylene (fluorenyl) (trimethylsilylcyclopentadienyl) titanium dichloride, dimethylsilylene (fluorenyl) (3,5- And bis (trimethylsilylcyclopentadienyl) titanium dichloride, dimethylsilylene (indenyl) (trimethylsilylcyclopentadienyl) titanium dichloride, dimethylsilylene (indenyl) (3,5-bistrimethylsilylcyclopentadienyl) titanium dichloride, and the like.

Specific examples of the half titanocene compound used in the present invention include the following compounds when the η-bonding cyclic anion ligand is a cyclopentadienyl group.
Cyclopentadienyl titanium trimethyl, cyclopentadienyl titanium triethyl, cyclopentadienyl titanium triisopropyl, cyclopentadienyl titanium tri-n-butyl, cyclopentadienyl titanium tri-sec-butyl, cyclopentadienyl titanium tri Methoxide, cyclopentadienyl titanium triethoxide, cyclopentadienyl titanium triisopropoxide, cyclopentadienyl titanium tributoxide, cyclopentadienyl titanium triphenyl, cyclopentadienyl titanium tri-m-tolyl, cyclo Pentadienyl titanium tri-p-tolyl, cyclopentadienyl titanium tri-m, p-xylyl,

  Cyclopentadienyl titanium tri-4-ethylphenyl, cyclopentadienyl titanium tri-4-hexylphenyl, cyclopentadienyl titanium tri-4-methoxyphenyl, cyclopentadienyl titanium tri-4-ethoxyphenyl, cyclopenta Dienyl titanium triphenoxide, cyclopentadienyl titanium trifluoride, cyclopentadienyl titanium tribromide, cyclopentadienyl titanium trichloride, cyclopentadienyl titanium tribromide, cyclopentadienyl titanium triiodide, cyclopentadi Enyl titanium methyl dichloride, cyclopentadienyl titanium dimethyl chloride,

  Cyclopentadienyl titanium ethoxide dichloride, cyclopentadienyl titanium diethoxide chloride, cyclopentadienyl titanium phenoxide dichloride, cyclopentadienyl titanium diphenoxide chloride, cyclopentadienyl titanium tribenzyl, cyclopentadienyl titanium trichloride -Dimethylamide, cyclopentadienyl titanium tri-diethylamide, cyclopentadienyl titanium tri-diisopropylamide, cyclopentadienyl titanium tri-di-sec-butyramide, cyclopentadienyl titanium tri-di-tert-butyramide, cyclo Pentadienyl titanium tri-ditrimethylsilylamide and the like.

As specific examples of the half titanocene compound used in the present invention, the above-mentioned “cyclopentadienyl” moiety is further replaced with any η-bonded cyclic anion arrangement as described in the specific example of the titanocene compound. A compound having a name formed by replacing the ligand is also included.
Furthermore, the half titanocene compounds listed below are also included.
[(N-tert-butyramide) (tetramethylcyclopentadienyl) -1,2-ethanediyl] titanium dichloride, [(N-tert-butyramide) (tetramethylcyclopentadienyl) dimethylsilane] titanium dichloride, [( N-methylamido) (tetramethylcyclopentadienyl) dimethylsilane] titanium dichloride, [(N-phenylamido) (tetramethylcyclopentadienyl) dimethylsilane] titanium dichloride, [(N-benzylamido) (tetramethylcyclo Pentadienyl) dimethylsilane] titanium dichloride, [(N-tert-butylamide) (cyclopentadienyl) -1,2-ethanediyl] titanium dichloride, [(N-tert-butylamide) (cyclo Ntadienyl) dimethylsilane] titanium dichloride, [(N-methylamido) (cyclopentadienyl) -1,2-ethanediyl] titanium dichloride, [(N-methylamido) (cyclopentadienyl) dimethylsilane] titanium dichloride, [( N-tert-butylamide) (indenyl) dimethylsilane] titanium dichloride, [(N-benzylamido) (indenyl) dimethylsilane] titanium dichloride, and the like.

In addition, compounds having names obtained by replacing the “dichloride” portion of these half titanocene compounds with arbitrary ones listed as titanocene compounds are also included.
These titanocene compounds or half titanocene compounds can be used alone or in combination. Among these, hydrogenation activity is high, and preferred compounds include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium di-m-tolyl, bis (cyclopentadienyl) titanium di-p. -Tolyl.
The titanocene compound or the half titanocene compound is preferable because it can further improve the hydrogenation activity by mixing and reacting with organic lithium, organic magnesium, or organic aluminum.

  As the organic lithium, RLi (wherein R is an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylamide group, an aryl group having 6 to 12 carbon atoms, an allyloxy group or an arylamide group, 7 to 20 carbon atoms) Hydrocarbons selected from the group consisting of alkylaryl groups, alkylallyloxy groups or alkylarylamide groups, arylalkyl groups having 7 to 20 carbon atoms, arylalkoxy groups, arylalkylamide groups, and alkenyl groups having 2 to 20 carbon atoms. Group), and specific examples include methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, methoxylithium, ethoxylithium, isopropoxylithium, butoxy Lithium, dimethylamidolith Lithium, diethylamidolithium, diisopropylamidolithium, dibutylamidolithium, diphenylamidolithium, phenyllithium, m-tolyllithium, p-tolyllithium, xylyllithium, methoxyphenyllithium, phenoxylithium, 4-methylphenoxylithium, 2,6 -Monolithium compounds such as diisopropylphenoxylithium, 2,4,6-triisopropylphenoxylithium and benzyllithium.

Moreover, the oligomer which has terminal living activity which added a small amount of monomers using said monolithium compound as an initiator, for example, polybutadienyl lithium, polyisoprenyl lithium, polystyryl lithium, etc. are mentioned.
Further, a compound having two or more lithium atoms in one molecule, for example, a dilithium compound which is a reaction product of diisopropenylbenzene and sec-butyllithium, divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene. The multilithium compound etc. which are the reaction products of these are also mentioned.
These organolithiums can be used alone or in combination. As addition amount with respect to a titanocene compound or a half titanocene compound, the range of 0.1-10 is preferable at Li / Ti (molar ratio). More preferably, it is the range of 0.2-5.

  Examples of the organic magnesium include dialkyl magnesium and alkyl halogen magnesium represented by Grignard reagent. Specific examples include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, ethyl butyl magnesium, dihexyl magnesium, methyl magnesium bromide, methyl magnesium chloride. Ethyl magnesium bromide, ethyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, hexyl magnesium bromide, cyclohexyl magnesium bromide, phenyl magnesium bromide, phenyl magnesium chloride, allyl magnesium bromide, allyl magnesium chloride and the like.

These organomagnesiums can be used alone or in combination. As addition amount with respect to a titanocene compound or a half titanocene compound, the range of 0.1-10 is preferable at Mg / Ti (molar ratio). More preferably, it is the range of 0.2-5.
Examples of organic aluminum include trialkylaluminum, dialkylaluminum chloride, and alkylmagnesium dichloride. Specific examples include trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum. Dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, diethylethoxyaluminum and the like can be used.

These organoaluminums can be used alone or in combination. As addition amount with respect to a titanocene compound or a half titanocene compound, the range of 0.1-10 is preferable at Al / Ti (molar ratio). More preferably, it is the range of 0.2-5.
Among these combinations, a mixture / reaction product of a titanocene compound and organoaluminum has a particularly high hydrogenation ability and can be suitably used in the present invention. In this case, it is presumed that a metallacycle compound is formed by the titanocene compound and the organoaluminum to form a Teve type complex.
Further, a Tebbe type complex obtained by selecting titanocene dichloride as the titanocene compound and trimethylaluminum as the organoaluminum and mixing and reacting at 1: 2 (molar ratio) has high hydrogenation ability. This TB type complex can be used as it is isolated from the reaction mixture, or the reaction mixture can be used as it is, but the method of using the reaction mixture as it is can eliminate the cumbersome work of isolating it. Is advantageous.

Since this reaction is a relatively slow reaction, it is necessary to take sufficient time. Specifically, a titanocene compound is dispersed or dissolved in an inert solvent, an organoaluminum compound is added, and the mixture is sufficiently stirred and reacted at a temperature of 0 ° C to 100 ° C. If the reaction temperature is too low, it takes too much time. On the other hand, if the reaction temperature is too high, side reactions are liable to occur and the hydrogenation ability decreases. The temperature is preferably 10 ° C to 50 ° C. In addition, since the reaction proceeds in two steps, it is necessary to spend a day or more at room temperature.
In order to further enhance the hydrogenation ability of these titanocene compounds or half titanocene compounds, alcohols, ethers, amines, ketones, phosphorus compounds and the like can be added as the second component or the third component.

Examples of alcohols include methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, phenol, and glycols such as ethylene glycol.
Examples of ethers include alkyl ethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether, and silyl ethers such as bistrimethylsilyl ether. .

Examples of amines include secondary amines such as dimethylamine, diethylamine, diisopropylamine, dibutylamine, diphenylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triphenylamine, N, N, N ′, N′-tetra. And tertiary amines such as methylethylenediamine.
Examples of ketones include dimethyl ketone, diethyl ketone, methyl ethyl ketone, methyl phenyl ketone, and ethyl phenyl ketone.
Examples of the phosphorus compound include compounds capable of coordinating with titanocene, and examples thereof include trimethylphosphine, triethylphosphine, and triphenylphosphine.

These compounds can be used alone or in combination. As addition amount with respect to a titanocene compound or a half titanocene compound, it is the range of 0.01-10 in molar ratio with respect to Ti. Preferably, it is the range of 0.02-5. More preferably, it is the range of 0.02-1.
As the component [B], in addition to the above titanocene compound, a compound containing platinum, palladium, palladium-chromium, nickel, and ruthenium can also be used.
Component [B] is preferably a Tbbe reagent or a Tbbe type complex.
In the present invention, the component [B] may be used for the polymerization after contacting with the component [A] in advance, or may be separately introduced into the polymerization reactor. The amount of each component used and the ratio of the amount used are not particularly limited, but the molar ratio of the metal in component [B] to the transition metal in component [A] is preferably 0.01 to 1000 times, more preferably. 0.1 to 10 moles. When the amount of the component [B] is small, the molecular weight is not improved, and when it is too large, the polymerization activity may be lowered.

  The ultra high molecular weight polyethylene resin composition of the present invention is an ultra high molecular weight polyethylene resin composition having at least two different molecular weights, and is ultra-high molecular weight polyethylene uniformly melted and dispersed from polyethylene polymer powders having two different molecular weights. It is a resin composition. In the ultrahigh molecular weight polyethylene resin composition of the present invention, the ultrahigh molecular weight polyethylene resin (A) and the polyethylene resin (B) are uniformly blended with a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, or the like within the above range. Can also be obtained by continuous multistage polymerization. In the ultrahigh molecular weight polyethylene resin composition of the present invention, a heat stabilizer, a weathering agent, a pigment, a dye, a lubricant, an inorganic filler such as carbon black, talc, glass fiber, etc. You may add in the range which does not impair the objective of this invention.

Next, the crystallization behavior via the hexagonal crystal form when the ultrahigh molecular weight polyethylene stretched molded article of the present invention is obtained by melt stretching will be described.
Wide-angle X-ray diffraction (WAXD) using BL40B2 of Spring8 (Super Photoring-8GeV), a large synchrotron radiation facility in Harima Science Park City, Hyogo Prefecture, as the melt-drawing process for obtaining the ultra-high molecular weight polyethylene stretched molded article of the present invention. ) Image change was performed by in-situ measurement. At that time, it was surprisingly found for the first time that hexagonal (100) h reflection, which is a crystalline form of polyethylene, is strongly expressed under melt drawing. This phenomenon has hardly been reported in the past, or only slight expression has been observed, and it has been observed remarkably only in melt stretching using ultrahigh molecular weight polyethylene that satisfies the conditions of the present invention. Although the cause is not certain, it is presumed that there is some correlation between the expression of the hexagonal (100) h reflection and the entanglement state of the molecular chain of the ultrahigh molecular weight polyethylene in the molten state.

It has also been clarified for the first time that, when the ultrahigh molecular weight polyethylene resin composition of the present invention is used in the stretching process at the time of melting, the stretch ratio is dramatically increased. Although melt drawing was possible with a single ultrahigh molecular weight polyethylene resin, the draw ratio was only about 10 times. When the ultrahigh molecular weight polyethylene resin composition of the present invention was used, the draw ratio was about 1.5. A stretching effect more than doubled was confirmed. In order to obtain a stretched molded product having stronger mechanical properties, the stretch ratio is preferably 11 times or more.
The method for preparing the pre-stretched molded body used when producing the ultra-high molecular weight polyethylene stretch molded body of the present invention is not particularly limited, but once dissolved in a compatible organic solvent, it is cooled and precipitated. And a method of recovering, drying and then melt pressing, or a method of directly melting and molding by a press molding method or the like. Among these, it is preferable to use the former method. For example, a suspension is prepared by uniformly dissolving ultra high molecular weight polyethylene in a liquid organic compound compatible with the ultra high molecular weight polyethylene.

  At this time, specific examples of the liquid organic compound compatible with the ultrahigh molecular weight polyethylene include n-nonane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-octadecane, and liquid paraffin. , Aliphatic hydrocarbon solvents such as kerosene, aromatic carbonization such as xylene, naphthalene, tetralin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene, dodecylbenzene, bicyclohexyl, decalin, methylnaphthalene, ethylnaphthalene Hydrogen solvents or hydrogenated derivatives thereof, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1,2,3-trichloropropane, dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene Halogenated carbonization of etc. Containing solvents, paraffinic process oil, naphthenic process oil, aromatic process oils, mineral oils such as aromatic process oils.

In the case of dissolving in these liquid organic compounds, if the concentration is low, a large amount of liquid organic compound is required to produce the target sheet-like molded product. On the other hand, if the concentration is high, it does not dissolve sufficiently and the entanglement is not uniform. When performing melt drawing, it is preferable that the molecular chains are entangled uniformly. In this way, the ultrahigh molecular weight polyethylene sample is added to the liquid organic compound so as to have a concentration of 0.2 wt%, and dissolved at a boiling point of the solvent for about 10 minutes under a nitrogen stream. In order to prevent the deterioration of the ultra-high molecular weight polyethylene during heating and dissolution, it is desirable to add a so-called general antioxidant such as phenol-based or phosphorus-based.
The suspension thus obtained was slowly cooled and then filtered under reduced pressure to prepare a gel-like mat sample. In order to replace the solvent, it was solidified by dipping in acetone, and then further sufficiently dried under reduced pressure. In order to suppress the extraction of the antioxidant, a predetermined amount of an antioxidant was further added to acetone for solvent replacement. The dry mat thus obtained was sandwiched between polyimide films and subjected to melt press molding at 180 ° C. for 10 minutes at 30 MPa. A method of gradually cooling to room temperature and producing a melt press having a thickness of about 0.7 mm can be exemplified.

[Differential operation calorimeter (DSC) measurement]
The DSC measurement of the produced sheet-like molded body was performed using a Perkin Elmer Pyris1 DSC under a nitrogen atmosphere at a temperature range of 25 ° C. to 180 ° C., a temperature increase rate of 10 ° C./min, and a sample mass of about 5 mg. It was measured.

[Melt stretching measurement]
The sample cut into a dumbbell shape from the sheet-like molded body was set in a high-temperature stretching apparatus and stretched. At this time, if the temperature of the entire stretched portion was controlled, the stretched portion was directly heated with a heat gun so that only the stretched portion had a constant temperature because breakage and stretching occurred from the chuck portion. It was confirmed in advance that the temperature of the stretched portion of the dumbbell had reached a predetermined temperature by a thermocouple. The stretching temperature at this time was 155 ° C., held for 5 minutes, and then melt-stretched under the conditions of a stretching speed of 24 mm / min and an initial sample length of 23 mm. In the melt drawing process, the drawing stress was simultaneously measured with a load cell (50N) manufactured by Kyowa Denki Co., Ltd. attached to a drawing device.
When the change in the crystal structure during the melt drawing process was measured by WAXD, a strong peak of hexagonal (100) h reflection was primarily confirmed in ultrahigh molecular weight polyethylene that can be melt drawn at 155 ° C. The ultra-high molecular weight polyethylene having a low molecular weight, which is considered to have little entanglement, appears when it is melt-drawn under a low temperature condition of, for example, 150 ° C., but the strength is low and sufficient drawing cannot be performed. The expression of the hexagonal (100) h reflection is presumed to have a certain degree of correlation with the entanglement of the ultra-high molecular weight polyethylene chain at the time of melting. In the case of low, the molecular chain was not sufficiently entangled at the time of melting, and could not be melt-stretched at a high temperature.

[In-situ measurement]
In-situ measurement was performed at BL40B2 of Spring 8, a large synchrotron radiation facility in Harima Science Park City, Hyogo Prefecture.
[Wide-angle X-ray diffraction measurement: WAXD]
The above high-temperature stretching apparatus was laid on BL40B2, and the wide-angle X-ray diffraction (WAXD) image change in the melt stretching process was performed under the conditions of a wavelength of 1 mm, an exposure time of 1.0 second, and an interval for data storage of about 5.5 seconds. Recording was performed using a CCD camera C4480 manufactured by Hamamatsu Photonics Co., Ltd.

[Solution viscosity measurement]
20 ml of decalin was charged with 20 mg of polymer and stirred at 150 ° C. for 2 hours to dissolve the polymer. The dropping time (t _s ) between the marked lines was measured using a Ubbelohde type viscometer with the solution at a high temperature of 135 ° C. Incidentally, not putting the polymer as a blank was measured drop time of only decahydronaphthalene a (t _b). The specific viscosity (η _sp / C) of the polymer was plotted according to the following formula, and the intrinsic viscosity (η) extrapolated to a concentration of 0 was determined.
_{η sp / C = (t s} / t b -1) /0.1
From this intrinsic viscosity (η), the viscosity average molecular weight (Mv) was determined according to the following formula.
Mv = 5.34 × 10 ⁴ η ^1.49

[Ultra high molecular weight polyethylene polymer raw material]
There is no restriction | limiting in particular as said ultra high molecular weight polyethylene polymer raw material, All the well-known raw materials used as a raw material of various polyethylene molded objects are mentioned. The raw material for the ultrahigh molecular weight polyethylene polymer may be granular, powder, pellet, or molded product, and among these, powder is particularly preferable. The particle diameter of the polyethylene polymer raw material is preferably 2000 μm or less, more preferably 1 to 2000 μm, still more preferably 10 to 1000 μm in terms of volume average particle diameter (D50). Further, in handling the conventional ultra high molecular weight polyethylene, preferably 0.20~0.50g / cm ³ as bulk specific gravity (B. D.), more preferably 0.30~0.50g / cm ^3. The particle size distribution of the ultra-high molecular weight polyethylene polymer raw material is desirably narrow in view of excellent uniformity of the obtained ultra-high molecular weight polyethylene stretch-formed product.
The melt stretching temperature of 155 ° C. is sufficiently higher than the melting point of the sheet-shaped molded body before stretching, and it is necessary that the sheet-shaped molded body is completely melted during melt stretching. In order to confirm the melting state of the sample at the time of stretching, when measured with a differential scanning calorimeter (DSC), the peak of the DSC curve in the range from 134 ° C to 136 ° C, that is, the melting point (Tm), In any case, it was confirmed that the melt was completely melted at 155 ° C. which is the melt stretching condition.

EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples unless it exceeds the gist.
[Example 1]
a) Component The ultrahigh molecular weight polyethylene of the present invention can be polymerized by, for example, the method described in Japanese Patent Application No. 2003-272830 to obtain a powdery polymer.
(Ethylene polymerization)
Isobutane, ethylene, hydrogen, a metallocene catalyst and a Tebbe reagent were continuously fed to a Bessel polymerization reactor equipped with a stirrer to produce polyethylene at a rate of 10 kg / Hr. Hydrogen having a purity of 99.99 mol% or more purified by contact with molecular sieves was used. Metallocene catalysts include [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene and bis (hydrogenated tallow alkyl) methylammonium tris (penta A mixture of fluorophenyl) (4-hydroxyphenyl) borate and triethylaluminum supported on silica treated with triethylaluminum was used. Isobutane as a solvent was supplied at 32 L / Hr. The metallocene-based catalyst was supplied with the solvent isobutane as a transfer liquid and hydrogen 10 NL / Hr (NL is Normal Liter) so that the production rate was 10 kg / Hr. The Tebbe reagent was prepared by stirring a 30 wt% hexane suspension of titanocene dichloride made by Wako Pure Chemical Industries, Ltd. and 60 mmol of a 1M hexane solution of trimethylaluminum at room temperature for 100 hours.

The obtained Tebbe reagent concentration was 11 μmol / L by a line different from the metallocene catalyst, the polymerization temperature was 65 ° C., and the polymerization pressure was 17 K / G. The polymerization slurry was continuously withdrawn so that the level of the polymerization reactor was kept constant, and the withdrawn slurry was sent to the drying process. There was no presence of bulk polymer, and the slurry removal piping was not blocked, and stable continuous operation was possible. The catalytic activity was 5400 g PE / g catalyst. The average molecular weight determined from the intrinsic viscosity of the thus obtained polyethylene in decalin (135 ° C.) was 10.66 million.
b) The polymerization temperature is 65 ° C., the polymerization pressure is 20 K / G, the metallocene catalyst is the above-mentioned solvent isobutane as a transfer liquid, hydrogen 2 NL / Hr (NL is Normal Liter), and the production rate is 10 kg / Hr. Example 1a) was carried out except that Also in this case, no bulk polymer was produced, and the slurry removal piping was not blocked, and the continuous operation was stable. The catalytic activity was 1400 g PE / g catalyst. The average molecular weight determined from the intrinsic viscosity of the obtained polyethylene in decalin (135 ° C.) was 1.73 million.
25 parts by mass of component a) and 75 parts by mass of component b) obtained here were once dissolved in a compatible organic solvent, cooled and precipitated, recovered, dried, and then melt pressed. A shaped compact was produced. When this sheet-like molded body was stretched at 155 ° C., a diffraction image of (100) h reflection derived from hexagonal crystals was obtained in the melt stretching process. The draw ratio at this time was 18.2 times.

[Example 2]
A molded body was obtained by the same sample preparation method as in Example 1 except that 50 parts by mass of component a) obtained in Example 1 and 50 parts by mass of component b) were obtained. When this sheet-like molded body was stretched at 155 ° C., a diffraction image of (100) h reflection derived from hexagonal crystals was obtained in the melt stretching process. The draw ratio at this time was 27.0 times.

[Example 3]
A molded body was obtained by the same sample preparation method as in Example 1 except that 75 parts by mass of the component obtained in Example 1a) and 25 parts by mass of component b) were used. When this sheet-like molded body was stretched at 155 ° C., a diffraction image of (100) h reflection derived from hexagonal crystals was obtained in the melt stretching process. The draw ratio at this time was 23.0 times.

[Comparative Example 1]
When a sheet-like molded body was prepared from the ultrahigh molecular weight polyethylene having a viscosity-average molecular weight of 10.660 million polymerized in Example 1 by the method described in Example 1 and melted and stretched at 155 ° C., it was uniform. A stretched molded article was obtained. The peak integrated intensity value of the diffraction pattern of the hexagonal (100) h reflection at this time is 1800 arb. The unit showed a very strong peak, but it was broken at a draw ratio of 10.5.

[Comparative Example 2]
When a sheet-like molded article was prepared from the ultrahigh molecular weight polyethylene having a viscosity average molecular weight of 1.73 million polymerized in Example 1 by the method described in Example 1 and melt stretched at 155 ° C., At this temperature, melt drawing could not be performed.

[Comparative Example 3]
The concentration of the Tebbe reagent is 0.3 μmol / L, the polymerization temperature is 70 ° C., the polymerization pressure is 20 K / G, the metallocene catalyst is the above-mentioned solvent isobutane as a transfer liquid, and hydrogen 4 NL / Hr (NL is Normal Liter), The same operation as in Example 1 was conducted except that the production rate was 10 kg / Hr. Also in this case, no bulk polymer was produced, and the slurry removal piping was not blocked, and the continuous operation was stable. The catalytic activity was 7500 g PE / g catalyst. The average molecular weight calculated | required from the intrinsic viscosity in the decalin (135 degreeC) of the obtained polyethylene was 5.11 million. When the obtained ultra-high molecular weight polyethylene was melt-drawn at 155 ° C., it was able to be drawn, but it was thinly stretched locally to form a uniform stretch.
Although the viscosity average molecular weight was higher than that of the composition obtained in Example 1, the viscosity average molecular weight could not be stretched at the above temperature. The results of Examples and Comparative Examples are shown in Table 1.

  Since the ultra high molecular weight polyethylene of the present invention is excellent in wear resistance and strength, sliding members such as gears, bearing members, artificial joint substitutes, ski sliding surfaces, abrasives, slips of various magnetic tapes It can be suitably used in the fields of sheets, flexible disk liners, bulletproof members, battery separators, various filters, foams, films, pipes, fibers, threads, fishing lines, cutting boards and the like.

Claims (6)

An ultrahigh molecular weight polyethylene resin composition comprising an ultrahigh molecular weight polyethylene resin (A) polymerized by a metallocene-based catalyst and a polyethylene resin (B) and having a viscosity average molecular weight of 1,000,000 or more. (A) is an ultrahigh molecular weight polyethylene resin having a viscosity average molecular weight (Mv) of 6 million to 12 million determined from the following formula (1) from the intrinsic viscosity in decalin at 135 ° C., and the polyethylene resin (B): The ratio of the viscosity average molecular weight of the polyethylene resin (B) to the viscosity average molecular weight of the ultra high molecular weight polyethylene resin (A) satisfies the following formula (2), and the ultra high molecular polyethylene resin (A) and the polyethylene resin: The ultra-high molecular weight polyester having a mass ratio to (B) in the range of 5:95 to 95: 5 parts by mass Ren resin composition.
^{Mv = 5.34 × 10 4 [η} ] -1.49 formula (1)
Mv (A) / Mv (B)> 1 Formula (2) The ultrahigh molecular weight polyethylene resin composition according to claim 1, wherein the polyethylene resin (B) has a viscosity average molecular weight of not less than 1 million determined from an intrinsic viscosity at 135 ° C. in decalin. After uniformly dissolving the liquid organic compound compatible with the ultrahigh molecular weight polyethylene resin composition, a dry mat is produced from the obtained suspension, and further a sheet-like molded body is produced by melt press molding, The ultrahigh molecular weight polyethylene resin composition according to claim 1, wherein the ultrahigh molecular weight polyethylene resin composition can be melt-drawn in an atmosphere at a temperature of 155 ° C. or higher. 4. The ultrahigh molecular weight according to claim 1, wherein the sheet-like molded product passes through a hexagonal crystal form, which is one of polyethylene crystal forms, during melt drawing in a high temperature atmosphere of 155 ° C. or higher. Polyethylene resin composition. The ultrahigh molecular weight polyethylene resin composition according to claim 1, wherein when the sheet-like molded body is melt-drawn in a high temperature atmosphere of 155 ° C. or higher, the draw ratio is 11 times or more. An ultrahigh molecular weight polyethylene molded article comprising the ultrahigh molecular weight polyethylene resin composition according to claim 1.