JP2005029731A - Ultrahigh molecular weight polyethylene - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultrahigh molecular weight polyethylene excellent in the balance of abrasion characteristic, mechanical property, and molding property, and low in density compared with the current ultrahigh molecular weight polyethylene, and excellent in flexibility. <P>SOLUTION: This ultrahigh molecular weight polyethylene is obtained using a metallocene catalyst, and has a viscosity average molecular weight (Mv) of not smaller than 2 million and the ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) measured by the GPC method of larger than 3. <P>COPYRIGHT: (C)2005,JPO&amp;NCIPI

Description

  The present invention relates to an ultrahigh molecular weight polyethylene obtained by using a metallocene-based catalyst, and a molded product and a fiber obtained using the same. Specifically, it is obtained using a metallocene catalyst, the viscosity average molecular weight (Mv) is 2 million or more, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is greater than 3. The present invention relates to a flexible ultra-high molecular weight polyethylene having excellent wear characteristics, mechanical properties and molding processability, having a lower density than conventional ultra-high molecular weight polyethylene, and a molded article and fiber thereof.

  Conventionally, ultra-high molecular weight polyolefin, especially ultra-high molecular weight polyethylene, is superior in impact resistance, wear resistance, slidability, and chemical resistance compared to general-purpose polyethylene of 1 million or less. Molding of sliding parts, etc. Can be used as a body. Further, by spinning, an ultrahigh molecular weight polyethylene fiber having high strength and high rigidity can be obtained. However, the ultra-high molecular weight polyethylene obtained by a normal Ziegler-Natta catalyst has a wide molecular weight distribution (Mw / Mn), and the ultra-high molecular weight component contained therein makes the molding processability of the molded product difficult. On the other hand, although the low molecular weight component contributes to the improvement of molding processability, it lowers mechanical properties such as impact resistance and wear resistance and promotes deterioration in chemical resistance. In addition, even when a fiber is used, the number of molecular chain ends (concentration) increases, which inhibits crystallization and lowers the strength of the fiber.

  For the purpose of improving these, Patent Document 1 proposes an ultrahigh molecular weight ethylene (co) polymer having a Mw / Mn of 3 or less using a metallocene catalyst, but the Mw / Mn is decreased. As a result, the low molecular weight component contributing to the molding processability is also reduced, and the molding processability of the molded body is lowered, and the compression press molding time is increased. Furthermore, since the obtained molded body is too hard and lacks flexibility, there are problems such as difficulty in bending and difficulty in forming a complicated shape. In addition, there is also a problem that it takes too much time to dissolve and disperse in a solvent in the spinning process even when the fiber is used.

  On the other hand, it is known that when an ethylene polymer is produced using a metallocene catalyst, an ethylene polymer having a high activity and a narrow molecular weight distribution can be obtained. However, in general, in the polymerization using a metallocene catalyst having a high initial polymerization rate, a rapid polymerization reaction occurs when the catalyst and ethylene come into contact with each other, and heat removal cannot catch up. Sites (heat spots) are generated, and as a result, a part of the particulate polymer has a melting point or higher, and the polymers are fused together to form a bulk polymer. In the case of a continuous process, when such a bulk polymer is generated, the polymer extraction pipe from the polymerization reactor is blocked, so that the polymer cannot be extracted and the continuous operation is hindered.

  In order to solve the above problem, Patent Document 2 and Patent Document 3 describe a method for producing an ethylene polymer, wherein a metallocene catalyst is previously brought into contact with hydrogen and then introduced into a polymerization reactor. However, since hydrogen, which is a chain transfer agent, is used, there is a limit to the molecular weight of the ethylene-based polymer obtained in this case, and it has not been possible to stably obtain ultrahigh molecular weight polyethylene.

JP 09-291112 A JP 2000-198804 A JP 2001-302716 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an ultrahigh molecular weight polyethylene excellent in the balance of wear characteristics, mechanical properties and molding processability and excellent in flexibility.

As a result of intensive studies to solve the above problems, the present inventors have found that an ultra-high molecular weight polyethylene having a molecular weight distribution larger than 3 cannot be obtained with a normal metallocene catalyst, and a molecular weight distribution when a specific metallocene catalyst is used. However, if the molecular weight is increased to 2 million or more, a bulk polymer is generated in the polymerization reactor and cannot be stably operated continuously. In the ultrahigh molecular weight polyethylene obtained by the Ziegler-Natta system, Although the molecular weight distribution could not be reduced to 10 or less, by combining a specific metallocene catalyst and a compound having hydrogenation ability, an ultra-high molecular weight polyethylene having a moderately wide molecular weight distribution was obtained, and it was efficient in industrial processes. Can be manufactured stably at a reasonable temperature without producing bulk polymer, and its ultra-high molecular weight Riechiren wear properties, mechanical properties, excellent balance of moldability, found that excellent in flexibility, leading to completion of the present invention.
That is, the present invention is as follows.

(1) Powdered polyethylene obtained by using a metallocene catalyst, having a viscosity average molecular weight (Mv) of 2 million or more, and a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Ultra high molecular weight polyethylene characterized in that Mn) is greater than 3.
(2) The ultrahigh molecular weight polyethylene as described in (1) above, wherein the relationship between density (ρ (g / cc)) and viscosity average molecular weight (Mv) satisfies the following formula (a).
ρ ≦ −9 × 10 ⁻¹⁰ × Mv + 0.937 (a)

(3) The density (ρ (g / cc)) is in the range of 0.915 or more, and the relationship between the density and the crystallinity (X (%)) satisfies the following formula (b): The ultra high molecular weight polyethylene according to any one of (1) to (2).
100X <630ρ−530 (b)
(4) The ultrahigh molecular weight polyethylene according to any one of (1) to (3) above, wherein the amount of terminal vinyl groups is 0.02 (ke / 1000C) or less.

(5) The ultra high molecular weight polyethylene according to any one of the above (1) to (4), wherein the residual Ti amount is 3 ppm or less and the residual Cl amount is 5 ppm or less.
(6) The ultra-high metal according to any one of (1) to (5) above, wherein the metallocene-based catalyst is formed using a compound represented by the following formula (c): Molecular weight polyethylene.
L _j W _k MX _p X ′ _q (c)

(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 metallacycle. 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)

(7) The ultrahigh metal according to any one of (1) to (6) above, wherein the metallocene catalyst is formed using a compound represented by the following formula (d): Molecular weight polyethylene.
[LH] ^{d +} [M _m Q _p ] ^d- (d)
(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 .)

(8) Any one of the above (1) to (7), which is obtained using [A] a metallocene catalyst previously brought into contact with a hydrogenating agent and [B] a compound having hydrogenation ability. The ultra high molecular weight polyethylene described.
(9) The hydrogenating agent is hydrogen and 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, the number of carbon atoms) 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. The ultra-high molecular weight polyethylene according to (8), characterized in that it is characterized.

  (10) The reaction mixture of a titanocene compound or a half titanocene compound alone, or one or more organic metal compounds selected from organic lithium, organic magnesium, and organic aluminum and a titanocene compound or a half titanocene compound. The ultrahigh molecular weight polyethylene according to any one of (8) to (9) above, wherein

(11) The ultrahigh molecular weight polyethylene as described in (10) above, wherein the titanocene compound or the half titanocene compound is a compound represented by the following formula (e):
L _j W _k TiX _p X ′ _q (e)
(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)

(12) A molded product obtained from the ultrahigh molecular weight polyethylene according to any one of (1) to (11).
(13) A fiber obtained from the ultrahigh molecular weight polyethylene according to any one of (1) to (11).

  The ultrahigh molecular weight ethylene polymer of the present invention has a viscosity average molecular weight (Mv) of 2 million or more, a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn) is larger than 3, It has an excellent balance of properties, mechanical properties and molding processability, has a density and crystallinity lower than conventional ultrahigh molecular weight polyethylene, and has excellent flexibility. Furthermore, even in an industrial process, it can be stably and continuously manufactured over a long period of time in an efficient temperature range.

The present invention will be specifically described below.
First, the specific aspect of ultra high molecular weight polyethylene is demonstrated. The ultra high molecular weight polyethylene of the present invention can be produced by homopolymerizing ethylene by suspension polymerization or gas phase polymerization.
In the suspension polymerization method, an inert hydrocarbon medium can be used as a medium, and the olefin itself can also be used as a solvent.

  Specific examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. And alicyclic hydrocarbons such as benzene, toluene, xylene and the like; halogenated hydrocarbons such as ethyl chloride, chlorobenzene and dichloromethane, and mixtures thereof.

The polymerization temperature in the present invention is usually preferably 60 ° C. or higher, more preferably 70 ° C. or higher and 150 ° C. or lower, more preferably 100 ° C. or lower.
The polymerization pressure is usually preferably from normal pressure to 10 MPa, more preferably from 0.2 to 5 MPa, and even more preferably from 0.5 to 3 MPa. The polymerization reaction may be batch, semi-continuous or continuous. Any method can be used.

  It is also possible to carry out the polymerization in two or more stages having different reaction conditions. Furthermore, as described in, for example, West German Patent Publication No. 3127133, the molecular weight of the resulting olefin polymer is adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. You can also In addition, in this invention, the other component useful for manufacture of ultra high molecular weight polyethylene other than each above components can be included.

The viscosity average molecular weight (Mv) of the ultrahigh molecular weight polyethylene of the present invention is determined by dissolving the ultrahigh molecular weight polyethylene in decalin at different concentrations and extrapolating the solution viscosity obtained at 135 ° C. to a concentration of 0 (η (Dl / g)) can be obtained by the following equation.
Mv = 5.34 × 10 ⁴ η ^1.49
The viscosity average molecular weight of the ultrahigh molecular weight polyethylene of the present invention determined from this formula is usually 2 million or more, preferably 5 million or more. Ultra high molecular weight polyethylene with a viscosity average molecular weight exceeding 2 million is excellent in abrasion resistance and strength, so sliding members such as gears, bearing members, artificial joint substitutes, ski sliding surfaces, abrasives, Features such as slip sheets for various magnetic tapes, flexible disk liners, bulletproof members, battery separators, various filters, foams, films, pipes, fibers, threads, fishing lines, cutting boards, etc. Have.

  The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ultrahigh molecular weight polyethylene of the present invention can be determined by GPC measurement. In the case of a polymer having a normal molecular weight range, about 20 mg of polymer is dissolved in 15 ml of a solvent (trichlorobenzene) and measured at 140 ° C., but in the case of the ultrahigh molecular weight polyethylene of the present invention, the solution viscosity is too high. Therefore, about 2 mg of polymer was dissolved in 15 ml of solvent and measured. The Mw / Mn of the ultrahigh molecular weight polyethylene of the present invention determined by this method is greater than 3 and 10 or less, preferably 3.8 or more and 8 or less.

Further, the density (ρ (g / cc)) of the ultrahigh molecular weight polyethylene of the present invention measured according to ASTM D1505 is 0.915 or more and 0.935 or less, preferably 0.930 or less. Thus, the ultrahigh molecular weight polyethylene of the present invention has a low density without introducing a comonomer, and a flexible molded article or fiber can be obtained. Moreover, since it is not necessary to introduce a comonomer, the polymerization activity does not decrease and high activity can be maintained.
Further, in the density (ρ (g / cc)) range of the ultrahigh molecular weight polyethylene defined above, the density (ρ (g / cc)) and the viscosity average molecular weight (Mv) satisfy the following relational expression.
ρ ≦ −9 × 10 ⁻¹⁰ × Mv + 0.9339

The crystallinity (X (%)) of the ultrahigh molecular weight polyethylene of the present invention was determined by DSC measurement. The sample was held at 50 ° C. for 1 minute, then heated to 180 ° C. at a rate of 200 ° C./minute, and held at 180 ° C. for 5 minutes. The temperature was further decreased to 50 ° C. at 10 ° C./min. After holding at 50 ° C. for 5 minutes, the temperature is raised to 180 ° C. at 10 ° C./min. In the melting curve obtained at that time, the baseline is drawn from 60 ° C. to 145 ° C. and the melting enthalpy (ΔH (J / g)) is obtained. Asked. The crystallinity (X (%)) of the ultrahigh molecular weight polyethylene of the present invention can be determined from this melting enthalpy using the following equation.
X = ΔH × 100/293

Further, the crystallinity (X (%)) of the ultrahigh molecular weight polyethylene of the present invention determined as described above and the density (ρ (g / cc)) satisfy the following relational expression.
100X <630ρ−530
Such a low crystallinity is a characteristic of the ultrahigh molecular weight polyethylene of the present invention and is a characteristic that can be clearly distinguished from a known ultrahigh molecular weight ethylene copolymer. With this low crystallinity, ultrahigh molecular weight polyethylene excellent in flexibility can be obtained.

The amount of terminal vinyl groups of the ultrahigh molecular weight polyethylene of the present invention can be determined by measuring the infrared absorption spectrum (IR) of the ultrahigh molecular weight polyethylene film, and the vinyl group content is the absorbance at the peak of 910 cm ⁻¹ (ΔA). And the thickness of the film (t (mm)) according to the following formula.
Amount of vinyl group (pieces / 1000 C) = 0.98 × ΔA / t

  The amount is 0.02 or less per 1000 carbons, preferably 0.005 or less. When there are many vinyl groups, it becomes difficult to produce ultra high molecular weight polyethylene. In other words, when this catalyst that easily generates terminal vinyl groups is used, unless the polymerization temperature is lowered to suppress the formation of terminal vinyl groups, sufficiently ultra-high molecular weight polyethylene cannot be obtained, and the polymerization activity also decreases. It is not preferable. In such a case, the molecular weight must be controlled by a small amount of hydrogen, and stable production is difficult from the viewpoint of manufacturing operation.

  The amount of Ti and the amount of Cl remaining in the ultrahigh molecular weight polyethylene of the present invention can be quantified by fluorescent X-rays or ICP (ion coupling plasma), and the remaining amounts are very small, 3 ppm or less and 5 ppm or less, respectively. Preferably, the residual Ti amount is 0.8 ppm or less, and the residual Cl amount is 3 ppm or less. Since the catalyst is highly active, the catalyst residue is small, and since a catalyst containing no Cl is used, an ultrahigh molecular weight polyethylene substantially free of Cl can be obtained.

As described above, the ultrahigh molecular weight polyethylene of the present invention containing no catalyst residue or Cl has high thermal stability, and the addition amount of an antioxidant or the like can be reduced or may not be required.
Next, the metallocene catalyst used in the present invention can form at least a) a transition metal compound having a cyclic η-bonding anion ligand and b) a complex that exhibits catalytic activity by reacting with the transition metal compound. It consists of two catalyst components of an activator.

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 (1).
L _j W _k MX _p X ′ _q (1)
(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 (1) 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 (1) 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 (1) (where j = 1).
Preferable examples of the compound represented by the formula (1) (where j = 1) include compounds represented by the following formula (3).

(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, dichlorodibenzonitrile palladium, dichlorodiacetonitrile palladium, dichloro (1,2-bisdiphenylphosphinoethane) palladium, bistri Phenylphosphine palladium bistetrafluoroborate, bis (2,2′-bipyridine) methyliron 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 (3)) 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 (2).
[LH] ^{d +} [M _m Q _p ] ^d- (2)
(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) Le) (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 (pentafluorophenyl) (4-hydroxy- Examples include cyclohexyl) borate, tris (pentafluorophenyl) (4- (4′-hydroxyphenyl) phenyl) borate, tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) 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 (4) 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 (5), 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 methylalumoxane containing a unit represented by the following formula (6), for example.

(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 elements of Group 2 or Group 13 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 (7).

(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 (7). 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, Diethyl silane, di-n-butyl silane, dioctyl silane, dioctadecyl silane, diphenyl silane, dibenzyl silane, ethenyl silane, 3-butenyl silane, 5-hexenyl silane, cyclohexenyl silane, 7-octenyl silane, 17-octadecenyl silane, Etc., 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.

  As a method for adding a hydrogenating agent to the catalyst transfer medium, for example, a hydrogenating agent supply line is connected to a catalyst transfer line provided for introducing the catalyst into the polymerization reactor, and the hydrogenating agent is added. By supplying to the line, a method for causing the medium to contain a hydrogenating agent, or a catalyst supply nozzle provided in the polymerization reactor for introducing a catalyst into the polymerization reactor, a hydrogenating agent supply line is provided. 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, for example, by the following general formula (8).

L _j W _k TiX _p X ′ _q (8)
(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 (cyclopentadienyl) titanium di-4 -Ethoxyphenyl, bis (cyclopentadienyl) titanium diphenoxide, bis (cyclopentadienyl) titanium difluoride, bis (cyclopentadienyl) titanium dibromide, bis (cyclopentadienyl) titanium dichloride, bis ( Cyclopentadienyl) tita Um dibromide, bis (cyclopentadienyl) titanium diiodide, bis (cyclopentadienyl) titanium chloride methyl,

  Bis (cyclopentadienyl) titanium chloride ethoxide, bis (cyclopentadienyl) titanium chloride phenoxide, bis (cyclopentadienyl) titanium dibenzyl, bis (cyclopentadienyl) titanium di-dimethylamide, bis (cyclo Pentadienyl) titanium di-diethylamide, bis (cyclopentadienyl) titanium di-diisopropylamide, bis (cyclopentadienyl) titanium di-sec-butylamide, bis (cyclopentadienyl) titanium di-di- tert-Butylamide, bis (cyclopentadienyl) 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.

  Furthermore, 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, (cyclopentadienyl) (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride, (pentamethylcyclopentadienyl) (1,3-bistrimethylsilylcyclopentadi Enyl) titanium dichloride, (fluorenyl) (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride, (indenyl) (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride, (tetrahydroindenyl) (1,3 -Bistrimethylsilylcyclopentadienyl) titanium dichloride and the like. 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, silylenebis (cyclopentadienyl) titanium dichloride, dimethyldimethylenebis (cyclopenta) Dienyl) titanium dichloride, dimethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (methylcycline) Pentadienyl) titanium dichloride, dimethylsilylene bis (trimethylsilyl cyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride,

  Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetra Methylcyclopentadienyl) (cyclopentadienyl) titanium dichloride, dimethylsilylene (fluorenyl) (indenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (trimethylsilylcyclopentadienyl) titanium dichloride, dimethylsilylene (tetra Methylcyclopentadienyl) (3,5-bistrimethylsilylcyclopentadienyl) titanium dichlora , Dimethylsilylene (cyclopentadienyl) (trimethylsilylcyclopentadienyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-bistrimethylsilylcyclopentadienyl) titanium dichloride, dimethylsilylene (fluorenyl) (Trimethylsilylcyclopentadienyl) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-bistrimethylsilylcyclopentadienyl) 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-ethyl phen Nyl, cyclopentadienyl titanium tri-4-hexylphenyl, cyclopentadienyl titanium tri-4-methoxyphenyl,

  Cyclopentadienyl titanium tri-4-ethoxyphenyl, cyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium trifluoride, cyclopentadienyl titanium tribromide, cyclopentadienyl titanium trichloride, cyclopentadienyl titanium trichloride Bromide, cyclopentadienyl titanium triiodide, cyclopentadienyl titanium methyl dichloride, cyclopentadienyl titanium dimethyl chloride, cyclopentadienyl titanium ethoxide dichloride, cyclopentadienyl titanium diethoxide chloride, cyclopentadienyl Titanium phenoxide dichloride, cyclopentadienyl titanium diphenoxide chloride, Lopentadienyl titanium tribenzyl, cyclopentadienyl titanium tri-dimethylamide, cyclopentadienyl titanium tri-diethylamide, cyclopentadienyl titanium tri-diisopropylamide, cyclopentadienyl titanium tri-di-sec-butylamide, Cyclopentadienyl titanium tri-di-tert-butyramide, cyclopentadienyl 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, alkylaryloxy 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 may be used as it is isolated from the reaction mixture or the reaction mixture may be used as it is, but the method of using the reaction mixture as it is can eliminate the troublesome work of isolating the industrial process. 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 is lowered.

The ultra high molecular weight polyethylene of the present invention can be molded using the same molding method as that of a normal ultra high molecular weight polyethylene. For example, the ultrahigh molecular weight polyethylene powder of the present invention can be obtained by various known molding methods such as a method in which ultra high molecular weight polyethylene powder is placed in a mold and compression-molded with heating for a long time or extrusion molding with a ram extruder. .
Alternatively, the ultrahigh molecular weight polyethylene powder of the present invention can be dissolved or mixed in an appropriate solvent or plasticizer to prepare a gel mixture, and ultrahigh elastic modulus and high strength fibers can be obtained by a known gel spinning technique.

The present invention will be described based on examples.
[Measurement of Mw / Mn]
Waters 150-C, ALC / GPC, Shodex AT-807S and Tosoh TSK-gelGMH-H16 were used in series as a column, and the solvent was measured at 140 ° C. using trichlorobenzene containing 10 ppm Irganox 1010 as a solvent. . A calibration curve was prepared using commercially available monodisperse polystyrene as a standard substance.

[Measurement of viscosity average molecular weight]
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

[Density measurement]
Measured according to ASTM D1505. As a test piece, a section cut from a press sheet was annealed at 120 ° C. for 1 hour and then cooled to room temperature over 1 hour.

[Measurement of crystallinity]
Using a differential scanning calorimeter [DSC7 manufactured by Perkin Elmer Co., Ltd.], held at 50 ° C. for 1 minute, heated to 180 ° C. at a rate of 200 ° C./min, held at 180 ° C. for 5 minutes, then 10 ° C. The temperature was lowered to 50 ° C./min. After maintaining at 50 ° C. for 5 minutes, the temperature was raised to 180 ° C. at 10 ° C./min, and in the melting curve obtained at that time, a baseline was drawn from 60 ° C. to 145 ° C. to determine melting enthalpy (J / g). A value obtained by dividing this by 293 (J / g) and multiplying by 100 was taken as the crystallinity (%).

[Measurement of terminal vinyl group content]
Ultra high molecular weight polyethylene powder was pressed at 180 ° C. to prepare a film. The infrared absorption spectrum (IR) of this film was measured using an apparatus of FT-IR5300A manufactured by JASCO Corporation. The vinyl group was calculated from the absorbance at the peak of 910 cm ⁻¹ (ΔA) and the film thickness (t (mm)) according to the following formula.
Amount of vinyl group (pieces / 1000 C) = 0.98 × ΔA / t

[Measurement of amount of residual Ti and Cl]
An appropriate amount of ultra-high molecular weight polyethylene powder was sampled and decomposed by adding nitric acid. A measurement sample was prepared by adding pure to this decomposition product. A commercially available standard solution for atomic absorption analysis was diluted with an aqueous nitric acid solution and used as a standard solution. ICP measurement was carried out using a device of JY138 manufactured by Rigaku.

[Calculation formula for calculated value 1]
The calculated value 1 was obtained from the viscosity average molecular weight Mv by the following formula.
Calculated value 1 = −9 × 10 ⁻¹⁰ × Mv + 0.937
[Calculation formula for calculated value 2]
The calculated value 2 was obtained from the above density ρ by the following formula.

[Example 1]
(Preparation of component [B])
A 3 wt% hexane suspension of 30 mmol titanocene dichloride manufactured by Wako Pure Chemical Industries, Ltd. and 60 mmol of a 1M hexane solution of trimethylaluminum were stirred at room temperature for 100 hours to prepare a Tebbe reagent.

(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 supplied at 0.13 mmol / Hr by a separate line from the metallocene catalyst. 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 5000 g PE / g catalyst. The polyethylene thus obtained had an average molecular weight of 9.2 million, a density of 0.9272 g / cc, and a crystallinity of 46%, as determined from the intrinsic viscosity in decalin (135 ° C.). Table 1 includes other values.

[Example 2]
The same procedure as in Example 1 was performed except that the Tube reagent was supplied at 0.013 mmol / 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 obtained polyethylene had an average molecular weight of 2.1 million, a density of 0.9300 g / cc, and a crystallinity of 52%, as determined from the intrinsic viscosity in decalin (135 ° C.). Table 1 includes other values.

[Example 3]
The same procedure as in Example 1 was performed except that the Tube reagent was supplied at 0.38 mmol / 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 obtained polyethylene had an average molecular weight of 11 million, a density of 0.9235 g / cc, and a crystallinity of 42%, as determined from the intrinsic viscosity in decalin (135 ° C.). Table 1 includes other values.

[Example 4]
The same procedure as in Example 1 was performed except that the Tube reagent was supplied at 0.038 mmol / 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 obtained polyethylene had an average molecular weight of 4.4 million, a density of 0.9275 g / cc, and a crystallinity of 48%, as determined from the intrinsic viscosity in decalin (135 ° C.). Table 1 includes other values.

[Comparative Example 1]
In Example 1, instead of the metallocene catalyst, ethylene was polymerized in the same manner as in Example 1 except that a Ziegler catalyst prepared according to the method described in Japanese Patent Publication No. 52-36788 was used. The catalytic activity was 7000 g PE / g catalyst. The resulting polyethylene had a viscosity average molecular weight of 2 million, a density of 0.939 g / cc, and a crystallinity of 64%, as determined from the intrinsic viscosity in decalin (135 ° C.). Table 1 includes other values.

[Comparative Example 2]
In Example 1, a metallocene catalyst prepared according to the method described in Example 1 of JP-A No. 09-291112 was used as the metallocene catalyst, and ethylene was polymerized without feeding the Teve reagent. The obtained polyethylene did not have an ultrahigh molecular weight, and the Melt Index value measured at 190 ° C. under a load of 2.16 kg was 1.0 g / 10 min.
In addition, an experiment was attempted in which the hydrogen feed amount was decreased from 10 NL / Hr in order to increase the molecular weight, but the slurry extraction piping was blocked and the operation was stopped.

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 (13)

  Polyethylene obtained using a metallocene catalyst, having a viscosity average molecular weight (Mv) of 2 million or more, and a ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by GPC An ultra-high molecular weight polyethylene characterized in that is greater than 3. The ultrahigh molecular weight polyethylene according to claim 1, wherein the relationship between density (ρ (g / cc)) and viscosity average molecular weight (Mv) satisfies the following formula (1).
ρ ≦ −9 × 10 ⁻¹⁰ × Mv + 0.937 (1) The density (ρ (g / cc)) is in the range of 0.915 or more, and the relationship between the density and the crystallinity (X (%)) satisfies the following formula (2): The ultra high molecular weight polyethylene according to any one of 2 above.
100X <630ρ−530 (2)   The ultra high molecular weight polyethylene according to any one of claims 1 to 3, wherein the amount of terminal vinyl groups is 0.02 (ke / 1000C) or less.   The ultra high molecular weight polyethylene according to any one of claims 1 to 4, wherein the amount of residual Ti is 3 ppm or less and the amount of residual Cl is 5 ppm or less. The ultrahigh molecular weight polyethylene according to any one of claims 1 to 5, wherein the metallocene catalyst is formed using a compound represented by the following 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 metallacycle. 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) The ultrahigh molecular weight polyethylene according to any one of claims 1 to 6, wherein the metallocene catalyst is formed by using a compound represented by the following formula (4).
[L−H] ^{d +} [M _m Q _p ] ^d− (4)
(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 .)   The ultrahigh molecular weight polyethylene according to any one of claims 1 to 7, which is obtained by using [A] a metallocene-based catalyst previously brought into contact with a hydrogenating agent and [B] a compound having hydrogenation ability. . The hydrogenating agent is hydrogen and 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, 7 to 20 carbon atoms) And a hydrocarbon group selected from the group consisting of an alkylalkyl group having 7 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms. The ultrahigh molecular weight polyethylene according to claim 8.   The compound having hydrogenation ability is a reaction mixture of a titanocene compound or a half titanocene compound alone, or a reaction mixture of at least one organometallic compound selected from organic lithium, organomagnesium, and organoaluminum with a titanocene compound or a half titanocene compound. The ultrahigh molecular weight polyethylene according to any one of claims 8 to 9. The ultrahigh molecular weight polyethylene according to claim 10, wherein the titanocene compound or the half titanocene compound is a compound represented by the following formula (5).
L _j W _k TiX _p X ′ _q (5)
(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)   The molded object obtained from the ultra high molecular weight polyethylene in any one of Claims 1-11. The fiber obtained from the ultra high molecular weight polyethylene in any one of Claims 1-11.