New catalyst for olefin polymerization

Abstract

To provide a catalyst for olefin polymerization that enables stable production of an ethylene polymer having a wide molecular weight distribution and having a greater amount of comonomer introduced into a high-molecular-weight region, so as to improve molding processability of metallocene polyethylene.SOLUTION: A catalyst for olefin polymerization includes a component (A-1) which is a metallocene compound represented by formula (1), a component (A-2) which is a metallocene compound represented by any one of formulas (2-1) to (2-5), and a component (B) which is a compound that reacts with the component (A-1) and the component (A-2) to generate a cationic metallocene compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel olefin polymerization catalyst, a method for producing an olefin polymer using the catalyst, and an olefin polymer produced by the method. More specifically, the present invention relates to an olefin polymerization catalyst containing two specific types of metallocene compounds and a compound that reacts with the metallocene compound to produce a cationic metallocene compound, a method for producing an olefin polymer using the catalyst, and an olefin polymer or ethylene polymer produced by the method. [Background technology]

[0002] Polyolefins produced using metallocene catalysts for olefin polymerization have been used in increasing amounts in recent years because they have high uniformity in polymer molecular structure, such as molecular weight distribution and copolymer composition distribution, and are excellent in various mechanical properties, such as impact strength and long life. However, although metallocene-based polyolefins have excellent mechanical properties, their narrow molecular weight distribution does not provide sufficient performance in properties important for the molding and processing of polyolefins, such as melt tension and melt fluidity.

[0003] One known method for improving the moldability of metallocene-based polyolefins is to broaden the molecular weight distribution by multistage polymerization using a metallocene catalyst (Patent Document 1). However, this method of broadening the molecular weight distribution by multistage polymerization poses other problems, such as construction costs and operation and management costs, due to the need to link and use polymerization reactive groups.

[0004] On the other hand, known methods for improving the insufficient molding processability of metallocene-based polyolefins include a method for improving the flowability and melt tension by introducing long chain branches into polyethylene through a polymerization reaction using a specific metallocene complex to increase the melt viscosity (Patent Document 2), and a method for designing a catalyst to prepare a polymer having multiple peaks in the molecular weight distribution (Patent Document 3).

[0005] As another approach to this problem, binary complex catalyst technology has been studied, in which a catalyst composition containing a combination of two types of complexes is used to produce polyethylene with a sufficient number of long-chain branches of appropriate length (Patent Documents 4 to 8). These patent documents attempt to introduce long-chain branched structures by designing binary complex catalysts using metal complexes containing bridged or unbridged cyclopentadienyl (Cp) groups. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 3-234717 [Patent Document 2] Japanese Patent Application Publication No. 2-276807 [Patent Document 3] Japanese Patent Application Publication No. 2017-197739 [Patent Document 4] Japanese Patent Application Laid-Open No. 2012-214780 [Patent Document 5] Japanese Patent Application Laid-Open No. 2017-145303 [Patent Document 6] Japanese Patent Application Publication No. 2019-059934 [Patent Document 7] Special Publication No. 2019-515997 [Patent Document 8] Japanese Patent Application Laid-Open No. 2010-043152 Summary of the Invention [Problem to be solved by the invention]

[0007] Several approaches have been proposed to improve the processability of polyolefins. First, attempts have been made to broaden the molecular weight distribution. A broader molecular weight distribution increases the proportion of low-molecular-weight components, thereby contributing to improved processability. Second, attempts have been made to introduce long-chain branches. The presence of high-molecular-weight components (roughly Mw = 100,000 to 10,000,000) among the various molecular weight ranges contained in polyolefins increases the long-term relaxation component in melt viscoelasticity, thereby increasing the swell ratio, memory effect, melt tension, and flowability ratio, which is beneficial for processability. The above-mentioned catalyst methods have been used to achieve such polymers, but the introduction of long-chain branching structures has been insufficient, and the resulting polyolefins have unsatisfactory physical properties in terms of processability. A third approach has been to design copolymers that exhibit an inverse comonomer composition distribution. The inverse comonomer composition distribution in ethylene-α-olefin copolymers is a distribution in which more α-olefins are copolymerized on the high molecular weight side, and from the viewpoint of preventing a decrease in product strength caused by an increase in the proportion of low molecular weight components in the first method described above, copolymers having an inverse comonomer composition distribution are also useful in terms of moldability, but copolymers obtained by this approach often do not have a long chain branched structure and are generally incompatible with the second approach described above. Therefore, there is room for improvement in the moldability of known polyolefins, and improved polyolefins are desired.

[0008] Furthermore, the inventors' investigations have revealed that in the case of binary complex catalysts such as those in Patent Documents 4 to 8, there are situations in which using multiple types of catalysts can be disadvantageous. In other words, the polymerization activity of a catalyst is affected by changes in conditions such as fluctuations in the hydrogen concentration for olefin polymerization. Because the effect varies depending on the catalyst, when multiple types of catalysts are used, even a slight change in conditions can cause a shift in the activity balance between the catalysts, which can affect polymer properties such as high load melt flow rate (HLMFR) and molecular weight distribution (MWD). As a result, even a slight change in polymerization conditions can have an overly sensitive effect on the molecular structure of the product polymer, and the quality of the polymer obtained can be inconsistent when using commercial plant operation management methods used with existing olefin polymerization catalysts, which has been a manufacturing problem.

[0009] In order to solve the problems of polyethylene produced by binary complex catalysts in the prior art and to improve the moldability and product strength of metallocene-based polyethylene, there has been a demand for an olefin polymerization catalyst capable of producing ethylene polymers having a broad molecular weight distribution, long chain branches in the high molecular weight region, and an inverted comonomer composition distribution. Furthermore, there has been a demand for a polymerization catalyst that can stably produce polymers with uniform properties. [Means for solving the problem]

[0010] The present inventors investigated factors that affect catalytic activity and found that catalyst activity is particularly sensitive to hydrogen concentration, which is one of the causes of rapid fluctuations in HLMFR and MWD. ​​Therefore, they discovered that by combining a metal complex with high catalytic activity and a metal catalyst with high copolymerization activity that have the same or similar tendency in their effects on hydrogen, polyolefins with excellent moldability and in which a large amount of comonomer is introduced into the high molecular weight region can be stably obtained without interfering with each other's catalytic activity, leading to the present invention.

[0011] That is, the present invention relates to an olefin polymerization catalyst and an olefin polymer specified in the following items. [1] An olefin polymerization catalyst comprising the following components (A-1), (A-2) and (B): Component (A-1): a metallocene compound represented by the following general formula (1): [ka] [In formula (1), M 1 represents a transition metal atom of Ti, Zr, or Hf, X 1 and X 2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing an oxygen atom or a nitrogen atom, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, R 3 ~R 6 , R 7 ~R 10 , R 6’ , R 10’ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms; R 3 ~R 6 and R 6’ Any one or more pairs of adjacent groups may be bonded to each other, including the carbon atoms to which they are bonded, to form a ring, R 7 ~R 10 and R 10’ any one or more pairs of adjacent groups may be bonded to each other, including the carbon atom to which they are bonded, to form an aliphatic ring; R 6’ and R 10’ may be linked together to form a divalent group represented by any of the following formulae: [ka] In the formula, E 1 and E 2 are respectively, -CR 31 2-, -SiR 31 2-, -NR 31 -,-PR31 is a divalent group selected from the group consisting of -, -O-, and -S-, where R 31 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R 31 may be bonded to form a cyclic structure), R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms, or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms; R 1 and R 2 may form a ring together with the carbon atoms to which they are attached, Q 1 and Q 2 represents a carbon atom, a silicon atom, or a germanium atom, R 1’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and adjacent substituents bond to each other with Q 1 and / or Q 2 may be bonded to form a ring, m is 0 or 1. When m is 0, Q 1 is R 6 directly bonded to a conjugated five-membered ring containing R 6’ and R 10’ are linked together to form a divalent group -Q 1 (R 1’ 2)-{Q 2 (R 1’ 2) m - If R 3 and R 4 are linked together to form a divalent group represented by any of the following formulas: [ka] In the formula, R 14each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms and containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms and containing an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms, and adjacent substituents may be bonded to each other via the carbon atoms to which they are bonded to form a ring, n 1 is 0 or 1, and n 1 If is 0, (CR 14 2) part does not exist, and (CR 14 2) The carbon atom adjacent to the conjugated five-membered ring is directly bonded to form an indenyl ring, R 17 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms and containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing an oxygen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms; R 18 represents a substituted or unsubstituted aryl group represented by the following general formula (1-a): [ka] [In formula (1-a), Y 1 represents an atom in group 14, 15, or 16 of the periodic table, and R 19 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, and each R 19 adjacent substituents may form a ring together with the atoms bonded thereto, and q is 0 or 1. When q is 0, Y 1 Substituent R 19is absent, p is 0 or 1, and when p is 0, formula (1-a) forms a 5-membered ring. where R 3 and R 4 are connected to each other to form -SC(R 17 )=C(R 18 )-, R 7 and R 10 is not a divalent group forming an aliphatic ring] Component (A-2): a metallocene compound represented by any one of the following general formulas (2-1) to (2-5): [ka] [In the formula, M 51 represents a transition metal atom of Ti, Zr, or Hf, X 51 and X 52 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms; Q 51 and Q 52 represents a carbon atom, a silicon atom, or a germanium atom, R 51 ~R 54 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and adjacent substituents bond to each other with Q 51 and / or Q 52 may be bonded to form a ring, m 2 is 0 or 1, and m 2 If is 0, Q 51 is R 59 , R 60 directly bonded to a conjugated five-membered ring containing R 55 ~R 68represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms which contains an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms, D represents a sulfur atom or an oxygen atom; n 2 is 0 or 1, and n 2 If is 0, R 61 and R 62 There is no carbon atom to which R is bonded. 63 The carbon atom to which is bonded and the conjugated five-membered ring are directly bonded to form an indenyl ring. Component (B): A compound that reacts with the metallocene compounds of components (A-1) and (A-2) to generate a cationic metallocene compound. [2] The olefin polymerization catalyst according to [1] above, wherein the component (A-1) is a metallocene compound represented by the following general formula (1-1-1) or (1-1-2): [ka] [In the formula, M 1 , X 1 , X 2 , E 1 , E 2 , R 1 ~R 4 , R 7 ~R 8 is as defined in [1], s is R present on the six-membered ring 11 , R 12 Each s may be the same or different and represents an integer of 0 to 4; R 11 , R 12each independently represent a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms which contains 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms which contains an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms; R 11 , R 12 If there are two or more instances of at least one of 11 Comrade, R 12 may be taken together to form a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing hydrocarbon group having 1 to 40 carbon atoms and containing 1 to 6 silicon atoms, a divalent halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a divalent hydrocarbon group having 1 to 40 carbon atoms and containing an oxygen atom, sulfur atom, nitrogen atom, or phosphorus atom, which may have a substituent. [3] The olefin polymerization catalyst according to [1] or [2], wherein the component (A-1) is a metallocene compound represented by any one of the following general formulae (1-1-1-1) to (1-1-1-5), (1-1-2-1) to (1-1-2-5): [ka] [In the formula, M 1 , X 1 , X 2 , E 1 , E 2 , R 3 , R 4 , R 7 , R 8 is as defined in [1], and R 11 , R 12 is as defined in [2], s is R present on the six-membered ring 11 , R 12 , R 13 Each s may be the same or different and represents an integer of 0 to 4; R 13each independently represent a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms which contains 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms which contains an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms; R 13 When two or more of these are present, they may be taken together to form a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing hydrocarbon group having 1 to 40 carbon atoms and containing 1 to 6 silicon atoms, a divalent halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a divalent hydrocarbon group having 1 to 40 carbon atoms and containing an oxygen atom, sulfur atom, nitrogen atom, or phosphorus atom, each of which may have a substituent. [4] The olefin polymerization catalyst according to any one of the above [1] to [3], wherein the component (A-1) is a meso compound. [5] In the formulas (2-1) to (2-5) of the component (A-2), m 2 The olefin polymerization catalyst according to any one of the above [1] to [4], wherein is 0. [6] In the formulas (2-4) and (2-5) of the component (A-2), n 2 The olefin polymerization catalyst according to any one of the above [1] to [4], wherein is 0. [7] In the formulas (2-1) to (2-5) of the component (A-2), R 55 ~R 68 The olefin polymerization catalyst according to any one of the above [1] to [6], wherein at least one of the above is represented by the following formula (7): [ka] [In formula (7), A 2 indicates an atom of group 14, 15 or 16 of the periodic table, R 75 ~R 79each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom, a sulfur atom or a nitrogen atom, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, and adjacent substituents may be bonded to each other, including the atom bonding thereto, to form a ring; p 2 is 0 or 1, and A 2 If is an atom in group 15 or 16 of the periodic table, p 2 is 0 and A 2 to R 75 does not exist, q 2 is 0 or 1, and q 2 If is 0, R 78 does not exist, and R 77 and the carbon atom to which R is bonded 79 is directly bonded to the carbon atom to which it is attached.] [8] In the formulas (2-1) to (2-5) of the component (A-2), R 57 , R 67 , R 61 ~R 63 The olefin polymerization catalyst according to [7] above, wherein at least one of the above is represented by the formula (7). [9] The olefin polymerization catalyst according to any one of the above [1] to [8], wherein D in the above formulas (2-1) to (2-5) of the component (A-2) is a sulfur atom.

[10] The olefin polymerization catalyst according to any one of the above [1] to [9], wherein the components (A-1) and (A-2) satisfy the following conditions (1) to (4): Condition (1): An olefin polymerization catalyst (Cat (A-1) ) in the presence of hydrogen molecules to polymerize olefins, HLMFR is an olefin polymer HLMFR (A-1) and an olefin polymerization catalyst (Cat(A-2) ) and HLMFR, which is an HLMFR of an olefin polymer obtained under the same conditions. (A-2) But HLMFR (A-1) ≧HLMFR (A-2) Satisfy. Condition (2):Cat (A-1) In the polymerization of olefins using (A-1) : the correlation coefficient α in the following definition formula, which represents the correlation between the unit (g olefin polymer / g catalyst / hour / MPa) (A-1) is between -10000 and +1000; Definition formula K (A-1) =α (A-1) Log[H2 / C2]+β (A-1) Here, the above formula represents the relationship between H2 / C2 and K when polymerization is performed at two H2 / C2 points separated by 0.05 mol% or more. (A-1) The coefficient α (A-1) is the slope of the line, and the intercept β (A-1) is the polymerization activity (K 1(A-1) ) Condition (3):Cat (A-2) The H2 / C2 and K obtained in the same way as condition (2) are (A-2) Correlation coefficient α (A-2) is between -10000 and +1000; Condition (4): α (A-1) and α (A-2) The absolute value of the difference |Δα| is 0 to 7030.

[11] The olefin polymerization catalyst according to any one of the above [1] to

[10] , wherein the components (A-1) and (A-2) satisfy the following condition (5): Condition (5): Said Cat (A-1) The weight average molecular weight Mw of an olefin polymer obtained by polymerizing an olefin in the presence of hydrogen molecules using (A-1) And Cat (A-2) The weight average molecular weight Mw of the olefin polymer obtained under the same conditions was calculated using (A-2) But, Mw (A-1) ≦Mw(A-2) Satisfy.

[12] The olefin polymerization catalyst according to any one of the above [1] to

[11] , wherein the components (A-1) and (A-2) satisfy the following condition (6): Condition (6): Said Cat (A-1) is the density of the olefin polymer obtained by polymerizing or copolymerizing olefins in the presence of hydrogen molecules using (A-1) And Cat (A-2) The density D of the olefin polymer obtained under the same conditions is calculated using (A-2) But, D (A-1) ≧D (A-2) Satisfy.

[13] The olefin polymerization catalyst according to any one of the above [1] to

[12] , further comprising the following component (C): Component (C): Microparticle carrier

[14] The olefin polymerization catalyst according to any one of the above [1] to

[13] , further comprising the following component (D): Component (D): Organoaluminum compound

[15] A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of the above [1] to

[14] .

[16] The method for producing an olefin polymer according to

[15] above, wherein the olefin is ethylene.

[17] The method for producing an olefin polymer according to the above

[15] or

[16] , wherein the obtained polymer satisfies the following conditions (i) to (iii): Condition (i): MFR is 0.001 to 1000 g / 10 min. Condition (ii): Density is 0.895 to 0.975 g / cm 3 is. Condition (iii): At least one of the following conditions (iii-1), (iii-2), (iii-3), and (iii-4) is satisfied; Condition (iii-1): The molecular weight distribution (Mw / Mn) determined by weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 or more and 100.0 or less. Condition (iii-2): The branching index g' measured by a GPC measuring device combining a differential refractometer, a viscosity detector, and a light scattering detector is the minimum value (g L ) is greater than or equal to 0.20 and less than or equal to 0.95. Condition (iii-3): Melt flow rate (MFR) at a temperature of 190°C and a load of 10 kg 10kg The FR, which is the ratio of the melt flow rate (MFR) at a temperature of 190°C and a load of 2.16 kg to the melt flow rate (MFR), is 6.5 or more and 100 or less. Condition (iii-4): The ratio (HLMFR / MFR) of the melt flow rate at a temperature of 190°C and a load of 21.6 kg (HLMFR) to the melt flow rate at a temperature of 190°C and a load of 2.16 kg (MFR) is 20 or more and 1000 or less. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide an olefin polymerization catalyst capable of stably producing a homogeneous ethylene polymer which has a broad molecular weight distribution, has long chain branches in the high molecular weight region, and can improve moldability. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 10 is a contour map showing the elution amount relative to the elution temperature and molecular weight measured by the CFC method in Example 6. [Figure 2] FIG. 10 is a contour map showing the elution amount relative to the elution temperature and molecular weight measured by the CFC method in Example 7. DETAILED DESCRIPTION OF THE INVENTION

[0014] One embodiment of the present invention is an olefin polymerization catalyst comprising: component (A-1): a metallocene compound represented by the above formula (1); component (A-2): a metallocene compound represented by any one of the above formulas (2-1) to (2-5); and component (B): a compound that reacts with component (A-1) and component (A-2) to produce a cationic metallocene compound.

[0015] The polymerization catalyst, the method for producing the polymerization catalyst, the constituent monomers of the polymer, the polymerization method, etc. will be described in detail below. In the following description, "polymerization" refers to a reaction in which a monomer forms a polymer of 20 or more monomers. The term "polymerization" collectively refers to the homopolymerization of one type of monomer and the copolymerization of multiple types of monomers, and when there is no need to particularly distinguish between the two, they will be collectively referred to simply as "polymerization." Furthermore, although the present invention also relates to a method for producing a polymer, the structure of a polymer itself cannot generally be uniquely determined by a chemical formula or the like. Therefore, in this specification, when describing a polymer, the polymer will be described using its production method, as necessary.

[0016] Hereinafter, when referring to specific substituents, hydrocarbon groups refer to straight-chain, branched-chain, or cyclic groups. The valency of the hydrocarbon group will be understood in context, but monovalent groups are represented by the suffix "-yl" and divalent groups by the suffix "-ene."

[0017] 1. Ingredient (A-1) The component (A-1) in the olefin polymerization catalyst of the present invention is a metallocene compound represented by the following general formula (1). [ka] [In formula (1), each group is defined as above.]

[0018] The metallocene compound of the formula (1) is highly efficient in producing polyolefins with a relatively low molecular weight and a narrow molecular weight distribution, which prevents the molecular weight distribution from broadening to the low molecular weight side, thereby leading to the production of olefin polymers (especially ethylene polymers) with improved surface tackiness and product strength. Furthermore, although the metallocene compound of the above formula (1) has excellent ethylene polymerization ability, its polymerization ability for olefins having 3 to 30 carbon atoms tends to be relatively low compared to other catalysts. Therefore, when a catalyst containing the metallocene compound of the above formula (1) is used for copolymerization of ethylene and an α-olefin, for example, a polymer with a low α-olefin content is produced on the low molecular weight side, and as a result, an olefin polymer (particularly an ethylene polymer) with improved product strength can sometimes be obtained with high productivity. Furthermore, when the metallocene compound of formula (1) is used alone as a catalyst, its catalytic activity generally exhibits a negative correlation with hydrogen concentration. Therefore, by combining it with any of the metallocene compounds of formulas (2-1) to (2-5) described below, a catalyst that is less affected by fluctuations in hydrogen concentration during polymerization reactions can be obtained. The metallocene compound of formula (1) tends to produce polymers that differ in molecular weight, molecular weight distribution, and comonomer incorporation level from the metallocene compounds of formulas (2-1) to (2-5) described below. However, because the correlation of catalytic activity with hydrogen concentration shows the same tendency, the overall characteristics of the resulting polymer do not vary significantly with fluctuations in hydrogen concentration. Here, a negative correlation means that catalytic activity tends to decrease with fluctuations in hydrogen concentration. A neutral correlation means that the magnitude of catalytic activity does not change with fluctuations in hydrogen concentration, or the change in activity is small. The criteria for determining whether the change is small or large will be explained as condition (2) described below.

[0019] In general formula (1), M 1 represents a transition metal atom of Ti, Zr, or Hf, preferably Zr or Hf, and more preferably Zr.

[0020] In general formula (1), X 1 and X2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing an oxygen atom or a nitrogen atom, a hydrocarbon-substituted amino group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. X 1 and X 2 Examples of the halogen atom represented by the formula (I) include a chlorine atom, a bromine atom, and an iodine atom. X 1 and X 2 Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group, and a benzyl group.

[0021] X 1 and X 2 Examples of the hydrocarbon group having 1 to 20 carbon atoms and containing an oxygen atom represented by the formula (I) include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, an i-butoxymethyl group, a t-butoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an acetyl group, a 1-oxopropyl group, a 1-oxo-n-butyl group, a 2-methyl-1-oxopropyl group, a 2,2-dimethyl-1-oxopropyl group, a phenylacetyl group, a diphenylacetyl group, a benzoyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-furyl group, and a 2-tetrahydrofuryl group.

[0022] X 1 and X 2Examples of the hydrocarbon group having 1 to 20 carbon atoms and containing a nitrogen atom, represented by the formula (I), include a dimethylaminomethyl group, a diethylaminomethyl group, a di-i-propylaminomethyl group, a bis(dimethylamino)methyl group, a bis(di-i-propylamino)methyl group, a (dimethylamino)(phenyl)methyl group, a methylimino group, an ethylimino group, a 1-(methylimino)ethyl group, a 1-(phenylimino)ethyl group, and a 1-[(phenylmethyl)imino]ethyl group. X 1 and X 2 Examples of the hydrocarbon-substituted amino group having 1 to 20 carbon atoms, represented by the formula (I), include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a di-i-propylamino group, a di-n-butylamino group, a di-i-butylamino group, a di-t-butylamino group, and a diphenylamino group. X 1 and X 2 Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a t-butoxy group, and a phenoxy group.

[0023] Preferred X 1 and X 2 Examples of the alkyl group include a chlorine atom, a bromine atom, a methyl group, an n-butyl group, an i-butyl group, a methoxy group, an ethoxy group, an i-propoxy group, an n-butoxy group, a phenoxy group, a dimethylamino group, and a di-i-propylamino group. Among these, a chlorine atom, a methyl group, and a dimethylamino group are particularly preferred.

[0024] R 3 , R 4 , R 5 , R 6 , R 6’ , R 7 , R 8 , R 9 , R 10 and R 10’each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms.

[0025] R 3 ~R 10 , R 6’ and R 10’ In the above, examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. R 3 ~R 10 , R 6’ and R 10’ In the formula (I), examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a propenyl group, an n-butyl group, an i-butyl group, a t-butyl group, a butenyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a cyclohexenyl group, a phenyl group, a cyclohexylmethyl group, a benzyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a 4-t-butylphenyl group, a 3,5-di-t-butylphenyl group, a biphenyl group, and a naphthyl group. R 3 ~R 10 In the formula, examples of the silicon-containing hydrocarbon group having 1 to 18 carbon atoms and including 1 to 6 silicon atoms include a bis(trimethylsilyl)methyl group and a bis(t-butyldimethylsilyl)methyl group.

[0026] R 3 ~R 10 , R 6’ and R 10’In the formula (I), examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include a bromomethyl group, a chloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group, a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a 2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a 2-chlorophenyl group, a 4-chlorophenyl group, a 2,3,4,5,6-pentafluorophenyl group, and a 4-trifluoromethylphenyl group.

[0027] R 3 ~R 10 , R 6’ and R 10’ In the formula (I), examples of the hydrocarbon group containing an oxygen atom and having 1 to 40 carbon atoms include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, an i-butoxymethyl group, a t-butoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an acetyl group, an acetoxy group, a 1-oxopropyl group, a 1-oxo-n-butyl group, a 2-methyl-1-oxopropyl group, a 2,2-dimethyl-1-oxopropyl group, a phenylacetyl group, a diphenylacetyl group, a benzoyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-furyl group, a 2-methylfuryl group, and a 2-tetrahydrofuryl group.

[0028] R 3 ~R 10 , R 6’ and R 10’In the formula (I), examples of the hydrocarbon group containing a sulfur atom and having 1 to 40 carbon atoms include a methylthiomethyl group, an ethylthiomethyl group, an n-propylthiomethyl group, an i-propylthiomethyl group, an n-butylthiomethyl group, an i-butylthiomethyl group, a t-butylthiomethyl group, a methylthioethyl group, an ethylthioethyl group, a thioacetyl group, a 1-thioxopropyl group, a 1-thioxo-n-butyl group, a 2-methyl-1-thioxopropyl group, a 2,2-dimethyl-1-thioxopropyl group, a phenylthioacetyl group, a diphenylthioacetyl group, a thiobenzoyl group, a 2-methylthiophenyl group, a 3-methylthiophenyl group, a 4-methylthiophenyl group, a 2-thienyl group, a 2-methylthienyl group, and a 2-tetrahydrothienyl group.

[0029] R 3 ~R 10 , R 6’ and R 10’ In the formula (I), examples of the hydrocarbon group containing a nitrogen atom and having 1 to 40 carbon atoms include a dimethylaminomethyl group, a diethylaminomethyl group, a di-i-propylaminomethyl group, a bis(dimethylamino)methyl group, a bis(di-i-propylamino)methyl group, a (dimethylamino)(phenyl)methyl group, a methylimino group, an ethylimino group, a 1-(methylimino)ethyl group, a 1-(phenylimino)ethyl group, and a 1-[(phenylmethyl)imino]ethyl group.

[0030] R 3 ~R 10 , R 6’ and R 10’ In the formula (I), examples of the hydrocarbon group containing a phosphorus atom and having 1 to 40 carbon atoms include a dimethylphosphinomethyl group, a diethylphosphinomethyl group, a di-i-propylphosphinomethyl group, a bis(dimethylphosphino)methyl group, a bis(di-i-propylphosphino)methyl group, a (dimethylphosphino)(phenyl)methyl group, a methylphosphanylidene group, an ethylphosphanylidene group, a 1-(methylphosphanylidene)ethyl group, a 1-(phenylphosphanylidene)ethyl group, and a 1-[(phenylmethyl)phosphanylidene]ethyl group.

[0031] R 3 ~R 10 , R 6’ and R 10’ In the formula, examples of the hydrocarbon-substituted silyl group having 1 to 40 carbon atoms include a trimethylsilyl group, a tri-t-butylsilyl group, a di-t-butylmethylsilyl group, a t-butyldimethylsilyl group, a triphenylsilyl group, a diphenylmethylsilyl group, and a phenyldimethylsilyl group.

[0032] R 3 ~R 10 , R 6’ and R 10’ In the formula (I), examples of the hydrocarbon group-substituted amino group having 1 to 40 carbon atoms include a dimethylamino group, a methylethylamino group, a diethylamino group, a (methyl)(n-propyl)amino group, a di-n-propylamino group, a dipropenylamino group, a di-i-propylamino group, a di-n-butylamino group, a di-i-butylamino group, a di-t-butylamino group, a di-n-pentylamino group, a di-n-hexylamino group, a di-n-octylamino group, a di-n-dodecylamino group, a (methyl)(phenyl)amino group, a diphenylamino group, a di(4-methylphenyl)amino group, a di(3,5-dimethylphenyl)amino group, and a dibenzylamino group.

[0033] Preferred R 3 ~R 10 , R 6’ and R 10’ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon-substituted silyl group having 1 to 40 carbon atoms, and is more preferably a hydrogen atom, a methyl group, a t-butyl group, or a trimethylsilyl group.

[0034] R 3 ~R 6 , and R 6’ Among these, any one or more pairs of adjacent groups may be bonded to each other, including the carbon atom to which they are bonded, to form a ring. When a ring is formed, the position of the ring is not particularly limited, but 3 or R 6 is preferably selected so as to be a part of the ring, and R 6’is preferably not selected as a group that forms a ring. There is no limitation on the number of ring members, but it is preferable that a 5- to 8-membered ring be formed, which can provide a stable ring structure. Specific examples of Cp groups that contain such ring structures include indene and azulene.

[0035] R 7 ~R 10 , and R 10’ Among these, any one or more pairs of adjacent groups may be bonded to each other, including the carbon atom to which they are bonded, to form an aliphatic ring. When an aliphatic ring is formed, the position of the aliphatic ring is not particularly limited, but 7 or R 10 is preferably selected so as to be a part constituting an aliphatic ring, and R 10’ is preferably not selected as a group that forms an aliphatic ring. There is no limitation on the number of ring members, but it is preferable that a 5- to 8-membered ring is formed, which provides a stable ring structure.

[0036] R 6’ and R 10’ may be linked to each other to form a divalent group represented by any of the following formulae: Accordingly, in one embodiment of the present invention, component (A-1) is a metallocene compound coordinated with a bridged cyclopentadienyl group. [ka] (In the above formula, the definitions of each group are as described above.)

[0037] R 6’ and R 10’ are connected to each other, -E 1 -C(R 1 )=C(R 2 )-E 2 When a divalent group represented by - is formed, that is, when two cyclopentadienyl groups in formula (1) are bridged by four elements, such a metallocene compound is represented by the following general formula (1-1). [ka]

[0038] E 1 and E 2 are R 3 ~R 6 Cyclopentadienyl ring containing R 2 a bridging group connecting the carbon atoms to which R is attached; 7 ~R 10 Cyclopentadienyl ring containing R 1 represents a bridging group connecting the carbon atoms to which the carbon atoms are bonded, and is selected from the following group: -CR 31 2-, -SiR 31 2-, -NR 31 -,-PR 31 -, -O-, -S- (where R 31 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R 31 may be bonded to form a ring structure) E 1 and E 2 Although they may be different from each other, they are preferably the same because this makes it easier to design molecules. 1 and E 2 are both -SiR 31 2 or CR 31 2-, where R 31 is preferably a hydrogen atom.

[0039] R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms; R 1 and R 2 may form a ring together with the carbon atom to which they are attached. When a ring is formed, it is preferably a 5- to 8-membered ring. Therefore, when a ring is formed, R 1and R 2 are taken together to form a divalent group obtained by removing one hydrogen atom from the above group other than hydrogen atoms and halogen atoms. When a ring is formed, the ring structure is 1 and R 2 The ring may have one or more unsaturated bonds in addition to the carbon-carbon double bond to which the carbon atom is bonded, and may be an aromatic ring. The ring may further have a substituent, or may have a structure in which two or more rings are condensed. Particularly preferred examples of the ring structure include a cyclohexene or benzene ring.

[0040] R 6’ and R 10’ are linked together to form a divalent group -Q 1 (R 1’ 2)-{Q 2 (R 1’ 2) m -, i.e., when two cyclopentadienyl groups in formula (1) are bridged by one or two elements, R 3 and R 4 are linked to each other to form a divalent group represented by any of the following formulas: [ka] (wherein each group is defined as above)

[0041] Therefore, R 6’ and R 10’ But, they are connected together to form -Q 1 (R 1’ 2)-{Q 2 (R 1’ 2) m When a divalent group represented by - is formed, such a metallocene compound is represented by the following general formula (1-2) or (1-3). [ka]

[0042] Q 1 and Q 2R represents a carbon atom, a silicon atom, or a germanium atom, respectively. 1’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and adjacent substituents bond to each other with Q 1 and / or Q 2 may be bonded to form a ring containing m, and when m is 0, Q 1 is R 6 The value of m is preferably 0.

[0043] In formula (1-2), the divalent group -C(R 14 )=C(R 14 )-C(R 14 )=C(R 14 )-{C(R 14 )2}- is R 3 and R 4 together with the carbon atom to which R is attached form a 6- or 7-membered ring. 14 R each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms, or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms. Adjacent substituents may be bonded together, including the carbon atom to which they are bonded, to form a ring. 14 Exemplary and preferred embodiments of R 3 The same applies to the exemplary and preferred embodiments of the present invention.

[0044] n 1 is 0 or 1, and n 1 If is 0, (CR 14 2) part does not exist, and (CR 14 2) The carbon atom adjacent to the conjugated five-membered ring is directly bonded to form an indenyl ring.

[0045] In formula (1-3), the divalent group -SC(R 17 )=C(R 18 )- is R3 and R 4 together with the carbon atom to which it is attached to form a thiophene ring, where R 3 and R 4 are connected to each other to form -SC(R 17 )=C(R 18 )-, R 7 and R 10 is not a divalent group that forms an aliphatic ring. Therefore, when one of the cyclopentadienyl groups of the metallocene compound in component (A-1) forms a fused heterocycle, the other does not form a fused ring.

[0046] The divalent group -SC(R 17 )=C(R 18 )-, R 17 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms and containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing an oxygen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms.

[0047] The divalent group -SC(R 17 )=C(R 18 )-, R 18 represents a substituted or unsubstituted aryl group represented by the following general formula (1-a). [ka] [In formula (1-a), each group is defined as above.] Y 1 represents an atom in group 14, 15, or 16 of the periodic table, and R 19 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, and each R 19adjacent substituents may form a ring together with the atoms bonded thereto, and q is 0 or 1. When q is 0, Y 1 Substituent R 19 is absent, p is 0 or 1, and when p is 0, formula (1-a) forms a 5-membered ring.

[0048] R 19 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, and each R 19 Adjacent substituents may be bonded together to form a ring, including the atom bonded thereto. q is 0 or 1, and Y 1 If Y is an atom in group 15 or 16 of the periodic table, q is 0 and Y 1 Substituent R 19 does not exist. When q is 0, Y 1 is preferably an oxygen atom. When q is 1, Y 1 is preferably a carbon atom. p is 0 or 1, and when p is 0, the above formula (1-a) forms a five-membered ring.

[0049] Y 1 If is a carbon atom, each R 19 It is preferable that at least one of R is not a hydrogen atom. 19 is preferably not a halogen atom. R 19 When the group represented by is other than a hydrogen atom, the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, the silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, the halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or the hydrocarbon-substituted silyl group having 1 to 20 carbon atoms is the same as the above-mentioned R 3The hydrocarbon-substituted amino group having 1 to 20 carbon atoms or the alkoxy group having 1 to 20 carbon atoms may be the same as the groups described above in the description of X 1 and X 2 Examples of the groups include the same groups as those described above.

[0050] Specific examples of the group represented by general formula (1-a) include a phenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-propylphenyl group, a 4-butylphenyl group, a 4-trimethylsilylphenyl group, a 4-(t-butyldimethylsilyl)phenyl group, a 3,5-bistrimethylsilylphenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, a 4-n-butoxyphenyl group, a 2-furyl group, a 2-(5-methyl)furyl group, a 2-(5-t-butyl)furyl group, a 2-(5-trimethylsilyl)furyl group, a 2-(4,5-dimethyl)furyl group, a 2-benzofuryl group, a 2-thienyl group, a 2-(5-methyl)thienyl group, a 2-(5-t-butyl)thienyl group, a 2-(5-trimethylsilyl)thienyl group, and a 2-(4,5-dimethyl)thienyl group.

[0051] In a more preferred embodiment, the metallocene compound represented by the general formula (1) has a structure in which R 5 and R 6 and R 9 and R 10 are linked by a divalent hydrocarbon group to form a ring. That is, a preferred embodiment of the metallocene compound represented by general formula (1) is a metallocene compound in which component (A-1) is represented by the following general formula (1-1-1) or (1-1-2): [ka] [wherein each group is defined as above]

[0052] In a more preferred embodiment, the metallocene compound represented by the general formula (1) is a metallocene compound represented by any one of the following general formulae (1-1-1-1) to (1-1-1-5) and (1-1-2-1) to (1-1-2-5). [ka]

[0053] In the compounds represented by any one of the above general formulae (1-1-1-1) to (1-1-1-5), (1-1-2-1) to (1-1-2-5), the group R 13 When present, it is preferred from the viewpoint of ligand design that the value of s is 2 or more and the molecules are arranged symmetrically. 13 Examples of the alkyl group include hydrocarbon groups having 1 to 6 carbon atoms, and a methyl group is more preferred.

[0054] Metallocene compounds represented by general formula (1) have the above-described structure. Among these compounds, meso compounds are preferably used as component (A-1). Meso compounds have multiple stereocenters but lack chirality. The present inventors discovered that the catalytic activity of metallocene compounds used as polymerization catalysts relative to hydrogen concentration is affected by steric factors. In particular, meso compounds among the compounds represented by general formula (1) exhibit a correlation of catalytic activity relative to changes in hydrogen concentration that is closer to that of the catalyst of component (A-2) described below. The present invention is based on the discovery of a combination of two complexes that have different means for imparting excellent processability to copolymers, but which exhibit a similar correlation of catalytic activity relative to changes in hydrogen concentration, thereby achieving more uniform polymer properties.

[0055] The metallocene compound represented by the general formula (1) is a compound having the above structure, but the metal M 1Other preferred embodiments of the cyclopentadienyl ring structure to which is coordinated are described below. In these embodiments, it is preferable that each substituent is arranged so that the metallocene compound of formula (1) becomes a meso compound.

[0056] In the formula (1), R 3 ~R 6 , R 7 ~R 10 The substituents of R 3 ~R 6 , R 7 ~R 10 In another embodiment, at least one of R 3 ~R 6 , R 7 ~R 10 Preferably, at least two of R are hydrocarbon groups having 1 to 20 carbon atoms. 3 ~R 6 , R 7 ~R 10 It is preferable that at least four of them are hydrocarbon groups having 1 to 20 carbon atoms. More specifically, in the formula (1), R 3 ~R 6 and at least one of R 7 ~R 10 and at least one of R 3 ~R 6 At least two of these and R 7 ~R 10 At least two of the above are preferably hydrocarbon groups each having 1 to 20 carbon atoms.

[0057] In another preferred embodiment, R 3 ~R 6 , R 7 ~R 10 At least one of the groups represents a substituent having a cyclic structure represented by the following general formula (8). [ka] In general formula (8), Z 2 represents an oxygen atom or a sulfur atom. R 80 ~R 82 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom, a sulfur atom, or a nitrogen atom, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms; R 80 ~R 82 Adjacent substituents may be bonded together, including the carbon atoms to which they are bonded, to form a ring.

[0058] R 80 ~R 82 In the formula, examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom, a sulfur atom or a nitrogen atom, the silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, the halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms or the hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms include those listed above for R 5 ~R 16 Specific examples of the group represented by general formula (8) include a 2-furyl group, a 2-(5-methyl)furyl group, a 2-(5-t-butyl)furyl group, a 2-(5-trimethylsilyl)furyl group, a 2-(4,5-dimethyl)furyl group, a 2-benzofuryl group, a 2-thienyl group, a 2-(5-methyl)thienyl group, a 2-(5-t-butyl)thienyl group, a 2-(5-trimethylsilyl)thienyl group, and a 2-(4,5-dimethyl)thienyl group.

[0059] When the group represented by general formula (8) is present, the group is R 3 ~R 6 , R 7 ~R 10 It may be in any position.

[0060] 2. Ingredient (A-2) The component (A-2) in the olefin polymerization catalyst of the present invention is a metallocene compound represented by any one of the following general formulas (2-1) to (2-5). [ka] [wherein each group is defined as above] The metallocene compounds of formulas (2-1) to (2-5) have a structure in which cyclopentadienyl derivatives, at least one of which is a fused heterocyclic group, are crosslinked. The metallocene compounds of formulas (2-1) to (2-5) have excellent copolymerization activity and produce polymers with relatively high molecular weights. Therefore, when a catalyst containing a metallocene compound of formulas (2-1) to (2-5) is used, a high-molecular-weight polymer component with a high comonomer content is introduced, enabling the production of olefin-based polymers (especially ethylene-based polymers) with improved moldability and product strength at high productivity. Furthermore, the metallocene compounds of formulas (2-1) to (2-5) exhibit a negative correlation between catalytic activity and hydrogen concentration, and their response to fluctuations in hydrogen concentration tends to be similar to that of the metallocene compound of formula (1). Therefore, when combined with the metallocene compound of formula (1), the binary complex catalyst as a whole exhibits small fluctuations in catalytic activity relative to hydrogen concentration, resulting in a binary complex catalyst that can produce more homogeneous polymers.

[0061] M 51 represents a transition metal atom of Ti, Zr, or Hf, preferably Zr or Hf, and more preferably Zr.

[0062] X 51 and X 52 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, an amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. 51 Specific examples of these groups bonded to the group X in general formula (1) are 1 , X 2 It is similar to the one mentioned above.

[0063] Q 51 and Q 52 R represents a carbon atom, a silicon atom, or a germanium atom. 51 ~R 54 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and adjacent substituents bond to each other with Q 51 and / or Q 52 may be bonded to form a ring containing m 2 is 0 or 1, and m 2 If is 0, Q 51 is R 59 ~R 62 It is directly bonded to a conjugated five-membered ring containing m 2 The value of is preferably 0. Specific examples and preferred embodiments of the values ​​of these groups connecting two Cp groups include the group Q in general formula (1), 1 , Q 2 , R 1’ It is similar to the one mentioned above.

[0064] D represents a sulfur atom or an oxygen atom. D is preferably a sulfur atom. When two or more Ds are present in one molecule, they may be different from each other, but are preferably the same type.

[0065] R 55 ~R 68 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms.

[0066] In formula (2-4) or (2-5), n 2 is 0 or 1, and n 2 If is 0, R 61 and R 62 There is no carbon atom to which R is bonded. 63 The carbon atom to which is bonded and the conjugated five-membered ring are directly bonded to form an indenyl ring. 2The value of is preferably 0.

[0067] The metallocene compounds represented by the general formulas (2-1) to (2-5) have the above-mentioned structures. 51 More preferred structures of the cyclopentadienyl ring to which is coordinated are described below.

[0068] R 55 ~R 68 In the formula, examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, the halogen-containing hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, the hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms or the hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms include the above-mentioned R 5 ~R 16 Examples of the groups include the same groups as those described above.

[0069] In another preferred embodiment, R 55 ~R 66 At least one of the groups represents a substituent having a cyclic structure represented by the following general formula (7). [ka] In general formula (7), A 2 indicates an atom in Group 14, 15, or 16 of the periodic table. R 75 , R 76 , R 77 , R 78 and R 79each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom, a sulfur atom or a nitrogen atom, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, and adjacent substituents may be bonded to each other, including the atom bonding thereto, to form a ring. p 2 is 0 or 1, and A 2 If is an atom in group 15 or 16 of the periodic table, p 2 is 0 and A 2 Substituent R 75 does not exist. 2 When is 0, A 2 is preferably an oxygen atom. 2 When is 1, A 2 is preferably a carbon atom. q 2 is 0 or 1, and q 2 If is 0, R 78 does not exist, and R 77 and the carbon atom to which R is bonded 79 is directly bonded to the carbon atom to which it is attached.

[0070] A 2 If is a carbon atom, R 75 ~R 79 Preferably, at least one of R is not a hydrogen atom. 75 ~R 79 is preferably not a halogen atom. R 75 ~R 79 When the group represented by is other than a hydrogen atom, the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, the silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, the halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or the hydrocarbon-substituted silyl group having 1 to 20 carbon atoms is the same as the above-mentioned R 5 ~R 16The same groups as those described in the explanation of X can be mentioned, and for the hydrocarbon group-substituted amino group having 1 to 20 carbon atoms or the alkoxy group having 1 to 20 carbon atoms, 1 and X 2 Examples of the groups include the same groups as those described above.

[0071] In another preferred embodiment, R 55 ~R 68 At least one of the groups represents a substituent having a cyclic structure represented by the following general formula (8). [ka] The definitions and preferred embodiments of each group in general formula (8) are the same as those described in formula (1).

[0072] The above-mentioned component (A-1) is highly efficient at producing polyolefins with narrow molecular weight distributions, and its relatively low copolymerizability results in the production of polymers with a low α-olefin content on the low molecular weight side. On the other hand, the bridged bis-Cp metallocene complex (component (A-2)) has good olefin copolymerizability. When ethylene is polymerized using these two types of complexes, polymers with different properties are obtained than those produced by a single metallocene complex. In particular, polymers showing an inverse comonomer composition distribution are easily obtained. Furthermore, the use of two types of complexes results in a broader molecular weight distribution. The compounds of component (A-1) and component (A-2) can be used in any combination as long as the conditions are met.

[0073] The olefin polymerization catalyst of the present invention contains the above-mentioned components (A-1) and (A-2), and each component is preferably selected so as to satisfy the following conditions (1) to (4).

[0074] Condition (1): An olefin polymerization catalyst (Cat (A-1) ) in the presence of hydrogen molecules to polymerize olefins, HLMFR is an olefin polymer HLMFR (A-1)and an olefin polymerization catalyst (Cat (A-2) ) and HLMFR, which is an HLMFR of an olefin polymer obtained under the same conditions. (A-2) But HLMFR (A-1) ≧HLMFR (A-2) Satisfy.

[0075] Like the melt flow rate (MFR), the HLMFR is a value that serves as a measure of the fluidity of a resin. As the molecular weight of a polymer decreases, the fluidity of the resin increases, so the HLMFR can be used as a measure to estimate the molecular weight. In the present invention, (A-1) plays a role in providing a low molecular weight polymer with a relatively narrow molecular weight distribution, so the HLMFR (A-1) ≧HLMFR (A-2) If the above condition is satisfied, the molecular weight distribution of the polymer will be broadened and a copolymer with excellent moldability can be obtained. (A-1) >HLMFR (A-2) It is more preferable to satisfy HLMFR (A-1) >5×HLMFR (A-2) It is more preferable to satisfy HLMFR (A-1) >10×HLMFR (A-2) It is particularly preferable that the following is satisfied. In this specification, HLMFR is a value measured in accordance with JIS K7210:2014 under conditions of 190°C and a load of 21.6 kg.

[0076] Condition (2):Cat (A-1) In the polymerization of olefins using (A-1) : the correlation coefficient α in the following definition formula, which represents the correlation between the unit (g olefin polymer / g catalyst / hour / MPa) (A-1) is between -10000 and +1000; Definition formula K (A-1) =α (A-1) Log[H2 / C2]+β (A-1) Here, the above formula represents the relationship between H2 / C2 and K when polymerization is performed at two H2 / C2 points separated by 0.05 mol% or more. (A-1)The coefficient α (A-1) is the slope of the line, and the intercept β (A-1) is the polymerization activity (K 1(A-1) )

[0077] The component (A-1) shows a tendency for the correlation between the polymerization activity and the hydrogen concentration to be negative. (A-1) When the value of is within the above range, the responsiveness to hydrogen when viewed alone of the catalyst becomes close to the tendency of component (A-2), and therefore the fluctuation in activity of the entire catalyst composition becomes small. Here, when the correlation coefficient according to the above definition formula is -1,000 to +1,000, the correlation with polymerization activity is defined as neutral, when it is less than -1,000, the correlation is negative, and when it is more than +1,000, the correlation is positive. The coefficient α (A-1) is more preferably -8000 to +1000, even more preferably -7000 to +700, and particularly preferably -6000 to +500. (A-1) It has been found that the absolute value of α increases as the polymerization temperature increases, and the coefficient α obtained in the same way when polymerization is performed at a temperature of 90°C is (A-1;90℃) is preferably −10,000 to +5,000, more preferably −10,000 to +4,000, and even more preferably −7,000 to +4,000, and the coefficient α obtained in the same manner by polymerization at a temperature of 70° C. (A-1;70℃) is preferably −10000 to +1000, more preferably −7000 to +700, even more preferably −6000 to +600, and particularly preferably −5000 to +500.

[0078] Condition (3):Cat (A-2) The H2 / C2 ratio and K obtained in the same manner as in condition (2) (A-2) Correlation coefficient α (A-2) is between -10000 and +1000; The component (A-2) shows a tendency for the correlation between the polymerization activity and the hydrogen concentration to be negative. (A-2)When the value of coefficient α is within the above range, the responsiveness to hydrogen when viewed alone becomes close to that of component (A-1), and fluctuations in activity throughout the catalyst composition become smaller. (A-2) is more preferably -8000 to +1000, further preferably -7000 to +700, and particularly preferably -6000 to +500. The coefficient α obtained in the same manner by polymerization at a temperature of 90°C (A-2;90℃) is preferably −10,000 to +5,000, more preferably −10,000 to +4,000, and even more preferably −7,000 to +4,000, and the coefficient α obtained in the same manner by polymerization at a temperature of 70° C. (A-2;70℃) is preferably −10000 to +1000, more preferably −7000 to +700, even more preferably −6000 to +600, and particularly preferably −5000 to +500.

[0079] Condition (4): α (A-1) and α (A-2) The absolute value of the difference |Δα| is 0 to 7030. When the above conditions (2) and (3) are satisfied, the responsiveness to hydrogen when viewed as a single catalyst has a negative correlation with each other and shows a similar tendency, but the smaller the difference in each correlation, the less the responsiveness to hydrogen when viewed as a binary complex catalyst as a whole fluctuates. The absolute value |Δα| is preferably 0 to 6000, more preferably 0 to 5000, even more preferably 0 to 4000, particularly preferably 0 to 3000, and most preferably 0 to 2000. The absolute value |Δα| obtained in the same manner when polymerized at a temperature of 90°C 90℃ is preferably 0 to 27,000, more preferably 0 to 26,000, and the absolute value |Δα| obtained in the same manner after polymerization at a temperature of 70°C is 70℃ is preferably 0 to 7000, more preferably 0 to 6000, even more preferably 0 to 5000, particularly preferably 0 to 4000, and most preferably 0 to 3000.

[0080] In one embodiment of the present invention, the olefin polymerization catalyst more preferably has the components (A-1) and (A-2) satisfying the following condition (5): Condition (5): Said Cat (A-1) The weight average molecular weight Mw of an olefin polymer obtained by polymerizing an olefin in the presence of hydrogen molecules using (A-1) And Cat (A-2) The weight average molecular weight Mw of the olefin polymer obtained under the same conditions was calculated using (A-2) But, Mw (A-1) ≦Mw (A-2) Satisfy. Component (A-2) has excellent olefin copolymerizability and gives a polymer with a relatively high molecular weight, which tends to increase the weight average molecular weight. (A-1) ≦Mw (A-2) If the above condition is satisfied, the copolymer will contain a large amount of high molecular weight components, and as a result, the copolymer will tend to incorporate a structure with a large amount of comonomers on the high molecular weight side, resulting in a copolymer with superior moldability and product strength. For this reason, it is preferable that component (A-2) is a catalyst that gives a polymer with a weight average molecular weight higher than that of component (A-1). (A-1) <Mw (A-2) It is more preferable to satisfy 3×Mw (A-1) <Mw (A-2) It is more preferable to satisfy 5 × Mw (A-1) <Mw (A-2) It is particularly preferable that the following is satisfied.

[0081] In one embodiment of the present invention, it is more preferable that the components (A-1) and (A-2) of the olefin polymerization catalyst satisfy the following condition (6): Condition (6): Said Cat (A-1) is the density of the olefin polymer obtained by polymerizing or copolymerizing olefins in the presence of hydrogen molecules using (A-1) And Cat (A-2) The density D of the olefin polymer obtained under the same conditions is calculated using (A-2) But, D (A-1) ≧D (A-2) Satisfy. Because component (A-2) has a strong tendency to incorporate comonomers into copolymers, polymers produced using component (A-2) as a catalyst tend to have a high comonomer content, resulting in a low density.(A-1) ≧D (A-2) If the above condition is satisfied, the copolymer tends to incorporate a structure containing a large amount of high molecular weight polymers with a high comonomer content, and a copolymer with excellent moldability and product strength can be obtained. For this reason, it is preferable that component (A-2) is a catalyst that gives a polymer with a lower density than component (A-1). That is, D (A-1) >D (A-2) It is preferable to satisfy D (A-1) >1.01×D (A-2) It is more preferable to satisfy D (A-1) >1.02×D (A-2) It is more preferable if D (A-1) >1.03×D (A-2) It is particularly preferable that D (A-1) >1.04×D (A-2) It is most preferable that the following conditions are satisfied.

[0082] 3.Method for synthesizing metallocene compounds The metallocene compound of the formula (1) can be synthesized by any method depending on the type of substituents or bonds. An example of a typical synthesis route is shown below. [ka]

[0083] In the above synthesis route, 3 is anionized with 1 equivalent of n-butyllithium or the like, then reacted with an excess amount of dimethyldichlorosilane, and the unreacted dimethyldichlorosilane is distilled off to obtain 4. The resulting 4 is then reacted with 2, which has previously been treated with 1 and 1 equivalent of an anionizing agent such as n-butyllithium, to obtain 5. 5 is then dianionized with 2 equivalents of n-butyllithium or the like, and then reacted with zirconium tetrachloride to obtain metallocene compound 6.

[0084] Metallocene compounds incorporating substituents different from those in the above synthesis examples can be synthesized by using the corresponding substituted raw materials. By using a substituted indene such as a phenyl group, 4-trimethylsilylphenyl group, 4-methylphenyl group, 4-i-propylphenyl group, 4-t-butylphenyl group, or 4-chlorophenyl group instead of the 5-methyl-2-furyl group at the 7-position of the indene in 1, a metallocene compound incorporating a corresponding substituent at the 4-position of the indenyl ring can be synthesized. Furthermore, by using a substituted indene such as an ethyl group, i-propyl group, t-butyl group, or phenyl group instead of the methyl group at the 1-position of the indene in 1, a metallocene compound incorporating a corresponding substituent at the 3-position of the indenyl ring can be synthesized. Alternatively, by using an indene in 1 in which the 1-position of the indene is unsubstituted, a metallocene compound incorporating an unsubstituted 3-position of the indenyl ring can be synthesized. Alternatively, by using a substituted indene having a substituent at at least one of the 4-, 5-, and 6-positions of the indene 1, a metallocene compound can be synthesized in which the corresponding substituents are introduced at the 5-, 6-, and 7-positions of the indenyl ring. Furthermore, by using a corresponding substituted cyclopentadiene, such as 2,3,5-trimethylcyclopentadiene or 2-ethyl-4,5-dimethylcyclopentadiene, instead of 3, metallocene compounds can be synthesized in which the corresponding substituents have been introduced into the cyclopentadiene.

[0085] Furthermore, by using a corresponding silane compound, such as diethyldichlorosilane, diphenyldichlorosilane, or 1,1-dichlorosilacyclobutane, instead of dimethyldichlorosilane as a crosslinking agent, it is possible to synthesize a metallocene compound having a corresponding crosslinking group. Also, by referring to Z. Naturforsch. 49b, 451-458 (1994), the crosslinking group structure when m is 1 and the crosslinking group structure when R 1 , R 2 , R 3 , and R 4 Q is bonded to 1 and Q 2It is possible to introduce a bridging group structure that forms a ring together with the metal M. By using titanium tetrachloride or hafnium tetrachloride instead of zirconium tetrachloride for the metal M, metallocene compounds in which the metal M is titanium or hafnium, respectively, can be synthesized. The metallocene compounds of the formula (1) above, such as those of the formula (1-1-1-1) and (1-1-2-1), which are preferred embodiments of the metallocene compound, can also be produced using a general synthesis method for metallocene compounds. Specifically, a general procedure involves synthesizing an indenyl lithium salt from indene and butyllithium, and then reacting two equivalents of the lithium salt with α,α'-dibromo-orthoxylene to synthesize α,α'-bis(1-indenyl)-orthoxylene, which is a ligand for the metallocene. Subsequently, a lithium salt of the ligand is synthesized using butyllithium, which is then reacted with zirconium tetrachloride to obtain the metallocene. By using various compounds having a cyclopentadienyl structure instead of the above-mentioned indene, it is possible to obtain metallocene compounds having a different cyclopentadienyl ring structure. In addition, when synthesizing the transition metal compound represented by formula (1), reference can be made to Example 1 of JP-A-9-286812 and the synthesis example of compound 1a described in Journal of Organometallic Chemistry 535 (1997) 29-32. 1 and R 2 A starting compound in which the carbon atoms corresponding to the carbon atoms to which R and R are bonded already form a monocyclic or polycyclic ring structure may be used, or a starting compound in which R and R are bonded to the carbon atoms to which R are bonded may be used during or at the final stage of synthesis. 1 and R 2 may be reacted to close the ring to form a cyclic structure.

[0086] The metallocene compounds of the above formulae (2-1) to (2-5) can be produced by methods known to those skilled in the art.

[0087] 4. [Component (B)] A compound that reacts with component (A-1) and component (A-2) to generate a cationic metallocene compound. The olefin polymerization catalyst of the present invention contains, as component (B), in addition to the above-mentioned components (A-1) and (A-2), a compound that reacts with the metallocene compounds of components (A-1) and (A-2) to form a cationic metallocene compound. The compound that reacts with component (A-1) and component (A-2) to form a cationic metallocene compound is not particularly limited and any known compound can be used, such as an organoaluminum oxy compound, a borane compound, or a borate compound.

[0088] When an organoaluminum oxy compound, a borane compound or a borate compound is used as component (B), the polymerization activity and copolymerizability are increased, thereby improving the productivity of olefin polymers.

[0089] A mixture of the organoaluminum oxy compound and the borane compound or borate compound can also be used as component (B). Furthermore, two or more of the borane compounds or borate compounds can be mixed and used. Each of these compounds will be described in more detail below.

[0090] (i) Organoaluminum oxy compounds The organoaluminum oxy compound has an Al-O-Al bond in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy compound is usually a product obtained by reacting an organoaluminum compound with water.

[0091] Among organoaluminum oxy compounds, those obtained by reacting alkylaluminum with water are generally called aluminoxanes and can be suitably used as component (B). Among aluminoxanes, methylaluminoxane (including those essentially consisting of methylaluminoxane (MAO)) is particularly suitable as an organoaluminum oxy compound. As the organoaluminum oxy compound, two or more of each organoaluminum oxy compound may be used in combination, or a solution in which the organoaluminum oxy compound is dissolved or dispersed in an inert hydrocarbon solvent described below may be used.

[0092] The reaction of organoaluminum with water is usually carried out in an inert hydrocarbon (solvent), which may be an aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, or xylene, but is preferably an aliphatic or aromatic hydrocarbon.

[0093] The organoaluminum compound used in the preparation of the organoaluminum oxy-compound may be any of the compounds represented by the following general formula (I), but trialkylaluminum is preferably used. R 40 t AlX 3 3-t (I) (In formula (I), R 40 represents a hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, such as an alkyl group, an alkenyl group, an aryl group, or an aralkyl group; X 3 represents a hydrogen atom or a halogen atom, and t represents an integer of 1≦t≦3.

[0094] Examples of the alkyl group of the trialkylaluminum include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, and dodecyl groups, with methyl being particularly preferred. The above organoaluminum compounds can be used alone or in combination of two or more.

[0095] The reaction ratio of water to the organoaluminum compound (water / Al molar ratio) is preferably 0.25 / 1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1 / 1, and the reaction temperature is usually in the range of -70 to 100°C, preferably -20 to 20°C. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. The water required for the reaction may not only be simple water, but also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate, etc., or components that can generate water in the reaction system.

[0096] (ii) Borane or borate compounds Furthermore, as component (B), the borane compounds and borate compounds described in paragraphs 0229 to 0242 of JP 2012-214780 A can be suitably used. Examples of such compounds include triphenylborane, tri(o-tolyl)borane, tri(p-tolyl)borane, tri(m-tolyl)borane, tri(o-fluorophenyl)borane, tris(p-fluorophenyl)borane, tris(m-fluorophenyl)borane, tris(2,5-difluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-trifluoromethylphenyl)borane, tris(3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoro ... tris(perfluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl), tris(perfluoroanthryl)borane, tris(perfluorobinaphthyl)borane, etc.; tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tributylammonium tetra(3,5-ditrifluoromethylphenyl)borate, tributylammonium tetra(perfluoronaphthyl)borate, dimethylanilinium tetra(pentafluorophenyl)borate, dimethylanilinium tetra(2,6-ditrifluoromethylphenyl)borate, dimethylanilinium tetra(3,5-ditrifluoromethylphenyl)borate, dimethylanilinium tetra(perfluoronaphthyl)borate, etc.; trityl tetra(pentafluorophenyl)borate, trityl tetra(2,6-ditrifluoromethylphenyl)borate, trityl tetra(pentafluorophenyl)borate, tetra(3,5-ditrifluoromethylphenyl)borate, trityl tetra(perfluoronaphthyl)borate, tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, tropinium tetra(3,5-ditrifluoromethylphenyl)borate, tropinium tetra(perfluoronaphthyl)borate, NaB(C6F5)4, NaB(2,6-(CF3)2-Ph)4, NaB(3,5-(CF3)2-Ph)4, NaB(C 10F7)4, HB(C6F5)4·2 ​​diethyl ether, HB(2,6-(CF3)2-Ph)4·2 diethyl ether, HB(3,5-(CF3)2-Ph)4·2 diethyl ether, HB(C 10 H7) 4·2 diethyl ether, etc.

[0097] (3-2) Layered silicates Layered silicates can be used as component (B), which can serve as both component (B) and component (C), which will be described later. By using a layered silicate as component (B), the polymerization activity and copolymerizability are increased, as in the case of using an organoaluminum oxy compound, a borane compound, or a borate compound, and therefore the productivity of olefin polymers is improved. Layered silicates are silicate compounds with a crystalline structure in which planes formed by ionic bonds or the like are stacked parallel to one another with weak bonding forces. Most layered silicates are naturally occurring, primarily as the main component of clay minerals, but these layered silicates are not limited to natural products and may also be artificially synthesized. Techniques for using these layered silicates as olefin polymerization catalyst components are well known in JP-A-5-301917, JP-A-8-127613, JP-A-2003-82018, JP-A-2017-165916, etc. Furthermore, compounds having similar effects, such as those listed in JP-A-2002-515522, etc., can also be suitably used as component (B) in the present invention.

[0098] Examples of layered silicates include known compounds described in "Clay Mineralogy" by Shiramizu Haruo, Asakura Shoten (1995), and specific examples include kaolin group compounds such as dickite, nacrite, kaolinite, anoxite, metahalloysite, and halloysite; serpentine group compounds such as chrysotile, lisardite, and antigorite; smectite group compounds such as montmorillonite, sauconite, beidellite, nontronite, saponite, taeniolite, hectorite, stevensite, bentonite, and sauconite; vermiculite group compounds such as vermiculite; mica group compounds such as mica, illite, sericite, and glauconite; attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, and chlorite group compounds.

[0099] More preferred layer silicates include smectites, vermiculites, and micas, such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, and taeniolite. Particularly preferred layer silicates are smectites.

[0100] Generally, natural layered silicates are often non-ion-exchangeable (non-swellable), and in such cases, it is preferable to subject them to a treatment to impart ion-exchangeability (or swelling ability) to give them desirable ion-exchangeability (or swelling ability). Among such treatments, the following chemical treatments are particularly preferred. Here, the chemical treatment can be either a surface treatment to remove impurities adhering to the surface or a treatment to affect the crystalline structure or chemical composition of the layered silicate. Known chemical treatment methods can be used, including the method described in JP-A-2003-82018. Specific examples include acid treatment, alkali treatment, metal salt treatment, and organic substance treatment. More preferred chemical treatments are acid treatment or metal salt treatment, specifically as follows: The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and oxalic acid, and more preferably selected from hydrochloric acid, sulfuric acid, and nitric acid.

[0101] The metal salt used in the metal salt treatment is an inorganic compound containing a cation containing at least one atom selected from the group consisting of Groups 2 to 14 atoms, preferably a compound consisting of a cation containing at least one atom selected from the group consisting of Groups 2 to 14 atoms and at least one anion selected from the group consisting of halogen atoms, inorganic acids, and organic acids, and more preferably a compound consisting of a cation containing at least one atom selected from the group consisting of Groups 2 to 14 atoms and at least one anion selected from the group consisting of Cl, Br, I, F, PO, SO, NO, CO, CO, ClO, OOCCH, CHCOCHCOCH, OCl, O(NO), O(ClO), O(SO), OH, OCl, OCl, OOCH, OOCCHCH, CHO, and CHO.

[0102] The proportions of the metallocene compounds of components (A-1) and (A-2) and the layered silicate as component (B) used are not particularly limited, but the following ranges are preferred: The total amount of components (A-1) and (A-2) supported is 0.0001 to 5 mmol, preferably 0.0005 to 0.5 mmol, more preferably 0.001 to 0.1 mmol, and particularly preferably 0.003 to 0.03 mmol per gram of layered silicate support.

[0103] 5.[Component (C)] The olefin polymerization catalyst of the present invention preferably uses, as an additional component, a particulate support (component (C)) which is an inorganic support, a particulate polymer support, or a mixture thereof. As the inorganic support, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof can be used.

[0104] Suitable metals that can be used for the inorganic support include, for example, iron, aluminum, nickel, and the like.

[0105] Metal oxides include single oxides or composite oxides of elements from Groups 1 to 14 of the Periodic Table, such as SiO2, Al2O3, MgO, CaO, BO3, TiO2, ZrO2, Fe2O3, Al2O3·MgO, Al2O3·CaO, Al2O3·SiO2, Al2O3·MgO·CaO, Al2O3·MgO·SiO2, Al2O3·CuO, Al2O3·Fe2O3, Al2O3·NiO, and SiO2·MgO. The above formulas are not molecular formulas but represent only the composition, and the structure and component ratios of the composite oxides used in the present invention are not particularly limited. The metal oxides used in the present invention may absorb small amounts of moisture and may contain small amounts of impurities. As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferred, and specifically, MgCl, CaCl, etc. are particularly preferred. As the metal carbonate, carbonates of alkali metals and alkaline earth metals are preferred, and specifically, magnesium carbonate, calcium carbonate, barium carbonate, etc. are included. Examples of carbonaceous materials include carbon black and activated carbon.

[0106] Any of the above inorganic carriers can be suitably used in the present invention, but metal oxides, silica, alumina, etc. are particularly preferred.

[0107] These inorganic supports are preferably used after being calcined in air or in an inert gas such as nitrogen or argon at 200 to 800°C, preferably 400 to 600°C, to adjust the amount of surface hydroxyl groups to 0.8 mmol / g to 1.5 mmol / g. The properties of these inorganic supports are not particularly limited, but the average particle size is usually 5 μm to 200 μm, preferably 10 μm to 150 μm, the average pore size is 20 Å to 1000 Å, preferably 50 Å to 500 Å, and the specific surface area is 150 m. 2 / g~1000m 2 / g, preferably 200m 2 / g~700m 2 / g, pore volume is 0.3 cm3 / g ~ 2.5 cm 3 / g, preferably 0.5 cm 3 / g ~ 2.0 cm 3 / g, apparent specific gravity is 0.20 g / cm 3 ~ 0.50 g / cm 3 , preferably 0.25 g / cm 3 ~ 0.45 g / cm 3 It is preferable to use an inorganic carrier having these properties.

[0108] The above-mentioned inorganic carrier can be used as it is, but after contacting these carriers with an organoaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, diisobutylaluminum hydride, or an organoaluminum oxy compound containing an Al-O-Al bond as a pretreatment, it can be used.

[0109] 6. [Component (D)] In the present invention, an organoaluminum compound can be further used as component (D) as needed. Specific examples of the organoaluminum compound include AlR j X 3-j (In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, X is a hydrogen atom, a halogen atom, an alkoxy group, and j is a number of 0 < j ≤ 3), such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, etc. of trialkylaluminum, or halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride and diethylaluminum methoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Among these, trialkylaluminum is particularly preferable. The amount of the organoaluminum compound used as component (D) is 0.01 to 10,000 millimoles, preferably 0.1 to 100 millimoles, more preferably 0.2 to 20 millimoles, and even more preferably 0.5 to 10 millimoles per 1 g of component (B).

[0110] 7. Production method of olefin polymerization catalyst The olefin polymerization catalyst used in the method for producing an olefin polymer of the present invention is produced by containing the above-mentioned component (A-1), component (A-2), (B), and, if necessary, component (C) and / or (D). The method for contacting the components (A) to (D) of the present invention when obtaining an olefin polymerization catalyst from the above-mentioned components (A) to (D) is not particularly limited. The order of contacting components (A-1), (A-2), (B), (C), and (D) is also not particularly limited. For example, the following methods can be optionally employed. Components (A-1) and (A-2) are contacted, then component (B) is contacted, and then components (C) and / or (D) are contacted. Either component (A-1) or component (A-2) is contacted with component (B), then the remaining component (A-1) and component (A-2) are contacted, and then components (C) and / or (D) are contacted. Either component (A-1) or component (A-2) is contacted with component (C) and / or (D), then the remaining component (A-1) and component (A-2) are contacted, and then component (B) is contacted. After component (B) is contacted with component (C) and / or (D), component (A-1) or component (A-2) is contacted in any order. A contact product obtained by contacting a product obtained by contacting component (A-1) and component (A-2) with component (C) and / or (D) is contacted with a contact product obtained by contacting component (B) with component (C) and / or (D).

[0111] In either contact method, the components are typically contacted with each other in an inert atmosphere such as nitrogen or argon, with or without stirring, in the presence of a liquid inert hydrocarbon, such as an aromatic hydrocarbon (typically having 6 to 12 carbon atoms) such as benzene, toluene, xylene, or ethylbenzene, or an aliphatic or alicyclic hydrocarbon (typically having 5 to 12 carbon atoms) such as pentane, heptane, hexane, decane, dodecane, or cyclohexane. This contact is typically carried out at a temperature of -100°C to 200°C, preferably -50°C to 100°C, and more preferably 0°C to 50°C, for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, and more preferably 30 minutes to 12 hours.

[0112] Furthermore, when component (A-1), component (A-2), component (B), and components (C) and / or (D) are brought into contact with each other, as described above, it is possible to use either an aromatic hydrocarbon solvent in which some components are soluble or slightly soluble, or an aliphatic or alicyclic hydrocarbon solvent in which some components are insoluble or slightly soluble.

[0113] When the contact reactions of the components are carried out stepwise, the solvent used in the previous step may be used as it is in the subsequent contact reaction without removing it. Alternatively, after the previous contact reaction using a soluble solvent, a liquid inert hydrocarbon in which certain components are insoluble or poorly soluble (e.g., an aliphatic, alicyclic, or aromatic hydrocarbon such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, or xylene) may be added to recover the desired product as a solid. Alternatively, after partially or completely removing the soluble solvent by drying, filtration, decantation, or the like to recover the desired product as a solid, the subsequent contact reaction of this desired product may be carried out using one of the above-mentioned inert hydrocarbon solvents. In the present invention, the contact reactions of the components may be carried out multiple times.

[0114] In the present invention, the proportions of component (A-1), component (A-2), component (B) and component (C) used are not particularly limited, but the following ranges are preferred.

[0115] When an organoaluminum oxy compound is used as component (B), the molar ratio (Al / M) of aluminum atoms in the organoaluminum oxy compound to the total of the transition metals (M) in components (A-1) and (A-2), which are the metallocene compounds of the present invention, is generally within the range of 1 to 100,000, preferably 5 to 2000, more preferably 50 to 1000, and particularly preferably 200 to 900. When a borane compound or a borate compound is used as component (B), the molar ratio (B / M) of boron atoms to the total transition metal (M) in components (A-1) and (A-2), which are the metallocene compounds of the present invention, is generally within the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10. Furthermore, when a mixture of an organoaluminum oxy compound and a borane compound and / or a borate compound is used as component (B), it is desirable that the proportions of aluminum atoms and boron atoms used in each compound in the mixture be the same as those described above relative to the total amount of the transition metal (M) in components (A-1) and (A-2), which are the metallocene compounds of the present invention. When a layered silicate is used as a carrier for component (B), the proportion of the layered silicate used is not particularly limited, but the following range is preferred: The amount of component (A-1) and component (A-2) supported is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, and more preferably 0.01 to 0.1 mmol per gram of layered silicate.

[0116] The amount of component (C) used as a fine particle carrier is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, and more preferably 0.01 to 0.1 mmol, of the total transition metal (M) in components (A-1) and (A-2) per 1 g of component (C).

[0117] The olefin polymerization catalyst can be obtained as a solid catalyst by contacting components (A-1), (A-2), (B), and (C) and / or (D) with one another using an appropriately selected contacting method as described above, followed by removal of the solvent. The solvent is desirably removed under normal pressure or reduced pressure at 0 to 200°C, preferably 20 to 150°C, and more preferably 20 to 100°C, for 1 minute to 100 hours, preferably 10 minutes to 50 hours, and more preferably 30 minutes to 20 hours.

[0118] The olefin polymerization catalyst can also be prepared by contacting component (A-1), component (A-2) with component (B) to remove the solvent, forming a solid catalyst component, which is then contacted with component (C) and / or (D) under polymerization conditions, or by contacting component (B) with component (C) and / or (D) to remove the solvent, forming a solid catalyst component, which is then contacted with component (A-1) and component (A-2) under polymerization conditions. In these contacting methods, the component ratios, contact conditions, and solvent removal conditions can be the same as those described above. The olefin polymerization catalyst thus obtained may be used after prepolymerization of monomers, if necessary.

[0119] 8. Method for producing olefin polymer The above-mentioned olefin polymerization catalyst can be used for olefin polymerization, particularly for the homopolymerization of ethylene or the copolymerization of ethylene with an olefin. Here, ethylene homopolymer refers to a polymer produced by supplying only ethylene to a reactor as a monomer raw material. The ethylene can be derived from at least one of petroleum-derived ethylene, biomass-derived ethylene, and ethylene obtained by chemical recycling.

[0120] The olefins used as comonomers include those having 3 to 30 carbon atoms, preferably 3 to 8 carbon atoms, and specific examples include propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene. Two or more olefins can also be copolymerized with ethylene. The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. When ethylene is copolymerized with another olefin, the amount of the other olefin can be selected arbitrarily within a range of 90 mol % or less of the total monomers, but is generally selected within a range of 40 mol % or less, preferably 30 mol % or less, and more preferably 10 mol % or less. Of course, it is also possible to use a small amount of a comonomer other than ethylene or an olefin. In this case, examples of the comonomer include compounds having a polymerizable double bond, such as styrenes such as styrene, 4-methylstyrene, and 4-dimethylaminostyrene; dienes such as 1,4-butadiene, 1,5-hexadiene, 1,4-hexadiene, and 1,7-octadiene; cyclic compounds such as norbornene and cyclopentene; and oxygen-containing compounds such as hexenol, hexenoic acid, and methyl octenoate.

[0121] In the present invention, the polymerization reaction can be carried out in the presence of the supported catalyst, preferably by slurry polymerization or gas-phase polymerization. In the case of slurry polymerization, ethylene or the like is polymerized in the presence or absence of an inert hydrocarbon solvent selected from aliphatic hydrocarbons such as isobutane, hexane, and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, in a state substantially free of oxygen and water. It goes without saying that liquid monomers such as liquid ethylene and liquid propylene can also be used as solvents. In the case of gas-phase polymerization, ethylene or the like is polymerized in a reactor into which gas streams of ethylene and comonomers are introduced, circulated, or circulated. In the present invention, gas-phase polymerization is more preferred.

[0122] [Polymerization temperature] The polymerization temperature for olefins according to the present invention is 0 to 250°C, preferably 20 to 110°C, more preferably 60 to 105°C, even more preferably 60 to 95°C, particularly preferably 60 to 90°C, and most preferably 60 to 85°C. At relatively low temperatures, the hydrogen-activity correlation of the catalyst of formula (1) tends to approach 0, and the hydrogen-activity correlations of the catalysts of formulas (2-1) to (2-5) tend to decrease. Therefore, it is preferable to carry out polymerization at a relatively low temperature range where the polymerization reaction proceeds.

[0123] [Ethylene partial pressure] The ethylene partial pressure in the olefin polymerization according to the present invention is preferably 0.1 MPa or more and less than 3 MPa, more preferably 0.3 MPa to 2.5 MPa, still more preferably 0.3 MPa to 1.4 MPa, and particularly preferably 0.5 MPa to 1.4 MPa. If the ethylene partial pressure is lower than 0.1 MPa, the polymerization activity may be low and the Mw may become too small, which is not preferable. An ethylene partial pressure of 3 MPa or higher is not preferable because it may result in an excessively large weight average molecular weight (Mw) or may require excessive pressure resistance in the polymerization reactor or post-treatment equipment, which may result in a deterioration in economic efficiency.

[0124] [Polymerization time] The polymerization time of the olefin according to the present invention is preferably 0.3 hours or more and less than 30 hours, more preferably 0.6 to 12 hours, and even more preferably 1 to 7 hours. If the polymerization time is shorter than 0.3 hours, the polymer yield per catalyst will be low and this is not economical. If the polymerization time exceeds 30 hours, the amount of polymer produced per volume of the polymerization reactor decreases, which is also uneconomical.

[0125] The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system.

[0126] Furthermore, the polymerization can be carried out without any problems even if a component for removing water, a so-called scavenger, is added to the polymerization system. Examples of such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, the organoaluminum oxycompounds, modified organoaluminum compounds containing branched alkyl groups, organozinc compounds such as diethylzinc and dibutylzinc, organomagnesium compounds such as diethylmagnesium, dibutylmagnesium, and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride. Among these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferred, with triethylaluminum being particularly preferred. The method can also be applied without any problems to multi-stage polymerization systems of two or more stages in which the polymerization conditions, such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature, are different from one another.

[0127] 9. Properties of Olefin Polymers An olefin polymer, particularly an ethylene polymer, produced using the olefin polymerization catalyst of the present invention preferably satisfies the following conditions (i) to (iii). Condition (i): MFR is 0.001 to 1000 g / 10 min. Condition (ii): Density is 0.895 to 0.975 g / cm 3 is. Condition (iii): At least one of the following conditions (iii-1), (iii-2), (iii-3), and (iii-4) is satisfied; Condition (iii-1): The molecular weight distribution (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 or more and 100 or less. Condition (iii-2): The branching index g' measured by a GPC measuring device combining a differential refractometer, a viscosity detector, and a light scattering detector is the minimum value (g L ) is greater than or equal to 0.20 and less than or equal to 0.95. Condition (iii-3): Melt flow rate (MFR) at a temperature of 190°C and a load of 10 kg 10kg The FR, which is the ratio of the melt flow rate (MFR) at a temperature of 190°C and a load of 2.16 kg to the melt flow rate (MFR), is 6.5 or more and 100 or less. Condition (iii-4): The ratio (HLMFR / MFR) of the melt flow rate at a temperature of 190°C and a load of 21.6 kg (HLMFR) to the melt flow rate at a temperature of 190°C and a load of 2.16 kg (MFR) is 20 or more and 1000 or less.

[0128] [Condition (i): MFR] The melt flow rate, i.e., MFR (190°C, 2.16 kg load) of the ethylene polymer obtained in the present invention is preferably 0.001 g / 10 min to 1000 g / 10 min, more preferably 0.005 g / 10 min to 200 g / 10 min, still more preferably 0.01 g / 10 min to 50 g / 10 min, and particularly preferably 0.02 g / 10 min to 5.0 g / 10 min.

[0129] [Condition (ii): Density] The density of the ethylene polymer obtained in the present invention is preferably 0.895 g / cm 3 ~0.975g / cm 3 and more preferably 0.900 g / cm 3 ~0.970g / cm 3 and more preferably 0.945 g / cm 3 ~0.965g / cm 3 The density can be adjusted by the type of polymerization catalyst or the combination thereof. Here, the density was measured in accordance with JIS-K7112, in which pellets were melted in a thermal compression molding machine at 160°C, cooled at a rate of 25°C / min to form a sheet with a thickness of 2 mm, and the sheet was conditioned in a room at 23°C for 48 hours, then placed in a density gradient tube and measured. A density within the above range is preferred because it provides an excellent balance of mechanical strengths such as rigidity, impact strength, and long-term durability.

[0130] [Condition (iii-1) Mw / Mn] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the olefin polymer obtained by the present invention, as measured by gel permeation chromatography (GPC), is preferably 3.5 or more, more preferably 3.7 or more, even more preferably 4.0 or more, and particularly preferably 5.0 or more, and is preferably 100 or less, more preferably 80 or less, even more preferably 60 or less, and particularly preferably 50 or less. Mw / Mn within the above range is preferred because it provides excellent molding processability such as melt tension and melt fluidity, and also provides an excellent balance of mechanical strengths such as rigidity, impact strength, and long-term durability.

[0131] In the present invention, the Mw and Mn of the olefin polymer are those measured by gel permeation chromatography (GPC).

[0132] [GPC method measurement] The retention volume was measured by GPC, and the molecular weight was calculated using a calibration curve prepared using standard polystyrenes. The standard polystyrenes used were all manufactured by Tosoh Corporation and were the following brands: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000. A calibration curve is created by injecting 0.2 mL of a solution dissolved in orthodichlorobenzene (ODCB) (containing 0.5 mg / mL of BHT (2,6-di-t-butyl-4-methylphenol)) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximating with the least squares method. For conversion to molecular weight, a general-purpose calibration curve is used, referring to "Size Exclusion Chromatography" by Mori Sadao (Kyoritsu Shuppan). The viscosity equation used in this case is [η] = K × M α The following values ​​are used: PS:K = 1.38 × 10 -4 , α=0.7 PE:K = 3.92 × 10 -4 , α=0.733 The GPC measurement conditions are as follows: Apparatus: Waters GPC (ALC / GPC 150C) Detector: Polymer Char IR-4 Column: Showa Denko AT-806MS (3 columns) Mobile phase solvent: o-dichlorobenzene (ODCB) Measurement temperature: 140℃ Flow rate: 1.0ml / min Injection amount: 0.3ml Sample preparation: A 1 mg / mL solution of the sample is prepared using ODCB (containing 0.5 mg / mL of BHT), and the sample is dissolved at 140°C for approximately 1 hour. The method for setting the baseline and intervals of the obtained chromatogram is well known to those skilled in the art.

[0133] [Condition (iii-2) Branching index] The olefin polymer obtained by the present invention preferably has a branching index g' of 0.20 to 0.95 at a molecular weight of 100,000 to 10,000,000, as measured by a GPC measuring device combining a differential refractometer, a viscosity detector, and a light scattering detector. The lower limit of gL may be 0.23 or more, 0.25 or more, 0.30 or more, 0.35 or more, or 0.40 or more. The upper limit of gL may be 0.93 or less, 0.90 or less, or 0.85 or less. A minimum branching index g' within the above range is preferred because it facilitates the production of an ethylene polymer with excellent moldability.

[0134] (i) Branch structure analysis by GPC-VIS A Waters Alliance GPCV2000 GPC system equipped with a differential refractometer (RI), a viscosity detector (viscometer), and a light scattering detector was used. A Wyatt Technology DAWN-HELEOS II multi-angle laser light scattering detector (MALLS) was used as the light scattering detector. The detectors were connected in the following order: MALLS, RI, and Viscometer. The mobile phase solvent was 1,2,4-trichlorobenzene (with the antioxidant Irganox 1076 added at a concentration of 0.5 mg / mL). The flow rate was 1 mL / min. Two Tosoh GMHHR-H(S) HT columns were used in series. The temperature of the column, sample injection port, and each detector was 140 °C. The sample concentration was 1 mg / mL. The injection volume (sample loop volume) was 0.2175 mL. To calculate the absolute molecular weight (M), the squared radius of inertia (Rg) obtained from MALLS, and the intrinsic viscosity ([η]) obtained from the Viscometer, the data processing software ASTRA (version 4.73.04) attached to MALLS was used, and calculations were performed with reference to the following literature.

[0135] References: 1.Developments in polymer characterization,vol.4.Essex:Applied Science;1984.Chapter 1. 2.Polymer,45,6495-6505(2004) 3.Macromolecules,33,2424-2436(2000) 4.Macromolecules,33,6945-6952(2000)

[0136] (ii) Calculation of branching index (g') The branching index (g') is calculated as the ratio (ηbranch / ηlin) of the intrinsic viscosity (ηbranch) obtained by measuring a sample with the above-mentioned viscometer to the intrinsic viscosity (ηlin) obtained by separately measuring a linear polymer. When long-chain branches are introduced into a polymer molecule, its radius of gyration decreases compared to a linear polymer molecule of the same molecular weight. Since a smaller radius of gyration results in a smaller intrinsic viscosity, the ratio of the intrinsic viscosity (ηbranch) of a branched polymer to the intrinsic viscosity (ηlin) of a linear polymer of the same molecular weight (ηbranch / ηlin) decreases as long-chain branches are introduced. Therefore, a branching index (g' = ηbranch / ηlin) less than 1 indicates the introduction of branches, and a smaller value indicates an increase in the amount of long-chain branches introduced. Here, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) is used as the linear polymer for comparison. The probability of introducing long-chain branches increases with increasing molecular weight (degree of polymerization) of the polymer, provided sufficient macromonomers that will become long-chain branches are present. Meanwhile, whether or not the main chain propagation reaction proceeds to a high molecular weight range while copolymerizing macromonomers depends largely on the capabilities of the olefin polymerization catalyst. It is believed that the novel olefin polymerization catalyst of the present invention can achieve this.

[0137] [Condition (iii-3)FR] The olefin polymer obtained by the present invention has a melt flow rate (MFR) of 190°C under a load of 10 kg. 10kg It is preferable that FR, which is the ratio of the melt flow rate (MFR) at a temperature of 190°C and a load of 2.16 kg to the melt flow rate (MFR), is 6.5 or more and 100 or less. When FR is in this range, the fluidity during melting becomes more suitable for molding. The lower limit of FR is more preferably 8 or more, even more preferably 8.5 or more, and particularly preferably 9 or more. The upper limit of FR is more preferably 80 or less, even more preferably 60 or less, and particularly preferably 50 or less. When FR is in the above range, an ethylene-based polymer having even better molding processability is easily obtained, which is preferable. The measurement conditions of MFR for determining the FR value are as described above.

[0138] [Condition (iii-4): HLMFR / MFR] The olefin polymer obtained by the present invention preferably has a ratio (HLMFR / MFR) of the melt flow rate (HLMFR) at a temperature of 190°C and a load of 21.6 kg to the melt flow rate (MFR) at a temperature of 190°C and a load of 2.16 kg, of more than 20 and not more than 1,000. The lower limit of HLMFR / MFR is more preferably 25 or more, even more preferably 30 or more, and particularly preferably 40 or more. The upper limit is more preferably 900 or less, even more preferably 800 or less, and particularly preferably 700 or less. Furthermore, it is empirically known that for olefin polymers produced using the same catalyst, the HLMFR / MFR increases as the MFR decreases, and this tendency is particularly noticeable in the MFR range of 1 or less. Therefore, it may be preferable for the olefin polymer obtained by the present invention to satisfy the following condition (iia): Condition (IIA): When MFR>1, as described above, HLMFR / MFR is preferably more than 20 and 500 or less. If MFR≦1, HLMFR / MFR>71×LogMFR+20 is satisfied. More preferably, HLMFR / MFR>71×LogMFR+25 is satisfied, More preferably, HLMFR / MFR>71×LogMFR+30 is satisfied. The upper limit of HLMFR / MFR is as described above, and MFR is usually 0.001 or more and 1000 or less. When the HLMFR / MFR value is in this range, the fluidity during melting becomes suitable for molding.

[0139] In this specification, MFR is a value measured in accordance with JIS K7210:2014 under conditions of 190°C and a load of 2.16 kg, and HLMFR is a value measured in accordance with the same JIS under conditions of a load of 21.6 kg.

[0140] Whether the olefin polymer obtained by the present invention has an inverse comonomer distribution can be evaluated by an integrated elution curve measured by cross fractionation chromatography (CFC). CFC consists of a temperature rising elution fractionation (TREF) section for crystallinity fractionation and a gel permeation chromatography (GPC) section for molecular weight fractionation. In CFC, the comonomer amount evaluated by TREF is calculated for each molecular weight measured by GPC, and the molecular weight and comonomer amount are displayed on a two-dimensional chart. This results in a "comonomer composition distribution," which comprehensively indexes the distribution of comonomer amounts and molecular weights of individual polymers contained in the entire copolymer. Ethylene-α-olefin copolymers obtained by conventional general catalytic polymerization often exhibit a so-called normal comonomer composition. In this state, the chart often tends to rise to the right and left, centered on the intersection of the temperature at which the elution amount reaches 50% by weight and the weight-average molecular weight. On the other hand, the preferred ethylene polymer of the present invention has a so-called inverse comonomer composition as one of its characteristics. When an inverse comonomer composition is present, the chart will either expand to the lower right or upper left, or will have an overall shape that is close to an ellipse.

[0141] Analytical techniques using CFCs are well known, as seen in International Publication WO 2015 / 152267 and elsewhere. Specifically, they are performed as follows: First, a polymer sample is completely dissolved in ODCB containing 0.5 mg / mL BHT at 140 °C. This solution is then injected through the sample loop of the instrument into a TREF column (a column packed with inert glass bead support) maintained at 140 °C. The solution is then gradually cooled to the specified first elution temperature to crystallize the polymer sample. After 30 minutes at the specified temperature, ODCB is passed through the TREF column. The eluted components are injected into the GPC section for molecular weight fractionation, and a chromatogram is obtained using an infrared detector (FOXBORO MIRAN 1A IR detector, measurement wavelength 3.42 μm). Meanwhile, the TREF section is heated to the next elution temperature. After obtaining a chromatogram at the first elution temperature, the eluted components at the second elution temperature are injected into the GPC section. By repeating the same procedure, chromatograms of the eluted components at each elution temperature are obtained.

[0142] The CFC measurement conditions are as follows: GPC column: Showa Denko AD-806MS (3 columns connected in series) Solvent: ODCB Sample concentration: 3mg / mL Injection volume: 0.4mL Crystallization rate: 1℃ / min Solvent flow rate: 1 mL / min GPC measurement time: 34 minutes Stabilization time after GPC measurement: 5 minutes Elution temperature (℃): 0,5,10,15,20,25,30,35,40,45,49,52,55,58,61,64,67,70,73,76,79,82,85,88,91,94,97,100,102,120,140

[0143] (Data Analysis) From the chromatograms of the eluted components at each elution temperature obtained by the measurement, the elution volume (proportional to the area of ​​the chromatogram) normalized so that the sum is 100% is determined. Furthermore, an integral elution curve for each elution temperature is calculated. This integral elution curve is differentiated with respect to temperature to obtain a differential elution curve. Furthermore, the molecular weight distribution is determined from each chromatogram using the following procedure. The conversion from retention volume to molecular weight is as described above for GPC measurements. In the chromatogram at the first elution temperature, the peak due to BHT added to the solvent may overlap with the low molecular weight side of the eluted components. In such cases, a baseline is drawn to determine the interval for determining the molecular weight distribution.

[0144] Furthermore, the whole weight average molecular weight is calculated from the elution ratio (weight % (wt%) in the table) and the weight average molecular weight (Mw in the table) at each elution temperature, and a graph (contour diagram) showing the elution amount relative to the elution temperature and molecular weight as contour lines is obtained from the molecular weight distribution and elution amount at each elution temperature according to the method described in the literature (S. Nakano, Y. Goto, Development of automatic Cross Fractionation: Combination of Crystallizability Fractionation and Molecular Weight Fractionation, J. Appl. Polym. Sci., vol. 26, pp. 4217-4231 (1981)).

[0145] The olefin polymer produced by the production method of the present invention can be isolated from the polymerization reactor and used for various purposes as a product in the form of granules, pellets, lumps, sheets, strands, melts, slurries, solutions, etc. Furthermore, the olefin polymer obtained using the olefin polymerization catalyst of the present invention is a polymer of stable quality due to the fact that the catalyst exhibits little fluctuation in activity with changes in the polymerization environment, and therefore various products of higher quality can be provided. Furthermore, it is also possible to copolymerize the olefin polymer with other monomers such as ethylene and olefins in the second or subsequent polymerization reactor of a multistage polymerization apparatus connected to the polymerization reactor for producing the olefin polymer. In this case, it is possible to produce various polyolefin resins having useful molecular weight distributions and comonomer distribution structures, which is preferable. [Example]

[0146] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The evaluations and resins used in the examples and comparative examples are as follows. The following catalyst synthesis step and polymerization step were all carried out under a purified nitrogen atmosphere, and the solvents used were dehydrated and purified using molecular sieves such as 4A and 13X.

[0147] 1. Various evaluation (measurement) methods (1)MFR: Measurement was carried out in accordance with JIS K6760 at 190°C under a load of 2.16 kg. MFR 5kg was measured in the same manner under the conditions of 190°C and a load of 5.0 kg. The HLMFR was similarly measured under conditions of 190°C and a load of 21.6 kg.

[0148] (2) Measurement of molecular weight Mw and molecular weight distribution (Mw / Mn): Measurement was carried out according to the method described in the above condition (i).

[0149] (1) Synthesis of component (A-1) (1) Meso-4,5-dimethyl-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound 11M) represented by the following chemical formula was synthesized according to the following method. [ka] (1-1) Synthesis of 1,2-bis(chloromethyl)-4,5-dimethylbenzene A 500 ml flask was charged with 10.00 g (0.09419 mol) of o-xylene and 94.20 ml (0.9487 mol) of concentrated hydrochloric acid and cooled to 0°C. To this was added 8.55 g (0.0377 mol) of 1-butyl-3-methylimidazolium tetrafluoroborate and 8.56 g (0.283 mol) of paraformaldehyde, followed by stirring at 70°C for 12 hours. An additional 94.20 ml (0.9487 mol) of concentrated hydrochloric acid and 2.85 g (0.0942 mol) of paraformaldehyde were added, followed by stirring at 70°C for an additional 12 hours. The reaction mixture was concentrated by evaporation under reduced pressure, 200 ml of distilled water was added, and the mixture was extracted three times with 200 ml of dichloromethane. The resulting organic phase was washed with 200 ml of distilled water and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column (petroleum ether) to obtain 18.00 g (yield 94%) of a white powder of 1,2-bis(chloromethyl)-4,5-dimethylbenzene.

[0150] (1-2) Synthesis of 1,2-bis(1-indenylmethyl)-4,5-dimethylbenzene A 500 ml flask was charged with 17.16 g (0.1477 mol) of indene and 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. 55.14 ml (0.1379 mol) of a 2.5 M n-butyllithium / n-hexane solution was added dropwise, and the mixture was allowed to warm to room temperature and stirred for 2 hours. The mixture was again cooled to -78 °C, and a solution of 10.00 g (0.04923 mol) of 1,2-bis(chloromethyl)-4,5-dimethylbenzene in 50 ml of THF was added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was slowly poured into 200 ml of distilled water and extracted three times with 250 ml of dichloromethane. The resulting organic phase was washed with 120 ml of saturated brine and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column (petroleum ether / ethyl acetate=10 / 1) to obtain 12.00 g (yield 67%) of yellow oil of 1,2-bis(1-indenylmethyl)-4,5-dimethylbenzene.

[0151] (1-3) Synthesis of meso-4,5-dimethyl-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride A 200 ml flask was charged with 1.99 g (5.49 mmol) of 1,2-bis(1-indenylmethyl)-4,5-dimethylbenzene and 60 ml of THF, and cooled to -78°C. 7.20 ml (11.4 mmol) of a 1.58 M n-butyllithium / n-hexane solution was added dropwise, and the mixture was allowed to warm to room temperature and stirred for 3 hours. A separately prepared solution of 1.54 g (6.61 mmol) of zirconium tetrachloride in 10 ml of n-hexane and 40 ml of THF was added at 0°C, and the mixture was stirred overnight while gradually warming to room temperature. The solvent was removed from the reaction mixture by distillation under reduced pressure, yielding a yellow powder. 35 ml of toluene was added to this powder at room temperature, and the mixture was stirred for 30 minutes. Insoluble matter was removed by filtration, and the solvent was removed from the filtrate by distillation under reduced pressure, yielding a yellow powder again. The resulting yellow powder was recrystallized from a mixed solvent of dichloromethane and n-hexane to obtain 0.284 g (yield 10%) of a yellow powder of meso-4,5-dimethyl-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound 11M). 1 H-NMR value (CDCl3): δ2.35(s,6H),δ3.99(d,2H),δ4.13(d,2H),δ5.97(d,2H),δ6.01 (d,2H),δ7.12(dd,2H),δ7.19(s,2H),δ7.31(dd,2H),δ7.42(d,2H),δ7.64(d,2H)

[0152] (2) Synthesis of component (A-1) (2) Racemic-4,5-dichloro-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound 11R) represented by the following chemical formula was synthesized according to the following method. [ka] (2-1) Synthesis of 1,2-bis(hydroxymethyl)-4,5-dichlorobenzene A 500 ml flask was charged with 10.0 g (46.1 mmol) of 4,5-dichlorophthalic anhydride and 250 ml of THF and cooled to 0°C. 2.62 g (69.1 mmol) of lithium aluminum hydride was added and stirred at 25°C for 16 hours. The reaction mixture was quenched with 11 ml of distilled water and 3 ml of 15% aqueous sodium hydroxide solution, and the insoluble material was removed by filtration. The solvent in the filtrate was evaporated to afford 8.70 g (91.2% yield) of crude 1,2-bis(hydroxymethyl)-4,5-dichlorobenzene.

[0153] (2-2) Synthesis of 1,2-bis(chloromethyl)-4,5-dichlorobenzene A 500 ml flask was charged with 6.00 g (29.0 mmol) of crude 1,2-bis(hydroxymethyl)-4,5-dichlorobenzene, 150 ml of dichloromethane, 11.0 g (57.7 mmol) of p-toluenesulfonyl chloride, 8.80 g (87.0 mmol) of triethylamine, and 354 mg (2.90 mmol) of dimethylaminopyridine, and the mixture was stirred at 25°C for 12 hours. 150 ml of distilled water was added, and the mixture was extracted three times with 150 ml of dichloromethane. The resulting organic phase was washed with 150 ml of saturated brine and dried over anhydrous sodium sulfate. The sodium sulfate was filtered, the solvent was removed under reduced pressure, and the mixture was purified using a silica gel column to obtain 5.20 g (73.5% yield) of 1,2-bis(chloromethyl)-4,5-dichlorobenzene.

[0154] (2-3) Synthesis of 1,2-bis(1-indenylmethyl)-4,5-dichlorobenzene A 300 ml flask was charged with 6.43 g (55.3 mmol) of indene and 150 ml of THF and cooled to -78°C. 22.66 ml (51.7 mmol) of a 2.50 M n-butyllithium / n-hexane solution was added dropwise, and the mixture was allowed to warm to room temperature and stirred for 2 hours. The mixture was cooled again to -78°C, and 4.50 g (18.5 mmol) of 1,2-bis(chloromethyl)-4,5-dichlorobenzene in 20 ml of THF was added. The mixture was allowed to warm to room temperature and stirred for 16 hours. The reaction mixture was slowly poured into 150 ml of distilled water and extracted three times with 150 ml of dichloromethane. The resulting organic phase was washed with 150 ml of saturated brine and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column (petroleum ether) to obtain 3.80 g (yield 51.1%) of 1,2-bis(1-indenylmethyl)-4,5-dichlorobenzene.

[0155] (2-4) Synthesis of racemic-4,5-dichloro-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride A 200 ml flask was charged with 1.21 g (3.00 mmol) of 1,2-bis(1-indenylmethyl)-4,5-dichlorobenzene and 50 ml of THF, and the mixture was cooled to -78 °C. 3.95 ml (6.24 mmol) of a 1.58 M n-butyllithium / n-hexane solution was added dropwise, and the mixture was stirred at -78 °C for 30 minutes, followed by stirring at room temperature for an additional hour. A separately prepared solution of 0.839 g (3.60 mmol) of zirconium tetrachloride in 5 ml of n-hexane and 20 ml of THF was added at 0 °C, and the mixture was stirred at room temperature for 4 hours. The solvent was removed from the reaction mixture by distillation under reduced pressure, yielding a yellow powder. 60 ml of toluene was added to this powder at room temperature, and the insoluble matter was removed by filtration. The solvent was removed from the filtrate by distillation under reduced pressure, yielding a yellow powder again. The obtained yellow powder was recrystallized from a mixed solvent of dichloromethane and diethyl ether to obtain 0.106 g (yield 6%) of a yellow powder of racemic-4,5-dichloro-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound 11R). 1H-NMR value (CDCl3): δ4.19(d,2H),δ4.32(d,2H), δ5.74(s,br,2H),δ6.28(s,br,2H),δ7.19(t,2H),δ7.32(t,2H),δ7.47(s,br,2H),δ7.60(s,2H),δ7.62(d,2H).

[0156] (3) Synthesis of component (A-1) (3) Dimethylsilylene(3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (metallocene compound 13) shown in the following chemical formula was synthesized according to the method described in paragraphs 0135 to 0139 of JP 2017-165726 A, and this was named metallocene compound 13. [ka]

[0157] (4) Synthesis of component (A-1) (4) Metallocene compound 14 shown in the following chemical formula was synthesized according to the method described in paragraphs 0140 to 0143 of JP-A No. 2013-227271. [ka]

[0158] (5) Synthesis of component (A-1) (5) Meso-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound 12M) shown in the following chemical formula was synthesized by referring to the procedure of Complex 1 described in the Experimental Section of Macromolecules 1995, 28, 4801-4805, and this was used as metallocene compound 12M. [ka]

[0159] (6) Preparation of component (A-2) Racemic dimethylsilylenebis-6-(2,5-dimethyl-3-phenylcyclopentadienyl-[1,2-b]-thiophene)zirconium dichloride (metallocene compound 22) shown in the following chemical formula was synthesized according to the procedure described in Example 1 of JP-A No. 2003-517010, and this was named metallocene compound 22. [ka]

[0160] (7) Preparation of component (A-2) Racemic dimethylsilylenebis-6-(2,5-dimethyl-3-(4-t-butylphenyl)cyclopentadienyl-[1,2-b]-thiophene)zirconium dichloride (metallocene compound 23) shown in the chemical formula below was obtained in the same manner as in (6) above, except that 2,5-dimethyl-3-phenylcyclopentadiene was changed to 2,5-dimethyl-3-(4-t-butylphenyl)cyclopentadienyl. [ka]

[0161] (7) Synthesis of comparative catalyst components As a comparative compound, racemic dimethylsilylenebis(2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl)zirconium dichloride (metallocene compound 21) shown in the following chemical formula was synthesized by synthesizing a ligand according to the procedure described in Synthesis Example 1 of Japanese Patent Application No. 2011-008562, using zirconium tetrachloride instead of hafnium tetrachloride, and this was named metallocene compound 21. [ka]

[0162] [Example 1] (1) Synthesis of olefin polymerization catalyst Under a nitrogen atmosphere, 10.0 g of silica particles calcined at 400°C for 7 hours were placed in a 500 ml two-neck flask and dried under reduced pressure for 1 hour using a vacuum pump while heating in a 150°C oil bath. Subsequently, 100 ml of toluene was added to form a slurry of silica, and then 26.7 ml of a 20% toluene solution of methylaluminoxane (manufactured by Grace) (equivalent to 80 mmol of Al) was added at 80°C. After stirring for 1 hour at 80°C, the mixture was washed three times with toluene to obtain a methylaluminoxane-supported silica slurry. In a separate 100 ml two-neck flask, under a nitrogen atmosphere, 104.5 mg of the above metallocene compound 11M (equivalent to 200 μmol of metallocene compound) and 33.4 mg of the above metallocene compound 22 (equivalent to 50 μmol of metallocene compound) were placed at room temperature and dissolved in 50 ml of toluene. The entire amount of the obtained toluene solution of the mixed metallocene compound was added to the above methylaluminoxane-supported silica slurry stirred at 40°C, and stirring was continued for 1 hour. Finally, after washing with hexane three times, the solvent was distilled off under reduced pressure to obtain an olefin polymerization catalyst powder.

[0163] (2) Manufacture of ethylene polymers A 2-liter stainless steel autoclave equipped with a stirrer and temperature controller was charged with 800 ml of thoroughly dehydrated and deoxygenated isobutane, 1.2 ml of 1-hexene, and 1.0 mmol of triisobutylaluminum, and the temperature was raised to 80°C with stirring. After adding a trace amount of hydrogen, ethylene was introduced until the partial pressure reached 1.0 MPa. 43 mg of the olefin polymerization catalyst prepared in (1) above was injected into the autoclave using nitrogen gas, and polymerization was continued for 60 minutes while maintaining the ethylene partial pressure at 1.0 MPa and the temperature at 80°C. 0.7 ml of 1-hexene was added during the polymerization, and the average molar ratio of hydrogen to ethylene (H2 / C2) during polymerization was 0.038 mol%. As a result, 197 g of ethylene polymer was produced. The MFR of the obtained polymer was 1.5 g / 10 min, the HLMFR was 44 g / 10 min, and the density was 0.9565 g / cm. 3 The results are summarized in the table.

[0164] Examples 2 to 7 Ethylene polymers were produced in the same manner as in Example 1, except that the types and ratios of the metallocene compounds were changed as shown in the table. The polymerization conditions and results are summarized in Table 1.

[0165] (Comparative Examples 1 to 8) Ethylene polymers were produced in the same manner as in Example 1 (Comparative Examples 1 to 8), except that the metallocene compounds were changed to the types and proportions shown in Table 1. As reference examples, ethylene polymers were produced using either component (A-1) or (A-2) alone as the catalyst.

[0166] [Table 1]

[0167] The copolymers obtained in the above examples and comparative examples were analyzed by GPC measurement and MFR measurement. The results are summarized in Table 2 together with the polymerization conditions.

[0168] [Table 2]

[0169] Explanation of experimental results As shown by Examples 1 to 5 in Table 1, by using metallocene compound 11M, metallocene compound 11R, and metallocene compound 13 as component (A-1) and metallocene compound 22 as component (A-2) as catalysts using two types of metallocene compounds in combination, polyethylenes could be produced over a wide HLMFR range, and all of them had large values ​​of FR, HLMFR / MFR, and Mw / Mn, and had fluidity suitable for melt molding. When ethylene was polymerized under the same conditions as in the above example using a catalyst containing metallocene compound 22 alone, the α (A-2) is -1310, and the α of metallocene compound 21 used as component (A-2) in Comparative Examples 1 to 8 is (A-2) The correlation between the polymerization activity and the hydrogen concentration tends to be negative or neutral, closer to 0, than +4890. On the other hand, the α of metallocene compound 11M, which is commonly used as component (A-1) in Examples 1 and 2 and Comparative Examples 1 to 3, (A-1) is -2150, which indicates a negative correlation between the polymerization activity and the hydrogen concentration. (A-2) The absolute value of the difference between (A-1) and α (A-2) The absolute value of the difference |Δα| between the two catalysts was 7040 for the binary complex catalysts used in Comparative Examples 1 to 3, i.e., catalyst combinations with significantly different correlations of polymerization activity with hydrogen concentration, whereas the binary complex catalysts used in Examples 1 to 5 had small values ​​of 840, 540, and 1080. In other words, the catalyst combinations had similar correlations of polymerization activity with hydrogen concentration, and the catalyst composition as a whole had a characteristic in which response to hydrogen was less likely to fluctuate, as is evident from the magnitude of the A value between each Example and Comparative Example in Table 1. The A value is the correlation coefficient A in the following formula, which represents the correlation between the H2 / C2 ratio (unit: mol%) and HLMFR (unit: g / 10 min) in olefin polymerization using the binary complex catalyst of the present invention. CAT is; Definition formula Log[HLMFR]=A CAT Log[H2 / C2]+B Here, the above formula represents an approximate straight line in the range of H2 / C2 = about 0.04 to about 0.2 mol% obtained from the relationship between H2 / C2 and HLMFR on a double logarithmic graph when polymerization is performed under the same conditions, and the coefficient A CAT is the slope of the line, and the intercept B is the logarithm of the HLMFR when H2 / C2 = 1 mol%. As an example of a catalyst that can be stably controlled in quality using standard management methods in the operation of a polyolefin manufacturing plant, a single catalyst such as metallocene compound 21 can be given. CAT is estimated to be about 4.0, whereas the A of the catalysts of Comparative Examples 7 and 8, which have very large |Δα| CAT The HLMFR is -22, and since it changes suddenly with even a slight change in hydrogen concentration, stable control is difficult. In addition, the catalysts of Comparative Examples 4 to 6 are two-way catalysts in which metallocene compounds of component (A-1) and component (A-2), which have very large |Δα| values, are combined in different ratios, just like the catalyst of Comparative Example 8. CAT is -0.9, which is extremely close to 0. This means that the catalyst does not allow for the HLMFR to be adjusted by changing the hydrogen concentration, as is done in the conventional way, and since such a catalyst cannot provide polyethylene resins with various HLMFRs, it is unsuitable for commercial use. The catalysts of Comparative Examples 1 to 3 are also two-way catalysts with very large |Δα| values, similar to the catalysts of Comparative Examples 4 to 6. CAT is -0.3, which is extremely close to 0, and for the same reason is unsuitable for commercial use. In contrast to these comparative examples, the binary complex catalysts used in Examples 1 to 5 are binary catalysts with a small |Δα| CAT The slope of the change in HLMFR with respect to H2 / C2 is 1.9 and 2.9, which are moderately positive values, and the A of the single catalyst of the above-mentioned metallocene compound 21, which can be controlled to have stable quality. CAT Since the HLMFR was 4.0 or less, it was shown that it was possible to easily adjust the HLMFR by adjusting the hydrogen concentration. As shown in Examples 6 and 7 in Table 1, polyethylene with large FR and Mw / Mn values ​​and flowability suitable for melt molding could be produced by using metallocene 23, which is component (A-2) different from metallocene compound 22 in Examples 1 to 5, as a catalyst combining two types of metallocene compounds, and metallocene compound 11R as component (A-1). Furthermore, CFC analysis showed that both Examples 6 and 7 showed a broad distribution toward the lower right of the chart, containing a large amount of high-molecular-weight, low-temperature eluting components with molecular weights exceeding 100,000 and elution temperatures below 88°C (Figures 1 and 2), indicating that a polymer with an inverse comonomer composition was obtained. When ethylene was polymerized under the same conditions as in the above example using a catalyst containing metallocene compound 23 alone, the α (A-2) is -280, and the correlation of polymerization activity with hydrogen concentration tends to be negative or neutral close to 0.(A-1) and α (A-2) The absolute value of the difference |Δα| between the binary complex catalysts used in Examples 6 and 7 was 490, which is a small combination of binary catalysts. CAT The slope of the change in HLMFR with respect to H2 / C2 is 0.5, which is a moderate positive value, and the A of the single catalyst of the above-mentioned metallocene compound 21, which can be controlled to have stable quality. CAT Since the HLMFR is 4.0 or less, it was shown that it is easy to adjust the HLMFR by the hydrogen concentration. In other words, the binary complex catalyst of the present invention was capable of producing olefin polymers with large values ​​of FR, HLMFR / MFR, and Mw / Mn, and which have flowability suitable for melt molding and product strength due to the inverse comonomer composition distribution, with stable quality over a wide HLMFR range.

Claims

1. An olefin polymerization catalyst comprising the following components (A-1), (A-2) and (B): Component (A-1): a metallocene compound represented by the following general formula (1): 【Chemistry 1】 [In formula (1), M １ represents a transition metal atom of Ti, Zr, or Hf, X １ and X ２ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms; R ３ ~R ６ , R ７ ~R １０ , R ６’ , R １０’ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms and containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms and containing an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms, or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms; R ３ ~R ６ and R ６’ any one or more pairs of adjacent groups may be bonded to each other to form a ring, including the carbon atoms to which they are bonded; R ７ ~R １０ and R １０’ any one or more pairs of adjacent groups may be bonded to each other, including the carbon atom to which they are bonded, to form an aliphatic ring, R ６’ and R １０’ may be linked together to form a divalent group represented by any of the following formulae: 【Chemistry 2】 In the formula, E １ and E ２ are respectively, -CR ３１ ２ -, -SiR ３１ ２ -, -NR ３１ -, -PR ３１ is a divalent group selected from the group consisting of -, -O-, and -S- (wherein R ３１ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R ３１ may be bonded to form a cyclic structure), R １ and R ２ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms, or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms; R １ and R ２ may form a ring together with the carbon atoms to which they are attached, Q １ and Q ２ represents a carbon atom, a silicon atom, or a germanium atom, R １’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and adjacent substituents bond to each other with Q １ and / or Q ２ may be bonded to form a ring, m is 0 or 1, and when m is 0, Q １ is R ６ directly bonded to a conjugated five-membered ring containing R ６’ and R １０’ are linked together to form a divalent group -Q １ (R １’ ２ ) - {Q ２ (R １’ ２ ) ｍ -, R ３ and R ４ are linked together to form a divalent group represented by any of the following formulas: 【Transformation 3】 In the formula, R １４ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms and containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms and containing an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms, and adjacent substituents may be bonded to each other via the carbon atoms to which they are bonded to form a ring, n １ is 0 or 1, and n １ If is 0, (CR １４ ２ ) portion does not exist, and (CR １４ ２ a carbon atom adjacent to the 5-membered ring is directly bonded to the carbon atom adjacent to the 5-membered ring to form an indenyl ring; R １７ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms and containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing an oxygen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms, R １８ represents a substituted or unsubstituted aryl group represented by the following general formula (1-a): 【Chemistry 4】 [In formula (1-a), Y １ represents an atom of Group 14, 15 or 16 of the periodic table, and R １９ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms; １９ adjacent substituents may form a ring together with the atoms bonded thereto, and q is 0 or 1. When q is 0, Y １ Substituent R １９ is absent, p is 0 or 1, and when p is 0, formula (1-a) forms a 5-membered ring. Here, R ３ and R ４ are connected to each other to form -SC(R １７ ) = C(R １８ )-, when a divalent group represented by R ７ and R １０ is not a divalent group forming an aliphatic ring. Component (A-2): a metallocene compound represented by any one of the following general formulas (2-1) to (2-5): 【Transformation 5】 [In the formula, M ５１ represents a transition metal atom of Ti, Zr, or Hf, X ５１ and X ５２ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms; Q ５１ and Q ５２ represents a carbon atom, a silicon atom, or a germanium atom, R ５１ ~R ５４ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and adjacent substituents bond to each other with Q ５１ and / or Q ５２ may be bonded to form a ring, m ２ is 0 or 1, and m ２ If is 0, Q ５１ is R ５９ , R ６０ directly bonded to a conjugated five-membered ring containing R ５５ ~R ６８ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms, D represents a sulfur atom or an oxygen atom; n ２ is 0 or 1, and n ２ If is 0, R ６１ and R ６２ There is no carbon atom to which R is bonded, ６３ and the conjugated five-membered ring are directly bonded to form an indenyl ring. Component (B): A compound that reacts with the metallocene compounds of components (A-1) and (A-2) to produce a cationic metallocene compound.

2. 2. The olefin polymerization catalyst according to claim 1, wherein the component (A-1) is a metallocene compound represented by the following general formula (1-1-1) or (1-1-2): 【Transformation 6】 [In the formula, M １ , X １ , X ２ , E １ , E ２ , R １ ~R ４ , R ７ ~R ８ is as defined in claim 1, s is R present on the 6-membered ring １１ , R １２ each s may be the same or different and represents an integer from 0 to 4; R １１ , R １２ each independently represent a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms and containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms and containing an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms, R １１ , R １２ When there are two or more of at least one of １１ Comrade, R １２ may be taken together to form a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing hydrocarbon group having 1 to 40 carbon atoms and containing 1 to 6 silicon atoms, a divalent halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a divalent hydrocarbon group having 1 to 40 carbon atoms and containing an oxygen atom, sulfur atom, nitrogen atom, or phosphorus atom, which may have a substituent.

3. The olefin polymerization catalyst according to claim 2, wherein the component (A-1) is a metallocene compound represented by any one of the following general formulas (1-1-1-1) to (1-1-1-5) and (1-1-2-1) to (1-1-2-5): 【Transformation 7】 [In the formula, M １ , X １ , X ２ , E １ , E ２ , R ３ , R ４ , R ７ , R ８ is as defined in claim 1, and R １１ , R １２ is as defined in claim 2, s is R present on the 6-membered ring １１ , R １２ , R １３ each s may be the same or different and represents an integer from 0 to 4; R １３ each independently represent a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms and containing 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms and containing an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, a hydrocarbon-group-substituted silyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms or a hydrocarbon-group-substituted amino group having 1 to 40 carbon atoms, R １３ When two or more of these are present, they may be taken together to form a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing hydrocarbon group having 1 to 40 carbon atoms and containing 1 to 6 silicon atoms, a divalent halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a divalent hydrocarbon group having 1 to 40 carbon atoms and containing an oxygen atom, sulfur atom, nitrogen atom, or phosphorus atom, each of which may have a substituent.

4. 2. The olefin polymerization catalyst according to claim 1, wherein the component (A-1) is a meso compound.

5. In the formulas (2-1) to (2-5) of the component (A-2), m ２ The olefin polymerization catalyst according to claim 1, wherein

6. In the formulas (2-4) and (2-5) of the component (A-2), n ２ The olefin polymerization catalyst according to claim 1, wherein

7. In the formulas (2-1) to (2-5) of the component (A-2), R ５５ ~R ６８ 2. The olefin polymerization catalyst according to claim 1, wherein at least one of the above is represented by the following formula (7): 【Transformation 8】 [In formula (7), A ２ represents an atom of Group 14, 15 or 16 of the periodic table, R ７５ ~R ７９ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom, a sulfur atom or a nitrogen atom, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms containing 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, and adjacent substituents may be bonded to each other, including the atom bonding thereto, to form a ring; p ２ is 0 or 1, and A ２ When is an atom of group 15 or 16 of the periodic table, p ２ is 0, and A ２ to R ７５ does not exist, q ２ is 0 or 1, and q ２ If is 0, R ７８ does not exist, and R ７７ and the carbon atom to which R ７９ is directly bonded to the carbon atom to which it is attached.

8. In the formulas (2-1) to (2-5) of the component (A-2), R ５７ , R ６７ , R ６１ ~R ６３ 8. The olefin polymerization catalyst according to claim 7, wherein at least one of the above is represented by formula (7).

9. 2. The olefin polymerization catalyst according to claim 1, wherein D in the formulas (2-1) to (2-5) of the component (A-2) is a sulfur atom.

10. 2. The olefin polymerization catalyst according to claim 1, wherein the components (A-1) and (A-2) satisfy the following conditions (1) to (4): Condition (1): An olefin polymerization catalyst (Cat （Ａ－１） ) in the presence of hydrogen molecules to polymerize an olefin, HLMFR of the olefin polymer obtained （Ａ－１） and an olefin polymerization catalyst (Cat （Ａ－２） ) and the HLMFR of the olefin polymer obtained under the same conditions. （Ａ－２） But HLMFR （Ａ－１） ≧ HLMFR （Ａ－２） Satisfy. Condition (2): Cat （Ａ－１） In the polymerization of olefins using H ２ / C ２ ratio and olefin polymerization activity (K （Ａ－１） : the correlation coefficient α in the following definition formula, which represents the correlation between the unit g olefin polymer / g catalyst / time / MPa （Ａ－１） is between −10,000 and +1,000; Definition K （Ａ－１） =α （Ａ－１） •Log[H ２ / C ２ ]+β （Ａ－１） Here, the above formula is the H of two points separated by 0.05 mol % or more. ２ / C ２ When polymerized with ２ / C ２ and K. （Ａ－１） H obtained from the relationship on the semi-logarithmic graph of ２ / C ２ = represents an approximate straight line between 0.04 and 0.15 mol%, and coefficient α （Ａ－１） is the slope of the line, and the intercept β （Ａ－１） Is, H ２ / C ２ = Polymerization activity at 1 mol% (K １（Ａ－１） ) Condition (3): Cat （Ａ－２） H obtained in the same way as condition (2) ２ / C ２ and K. （Ａ－２） Correlation coefficient α （Ａ－２） is between −10,000 and +1,000; Condition (4): α （Ａ－１） and α （Ａ－２） The absolute value |Δα| of the difference is 0 to 7030.

11. 2. The olefin polymerization catalyst according to claim 1, wherein the components (A-1) and (A-2) satisfy the following condition (5): Condition (5): The above Cat （Ａ－１） The weight average molecular weight Mw of an olefin polymer obtained by polymerizing an olefin in the presence of hydrogen molecules using （Ａ－１） And Cat （Ａ－２） The weight average molecular weight Mw of the olefin polymer obtained under the same conditions was calculated using （Ａ－２） But, Mw （Ａ－１） ≦Mw （Ａ－２） Satisfy.

12. 2. The olefin polymerization catalyst according to claim 1, wherein the components (A-1) and (A-2) satisfy the following condition (6): Condition (6): The above Cat （Ａ－１） is the density of the olefin polymer obtained by polymerizing or copolymerizing an olefin in the presence of hydrogen molecules using （Ａ－１） And Cat （Ａ－２） The density D of the olefin polymer obtained under the same conditions is calculated using （Ａ－２） But, D （Ａ－１） ≧D （Ａ－２） Satisfy.

13. 2. The olefin polymerization catalyst according to claim 1, further comprising the following component (C): Component (C): Microparticle carrier

14. 2. The olefin polymerization catalyst according to claim 1, further comprising the following component (D): Component (D): Organoaluminum compound

15. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 14.

16. 16. The method for producing an olefin polymer according to claim 15, wherein the olefin is ethylene.

17. 16. The method for producing an olefin polymer according to claim 15, wherein the polymer obtained satisfies the following conditions (i) to (iii): Condition (i): MFR is 0.001 to 1000 g / 10 min. Condition (ii): Density is 0.895 to 0.975 g / cm ３ is. Condition (iii): At least one of the following conditions (iii-1), (iii-2), (iii-3), and (iii-4) is satisfied; Condition (iii-1): The molecular weight distribution (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 or more and 100.0 or less. Condition (iii-2): The branching index g' measured by a GPC measuring device combining a differential refractometer, a viscosity detector, and a light scattering detector is the minimum value (g Ｌ ) is 0.20 or more and 0.95 or less. Condition (iii-3): Melt flow rate (MFR) at a temperature of 190°C and a load of 10 kg １０ｋｇ FR, which is the ratio of the melt flow rate (MFR) at a temperature of 190°C and a load of 2.16 kg to the melt flow rate (MFR), is 6.5 or more and 100 or less. Condition (iii-4): The ratio (HLMFR / MFR) of the melt flow rate at a temperature of 190°C and a load of 21.6 kg (HLMFR) to the melt flow rate at a temperature of 190°C and a load of 2.16 kg (MFR) is 20 or more and 1,000 or less.

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