Novel catalyst for olefin polymerization

Abstract

This invention provides a catalyst for olefin polymerization that can produce ethylene-based polymers with a high degree of design flexibility and versatile applications. [Solution] The catalyst for olefin polymerization comprises (A-1) a transition metal complex compound represented by formula (1), (A-2) a metallocene compound containing a transition metal atom from groups 4 to 6 of the periodic table that gives an olefin polymer with a lower HLMFR than that using (A-1), and (B) a compound that reacts with the compounds of components (A-1) and (A-2) to produce a cationic complex compound, wherein the correlation between the hydrogen / olefin ratio during polymerization conditions and the HLMFR of the olefin polymer obtained from components (A-1) and (A-2) is within a certain range. TIFF2026167649000052.tif44161

Description

[Technical Field]

[0001] The present invention relates to a novel catalyst for olefin polymerization, 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 a catalyst for olefin polymerization comprising two specific transition metal complex compounds and a compound that reacts with the compounds to produce a cationic 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, known as catalysts for olefin polymerization, exhibit high uniformity in polymer molecular structure, such as molecular weight distribution and copolymer composition distribution, and possess excellent mechanical properties, including impact strength and long lifespan. As a result, their use has been increasing in recent years. However, while conventional metallocene-based polyolefins have excellent mechanical properties, their narrow molecular weight distribution meant they did not adequately meet the performance requirements for important properties in polyolefin molding, such as melt tension and melt flowability.

[0003] A method for improving the moldability of metallocene polyolefins is known to broaden the molecular weight distribution by multi-stage polymerization (Patent Document 1). However, the method of broadening the molecular weight distribution by multi-stage polymerization presents other problems such as construction costs and operational management costs for linking polymerization reaction groups. Therefore, alternative methods include a method for improving fluidity and melt tension by introducing long-chain branching into polyethylene during the polymerization reaction to increase melt viscosity (Patent Document 2), and a method for designing a catalyst to prepare a polymer having multiple peaks in its molecular weight distribution (Patent Document 3).

[0004] Another approach to this problem is the study of binary complex catalyst technology, which uses catalyst compositions containing combinations of two types of complexes (Patent Documents 4-8). These patent documents attempt to introduce long-chain branched structures by designing binary complex catalysts using two types of metal complexes. Furthermore, because there is a difference in polymerization ability between the two types of complexes, a range of molecular weight distribution is created in the resulting polyolefins, which is expected to contribute to multifunctionality and high performance, including moldability. In many of these binary complex catalysts, the molecular weight distribution of the resulting polyolefins is bimodal. [Prior art documents] [Patent Documents]

[0005] [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 Publication No. 2017-197739 [Patent Document 4] Japanese Patent Publication No. 2012-214780 [Patent Document 5] Japanese Patent Publication No. 2017-145303 [Patent Document 6] Japanese Patent Publication No. 2019-059934 [Patent Document 7] Special Publication No. 2019-515997 [Patent Document 8] Japanese Patent Publication No. 2010-043152 [Overview of the project] [Problems that the invention aims to solve]

[0006] While binary complex catalysts, such as those described in Patent Documents 4-8, are used as one method for designing polymerization catalysts for polyolefins, our research has revealed that using multiple types of catalysts can be disadvantageous in certain situations. Specifically, the polymerization activity of a catalyst is affected by changes in conditions such as fluctuations in hydrogen concentration and temperature for olefin polymerization. The degree of this effect varies depending on the catalyst, but if the catalyst that produces low molecular weight polyolefins in a binary complex catalyst is affected by changes in conditions, a large amount of low molecular weight components may be mixed into the resulting polyolefin. There are concerns that an increase in the proportion of low molecular weight components may lead to a decrease in product strength. Furthermore, in ethylene-α-olefin copolymers, conventional complex catalysts often produce polymers with a composition known as a "forward comonomer composition," where α-olefins are copolymerized in a low molecular weight region within the molecular weight distribution. This increases the amount of low-density and low-molecular-weight components, which also contributes to a decrease in product strength. In addition, once the type and ratio of complex catalysts are determined, it becomes impossible to control the shape of the molecular weight distribution of the resulting polyolefin depending on other factors, leading to problems such as the inability to supply products of stable quality and the limitation of polymer design diversity, preventing the application of a single catalyst system to multiple uses.

[0007] There has been a need for an olefin polymerization catalyst that can overcome the problems of conventional binary complex catalysts used for polyethylene, and produce ethylene-based polymers that offer greater flexibility in polymer design and are suitable for a wide range of applications. [Means for solving the problem]

[0008] The inventors investigated factors that affect HLMFR and molecular weight and found that some olefin polymerization catalysts are less affected by hydrogen concentration in terms of HLMFR and molecular weight. By combining such catalysts with highly catalytically active metallocene complexes, the inventors diligently investigated whether it would be possible to construct a catalytic system in which only one of the binary complex catalysts is linked to changes in reaction conditions in terms of HLMFR and molecular weight. As a result, they discovered a catalytic system that allows control of only the molecular weight distribution in the high molecular weight region by changing the hydrogen concentration without inhibiting the catalytic activity of each other, leading to the present invention. Furthermore, they found that this catalyst can be used to obtain polyolefins having a so-called reverse comonomer composition, which are advantageous in terms of moldability and other aspects.

[0009] In other words, the present invention relates to catalysts for olefin polymerization as specified in the following sections. [1] An olefin polymerization catalyst comprising the following components (A-1), (A-2), and (B), characterized in that components (A-1) and (A-2) satisfy the following conditions (1) to (4). Component (A-1): Transition metal complex compound represented by the following formula (1) [ka] [In formula (1), M 1 This represents transition metal atoms selected from groups 8 and 9 of the periodic table. X 1 is a hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom, a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms containing a silicon atom, a hydrocarbon group substituted with a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, where r is M 1 The valence is shown, A 1 and A 2 M 1 A ligand having an atom selected from groups 15 and 16 of the periodic table that coordinates to (where A 1 , A 2 This indicates that the structure may be the same or different within the same compound. Q1 is M 1 has at least one pair of unshared electron pairs or a π bond capable of coordinating to, A 1 and A 2 represents a linking group that crosslinks at any position.] Component (A-2): A metallocene compound containing a transition metal atom of Groups 4 to 6 of the periodic table Component (B): A compound that reacts with the compounds of component (A-1) and component (A-2) to form a cationic complex compound Condition (1): The HLMFR, which is the HLMFR of the olefin polymer obtained by polymerizing an olefin in the presence of hydrogen molecules using an olefin polymerization catalyst (Cat that contains component (A-1) and (B) but does not contain (A-2) (A-1) ), and the HLMFR, which is the HLMFR of the olefin polymer obtained under the same conditions using an olefin polymerization catalyst (Cat that contains component (A-2) and (B) but does not contain (A-1) (A-1) (A-2) ) satisfy that HLMFR (A-2) ≧HLMFR (A-1) (A-2) . Condition (2): In the polymerization of olefin using Cat (A-1) , the correlation coefficient γ in the following defined formula, which represents the correlation between the ratio of hydrogen to olefin (H2 / C2 ratio) and HLMFR that is the HLMFR of the olefin polymer (A-1) (A-1) is from -2.0 to +1.0; Defined formula Log[HLMFR (A-1) =γ (A-1) ·Log[H2 / C2]+δ Here, the above formula represents an approximate straight line in the range of H2 / C2=0.05 to 0.15 mol% obtained from the relationship on the double logarithmic graph of H2 / C2 and HLMFR when polymerized at a temperature of 80°C at two points of H2 / C2 separated by 0.05 mol% or more (A-1) , the coefficient γ (A-1) is the slope of the straight line, and the intercept δ is the logarithmic value of HLMFR when H2 / C2=1 mol%. Provided that when the HLMFR at H2 / C2=0.1 mol% (A-1) is 10 or more, the HLMFR in the above defined formula (A-1) is MFR (A-1) ​​​This shall be used as a substitute. Condition (3):Cat (A-2) The H2 / C2 ratio obtained at a temperature of 80°C under the same conditions as (2) and the HLMFR of the olefin polymer are HLMFR (A-2) The correlation coefficient γ (A-2) However, it is above +1.0 and below +10. Condition (4): γ (A-1) and gamma (A-2) The absolute value of the difference |Δγ| is greater than 0 and less than or equal to 10. [2] The catalyst for olefin polymerization according to [1], characterized in that the components (A-1) and (A-2) satisfy the following condition (5). Condition (5): Said Cat (A-1) Using this method, the weight-average molecular weight Mw of the olefin polymer obtained by polymerizing olefins in the presence of hydrogen molecules was determined by GPC measurement. (A-1) And, Cat (A-2) Using this method, the weight-average molecular weight Mw of the olefin polymer obtained under the same conditions (A-2) However, Mw (A-1) ≤Mw (A-2) It satisfies the condition. [3] The catalyst for olefin polymerization according to [1] or [2], characterized in that the components (A-1) and (A-2) satisfy the following condition (6). Condition (6): Said Cat (A-1) D is the density of the olefin polymer obtained by polymerizing or copolymerizing olefins in the presence of hydrogen molecules. (A-1) And, Cat (A-2) Using this method, the density D of the olefin polymer obtained under the same conditions (A-2) However, D (A-1) ≧D (A-2) It satisfies the condition. [4] A catalyst for olefin polymerization according to any of [1] to [3] above, characterized in that component (A-1) satisfies at least one of the following conditions (A-1-1) and (A-1-2). Condition (A-1-1); A 1 and A 2 However, M 1 It has at least one nitrogen atom that coordinates to it. Condition (A-1-2); Q 1 However, M1 It has at least one lone pair of electrons or a π bond coordinated to it. [5] A catalyst for olefin polymerization according to any of [1] to [4] above, characterized in that the component (A-1) is a transition metal complex compound represented by the following general formula (1-1). [ka] [In the formula, M 1 , X 1 , r is as defined in claim 1, R 1 ~R 3 Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 40 carbon atoms, a halogen atom-containing hydrocarbon group having 1 to 40 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom-containing hydrocarbon group having 1 to 40 carbon atoms. R 4 , R 5 Each of these independently represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms including a silicon atom, a halogen-containing hydrocarbon group having 1 to 40 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom containing a hydrocarbon group having 1 to 40 carbon atoms. R 6 , R 7 Each of these independently represents a hydrocarbon group having 1 to 40 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms containing a silicon atom, a halogen-containing hydrocarbon group having 1 to 40 carbon atoms, or a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom. R atoms other than hydrogen atoms and halogen atoms 1 ~R 3 , R other than hydrogen atoms 4 ~R 7 Each of these substituents may independently form a ring by bonding with adjacent substituents, including the carbon and nitrogen atoms to which they are bonded. [6] In the above general formula (1-1), R 6 , R 7A catalyst for olefin polymerization according to any of [1] to [5] above, characterized in that at least one of the members is a substituted or unsubstituted aryl group represented by the following general formula (1-a). [ka] [In formula (1-a), A 3 R represents atoms in groups 14, 15, or 16 of the periodic table. 8 ~R 12 Each of these 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 with 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 with 1 to 20 carbon atoms, and R 8 ~R 12 The substituents may form a ring with the atoms they are bonded to, and t is 0 or 1, and when t is 0, A 3 to substituent R 8 If not present, s is 0 or 1, and if s is 0, then equation (1-a) forms a 5-membered ring. [7] In the above general formula (1-a), R 8 ~R 12 The catalyst for olefin polymerization of [6] is characterized in that at least one pair of adjacent substituents form a ring together with the atoms bonded to them. [8] In the above general formula (1-1), R 4 , R 5 A catalyst for olefin polymerization according to any of the [5] to [7] above, characterized in that at least one of the is a hydrocarbon group having 1 to 40 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 40 carbon atoms including a silicon atom, a halogen atom-containing hydrocarbon group having 1 to 40 carbon atoms, or a hydrocarbon group having 1 to 40 carbon atoms including an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom. [9]M 1 A catalyst for olefin polymerization from any of the above [1] to [8], wherein the element is Fe.

[0010] Further, the present invention also relates to the olefin polymerization catalyst specified in each of the following items.

[10] The olefin polymerization catalyst according to any one of the above [1] to [9], wherein the component (A-2) is a metallocene compound represented by the following general formula (2).

Chemical Formula

Chemical Formula

[11] A catalyst for olefin polymerization according to any of [1] to

[10] above, characterized in that the component (A-2) is a metallocene compound represented by the following general formula (2-1). [ka] [In formula (2-1), M 51 , X 51 , X 52 Q 51 Q 52 , R 51 ~R 54 m is as defined above, R 55 ~R 62 This represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms including 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. 55 , R 58 , R 59 and R 62 Of these, at least two are not hydrogen atoms, R 55 and R 56 , R 56 and R 57or R 57 and R 58 Any one of the sets, and R 59 and R 60 , R 60 and R 61 or R 61 and R 62 Any one of these pairs may be bonded to each other, forming a ring, containing the carbon atoms to which they bond.

[12] A catalyst for olefin polymerization according to any of [1] to

[11] above, characterized in that the component (A-2) is a metallocene compound represented by the following general formula (2-2). [ka] [In formula (2-2), M 51 , X 51 , X 52 Q 51 Q 52 , R 51 ~R 54 m and n are as defined above. R 55 , R 56 , R 59 , R 60 Each of these 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 including an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom, a hydrocarbon-substituted silyl group having 1 to 40 carbon atoms, or a hydrocarbon-substituted amino group having 1 to 40 carbon atoms. R 63 ~R 68 As defined above, R 69 ~R 74 R 63 ~R 68 It is similar to [this].

[13] A catalyst for olefin polymerization according to any of [1] to

[12] above, characterized in that the component (A-2) is a metallocene compound represented by any of the following general formulas (2-3-1) to (2-3-5). [ka] [In the formula, M 51 , X 51 , X 52 Q 51 Q 52 , R 51 ~R 54 , m, n, R 55 , R 56 , R 59 , R 60 , R 63 ~R 68 This is as defined above, R 86 , R 87 Each of these 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 including an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom, a hydrocarbon-substituted silyl group having 1 to 40 carbon atoms, or a hydrocarbon-substituted amino group having 1 to 40 carbon atoms. [D represents a sulfur atom or an oxygen atom]

[14] A catalyst for olefin polymerization according to any of [1] to

[13] above, characterized in that the component (A-2) is a metallocene compound represented by the following general formula (2-4). [ka] [In formula (2-4), M 51 , X 51 , X 52 Q 51 Q 52 , R 51 ~R 54 m and n are as defined above. R 55 ~R 60 , R 63 ~R 68Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms including 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 R 55 ~R 58 R may be bonded to adjacent substituents, including the carbon atom to which they are bonded, forming an aliphatic ring. 63 ~R 68 The substituents may be bonded to each other by adjacent substituents, including the carbon atom to which they are bonded, to form a ring.

[15] A catalyst for olefin polymerization according to any of [1] to

[14] , further comprising the following component (C). Ingredient (C): Particulate carrier

[16] A catalyst for olefin polymerization according to any of [1] to

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

[0011] The present invention also relates to methods for producing olefin polymers as specified in the following sections.

[17] A method for producing an olefin polymer, characterized by polymerizing or copolymerizing an olefin in the presence of any of the olefin polymerization catalysts described in [1] to

[16] above.

[18] A method for producing the olefin polymer according to

[17] , characterized in that the olefin is ethylene.

[19] A method for producing the olefin polymer according to

[17] or

[18] , characterized in that the polymer obtained satisfies the following conditions (i) to (iii). Condition (i): MFR is between 0.001 and 1000 g / 10 min. Condition (ii): Density of 0.895-0.975 g / cm³ 3 That is the case. 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) measured by gel permeation chromatography (GPC) using weight-average molecular weight (Mw) and number-average molecular weight (Mn) is 3.5 or greater and 100 or less. Condition (iii-2): The lowest value (g) of the branching index g' between a molecular weight of 100,000 and 1,000,000, measured by a GPC measuring device combining a differential refractometer, viscosity detector, and light scattering detector. L The value is between 0.20 and 0.98. Condition (iii-3): Melt flow rate (MFR) at a temperature of 190°C and a load of 10 kg. 10kg ) and 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, is 6.5 or higher and 100 or lower. Condition (iii-4): The 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 is 15 or greater and 1000 or less. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide an olefin polymerization catalyst that can produce ethylene-based polymers with a high degree of freedom in polymer design and that can be applied to a wide range of uses. Furthermore, this catalyst can be used to provide polyolefins having a so-called reverse comonomer composition, which are advantageous in terms of moldability and other aspects. [Brief explanation of the drawing]

[0013] [Figure 1] This figure shows the GPC charts of the olefin polymers obtained in Examples 1 to 6. [Figure 2] This figure shows the GPC charts of the olefin polymers obtained in Comparative Examples 1 to 3. [Figure 3] This figure shows the GPC charts of the olefin polymers obtained in Examples 15-17. [Figure 4] This figure shows the GPC charts of the olefin polymers obtained in Examples 18-20. [Figure 5] This figure shows the GPC charts of the olefin polymers obtained in Examples 21-23. [Figure 6] This figure shows the GPC charts of the olefin polymers obtained in Examples 24-26. [Figure 7] This figure shows the GPC charts of the olefin polymers obtained in Examples 27-29. [Figure 8] This figure shows the CFC chart of the olefin polymers obtained in Reference Example 2 and Examples (1, 2, 4, 7~12). [Figure 9] This figure shows the CFC chart of the olefin polymers obtained in Reference Example 2 and Examples (13-15, 17, 18, 21, 22, 25, 29). [Modes for carrying out the invention]

[0014] One aspect of the present invention is an olefin polymerization catalyst containing component (A-1): a transition metal complex compound represented by formula (1) above, component (A-2): a metallocene compound represented by formula (2) above, and component (B): a compound that reacts with components (A-1) and (A-2) to produce a cationic complex compound.

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

[0016] In the following, when referring to specific substituents, the term "hydrocarbon group" refers to a linear, branched, or cyclic group. The valency of a hydrocarbon group is understood from the context, but monovalent groups are indicated by the suffix "-yl," and divalent groups by the suffix "-ene."

[0017] When a compound is thought to have stereoisomers due to each substituent or compound having an atom that acts as a chiral center, a chiral axis, or a chiral plane, as described below, each compound contains its respective stereoisomer or a mixture thereof in any proportion.

[0018] 1. Ingredients (A-1) Component (A-1) in the olefin polymerization catalyst of the present invention is a transition metal complex compound represented by the following formula (1). [ka] [In formula (1), the definitions of each group are as described above.]

[0019] The compound of formula (1) above is more efficient than metallocene catalysts in producing polyolefins with slightly lower molecular weights as an olefin polymerization catalyst. Furthermore, when the compound of formula (1) is used alone as an olefin polymerization catalyst, the correlation between hydrogen concentration and HLMFR and molecular weight is small, generally showing a neutral to small negative correlation. Therefore, the physical properties of polyolefins obtained using the compound of formula (1) above are less affected by fluctuations in hydrogen concentration during the polymerization reaction. By combining this with the metallocene compound of formula (2), described later, a binary complex catalyst can be obtained in which the effects of hydrogen concentration fluctuations during the polymerization reaction appear only in high molecular weight polyolefins. Moreover, it has been found that these catalyst combinations act as polymerization catalysts without substantially inhibiting each other's activity. Here, a neutral correlation means that HLMFR and molecular weight do not change or change only slightly with respect to fluctuations in hydrogen concentration. A negative correlation means that HLMFR tends to decrease with respect to fluctuations in hydrogen concentration. The criteria for judging whether the change is small or large will be explained later as condition (2).

[0020] M 1 represents a transition metal atom selected from Groups 8 and 9 of the periodic table. Specifically, it represents iron, ruthenium, osmium, cobalt, rhodium, and iridium. M 1 is preferably iron or cobalt, and more preferably iron.

[0021] X 1 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 nitrogen atom or a silicon atom, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. X 1 is preferably a hydrocarbon group having 1 to 10 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 10 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 12 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms; a silicon-containing hydrocarbon group having 1 to 12 carbon atoms such as trimethylsilyl group and bis(trimethylsilyl)methyl group, and among these, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms or a nitrogen-containing hydrocarbon group having 1 to 12 carbon atoms is more preferred. r represents the valence of M 1 , and X 1 is present in a number of r per molecule, and when r is 2 or more, each X may be the same or different.

[0022] A 1 and A 2 each represent a ligand having an atom selected from Groups 15 and 16 of the periodic table that coordinates to M 1 . A 1 and A 2 may have the same structure or different structures in the same compound, and are preferably of the same type from the viewpoint of economic efficiency of ligand synthesis. A 1 and A 2 Specific examples include (substituted) amino group-containing hydrocarbon groups such as diethylaminomethyl, dimethylaminomethyl, diallylaminomethyl, methyl(trimethylsilyl)aminomethyl, N-methyliminomethyl, 1-(N-phenylimino)-1-ethyl, 1-(N-mesitylimino)-1-ethyl, α-(N-phenylimino)benzyl, N 1 ,N 1 ,N2 -trimethylamidino and other imino-substituted hydrocarbon groups, nitrogen-containing substituents such as N-methyl-2-piperidyl, N-methyl-2-pyrrolidyl, 2-pyridyl, 2-pyrazinyl, N-methyl-2-indolyl, N-methyl-2-pyrrolyl, N-ethyl-3-pyrazolyl and other nitrogen-containing cyclic substituents; phosphorus-containing substituents obtained by replacing the nitrogen atom of these nitrogen-containing substituents and the like with a phosphorus atom; alkoxyl group-containing hydrocarbon groups such as methoxymethyl and methoxyethoxyethyl; carbonyl-containing groups such as formyl, benzoyl, acetyl, 2-oxopropyl and methoxycarbonyl; oxygen-containing cyclic substituents such as furyl, pyranyl, tetrahydropyranyl and 2-dioxolanyl; and sulfur-containing substituents, selenium-containing substituents, and tellurium-containing substituents obtained by replacing the oxygen atom of these oxygen-containing substituents with a sulfur atom, a selenium atom, or a tellurium atom.

[0023] Further, substituents containing two or more Group 15 and 16 elements of the periodic table, such as ((dimethylphosphino)methyl)methylamino, acetylmethylamino, N-allyl-3-morpholino, N-methyl-1-phenothiazinyl, N-methoxyiminomethyl, and benzenesulfinyl, are also exemplified. Among these, nitrogen-containing substituents such as dimethylaminomethyl group, 1-(N-phenylimino)-1-ethyl group, and 2-pyridyl group, phosphorus-containing substituents obtained by replacing the nitrogen atom of these nitrogen-containing substituents with a phosphorus atom, and substituents containing two or more Group 15 and 16 elements of the periodic table having at least one nitrogen or phosphorus atom, such as ((dimethylphosphino)methyl)methylamino group, acetylmethylamino group, and N-methoxyiminomethyl group, are preferred. A 1 and A 2 is more preferred to have at least one nitrogen atom that coordinates to M 1 , and specifically, substituents containing at least one nitrogen atom, such as N-methyliminomethyl, 1-(N-phenylimino)-1-ethyl, 1-(N-mesitylimino)-1-ethyl, and N-methoxyiminomethyl, are preferred. Among these, substituents having an imino group such as N-methyliminomethyl, 1-(N-phenylimino)-1-ethyl, and 1-(N-mesitylimino)-1-ethyl are particularly preferred.

[0024] Q 1 M 1 It has at least one lone pair of electrons or a π bond that can coordinate to A 1 and A 2 It shows a bonding group that crosslinks at any position. Q 1 However, M 1 It is preferable that it has at least one lone pair of electrons or a π bond coordinated to it. 1 It preferably contains one or more atoms from groups 15 and 16 of the periodic table. Here, "coordinateable" means a lone pair of electrons or a π bond, for example, Q 1 One or more periodic table group 15 and 16 atoms contained within the same complex are central metal M 1 This includes cases where they are actually coordinated, Q 1 The π bond contained in or one or more periodic table group 15, 16 atoms actually constitutes the central metal M within the same complex. 1 Even when not coordinated, if the bond angles, bond lengths, and dihedral angles between the atoms constituting the complex ligand are arbitrarily changed within the range that is normally known to be possible for each bond, Q 1 The π bond contained in or one or more periodic table group 15, 16 atoms, the central metal M within the same complex 1 This also includes cases where they can be brought close enough to form a coordinate bond.

[0025] Q 1Specific examples include N-methyl-2-azapropane-1,3-diyl, 2-dimethylaminopropane-1,3-diyl, N-methylpyrrole-2,5-diyl, 2,6-pyridinediyl, 2,6-pyrazinediyl, 2,2'-bipyridine-6,6'-diyl, 4-methyl-2,6-morpholinediyl, 2-phosphapropane-1,3-diyl, 2-methoxypropane-1,3-diyl, and 2-oxapropane-1,3-diyl. Examples include bonding groups with lone pairs of electrons such as yl, 3-oxapentane-1,5-diyl, 2,5-franziyl, 2-thiapropane-1,3-diyl, 2,5-thiophenediyl, and 1-methylphosphole-2,5-diyl, as well as bonding groups with π bonds such as 3-hexenylene, 3-hexynylene, 2,4-heptadienylene, 2-(2-ethenyl)propane-1,3-diyl, and 1,4-diethylbenzenediyl. Among these, bonding groups having nitrogen, oxygen, or sulfur atoms, such as N-methyl-2-azapropane-1,3-diyl, 2-dimethylaminopropane-1,3-diyl, N-methylpyrrole-2,5-diyl, 2,6-pyridinediyl, 2,6-pyrazinediyl, 2,2'-bipyridine-6,6'-diyl, 4-methyl-2,6-morpholinediyl, 2-methoxypropane-1,3-diyl, 2-oxapropane-1,3-diyl, 3-oxapentane-1,5-diyl, 2,5-franziyl, 2-thiapropane-1,3-diyl, and 2,5-thiophenediyl, and bonding groups having π bonds, such as 3-hexenylene, 3-hexynylene, 2,4-heptadienylene, 2-(2-ethenyl)propane-1,3-diyl, and 1,4-diethylbenzenediyl, are preferred. Furthermore, among these bonding groups, those in which at least one lone pair of electrons or a π bond is actually coordinated to the central metal M are particularly preferred.

[0026] A 1 , A 2 Q 1Each of these may have further substituents at any position. Examples of substituents include halogen atoms, hydrocarbon groups having 1 to 40 carbon atoms, silicon-containing hydrocarbon groups having 1 to 40 carbon atoms including silicon atoms, halogen-containing hydrocarbon groups having 1 to 40 carbon atoms, and hydrocarbon groups having 1 to 40 carbon atoms including oxygen atoms, sulfur atoms, nitrogen atoms, or phosphorus atoms.

[0027] Component (A-1) preferably satisfies at least one of the following conditions (A-1-1) and (A-1-2) from the various definitions of formula (1) above. Condition (A-1-1); A 1 and A 2 However, M 1 It has at least one nitrogen atom that coordinates to it. Condition (A-1-2); Q 1 However, M 1 It has at least one lone pair of electrons or a π bond coordinated to it.

[0028] A more specific example of component (A-1) is the transition metal complex compound represented by the following general formula (1-1). [ka] (The various groups in the formula are as defined above.)

[0029] R 1 ~R 3 Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms including a silicon atom, a halogen-containing hydrocarbon group having 1 to 40 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom, or a hydrocarbon group having 1 to 40 carbon atoms including a phosphorus atom. 1 ~R 3 When R is anything other than a hydrogen atom or a halogen atom, adjacent substituents may bond to each other, including the carbon and nitrogen atoms to which they are bonded, to form a ring. 1 is R 4 It may also form a ring, R 3 is R 5It may also form a ring. 1 ~R 3 Preferably, the group is chemically inert.

[0030] R 4 , R 5 Each of these independently represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms including a silicon atom, a halogen-containing hydrocarbon group having 1 to 40 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom containing a hydrocarbon group having 1 to 40 carbon atoms. 4 , R 5 It is preferable that the group is chemically inert. Also, R 4 , R 5 It is preferable that at least one of them is a hydrocarbon group having 1 to 40 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 40 carbon atoms including a silicon atom, a halogen atom-containing hydrocarbon group having 1 to 40 carbon atoms, or a hydrocarbon group having 1 to 40 carbon atoms including an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom. 4 ~R 7 When the atom is anything other than a hydrogen atom, adjacent substituents may bond to each other, including the carbon and nitrogen atoms to which they are bonded, to form a ring.

[0031] R 6 , R 7 Each of these independently represents a hydrocarbon group having 1 to 40 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms containing a silicon atom, a halogen-containing hydrocarbon group having 1 to 40 carbon atoms, or a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom. 6 , R 7 When R is an atom other than a hydrogen atom, adjacent substituents may bond to each other, including the carbon and nitrogen atoms to which they are bonded, to form a ring. 6 , R 7 Preferably, the group is chemically inert.

[0032] Furthermore, R 6 , R 7At least one of these is preferably a substituted or unsubstituted aryl group represented by the following general formula (1-a). [ka] [In formula (1-a), A 3 R represents an atom from group 14, 15, or 16 of the periodic table. 8 ~R 12 Each of these 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 with 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 with 1 to 20 carbon atoms, and R 8 ~R 12 The substituents may form a ring with the atoms they are bonded to, and t is 0 or 1, and when t is 0, A 3 to substituent R 8 If not present, s is 0 or 1, and if s is 0, then equation (1-a) forms a 5-membered ring.

[0033] In the above general formula (1-a), R 8 ~R 12 Of these, at least one pair of adjacent substituents may form a ring together with the atoms to which they are bonded.

[0034] The definitions relating to equation (1) above can take any combination, as long as the transition metal complex compound represented by equation (1) can exist stably. 1 , A 1 Or A 2 The group 15 or group 16 atoms included, Q 1 It is preferable that the atoms or groups of atoms having lone pairs of electrons or π bonds are selected so as to form a 5- to 7-membered ring.

[0035] 2. Ingredients (A-2) Component (A-2) is a metallocene compound containing a transition metal atom of Groups 4 to 6 of the periodic table, and exhibits predetermined catalytic activity. A metallocene catalyst such as zirconocene is excellent in copolymerization activity as an olefin polymerization catalyst, and has a high ability to give a random copolymer having a high molecular weight and a narrow molecular weight distribution. Further, it has been clarified that hydrogen is involved in the polymerization reaction mechanism of the metallocene catalyst, and it is possible to control HLMFR and the molecular weight by adding a trace amount of hydrogen to the polymerization reaction system.

[0036] A preferable component (A-2) in the olefin polymerization catalyst of the present invention is a metallocene compound represented by the following general formula (2).

Chemical Formula

[0037] M 51 is a transition metal element of Groups 4 to 6 of the periodic table, and represents any one of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W. More preferably, it represents any transition metal atom of Ti, Zr or Hf.

[0038] X 51 and X 52 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 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.

[0039] X 51 and X 52 Examples of halogen atoms represented by include chlorine, bromine, and iodine atoms. X 51 and X 52 Examples of hydrocarbon groups having 1 to 20 carbon atoms, as shown by , include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, and benzyl group.

[0040] X 51 and X 52 Examples of hydrocarbon groups with 1 to 20 carbon atoms containing an oxygen atom, as shown by , include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, acetyl group, 1-oxopropyl group, 1-oxo-n-butyl group, 2-methyl-1-oxopropyl group, 2,2-dimethyl-1-oxopropyl group, phenylacetyl group, diphenylacetyl group, benzoyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-furyl group, and 2-tetrahydrofuryl group.

[0041] X 51 and X 52 Examples of hydrocarbon groups with 1 to 20 carbon atoms containing a nitrogen atom, as shown by , include dimethylaminomethyl group, diethylaminomethyl group, di-i-propylaminomethyl group, bis(dimethylamino)methyl group, bis(di-i-propylamino)methyl group, (dimethylamino)(phenyl)methyl group, methylimino group, ethylimino group, 1-(methylimino)ethyl group, 1-(phenylimino)ethyl group, and 1-[(phenylmethyl)imino]ethyl group. X 51 and X 52Examples of hydrocarbon group-substituted amino groups having 1 to 20 carbon atoms, as shown by , include dimethylamino group, diethylamino group, di-n-propylamino group, di-i-propylamino group, di-n-butylamino group, di-i-butylamino group, di-t-butylamino group, and diphenylamino group. X 51 and X 52 Examples of alkoxy groups having 1 to 20 carbon atoms, as shown, include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy, and phenoxy groups.

[0042] Preferred X 51 and X 52 Examples of these groups include chlorine atoms, bromine atoms, methyl groups, n-butyl groups, i-butyl groups, methoxy groups, ethoxy groups, i-propoxy groups, n-butoxy groups, phenoxy groups, dimethylamino groups, and di-i-propylamino groups. Among these, chlorine atoms, methyl groups, and dimethylamino groups are particularly preferred.

[0043] R 55 ~R 62 , R 84 , R 85 Each of these 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 including an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom, a hydrocarbon-substituted silyl group having 1 to 40 carbon atoms, or a hydrocarbon-substituted amino group having 1 to 40 carbon atoms.

[0044] R 55 ~R 62 , R 84 , R 85 Examples of halogen atoms include chlorine atoms, bromine atoms, and iodine atoms. R 55 ~R 62 , R 84 , R 85Examples of hydrocarbon groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, propenyl group, n-butyl group, i-butyl group, t-butyl group, butenyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, cyclohexenyl group, phenyl group, cyclohexylmethyl group, benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, biphenyl group, naphthyl group, and the like. R 55 ~R 62 , R 84 , R 85 Examples of silicon-containing hydrocarbon groups having 1 to 18 carbon atoms and containing silicon atoms numbering 1 to 6 include bis(trimethylsilyl)methyl group and bis(t-butyldimethylsilyl)methyl group.

[0045] R 55 ~R 62 , R 84 , R 85 Examples of halogen-containing hydrocarbon groups having 1 to 20 carbon atoms include bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromocyclopentyl group, 2,3-dibromocyclopentyl group, 2-bromo-3-iodocyclopentyl group, 2,3-dibromocyclohexyl group, 2-chloro-3-iodocyclohexyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6-pentafluorophenyl group, and 4-trifluoromethylphenyl group.

[0046] R 55 ~R 62 , R 84 , R 85Examples of hydrocarbon groups containing an oxygen atom and having 1 to 40 carbon atoms include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, acetyl group, acetoxy group, 1-oxopropyl group, 1-oxo-n-butyl group, 2-methyl-1-oxopropyl group, 2,2-dimethyl-1-oxopropyl group, phenylacetyl group, diphenylacetyl group, benzoyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-furyl group, 2-methylfuryl group, and 2-tetrahydrofuryl group.

[0047] R 55 ~R 62 , R 84 , R 85 Examples of hydrocarbon groups having 1 to 40 carbon atoms and containing a sulfur atom include methylthiomethyl group, ethylthiomethyl group, n-propylthiomethyl group, i-propylthiomethyl group, n-butylthiomethyl group, i-butylthiomethyl group, t-butylthiomethyl group, methylthioethyl group, ethylthioethyl group, thioacetyl group, 1-thioxopropyl group, 1-thioxo-n-butyl group, 2-methyl-1-thioxopropyl group, 2,2-dimethyl-1-thioxopropyl group, phenylthioacetyl group, diphenylthioacetyl group, thiobenzoyl group, 2-methylthiophenyl group, 3-methylthiophenyl group, 4-methylthiophenyl group, 2-thienyl group, 2-methylthienyl group, and 2-tetrahydrothienyl group.

[0048] R 55 ~R 62 , R 84 , R 85Examples of hydrocarbon groups having 1 to 40 carbon atoms and containing a nitrogen atom include dimethylaminomethyl group, diethylaminomethyl group, di-i-propylaminomethyl group, bis(dimethylamino)methyl group, bis(di-i-propylamino)methyl group, (dimethylamino)(phenyl)methyl group, methylimino group, ethylimino group, 1-(methylimino)ethyl group, 1-(phenylimino)ethyl group, and 1-[(phenylmethyl)imino]ethyl group.

[0049] R 55 ~R 62 , R 84 , R 85 Examples of hydrocarbon groups containing a phosphorus atom and having 1 to 40 carbon atoms include dimethylphosphinomethyl group, diethylphosphinomethyl group, di-i-propylphosphinomethyl group, bis(dimethylphosphino)methyl group, bis(di-i-propylphosphino)methyl group, (dimethylphosphino)(phenyl)methyl group, methylphosphanylidene group, ethylphosphanylidene group, 1-(methylphosphanylidene)ethyl group, 1-(phenylphosphanylidene)ethyl group, and 1-[(phenylmethyl)phosphanylidene]ethyl group.

[0050] R 55 ~R 62 , R 84 , R 85 Examples of hydrocarbon group-substituted silyl groups having 1 to 40 carbon atoms include trimethylsilyl group, tri-t-butylsilyl group, di-t-butylmethylsilyl group, t-butyldimethylsilyl group, triphenylsilyl group, diphenylmethylsilyl group, and phenyldimethylsilyl group.

[0051] R 55 ~R 62 , R 84 , R 85Examples of hydrocarbon group-substituted amino groups having 1 to 40 carbon atoms include dimethylamino group, methylethylamino group, diethylamino group, (methyl)(n-propyl)amino group, di-n-propylamino group, dipropenylamino group, di-i-propylamino group, di-n-butylamino group, di-i-butylamino group, di-t-butylamino group, di-n-pentylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-dodecylamino group, (methyl)(phenyl)amino group, diphenylamino group, di(4-methylphenyl)amino group, di(3,5-dimethylphenyl)amino group, and dibenzylamino group.

[0052] Preferred R 55 ~R 62 , R 84 , R 85 These include a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 40 carbon atoms, with a hydrogen atom, a methyl group, a t-butyl group, or a trimethylsilyl group being more preferred.

[0053] R 55 ~R 58 , R 84 Any one of the adjacent pairs and R 59 ~R 62 , R 85 Any one or more adjacent pairs of these groups may bond to each other, including the carbon atom to which they are bonded, forming an aliphatic ring, an aromatic ring, or a heterocycle. When a ring is formed, its position is not particularly limited. There is no limit to the number of ring members, but it is preferable to form a 5-8 membered ring to obtain a stable ring structure. Specific examples of Cp groups containing such a ring structure include indene, azulene, thiopentalene, and azapentalene, with indene and azulene being preferred, and indene being more preferred.

[0054] R 84 and R 85These may be linked together to form a divalent group represented by any of the following formulas. Therefore, in one embodiment of the present invention, component (A-2) is a metallocene compound to which a crosslinked cyclopentadienyl group is coordinated. [ka]

[0055] R 84 and R 85 However, they are linked together, forming a divalent group -E 21 -(R 88 )C=C(R 89 )-E 22 If a - is formed, such a metallocene compound is represented by the following general formula (2-0). [ka]

[0056] E 21 and E 22 These are, respectively, R 55 A cyclopentadienyl ring containing R 88 A bridging group that bonds to the carbon atoms to which it is bonded, R 59 A cyclopentadienyl ring containing R 89 This indicates a bridging group that bonds to the carbon atom to which it is bonded, and is selected from the following group. -CR 100 2-, -SiR 100 2-, -NR 100 -,-PR 100 -, -O-, -S- (Here, R 100 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and has two R 100 (They may combine to form a ring structure.) E 21 and E 22 They may be different from each other, but it is preferable that they be the same because many of them make molecular design easier. 21 and E 22 All of these are -SiR 100 2- or -CR 100It is preferable that it be 2-, where R 100 It is preferable that it is a hydrogen atom.

[0057] R 88 and R 89 Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms including 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 R 88 and R 89 These may form a ring together with the carbon atoms to which they are bonded. When a ring is formed, it is preferable that it be a 5-8 membered ring. Therefore, when a ring is formed, R 88 and R 89 Together, they form a divalent group obtained by removing one hydrogen atom from the above groups other than hydrogen and halogen atoms. In the case of forming a ring, the ring structure is R 88 and R 89 In addition to the carbon-carbon double bond to which it is bonded, it may have one or more unsaturated bonds, and it may be an aromatic ring. Furthermore, it may have further substituents on the ring, or it may have a structure in which two or more rings are fused. Particularly preferred examples of ring structures are cyclohexene or benzene rings.

[0058] R 84 and R 85 However, they are linked together, forming a divalent group -Q 51 (R 51 R 52 )-{Q 52 (R 53 R 54 )} m If a - is formed, such a metallocene compound is represented by the following general formula (2-1). [ka]

[0059] Q 51and Q 52 R represents a carbon atom, a silicon atom, or a germanium atom, respectively. 51 ~R 54 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and they are bonded together by adjacent substituents. 51 and / or Q 52 It may include and bond to form a ring. m is 0 or 1, and if m is 0, Q 51 R 55 It directly bonds to a conjugated 5-membered ring containing . The value of m is preferably 0.

[0060] R 84 and R 85 However, they are linked together, forming a divalent group -Q 51 (R 51 R 52 )-{Q 52 (R 53 R 54 )} m - If R 55 ~R 58 Any one of the adjacent pairs and R 59 ~R 62 Any one adjacent pair of these may be linked together to form a divalent group represented by one of the following formulas. [ka]

[0061] divalent group -C(R 68 )=C(R 67 )-C(R 66 )=C(R 65 )-{C(R 63 R 64 )} n - is R 3 and R 4 Together with the carbon atom to which it is bonded, it forms a 6-membered or 7-membered ring. In the formula, R 63 ~R 68Each of these 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 including an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom, a hydrocarbon-substituted silyl group having 1 to 40 carbon atoms, or a hydrocarbon-substituted amino group having 1 to 40 carbon atoms, and may be bonded to adjacent substituents, including the carbon atoms to which they are bonded, to form a ring. 63 ~R 68 Examples and preferred embodiments are R 59 This is similar to the examples and preferred embodiments.

[0062] n is either 0 or 1, and if n is 0, (CR 63 R 64 The ) part does not exist, (CR 63 R 64 The carbon atom adjacent to the 5-membered ring is directly bonded to it to form an indenyl ring.

[0063] divalent group -SC(R 83 )=C(R 82 )- combines with the carbon atom of the Cp ring to form a thiophene ring. 83 This represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms.

[0064] divalent group -SC(R 83 )=C(R 82 )- in R 82 This represents a substituted or unsubstituted aryl group shown by the following general formula (2-a). [ka] [In formula (2-a), Y represents an atom of group 14, 15, or 16 of the periodic table, and R 75 ~R 79Each of these 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 with 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 with 1 to 20 carbon atoms, and R 75 ~R 79 The substituents may form a ring with the atoms they are bonded to. If q is 0 or 1 and Y is an atom from group 15 or 16 of the periodic table, then q is 0 and Y has substituent R 75 It does not exist. When q is 0, Y is preferably an oxygen atom. When q is 1, Y is preferably a carbon atom. p is 0 or 1, and when p is 0, formula (2-a) forms a 5-membered ring.

[0065] If Y is a carbon atom, R 75 ~R 79 It is preferable that at least one of them is not a hydrogen atom. Furthermore, R 75 ~R 79 Preferably, it is not a halogen atom. R 75 ~R 79 When the group indicated is anything other than a hydrogen atom, for halogen atoms, C1-C20 hydrocarbon groups, C1-C20 hydrocarbon groups containing oxygen or nitrogen atoms, C1-C18 silicon-containing hydrocarbon groups containing 1-6 silicon atoms, C1-C20 halogen-containing hydrocarbon groups, or C1-C20 hydrocarbon group-substituted silyl groups, the above-mentioned R 59 Similar groups to those described above can be cited, and for hydrocarbon-substituted amino groups with 1 to 20 carbon atoms, or alkoxy groups with 1 to 20 carbon atoms, see the aforementioned X 51 and X 52 Similar to the bases shown in the explanation can be cited.

[0066] The groups represented by general formula (2-a) specifically include phenyl group, 4-trimethylsilylphenyl group, 4-(t-butyldimethylsilyl)phenyl group, 3,5-bistrimethylsilylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-isopropoxyphenyl group, 4-n-butoxyphenyl group, 2-furyl group, 2-(5-methyl)furyl group, 2-(5-t-butyl)furyl group, 2-(5-trimethylsilyl)furyl group, 2-(4,5-dimethyl)furyl group, 2-benzofuryl group, 2-thienyl group, 2-(5-methyl)thienyl group, 2-(5-t-butyl)thienyl group, 2-(5-trimethylsilyl)thienyl group, and 2-(4,5-dimethyl)thienyl group.

[0067] The metallocene compounds represented by general formula (2) are compounds having the structure described above, but the metal M 51 The structure of the cyclopentadienyl ring to which R is coordinated is as follows: 55 ~R 62 At least one of these can be a substituent having a cyclic structure represented by the general formula (2-a).

[0068] In another preferred embodiment, R 55 ~R 62 At least one of these may represent a substituent having a cyclic structure represented by the following general formula (8). [ka] In general formula (8), Z 2 This represents an oxygen atom or a sulfur atom. R 90 ~R 92 Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom, a sulfur atom, or a hydrocarbon group having 1 to 20 carbon atoms containing 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 with 1 to 20 carbon atoms, and R 90 ~R 92These substituents may be bonded to each other by adjacent substituents, including the carbon atom to which they are bonded, to form a ring.

[0069] R 90 ~R 92 In this context, the halogen atom, the C1-C20 hydrocarbon group, the C1-C20 hydrocarbon group containing an oxygen atom, a sulfur atom, or a nitrogen atom, the C1-C18 silicon atom-containing hydrocarbon group containing 1-6 silicon atoms, the C1-C20 halogen atom-containing hydrocarbon group, or the C1-C20 hydrocarbon group-substituted silyl group are as described above. 55 Examples similar to those given in the explanations above can be cited.

[0070] The groups represented by general formula (8) include, specifically, phenyl group, 4-trimethylsilylphenyl group, 4-(t-butyldimethylsilyl)phenyl group, 3,5-bistrimethylsilylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-isopropoxyphenyl group, 4-n-butoxyphenyl group, 2-furyl group, 2-(5-methyl)furyl group, 2-(5-t-butyl)furyl group, 2-(5-trimethylsilyl)furyl group, 2-(4,5-dimethyl)furyl group, 2-benzofuryl group, 2-thienyl group, 2-(5-methyl)thienyl group, 2-(5-t-butyl)thienyl group, 2-(5-trimethylsilyl)thienyl group, and 2-(4,5-dimethyl)thienyl group.

[0071] The metallocene compound represented by general formula (2-1) has a ligand with a structure in which two cyclopentadienyl groups are bridged, although the two substituents on the cyclopentadienyl group may together form a ring. In a preferred embodiment, the metallocene compound represented by general formula (2) has a ligand with a structure in which any two aromatic rings, which may be the same, are bridged from among the cyclopentadienyl group, indenyl group, and azurenyl group. In a preferred embodiment of the present invention, component (A-2) is characterized in that the metallocene compound represented by the following formula (2-2). [ka] [In equation (2-2), the definitions of each group are as described above.]

[0072] R 55 , R 56 , R 59 , R 60 , R 63 ~R 74 In this, the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, the silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, the halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 1 to 40 carbon atoms including 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 are as described above. 59 Examples similar to those given in the explanations above can be cited.

[0073] In the above formula (2-2) of component (A-2), it is preferable that n is 0 in each case.

[0074] In the above formula (2-2) of the above component (A-2), R 55 , R 56 , R 59 , R 60 , R 63 ~R 74 At least one of these may be the group represented by formula (7) or formula (8). In that case, R 63 ~R 65 and 69 ~R 71 It is more preferable that at least one of the groups is represented by formula (7) above. Also, R 55 , R 59 At least one of the following, or R 63 ~R 65 and R 69 ~R 71 It is more preferable that at least one of the groups is represented by formula (8) above.

[0075] In one preferred embodiment of the present invention, component (A-2) is a metallocene compound represented by any of the following general formulas (2-3-1) to (2-3-5). [ka] [In the formula, M 51 , X 51 , X 52 Q 51 Q 52 , R 51 ~R 54 , m, n, R 55 , R 56 , R 59 , R 60 , R 63 ~R 68 As defined above, R 86 , R 87 Each of these 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 including an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom, a hydrocarbon-substituted silyl group having 1 to 40 carbon atoms, or a hydrocarbon-substituted amino group having 1 to 40 carbon atoms. [D represents a sulfur atom or an oxygen atom]

[0076] In one preferred embodiment of the present invention, component (A-2) is a metallocene compound represented by the following general formula (2-4). [ka] [In formula (2-4), M 51 , X 51 , X 52 Q 51 Q 52 , R 51 ~R 54 m and n are as defined above. R 55 ~R 60 , R 63 ~R 68Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms including 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 R 55 ~R 58 R may be bonded to adjacent substituents, including the carbon atom to which they are bonded, forming an aliphatic ring. 63 ~R 68 The substituents may be bonded to each other by adjacent substituents, including the carbon atom to which they are bonded, to form a ring.

[0077] The olefin polymerization catalyst of the present invention comprises the above-mentioned components (A-1) and (A-2), wherein each component is selected to satisfy the following conditions (1) to (4).

[0078] Condition (1): An olefin polymerization catalyst (Cat) containing components (A-1) and (B) but not (A-2). (A-1) HLMFR is an olefin polymer obtained by polymerizing olefins in the presence of hydrogen molecules using ). (A-1) And, an olefin polymerization catalyst (Cat) containing components (A-2) and (B) but not (A-1). (A-2) Using ), the HLMFR of the olefin polymer obtained under the same conditions is HLMFR (A-2) However, HLMFR (A-1) ≥HLMFR (A-2) It satisfies the condition.

[0079] HLMFR, like melt flow rate (MFR), is a value that measures the fluidity of a resin. Since the fluidity of a resin increases as the molecular weight of the polymer decreases, HLMFR can be used as a measure to estimate the molecular weight. In this invention, (A-1) plays the role of providing a low molecular weight polymer, so HLMFR (A-1) ≥HLMFR (A-2)When this condition is satisfied, the molecular weight distribution of the polymer broadens, and a copolymer with superior moldability can be obtained. HLMFR (A-1) >HLMFR (A-2) Satisfying the following is more preferable, HLMFR (A-1) >5×HLMFR (A-2) Satisfying the following is even more preferable: HLMFR (A-1) >10×HLMFR (A-2) Satisfying this condition is particularly desirable. In this specification, HLMFR is defined as the value measured under conditions of 190°C and a 21.6 kg load, in accordance with JIS K7210:2014.

[0080] Condition (2):Cat (A-1) In the polymerization of olefins using [a specific method], the ratio of hydrogen to olefin (H2 / C2 ratio) and the HLMFR of the olefin polymer are important. (A-1) The correlation coefficient γ in the following definition formula represents the correlation between the two. (A-1) However, the range is between -2.0 and +1.0; Definition formula Log[HLMFR (A-1) ]=γ (A-1) ·Log[H2 / C2]+δ Here, the above equation represents the relationship between H2 / C2 and HLMFR when polymerized at a temperature of 80°C using H2 / C2 at two points separated by 0.05 mol% or more. (A-1) This represents the approximate straight line between H2 / C2 = 0.05 and 0.15 mol%, obtained from the relationship on a log-log graph, with coefficient γ. (A-1) δ is the slope of the line, and the intercept δ is the logarithm of the HLMFR when H2 / C2 = 1 mol%. However, the HLMFR when H2 / C2 = 0.1 mol% is... (A-1) When it is 10 or more, HLMFR in the above definition formula (A-1) is MFR (A-1) This shall be used as a substitute.

[0081] Component (A-1) tends to have a negative or neutral correlation with hydrogen concentration, where the correlation coefficient of HLMFR is close to 0. (A-1)When the value of is within the above range, the response to hydrogen when the catalyst is considered alone will be mild. Here, a correlation coefficient of -1.0 to +1.0 according to the above definition formula is defined as a neutral correlation of polymerization activity, a correlation of less than -1.0 to -2.0 is defined as a weak negative correlation, a correlation of less than -2.0 is defined as a negative correlation, a correlation of greater than +1.0 to +2.0 is defined as a weak positive correlation, and a correlation of greater than +2.0 is defined as a positive correlation. The above coefficient γ (A-1) Preferably, the range is -1.5 to +1.0, more preferably -1.2 to +1.0, even more preferably -1.0 to +1.0, particularly preferably -1.0 to +0.8, and most preferably -1.0 to +0.6.

[0082] Condition (3):Cat (A-2) The H2 / C2 ratio obtained at a temperature of 80°C under the same conditions as (2) and the HLMFR of the olefin polymer are HLMFR (A-2) The correlation coefficient γ (A-2) However, it is greater than +1.0 and less than or equal to +10; Component (A-2) shows a weak positive to positive correlation between HLMFR and hydrogen concentration. Correlation coefficient γ (A-2) When the value of γ falls within the above range, a response to hydrogen occurs as observed when the catalyst is considered alone, making it possible to control the properties of the polymer by adjusting the hydrogen concentration. (A-2) The coefficient γ is preferably +1.5 to +10, more preferably +1.5 to +8, even more preferably +1.5 to +7.0, particularly preferably +2.0 to +7.0, and most preferably +2.0 to +6.0. (A-2) When this value exceeds 10, the responsiveness to hydrogen concentration becomes too sensitive, which can hinder the precise control of the polymer's properties.

[0083] Condition (4): γ (A-1) and gamma (A-2) The absolute value of the difference |Δγ| is greater than 0 and less than or equal to 10. If conditions (2) and (3) above are met, the influence of responsiveness to hydrogen will be limited to polyolefins in the high molecular weight range. However, if the difference in the correlation between each component is within the above range, the influence of responsiveness to hydrogen when viewed as a whole binary complex catalyst will be evaluated as originating solely from component (A-2). The above absolute value |Δγ| is preferably 0.5 to 10, more preferably 0.5 to 8.0, even more preferably 1.0 to 8.0, particularly preferably 1.4 to 7.0, and most preferably 1.8 to 6.0.

[0084] In one embodiment of the present invention, it is more preferable that the catalyst for olefin polymerization satisfies the following condition (5) in components (A-1) and (A-2). Condition (5): Said Cat (A-1) Using this method, the weight-average molecular weight Mw of the olefin polymer obtained by polymerizing olefins in the presence of hydrogen molecules was determined by GPC measurement. (A-1) And, Cat (A-2) Using this method, the weight-average molecular weight Mw of the olefin polymer obtained under the same conditions (A-2) However, Mw (A-1) ≤Mw (A-2) It satisfies the condition. Component (A-2) exhibits excellent olefin copolymerization properties and yields a polymer with a relatively high molecular weight, thus tending to have a high weight-average molecular weight. (A-1) ≤Mw (A-2) When this condition is satisfied, the copolymer will contain a large amount of high molecular weight components, and as a result, the structure with a large amount of comonomers on the high molecular weight side will tend to be incorporated, making it possible to obtain 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 having a larger weight-average molecular weight than component (A-1). Mw (A-1) <Mw (A-2) Satisfying this condition is more preferable, 3 × Mw (A-1) <Mw (A-2) Satisfying the following is even more preferable: 5 × Mw (A-1) <Mw (A-2) Satisfying this condition is particularly desirable.

[0085] In one embodiment of the present invention, it is even more preferable that the catalyst for olefin polymerization satisfies the following condition (6) in components (A-1) and (A-2). Condition (6): Said Cat (A-1) D is the density of the olefin polymer obtained by polymerizing or copolymerizing olefins in the presence of hydrogen molecules. (A-1) And, Cat (A-2) Using this method, the density D of the olefin polymer obtained under the same conditions (A-2) However, D (A-1) ≧D (A-2) It satisfies the condition. Component (A-2) has a strong property of incorporating comonomers into the copolymer. Therefore, polymers using component (A-2) as a catalyst tend to have a higher comonomer content, resulting in a lower density. D (A-1) ≧D (A-2) When this condition is satisfied, the copolymer tends to incorporate a structure with a high molecular weight polymer having a high comonomer content, and a copolymer with superior moldability and product strength can be obtained. For this reason, it is preferable that component (A-2) is a catalyst that yields a polymer with a lower density than component (A-1). That is, D (A-1) >D (A-2) It is preferable that the following conditions are met, D (A-1) >1.01×D (A-2) Satisfying this condition is more preferable, D (A-1) >1.02×D (A-2) It is even more preferable if the following is satisfied, D (A-1) >1.03×D (A-2) Satisfying this condition is particularly preferable, D (A-1) >1.04×D (A-2) It is most desirable if this condition is satisfied.

[0086] 3. Synthesis methods for each catalyst component (3-1) Method for synthesizing transition metal complex compounds of formula (1) The transition metal complex compound of formula (1) above can be produced using commonly known synthesis methods. As an example of a general procedure for complex synthesis, the synthesis of the transition metal complex compound represented by general formula (1-1) above can be performed by reacting a pyridine derivative having an acetyl group at the 2,6-position with two equivalents of an amine in the presence of an acid to obtain a tridentate ligand, and then reacting it with a metal salt to obtain the compound of formula (1-1). For specific preparation methods, refer to the method described in the literature (Supporting Information, Journal of American Chemical Society, Vol. 120, p. 4049).

[0087] (3-2) Method for synthesizing metallocene compounds When synthesizing the metallocene compound of formula (2) above, one can refer to, for example, synthesis example 1 in Japanese Patent Publication No. 2012-149160 or synthesis example in Japanese Patent Publication No. 2023-153037.

[0088] 4. [Component (B)] A compound that reacts with component (A-1) or component (A-2) to produce a cationic complex compound. The olefin polymerization catalyst of the present invention includes, as component (B), a compound that reacts with a compound of component (A-1) or component (A-2) to form a cationic complex compound, in addition to the above-mentioned components (A-1) and (A-2). The compounds that react with components (A-1) and (A-2) to form cationic complex compounds are not particularly limited and any known components can be used. Examples include organoaluminum oxy compounds, borane compounds, and borate compounds. Neutral Lewis acids are particularly suitable as compounds that react with component (A-1).

[0089] Using organoaluminum oxy compounds, borane compounds, or borate compounds as component (B) increases polymerization activity and copolymerizability, thereby improving the productivity of olefin polymers.

[0090] Furthermore, as component (B), a mixture of the aforementioned organoaluminum oxy compound and the above-mentioned borane compound or borate compound may be used. In addition, two or more of the above-mentioned borane compounds or borate compounds may be used in combination. The following provides a more detailed explanation of each of these compounds.

[0091] (i) Organic aluminum oxy compounds Organoaluminum oxy compounds have Al-O-Al bonds in their molecules, with the number of bonds typically ranging from 1 to 100, preferably from 1 to 50. Such organoaluminum oxy compounds are usually products obtained by reacting an organoaluminum compound with water.

[0092] Among organoaluminum oxy compounds, those obtained by reacting alkylaluminum with water are usually called aluminoxanes and can be suitably used as component (B). Furthermore, among aluminoxanes, methylaluminoxanes (those substantially composed of methylaluminoxane (MAO), including polymethylaluminoxanes) are particularly suitable as organoaluminum oxy compounds. Furthermore, two or more organoaluminum oxy compounds can be used in combination as the organoaluminum oxy compound, or a solution obtained by dissolving or dispersing the organoaluminum oxy compound in an inert hydrocarbon solvent, as described later, may be used.

[0093] The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). Suitable inert hydrocarbons include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene; however, the use of aliphatic or aromatic hydrocarbons is preferred.

[0094] Any organoaluminum compound represented by the following general formula (I) can be used for the preparation of organoaluminum oxy compounds, but trialkylaluminum is preferred. R 40 t AlX 3 3-t ...(I) (In formula (I), R 40 X represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms. 3 (where 't' represents a hydrogen atom or a halogen atom, and 't' represents an integer between 1 and 3.)

[0095] Examples of alkyl groups in trialkylaluminum include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, and dodecyl groups, but among these, a methyl group is particularly preferred. The above organoaluminum compounds can be used individually or in combination of two or more types.

[0096] The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably 0.25 / 1 to 1.2 / 1, particularly 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 from 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As the water required for the reaction, not only plain water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate, etc., or components that can generate water in the reaction system can be used.

[0097] (ii) Borane or borate compound Furthermore, as component (B), borane compounds and borate compounds described in paragraphs 0229 to 0242 of Japanese Patent Publication No. 2012-214780 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, and tris(2,6-ditrifluoromethylphenyl)borane. Oromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl), tris(perfluoroantryl)borane, tris(perfluorobinaphthyl)borane, etc., as well as 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., as well as trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, trityl Tra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, tropiniumtetra(pentafluorophenyl)borate, tropiniumtetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(3,5-ditrifluoromethylphenyl)borate, tropiniumtetra(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 Examples include H7)4·2-diethyl ether.

[0098] (iii) Neutral Lewis acids In particular, for component (A-1), X is derived from the compound of formula (1) above. 1 A neutral Lewis acid that can extract H from a metal atom, and / or H from a metal atom. - Compounds to which the additive component can be added can be used. Such compounds include the organoaluminum oxy compounds, boranes, and borates mentioned above, but antimony pentafluoride can also be used.

[0099] (3-2) Layered silicates Layered silicate can be used as component (B). Layered silicate can be used as a component that serves as both component (B) and component (C) described later. By using a layered silicate as component (B), polymerization activity and copolymerizability are enhanced, similar to when using organoaluminum oxy compounds, borane compounds, or borate compounds, thereby improving the productivity of olefin polymers. Layered silicates are silicate compounds that have a crystalline structure in which planes formed by ionic bonds, etc., are stacked parallel to each other with weak bonding forces. Most layered silicates occur naturally mainly 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 catalyst components for olefin polymerization are well known in Japanese Patent Publication No. 5-301917, Japanese Patent Publication No. 8-127613, Japanese Patent Publication No. 2003-82018, Japanese Patent Publication No. 2017-165916, etc. Furthermore, compounds listed in Japanese Patent Publication No. 2002-515522, etc., which have similar effects, can also be suitably used as component (B) in the present invention.

[0100] Examples of layered silicates include known compounds described in Haruo Shiramizu's "Clay Mineralogy" (Asakura Shoten, 1995), and specific examples include kaolin group compounds such as dickite, nacrite, kaolinite, anoxite, metahaloysite, and halloysite; serpentine group compounds such as chrysotile, lizardite, and antigorite; smectite group compounds such as montmorillonite, sauconite, beidelite, nontronite, saponite, teniolite, hectorite, stevensite, bentonite, and souconite; vermiculite group compounds such as vermiculite; mica group compounds such as mica, illite, sericite, and erythrocyte; and atapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, and chlorite group compounds.

[0101] More preferred layered silicates include smectites such as montmorillonite, sauconite, beiderite, nontronite, saponite, hectorite, stevensite, bentonite, and teniolite, as well as vermiculites and micas. Smectites are particularly preferred as layered silicates.

[0102] Generally, natural layered silicates are often non-ion-exchangeable (non-swelling), and in such cases, it is preferable to perform treatments to impart ion-exchangeability (or swelling) properties. Among such treatments, the following chemical treatments are particularly preferred. Here, chemical treatment can refer to either surface treatment to remove impurities adhering to the surface or treatment that affects the crystal structure and chemical composition of the layered silicate. As for chemical treatment methods, known chemical treatment methods can be applied, including the method described in Japanese Patent Publication No. 2003-82018. Specifically, examples include acid treatment, alkali treatment, metal salt treatment, and organic treatment, with acid treatment or metal salt treatment being more preferred, and these being 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.

[0103] Furthermore, the metal salt used in the metal salt treatment is an inorganic compound containing a cation comprising at least one atom selected from the group consisting of group 2 to 14 atoms. Preferably, it is a compound comprising a cation comprising at least one atom selected from the group consisting of group 2 to 14 atoms and at least one anion selected from the group consisting of halogen atoms, inorganic acids, and organic acids. More preferably, it is a compound comprising a cation comprising at least one atom selected from the group consisting of group 2 to 14 atoms and at least one anion selected from the group consisting of Cl, Br, I, F, PO4, SO4, NO3, CO3, C2O4, ClO4, OOCCH4, CH3COCHCOCH3, OCl2, O(NO3)2, O(ClO4)2, O(SO4), OH, O2Cl2, OCl3, OOCH, OOCCH2CH3, C2H4O4, and C6H5O7.

[0104] The ratio of the compounds of component (A-1) and component (A-2) to the layered silicate as component (B) is not particularly limited, but the following ranges are preferred. The total amount of components (A-1) and (A-2) supported per gram of layered silicate carrier 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.

[0105] 5.[Component (C)] The olefin polymerization catalyst of the present invention preferably uses a fine particle carrier (component (C)), which is an inorganic carrier, a particulate polymer carrier, or a mixture thereof, as an additional component. As the inorganic carrier, metals, metal oxides, metal chlorides, metal carbonates, carbonaceous materials, or mixtures thereof can be used.

[0106] Suitable metals that can be used as inorganic carriers include, for example, iron, aluminum, and nickel.

[0107] Furthermore, examples of metal oxides include single or complex oxides of elements from groups 1 to 14 of the periodic table. For example, various natural or synthetic single or complex oxides such as SiO2, Al2O3, MgO, CaO, B2O3, TiO2, ZrO2, Fe2O3, Al2O3·MgO, Al2O3·CaO, Al2O3·SiO2, Al2O3·MgO·CaO, Al2O3·MgO·SiO2, Al2O3·CuO, Al2O3·Fe2O3, Al2O3·NiO, and SiO2·MgO can be cited. Here, the above formulas represent only the composition, not the molecular formula, and the structure and component ratio of the complex oxides used in the present invention are not particularly limited. In addition, the metal oxides used in the present invention may absorb small amounts of moisture and may contain small amounts of impurities. As metal chlorides, alkali metal and alkaline earth metal chlorides are preferred, and specifically MgCl2 and CaCl2 are particularly preferred. As metal carbonates, alkali metal and alkaline earth metal carbonates are preferred, and specifically, magnesium carbonate, calcium carbonate, and barium carbonate are examples. Examples of carbonaceous materials include carbon black and activated carbon.

[0108] All of the above inorganic supports can be suitably used in the present invention, but the use of metal oxides, silica, alumina, and the like is particularly preferred.

[0109] These inorganic supports are usually calcined at 200°C to 800°C, preferably 400°C to 600°C, in air or inert gas such as nitrogen or argon, to adjust the amount of surface hydroxyl groups to 0.8 mmol / g to 1.5 mmol / g before use. While there are no particular restrictions on the properties of these inorganic supports, typically the average particle size is 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 m². 2 / g~1000m 2 / g, preferably 200m 2 / g~700m 2 / g, pore volume is 0.3 cm³3 / g to 2.5 cm 3 / g, preferably 0.5 cm 3 / g to 2.0 cm 3 / g, and an apparent specific gravity of 0.20 g / cm 3 to 0.50 g / cm 3 , preferably 0.25 g / cm 3 to 0.45 g / cm 3 is preferably used.

[0110] The above-mentioned inorganic carrier can be used as it is, but it can also be used after being brought into contact 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.

[0111] 6. [Component (D)] In the present invention, an organoaluminum compound can be further used as component (D) as necessary. Specific examples of the organoaluminum compound include AlR j X 3-j (wherein R is a C1 to C20 hydrocarbon group, X is a hydrogen atom, a halogen atom, or an alkoxy group, and j is a number satisfying 0<j≦3), such as trialkylaluminums including trimethylaluminum, triethylaluminum, tripropylaluminum, and triisobutylaluminum, or halogen- or alkoxy-containing alkylaluminums including diethylaluminum monochloride and diethylaluminum methoxide. In addition, aluminoxanes such as methylaluminoxane and the like can also be used. Among these, trialkylaluminum is particularly preferred. The amount of the organoaluminum compound as component (D) to be used is 0.01 to 10000 mmol, preferably 0.1 to 100 mmol, more preferably 0.2 to 20 mmol, and still more preferably 0.5 to 10 mmol, per 1 g of component (B).

[0112] 7. Method for producing catalysts for olefin polymerization The olefin polymerization catalyst used in the method for producing olefin polymers of the present invention is manufactured comprising the above components (A-1), (A-2), (B), and optionally (C) and / or (D). The method of contacting each component when obtaining an olefin polymerization catalyst from the above components (A) to (D) of the present invention is not particularly limited. Furthermore, the contact order of components (A-1), (A-2), (B), (C), and (D) is not particularly limited. For example, the following method can be arbitrarily adopted. • Bring components (A-1) and (A-2) into contact, then component (B) into contact, and then component (C) and / or (D) into contact. - Contact either component (A-1) or component (A-2) with component (B), then contact the remaining component (A-1) and component (A-2), and finally contact component (C) and / or (D). - Either component (A-1) or component (A-2) is brought into contact with component (C) and / or (D), then the remaining component (A-1) and component (A-2) are brought into contact, and finally component (B) is brought into contact. After bringing component (B) and component (C) and / or (D) into contact, bring component (A-1) or component (A-2) into contact in any order. The product obtained by contacting components (A-1) and (A-2) is brought into contact with the contact product obtained by contacting component (C) and / or (D), and the contact product obtained by contacting component (B) with component (C) and / or (D) is brought into contact with each other.

[0113] In any contact method, the components are typically brought into contact with each other under stirring or without stirring in an inert atmosphere such as nitrogen or argon, in the presence of liquid inert hydrocarbons such as aromatic hydrocarbons (usually with 6 to 12 carbon atoms) such as benzene, toluene, xylene, and ethylbenzene, and aliphatic or alicyclic hydrocarbons (usually with 5 to 12 carbon atoms) such as pentane, heptane, hexane, decane, dodecane, and cyclohexane. This contact is usually carried out at a temperature of -100°C to 200°C, preferably -50°C to 100°C, more preferably 0°C to 50°C, for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, and even more preferably 30 minutes to 12 hours.

[0114] Furthermore, as described above, when components (A-1), (A-2), (B), and (C) and / or (D) come into contact, either aromatic hydrocarbon solvents in which certain components are soluble or sparingly soluble, or aliphatic or alicyclic hydrocarbon solvents in which certain components are insoluble or sparingly soluble, can be used.

[0115] When the contact reactions between components are carried out in steps, the solvent used in the preceding step may be used directly as the solvent for the subsequent contact reaction without removing it. Alternatively, after the initial contact reaction using a soluble solvent, a liquid inert hydrocarbon in which certain components are insoluble or sparingly soluble (for example, aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, and xylene) may be added to recover the desired product as a solid, or after removing part or all of the soluble solvent by means of drying, filtration, decantation, etc., to obtain 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. The present invention does not prevent the contact reactions of each component from being carried out multiple times.

[0116] 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.

[0117] When an organoaluminum oxy compound is used as component (B), it is desirable that the molar ratio (Al / M) of aluminum atoms in the organoaluminum oxy compound to the total amount of transition metals (M) in components (A-1) and (A-2) be in the range of 1 to 100,000, preferably 5 to 2,000, more preferably 50 to 1,000, and particularly preferably 200 to 900. Furthermore, when using a borane compound or borate compound as component (B), it is desirable that the molar ratio of boron atoms (B / M) to the total amount of transition metals (M) in components (A-1) and (A-2) be in the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10. Furthermore, when using a mixture of an organoaluminum oxy compound and a borane compound and / or a borate compound as component (B), it is desirable that the proportion of aluminum atoms and boron atoms used for each compound in the mixture be the same as described above, relative to the total amount of transition metal (M) in components (A-1) and (A-2). Furthermore, when using layered silicate as a carrier for component (B), the proportion of layered silicate used is not particularly limited, but the following range is preferred. The amount of components (A-1) and (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. The ratio of components (A-1) and (A-2) used is determined each time, taking into account the ratio of polymerization activity that both components will exhibit, within the range where a polymer design of an olefin polymer suitable for the target product application can be realized. 1 ) molar ratio (M 1 It is desirable that the value of / M) is usually in the range of 0.01 to 0.99, preferably 0.03 to 0.97, more preferably 0.05 to 0.95, and particularly preferably 0.10 to 0.90.

[0118] The amount of component (C), which is a fine particle carrier, used is such that the total amount of transition metal (M) in components (A-1) and (A-2) is 0.0001 to 5 mmol per gram of component (C), preferably 0.001 to 0.5 mmol, and more preferably 0.01 to 0.1 mmol.

[0119] A catalyst for olefin polymerization can be obtained as a solid catalyst by bringing components (A-1), (A-2), (B), and (C) and / or (D) into contact with each other using one of the aforementioned contact methods as appropriate, and then removing the solvent. The solvent removal is preferably carried out under normal pressure or reduced pressure at 0 to 200°C, preferably 20 to 150°C, more preferably 20 to 100°C for 1 minute to 100 hours, preferably 10 minutes to 50 hours, and even more preferably 30 minutes to 20 hours.

[0120] Furthermore, the catalyst for olefin polymerization can also be prepared by contacting components (A-1), (A-2), and (B) to remove the solvent, obtaining a solid catalyst component, and then contacting it with components (C) and / or (D) under polymerization conditions. Alternatively, components (B), (C), and / or (D) can be contacted to remove the solvent, obtaining a solid catalyst component, and then contacting it with components (A-1) and (A-2) under polymerization conditions. In these contact methods as well, the same component ratios, contact conditions, and solvent removal conditions as described above can be used. The olefin polymerization catalyst thus obtained may be used after prepolymerization of monomers, if necessary.

[0121] 8. Method for producing olefin polymers The olefin polymerization catalyst described above can be used for olefin polymerization, particularly for the homopolymerization of ethylene or copolymerization of ethylene and olefins. Here, ethylene homopolymer refers to a polymer produced by supplying only ethylene as a monomer raw material to the reactor. The ethylene can be at least one of the following raw materials: ethylene derived from petroleum, ethylene derived from biomass, or ethylene obtained through chemical recycling.

[0122] The olefins used as comonomers include those with 3 to 30 carbon atoms, preferably 3 to 8 carbon atoms. Specific examples include propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene. It is also possible to copolymerize two or more olefins with ethylene. The copolymerization can be alternating copolymerization, random copolymerization, or block copolymerization. When copolymerizing ethylene with other olefins, the amount of the other olefin can be arbitrarily selected within a range of 90 mol% or less of the total monomer, 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 small amounts of comonomers other than ethylene and olefins. In this case, examples of polymerizable double-bonded compounds include 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.

[0123] In the present invention, the polymerization reaction can be carried out in the presence of the supported catalyst described above, preferably by slurry polymerization or gas-phase polymerization. In the case of slurry polymerization, ethylene and the like are 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 where oxygen, water, etc., are substantially excluded. 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 and the like are polymerized in a reactor in which a gas stream of ethylene or comonomer is introduced, circulated, or circulated. In the present invention, a more preferred polymerization method is gas-phase polymerization.

[0124] [Polymerization temperature] The polymerization temperature of the olefin 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 (2) tends to decrease, making it possible to control the physical properties of the resulting polymer more precisely. Therefore, it is preferable to carry out polymerization in a relatively low temperature range where the polymerization reaction proceeds.

[0125] [Ethylene partial pressure] The ethylene partial pressure in the polymerization of olefins 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, even 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, polymerization activity may be low or Mw may become too small, which is undesirable. When the ethylene partial pressure exceeds 3 MPa, the weight-average molecular weight (Mw) may become too large, or the polymerization reactor and post-treatment equipment may require excessive pressure resistance, worsening economic efficiency, which is undesirable.

[0126] [Polymerization time] The polymerization time for the olefin according to the present invention is preferably 0.3 hours or more and less than 30 hours, more preferably 0.6 hours to 12 hours, and even more preferably 1 hour to 7 hours. Polymerization times shorter than 0.3 hours result in low polymer yield per catalyst, making it uneconomical. When the polymerization time exceeds 30 hours, the polymer yield per unit volume of the polymerization reactor decreases, making it uneconomical.

[0127] The molecular weight of the resulting polymer can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, but molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system.

[0128] Furthermore, the polymerization can be carried out without any problems even if a component for removing moisture, a so-called scavenger, is added to the polymerization system. Suitable scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum; the aforementioned organoaluminum oxy compounds; modified organoaluminum compounds containing branched alkyl groups; organozinc compounds such as diethylzinc and dibutylzinc; organomagnesium compounds such as diethylmagnesium, dibutylmagnesium, and ethylbutylmagnesium; and greenya 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 problems to multi-stage polymerization methods with two or more stages where polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature differ from each other.

[0129] 9. Properties of polyolefin polymers Olefin polymers, particularly ethylene polymers, produced using the olefin polymerization catalyst of the present invention preferably satisfy the following conditions (i) to (iii). Condition (i): MFR is between 0.001 and 1000 g / 10 min. Condition (ii): Density of 0.895-0.975 g / cm³ 3 That is the case. 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) measured by gel permeation chromatography (GPC) using weight-average molecular weight (Mw) and number-average molecular weight (Mn) is 3.5 or greater and 100 or less. Condition (iii-2): The lowest value (g) of the branching index g' between a molecular weight of 100,000 and 1,000,000, measured by a GPC measuring device combining a differential refractometer, viscosity detector, and light scattering detector. L The value is between 0.20 and 0.98. Condition (iii-3): Melt flow rate (MFR) at a temperature of 190°C and a load of 10 kg. 10kg ) and 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, is 6.5 or higher and 100 or lower. Condition (iii-4): The 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 is 15 or greater and 1000 or less.

[0130] [Condition (i): MFR] The melt flow rate of the ethylene-based polymer obtained in the present invention, i.e., the MFR (at 190°C and a 2.16 kg load), is preferably 0.001 g / 10 min to 1000 g / 10 min, more preferably 0.005 g / 10 min to 200 g / 10 min, even 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.

[0131] [Condition (ii): Density] The density of the ethylene-based polymer obtained in this invention is preferably 0.895 g / cm³. 3 ~0.975g / cm 3 More preferably 0.900 g / cm³ 3 ~0.970g / cm 3 And more preferably 0.915 g / cm³ 3 ~0.965g / cm 3 And, particularly preferably, 0.940 g / cm³. 3 ~0.965g / cm 3 The density can be adjusted by the type or combination of polymerization catalysts. Here, the density was measured in accordance with JIS-K7112, by melting the pellets in a heat compression molding machine at a temperature of 160°C, then cooling them at a rate of 25°C / min to form a sheet with a thickness of 2 mmt, and then conditioned this sheet in a room at a temperature of 23°C for 48 hours before being placed in a density gradient tube. A density within the above range is preferable because it provides an excellent balance of mechanical strength, such as rigidity, impact strength, and long-term durability.

[0132] [Condition (iii-1) Mw / Mn] The ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn) of the olefin polymer obtained by the present invention, as measured by gel permeation chromatography (GPC), is preferably 3.5 or higher, more preferably 3.7 or higher, even more preferably 4.0 or higher, particularly preferably 5.0 or higher, preferably 100 or lower, more preferably 80 or lower, even more preferably 60 or lower, and particularly preferably 50 or lower. A Mw / Mn within the above range is preferable because it provides excellent molding properties such as melt tension and melt fluidity, as well as an excellent balance of mechanical strength, such as rigidity, impact strength, and long-term durability.

[0133] In this invention, Mw and Mn of the olefin polymer refer to those measured by gel permeation chromatography (GPC).

[0134] [GPC method measurement] The measured retention capacity is determined by the GPC method, and the conversion from the measured retention capacity to molecular weight is performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrene used is the following brands manufactured by Tosoh Corporation: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000. Calibration curves are created by injecting 0.2 mL of a solution of orthodichlorobenzene (ODCB) (containing 0.5 mg / mL of BHT (2,6-di-t-butyl-4-methylphenol)) so that each component is at 0.5 mg / mL. The calibration curves are approximated using a cubic equation obtained by the least squares method. For conversion to molecular weight, a general calibration curve is used, referring to "Size Exclusion Chromatography" by Sadao Mori (Kyoritsu Shuppan). The viscosity formula used in this process is [η] = K × M α The following values ​​will be used. PS: K = 1.38 × 10 -4 α=0.7 PE:K = 3.92 × 10 -4 , α=0.733 The measurement conditions for GPC are as follows: Equipment: Waters GPC (ALC / GPC 150C) Detector: Polymer Char IR-4 Columns: Showa Denko AT-806MS (3 pieces) Mobile phase solvent: o-dichlorobenzene (ODCB) Measurement temperature: 140℃ Flow rate: 1.0ml / min Injection amount: 0.3ml Sample preparation: Prepare a 1 mg / mL solution of the sample using ODCB (containing 0.5 mg / mL of BHT), and dissolve it at 140°C for approximately 1 hour. The method for setting the baseline and interval of the obtained chromatogram is well known to those skilled in the art.

[0135] [Condition (iii-2) Branch Index] The olefin polymer obtained by the present invention preferably has a minimum value (gL) of branching index g' between 100,000 and 1,000,000 molecular weight, measured by a GPC measuring device combining a differential refractometer, a viscosity detector, and a light scattering detector, between 0.20 and 0.98. The lower limit of gL may be 0.23 or higher, 0.25 or higher, 0.30 or higher, 0.35 or higher, or 0.40 or higher. The upper limit of gL may be 0.93 or lower, 0.90 or lower, or 0.85 or lower. It is preferable that the minimum value (gL) of the branching index is within the above range because it is easier to obtain an ethylene polymer with excellent moldability.

[0136] (i) Branching structure analysis using GPC-VIS A Waters Alliance·GPCV2000 GPC system equipped with a differential refractometer (RI), viscometer, and 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 order of 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 conjunction. The temperature of the columns, sample injection section, and each detector was 140°C. The sample concentration was 1 mg / mL. The injection volume (sample loop volume) was 0.2175 mL. The absolute molecular weight (M), radius of square inertia (Rg) obtained from MALLS, and the intrinsic viscosity ([η]) obtained from the Viscometer were calculated using ASTRA (version 4.73.04), the data processing software included with MALLS, and the following literature was used as a reference.

[0137] 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)

[0138] (ii) Calculation of the branching index (g') The branching index (g') is calculated as the ratio (ηbranch / ηlin) of the intrinsic viscosity (ηbranch) obtained by measuring the sample with the Viscometer described above and the intrinsic viscosity (ηlin) obtained by separately measuring the linear polymer. When long-chain branching is introduced into a polymer molecule, its radius of inertia decreases compared to a linear polymer molecule of the same molecular weight. Since a smaller radius of inertia leads to 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 branching is introduced. Therefore, when the branching index (g' = ηbranch / ηlin) is less than 1, it means that branching has been introduced, and as this value decreases, it means that the number of introduced long-chain branches increases. Here, the linear polymer used for comparison is linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology). The probability of long-chain branching being introduced increases as the molecular weight (degree of polymerization) of the polymer increases, provided that there are enough macromonomers that can branch long chains. On the other hand, whether or not the main chain growth reaction proceeds to the high molecular weight region while copolymerizing macromonomers largely depends on the capability of the olefin polymerization catalyst. The novel olefin polymerization catalyst of the present invention is thought to be able to achieve this.

[0139] [Condition (iii-3)FR] The olefin polymer obtained by the present invention has a melt flow rate (MFR) at a temperature of 190°C and a load of 10 kg. 10kg Preferably, the ratio of the melt flow rate (MFR) at a temperature of 190°C and a load of 2.16 kg, known as FR, is between 6.5 and 100. When FR is within this range, the fluidity during melting becomes more suitable for molding. The lower limit of FR is more preferably 8 or higher, even more preferably 8.5 or higher, and particularly preferably 9 or higher. The upper limit of FR is more preferably 80 or lower, even more preferably 60 or lower, and particularly preferably 50 or lower. When FR is within the above range, it is preferable because it is easier to obtain an ethylene-based polymer with even better moldability. The measurement conditions for MFR to determine the value of FR are as described above.

[0140] [Condition (iii-4): HLMFR / MFR] The olefin polymer obtained by the present invention preferably has a ratio (HLMFR / MFR) of more than 15 and 1000 or less between the melt flow rate (HLMFR) at 190°C and a load of 21.6 kg and the melt flow rate (MFR) at 190°C and a load of 2.16 kg. The lower limit of HLMFR / MFR is more preferably 20 or more, even more preferably 25 or more, and particularly preferably 30 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 in olefin polymers produced with the same catalyst, the HLMFR / MFR increases as the MFR decreases, and this trend is particularly pronounced in the region where the MFR is 1 or less. Therefore, the olefin polymer obtained by the present invention may be preferable if it satisfies the following condition (iia). Condition (IIA): If MFR > 1, as mentioned above, it is preferable that HLMFR / MFR is greater than 15 and less than or equal to 500. If MFR ≤ 1, then HLMFR / MFR > 71 × LogMFR + 15 is satisfied. More preferably, satisfy HLMFR / MFR > 71 × LogMFR + 20, More preferably, HLMFR / MFR > 71 × LogMFR + 25. As mentioned above, the upper limit for HLMFR / MFR is as follows, and MFR is typically between 0.001 and 1000. When the HLMFR / MFR value falls within this range, the fluidity during melting becomes suitable for molding.

[0141] In this specification, MFR shall be the value measured under conditions of 190°C and a load of 2.16 kg, in accordance with JIS K7210:2014. HLMFR shall be the value measured under conditions of a load of 21.6 kg, in accordance with the same JIS standard.

[0142] The olefin polymer produced by the manufacturing method of the present invention can be isolated from the polymerization reactor and used for various applications as a product in various forms such as granules, pellets, lumps, sheets, strands, melts, slurries, and solutions. Furthermore, because the olefin polymer obtained using the olefin polymerization catalyst of the present invention exhibits little fluctuation in activity with respect to changes in the polymerization environment, it is possible to provide a polymer of stable quality, thereby offering various products of higher quality. Furthermore, in the second and subsequent stages of a multi-stage polymerization apparatus connected to a polymerization reactor for olefin polymer production, copolymerization with other monomers such as ethylene and olefins is also possible. In this case, it is preferable because it becomes possible to produce various polyolefin resins having beneficial molecular weight distributions and comonomer distribution structures. [Examples]

[0143] The present invention will be described in 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. Furthermore, all of the following catalyst synthesis and polymerization steps were carried out under a purified nitrogen atmosphere, and the solvents used were those that had been dehydrated and purified using molecular sieves such as 4A and 13X.

[0144] 1. Various evaluation (measurement) methods (1) MFR: Measurements were taken in accordance with JIS K6760, at 190°C and under a 2.16 kg load. HLMFR was similarly measured under conditions of 190°C and a 21.6 kg load.

[0145] (2) Measurement of molecular weight Mw and molecular weight distribution (Mw / Mn): The measurement was performed using the method described in item (i) above.

[0146] Manufacturing Example 1 <Manufacturing Example 1-1> Synthesis of component (A-1) 1 (Fe compound 31) The compound (Fe compound 31) shown in the chemical formula below was synthesized by referring to the method described in Example 32 of Japanese Patent Publication No. 2011-17014, and this was designated as Fe compound 31. [ka]

[0147] <Manufacturing Example 1-2> Synthesis of component (A-1) 2 (Fe compound 32) The compound (Fe compound 32) shown in the chemical formula below was synthesized by referring to the method described in Example 40 of Japanese Patent Publication No. 2011-17014, and this was designated as Fe compound 32. [ka]

[0148] <Manufacturing Example 1-3> Synthesis of Component (A-1) 3 (Fe Compound 33) The compound (Fe compound 33) shown in the chemical formula below was synthesized by referring to the method described in Example 9.2 of Japanese Patent Publication No. 2003-96134, and this was designated as Fe compound 33. [ka]

[0149] <Manufacturing Example 1-4> Synthesis of Component (A-1) 4 (Fe Compound 34) The compound (Fe compound 34) shown in the chemical formula below was synthesized by referring to the method described in Example 32 of Japanese Patent Publication No. 2011-17014, and this was designated as Fe compound 34. [ka]

[0150] <Manufacturing Example 1-5> Synthesis of Component (A-1) 5 (Fe Compound 35) The compound (Fe compound 35), shown in the chemical formula below, was synthesized by the following method. First, 2,6-diacetylpyridine and the two corresponding substituted anilines, 2,6-dichloroaniline and 2,4,6-trimethylaniline, were reacted under reflux under acid catalyst. The desired ligand was isolated from the resulting mixture by preparative HPLC. Using the ligand thus obtained, Fe compound 35 was synthesized according to standard procedures. [ka]

[0151] Manufacturing Example 2 <Manufacturing Example 2-1> Synthesis of component (A-2) 1 (metallocene compound 12M) Meso-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound 12M), shown in the chemical formula below, was synthesized by synthesizing meso-1 based on the procedure for Complex 1 described in the Experimental Section of Macromolecules 1995, 28, 4801-4805, and this was designated as metallocene compound 12M. [ka]

[0152] <Manufacturing Example 2-2> Synthesis of Component (A-2) 2 (Metallocene Compound 13) The dimethylsilylene (3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride (metallocene compound 13), shown in the chemical formula below, was synthesized according to the method described in paragraphs 0135 to 0139 of Japanese Patent Application Publication No. 2017-165726, and this was designated as metallocene compound 13. [ka]

[0153] <Manufacturing Example 2-3> Synthesis of Component (A-2) 3 (Metallocene Compound 14) The metallocene compound 14 shown in the chemical formula below was synthesized according to the method described in paragraphs 0140 to 0143 of Japanese Patent Publication No. 2013-227271, and this was designated as metallocene compound 14. [ka]

[0154] <Manufacturing Example 2-4> Synthesis of Component (A-2) 4 (Metallocene Compound 21) Racemi-dimethylsilylenebis(2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl)zirconium dichloride (metallocene compound 21), shown in the chemical formula below, was synthesized by synthesizing the ligand according to the procedure described in Synthesis Example 1 of Japanese Patent Application No. 2011-008562, using zirconium tetrachloride instead of hafnium tetrachloride. [ka]

[0155] <Manufacturing Example 2-5> Synthesis of Component (A-2) 5 (Metallocene Compound 22) Racemi-dimethylsilylenebis-6-(2,5-dimethyl-3-phenylcyclopentadienyl-[1,2-b]-thiophene)zirconium dichloride (metallocene compound 22), shown in the chemical formula below, was synthesized according to the procedure described in Example 1 of Japanese Patent Publication 2003-517010, and this was designated as metallocene compound 22. [ka]

[0156] <Manufacturing Example 2-6> Synthesis of Component (A-2) 6 (Metallocene Compound 23) Metallocene compound 23 was obtained in the same manner as in Preparation Example 2-5, except that 2,5-dimethyl-3-phenylcyclopentadiene was replaced with 2,5-dimethyl-3-(4-t-butylphenyl)cyclopentadienyl. [ka]

[0157] <Manufacturing Example 2-7> Synthesis of Component (A-2) 7 (Metallocene Compound 51) The metallocene compound 51 shown in the chemical formula below was synthesized by following the method described in Example 12 of U.S. Patent No. 5336795, yielding metallocene compound 51, which is bis(n-butylphenylcyclopentadienyl)hafnium dichloride (abbreviated as BCH). [ka]

[0158] [Example 1] (1) Synthesis of catalysts for olefin polymerization Under a nitrogen atmosphere, 10.0 g of silica particles calcined at 400°C for 7 hours were placed in a 500 ml two-necked flask and dried under reduced pressure using a vacuum pump while heating in a 150°C oil bath for 1 hour. Subsequently, 100 ml of toluene was added to form a slurry of silica, and then 26.7 ml of a toluene solution (20%) of methylaluminoxane manufactured by Grace (equivalent to 80 mmol of Al) was added at 80°C. After stirring at 80°C for 1 hour, the mixture was washed three times with toluene to obtain a methylaluminoxane-supported silica slurry. Separately, under a nitrogen atmosphere, 134 mg of the above Fe compound 31 (equivalent to 250 μmol of Fe compound) and 84.5 mg of the above metallocene compound 21 (equivalent to 100 μmol of metallocene compound) were placed in a 100 ml two-necked flask at room temperature and dissolved in 50 ml of toluene. The entire amount of the resulting 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 three times with hexane, the solvent was removed by vacuum distillation to obtain a catalyst powder for olefin polymerization.

[0159] [Example 1] (1) Synthesis of catalysts for olefin polymerization Under a nitrogen atmosphere, 10.0 g of silica particles, calcined at 200°C for 2 hours and then at 400°C for 7 hours, were placed in a 500 ml two-necked flask and dried under reduced pressure using a vacuum pump while heating in a 150°C oil bath for 1 hour. Subsequently, 100 ml of toluene was added to form a slurry of silica, and then 26.7 ml of a toluene solution (20%) of methylaluminoxane manufactured by Grace (equivalent to 80 mmol of Al) was added at room temperature. After stirring at 80°C for 1 hour, the mixture was washed three times with toluene to obtain a methylaluminoxane-supported silica slurry. In a separately prepared 100 ml two-necked flask, under a nitrogen atmosphere at room temperature, 85.2 mg of the above Fe compound 31 (equivalent to 150 μmol of Fe compound) and 84.5 mg of the above metallocene compound 21 (equivalent to 100 μmol of metallocene compound) were placed and dissolved in 50 ml of toluene. The entire amount of the resulting toluene solution of the mixture was added to the above methylaluminoxane-supported silica slurry, which had been stirred at 40°C, and stirring was continued for 1 hour. Finally, after washing three times with hexane, the solvent was removed by vacuum distillation to obtain a catalyst powder for olefin polymerization.

[0160] (2) Production of ethylene polymers In a 2-liter stainless steel autoclave equipped with stirring and temperature control devices, 800 ml of thoroughly dehydrated and deoxygenated isobutane, 5 ml of 1-hexene, and 1.0 mmol of triisobutylaluminum were introduced, and the temperature was raised to 80°C while stirring. After introducing a small amount of hydrogen, ethylene was introduced until the partial pressure reached 1.0 MPa. Then, 35 mg of the olefin polymerization catalyst obtained in (1) above was injected under pressure with nitrogen gas, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 1.0 MPa and a temperature of 80°C. The amount of 1-hexene supplied during polymerization was 2.5 ml, and the average molar ratio of hydrogen to ethylene (H2 / C2) during polymerization was 0.117 mol%. As a result, 212 g of ethylene polymer powder was produced. The obtained polymer powder had an HLMFR of 0.12 g / 10 min and a density of 0.939 g / cm³. 3 That was the case.

[0161] (3) Analysis of ethylene polymers The analysis of the ethylene polymer was performed on pellets obtained by heating, melting, and kneading the ethylene polymer powder obtained in (2) above. The heating, melting, and kneading was carried out under the following conditions after thoroughly purging the apparatus with nitrogen gas. Mixing conditions: DSM Xplore melting and mixing device used, sample input amount 10-12g, barrel temperature 190℃, screw rotation speed 100 RPM, mixing time 1 minute. Heat stabilizer: Blend 2 mg of Irganox B225 per 1 g of polymerized powder. The analysis results are summarized in Tables 1 and 2.

[0162] (Example 2) The catalyst amount was changed to 32 mg, and the ethylene pressure was adjusted so that the average molar ratio of hydrogen to ethylene (H2 / C2) during polymerization was greater than that in Example 1. The average H2 / C2 at this time was 0.278 mol%. The ethylene polymer was produced in the same manner as in Example 1. The polymerization conditions and results are summarized in Tables 1 and 2.

[0163] (Examples 3-29) Ethylene polymers were produced in the same manner as in Example 1, except for adjustments to the type or amount of catalyst and the ethylene pressure. The polymerization conditions and results are summarized in Tables 1 and 2.

[0164] (Comparative Examples 1-5) As shown in Table 1, ethylene polymers were produced in the same manner as in Example 1, except that the types and proportions of metallocene compounds were changed as shown in the table (Comparative Examples 1-5). In addition, as reference examples and comparative reference examples, ethylene polymers were produced using either component (A-1) or (A-2) individually as catalysts. The ethylene polymers obtained in the reference examples and comparative reference examples were analyzed using ethylene polymer powder.

[0165] [Table 1]

[0166] [Table 2]

[0167] The copolymers obtained in the above examples and comparative examples were analyzed by GPC and MFR measurements. The results are summarized in Tables 3 and 4.

[0168] [Table 3]

[0169] [Table 4]

[0170] Explanation of experimental results As shown in the various reference examples in Tables 3 and 4, component (A-1) correlates with the HLMFR γ in relation to the change in the H2 / C2 ratio. (A-1) This shows a small negative value. On the other hand, component (A-2) shows the correlation of HLMFR γ with respect to the change in the H2 / C2 ratio. (A-2) It shows a slightly large positive value. In Examples 1 to 6, polyolefins were successfully produced over a wide HLMFR range using catalysts employing two types of metal complexes. Furthermore, all of these examples exhibited high FR, HLMFR / MFR, and Mw / Mn values, demonstrating fluidity suitable for melt molding. Additionally, as shown in Figure 1, GPC measurements of the molecular weight distribution revealed that the low-molecular-weight polymers, primarily produced by Fe compounds, maintained a nearly constant molecular weight peak, unaffected by fluctuations in the H2 / C2 ratio. In contrast, the high-molecular-weight polymers, produced by metallocene compounds, showed fluctuations in their molecular weight peak, influenced by changes in the H2 / C2 ratio. On the other hand, in comparative examples where a catalyst with a large γ value was used as a component for producing low molecular weight polyolefins (corresponding to component (A-1) in each example), it can be seen that both molecular weight peaks of the polyolefin observed by GPC measurement change in conjunction with fluctuations in hydrogen concentration (Figure 2). In particular, as the hydrogen concentration increases, the molecular weight peak in the low molecular weight region shifts to the lower molecular weight side, so it is expected that the proportion of low molecular weight components in the polyolefin will increase, affecting moldability and strength.

[0171] Comonomer distribution of polymers One approach to improving the product strength of olefin polymers is to design copolymers that exhibit an inverse comonomer composition distribution. In ethylene-α-olefin copolymers, the inverse comonomer composition distribution is the distribution in which more α-olefins are copolymerized on the high molecular weight side, and copolymers with an inverse comonomer composition distribution are considered useful from the viewpoint of product strength. Whether the olefin polymer obtained by the present invention has an inverse comonomer distribution can be evaluated by the integral elution curve measured by cross-fractionation chromatography (CFC). CFC consists of a temperature-reduced elution fractionation (TREF) section that performs crystalline fractionation and a gel permeation chromatography (GPC) section that performs molecular weight fractionation. In CFC, the amount of comonomer evaluated by TREF is determined for each molecular weight measured by GPC, and the molecular weight and comonomer amount are represented in a two-dimensional chart. This shows the "comonomer composition distribution," which is an index that comprehensively indicates the distribution of comonomer amount and molecular weight of individual polymers contained in the entire copolymer. Conventional ethylene-α-olefin copolymers obtained by general catalytic polymerization often exhibit a so-called normal comonomer composition. In this state, the chart often tends to slope upward from the intersection of the temperature at which the elution amount is 50% by weight and the weight-average molecular weight. On the other hand, a preferred ethylene-based polymer of the present invention has a so-called inverse comonomer composition as one of its characteristics. When it has an inverse comonomer composition, the chart tends to spread in the direction of the lower right or upper left, or a chart with an overall shape close to an ellipse is obtained.

[0172] Analytical techniques using CFCs are well-known, as described in publications such as WO2015 / 152267, and are specifically performed as follows: First, the polymer sample is completely dissolved in an ODCB containing 0.5 mg / mL of BHT at 140°C. This solution is then injected through the instrument's sample loop into a TREF column (a column packed with inert glass beads) maintained at 140°C, and gradually cooled to a predetermined first elution temperature to crystallize the polymer sample. After holding at the predetermined temperature for 30 minutes, the ODCB is passed through the TREF column, injecting the eluted components 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, and after obtaining the chromatogram at the first elution temperature, the eluted components at the second elution temperature are injected into the GPC section. The same operation is repeated thereafter to obtain chromatograms of the eluted components at each elution temperature.

[0173] The measurement conditions for CFCs are as follows: GPC column: AD-806MS manufactured by Showa Denko Co., Ltd. (3 columns connected in series) Solvent: ODCB Sample concentration: 3 mg / 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

[0174] (Data analysis) From the chromatograms of the eluted components at each elution temperature obtained by measurement, the normalized elution amount (proportional to the area of ​​the chromatogram) is determined so that the sum equals 100%. Furthermore, the integral elution curve with respect to elution temperature is calculated. By differentiating this integral elution curve with respect to temperature, the differential elution curve is obtained. In addition, the molecular weight distribution is determined from each chromatogram using the following procedure. The conversion from retention capacity to molecular weight is as described earlier for GPC measurement. Note that 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 component; in such cases, a baseline is drawn to determine the interval for calculating the molecular weight distribution.

[0175] Furthermore, the weight-average molecular weight of the whole molecule is determined from the elution rate (wt%) in the table and the weight-average molecular weight (Mw in the table) at each elution temperature. From the molecular weight distribution and elution amount at each elution temperature, a graph (contour plot) showing the elution amount as contour lines with respect to elution temperature and molecular weight is obtained 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)).

[0176] Using the method described above, CFC charts were created for the polyolefins obtained in Reference Example 2 and the Examples. The results are shown in Figures 8 and 9. For the polyolefin obtained in Reference Example 2, the chart slopes upward from the intersection of the temperature at which the elution amount is 50% by weight and the weight-average molecular weight, indicating a so-called normal comonomer composition. In contrast, for the polyolefins obtained in the Examples, the charts either spread downwards to the right or were generally close to an ellipse shape. In other words, these polyolefins have a reverse comonomer composition, and it can be said that polyolefins with high product strength have been obtained.

Claims

1. An olefin polymerization catalyst comprising the following components (A-1), (A-2), and (B), characterized in that components (A-1) and (A-2) satisfy the following conditions (1) to (4). Component (A-1): Transition metal complex compound represented by the following formula (1) 【Chemistry 1】 [In formula (1), M １ This represents transition metal atoms selected from groups 8 and 9 of the periodic table. X １ is a hydrocarbon group having 1 to 20 carbon atoms, containing a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom, a nitrogen atom, or a silicon atom, a hydrocarbon group substituted with a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, where r is M １ The valence is shown, A １ and A ２ M １ Ligands having atoms selected from groups 15 and 16 of the periodic table that coordinate to (where A １ A ２ This indicates that the structure may be the same or different within the same compound. Q １ represents at least one pair of non-covalent electrons or a π bond capable of coordinating to M １ , and represents a linking group that crosslinks A １ and A ２ at an arbitrary position.] Component (A-2): Metallocene compound containing transition metal atoms from groups 4-6 of the periodic table. Component (B): A compound that reacts with the compounds of components (A-1) and (A-2) to produce a cationic complex compound. Condition (1): An olefin polymerization catalyst (Cat) containing components (A-1) and (B) but not (A-2). （Ａ－１） HLMFR is an olefin polymer obtained by polymerizing olefins in the presence of hydrogen molecules using ). （Ａ－１） And, a catalyst for olefin polymerization (Cat) that contains components (A-2) and (B) but does not contain (A-1). （Ａ－２） Using ) the HLMFR of the olefin polymer obtained under the same conditions （Ａ－２） However, HLMFR （Ａ－１） ≥HLMFR （Ａ－２） It satisfies the condition. Condition (2): Cat （Ａ－１） In the polymerization of olefins using [a specific method], the ratio of hydrogen to olefin (H) ２ / C ２ HLMFR is an olefin polymer (ratio) （Ａ－１） The correlation coefficient γ in the following definition formula represents the correlation between the two. （Ａ－１） However, the range is -2.0 to +1.0; Definition of Log[HLMFR] （Ａ－１） ] = γ （Ａ－１） •Log[H ２ / C ２ ] + δ Here, the above equation is for two points H that are separated by 0.05 mol% or more. ２ / C ２ When H polymerized at a temperature of 80°C ２ / C ２ and HLMFR （Ａ－１） H obtained from the relationship on a log-log graph ２ / C ２ = Represents an approximate straight line between 0.05 and 0.15 mol%, with coefficient γ. （Ａ－１） is the slope of the line, and the intercept δ is H ２ / C ２ = This is the logarithm of HLMFR when it is 1 mol%. ２ / C ２ = HLMFR at 0.1 mol% （Ａ－１） When it is 10 or more, HLMFR in the above definition formula （Ａ－１） is MFR （Ａ－１） This shall be used as a substitute. Condition (3): Cat （Ａ－２） H obtained at a temperature of 80°C in the same manner as condition (2) ２ / C ２ HLMFR is a ratio of olefin polymers. （Ａ－２） The correlation coefficient γ （Ａ－２） However, it is above +1.0 and below +10. Condition (4): γ （Ａ－１） and gamma （Ａ－２） The absolute value of the difference between the two, |Δγ|, is greater than 0 and less than or equal to 10.

2. The catalyst for olefin polymerization according to claim 1, characterized in that 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 the olefin polymer obtained by polymerizing olefins in the presence of hydrogen molecules was determined by GPC measurement. （Ａ－１） And, Cat （Ａ－２） Using this method, the weight-average molecular weight Mw of the olefin polymer obtained under the same conditions （Ａ－２） However, Mw （Ａ－１） ≤Mw （Ａ－２） It satisfies the condition.

3. The catalyst for olefin polymerization according to claim 1, characterized in that the components (A-1) and (A-2) satisfy the following condition (6). Condition (6): The above Cat （Ａ－１） D is the density of the olefin polymer obtained by polymerizing or copolymerizing olefins in the presence of hydrogen molecules. （Ａ－１） And, Cat （Ａ－２） Using this method, the density D of the olefin polymer obtained under the same conditions （Ａ－２） However, D （Ａ－１） ≥ D （Ａ－２） It satisfies the condition.

4. The catalyst for olefin polymerization according to claim 1, characterized in that component (A-1) satisfies at least one of the following conditions (A-1-1) and (A-1-2). Condition (A-1-1); A １ and A ２ However, M １ It has at least one nitrogen atom that coordinates to it. Condition (A-1-2); Q １ However, M １ It has at least one lone pair of electrons or a π bond coordinated to it.

5. The catalyst for olefin polymerization according to claim 1, characterized in that the component (A-1) is a transition metal complex compound represented by the following general formula (1-1). 【Chemistry 2】 [In the formula, M １ , X １ , r is as defined in claim 1, R １ ~R ３ Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 40 carbon atoms, a halogen atom-containing hydrocarbon group having 1 to 40 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom-containing hydrocarbon group having 1 to 40 carbon atoms. R ４ , R ５ Each of these independently represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 40 carbon atoms, a halogen atom-containing hydrocarbon group having 1 to 40 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom-containing hydrocarbon group having 1 to 40 carbon atoms. R ６ , R ７ Each of these independently represents a hydrocarbon group having 1 to 40 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms containing a silicon atom, a halogen-containing hydrocarbon group having 1 to 40 carbon atoms, or a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom. R other than hydrogen atoms and halogen atoms １ ~R ３ , R other than hydrogen atoms ４ ~R ７ Each of these substituents may independently form a ring by bonding with adjacent substituents, including the carbon and nitrogen atoms to which they are bonded.

6. In the above general formula (1-1), R ６ , R ７ The catalyst for olefin polymerization according to claim 5, characterized in that at least one of the members is a substituted or unsubstituted aryl group represented by the following general formula (1-a). 【Transformation 3】 [In formula (1-a), A ３ R represents an atom from group 14, 15, or 16 of the periodic table. ８ ~R １２ Each of these 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 with 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 with 1 to 20 carbon atoms, R ８ ~R １２ The substituents may form a ring with the atoms they are bonded to, and t is 0 or 1, and when t is 0, A ３ A substituent R ８ If not present, s is 0 or 1, and if s is 0, then equation (1-a) forms a 5-membered ring.

7. In the above general formula (1-a), R ８ ~R １２ The catalyst for olefin polymerization according to claim 6, characterized in that at least one pair of adjacent substituents together with the atoms bonded to them form a ring.

8. In the aforementioned general formula (1-1), R ４ , R ５ at least one of which is a hydrocarbon group having 1 to 40 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 40 carbon atoms containing a silicon atom, a halogen atom-containing hydrocarbon group having 1 to 40 carbon atoms, or a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, the olefin polymerization catalyst according to claim 5.

9. M １ The catalyst for olefin polymerization according to claim 1, wherein is Fe.

10. The catalyst for olefin polymerization according to claim 1, characterized in that the component (A-2) is a metallocene compound represented by the following general formula (2). 【Chemistry 4】 [In formula (2), M ５１ This represents a transition metal atom of Ti, Zr, or Hf. X ５１ and X ５２ Each of these 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 with 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. R ５５ to R ６２ , R ８４ , R ８５ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms that contains 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms that 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, and R ５５ to R ５８ , R ８４ any one adjacent pair among them and R ５９ to R ６２ , R ８５ any one or more adjacent pairs among them may be bonded to each other together with the carbon atoms to which they are bonded to form an aliphatic ring, an aromatic ring or a heterocycle, R ８４ and R ８５ These may be linked together to form a divalent group represented by one of the following formulas: 【Transformation 5】 In the formula, E ２１ and E ２２ These are, respectively, -CR １００ ２ -, -SiR １００ ２ -, -NR １００ -, -PR １００ A divalent group selected from the group consisting of -, -O-, and -S- (where R １００ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and has two R １００ They may combine to form a ring structure.) R ８８ and R ８９ Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing a silicon atom having 1 to 18 carbon atoms, a hydrocarbon group containing a halogen atom 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 with a hydrocarbon group having 1 to 40 carbon atoms, or a hydrocarbon group substituted with a hydrocarbon group having 1 to 40 carbon atoms, and R ８８ and R ８９ These may form a ring together with the carbon atoms to which they are bonded. Q ５１ and Q ５２ This refers to a carbon atom, a silicon atom, or a germanium atom. R ５１ ~R ５４ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Q is formed by the bonding of adjacent substituents to each other. ５１ and / or Q ５２ It may include and bond to form a ring, m is either 0 or 1, and if m is 0, Q ５１ R ５９ It is directly bonded to a five-membered ring containing, R ８４ and R ８５ However, they are linked together, forming a divalent group -Q ５１ (R ５１ R ５２ ) - {Q ２５ (R ５３ R ５４ )} ｍ If a negative is formed, R ５５ ~R ５８ One of the adjacent pairs and R ５９ ~R ６２ Any one adjacent pair of these may be linked together to form a divalent group represented by one of the following formulas: 【Transformation 6】 In the formula, R ６３ ~R ６８ Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms including 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 together, including the carbon atoms to which they are bonded, to form a ring. n is either 0 or 1, and if n is 0, (CR ６３ R ６４ ) part does not exist, (CR ６３ R ６４ The carbon atom adjacent to the 5-membered ring is directly bonded to it, forming an indenyl ring. R ８３ This refers to a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. R ８２ This refers to a substituted or unsubstituted aryl group represented by the following general formula (2-a): 【Transformation 7】 [In formula (2-a), Y represents an atom of group 14, 15, or 16 of the periodic table, and R ７５ ~R ７９ Each of these 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 with 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 with 1 to 20 carbon atoms, R ７５ ~R ７９ The substituents may form a ring with the atoms they are bonded to, and q is either 0 or 1. If q is 0, Y has substituent R ７５ If there is no such element, p is either 0 or 1, and if p is 0, then equation (2-a) forms a five-membered ring.

11. The catalyst for olefin polymerization according to claim 1, characterized in that the component (A-2) is a metallocene compound represented by the following general formula (2-1). 【Transformation 8】 [In formula (2-1), M ５１ , X ５１ , X ５２ Q ５１ Q ５２ , R ５１ ~R ５４ ,m is as defined in claim 10, R ５５ ~R ６２ R represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms including 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. ５５ , R ５８ , R ５９ and R ６２ Of these, at least two are not hydrogen atoms, R ５５ and R ５６ , R ５６ and R ５７ or R ５７ and R ５８ Any one set, and R ５９ and R ６０ , R ６０ and R ６１ or R ６１ and R ６２ Any one of these pairs may be bonded to each other, including the carbon atoms to which they are bonded, to form a ring.

12. The catalyst for olefin polymerization according to claim 1, characterized in that the component (A-2) is a metallocene compound represented by the following general formula (2-2). 【Chemistry 9】 [In formula (2-2), M ５１ , X ５１ , X ５２ Q ５１ Q ５２ , R ５１ ~R ５４ m and n are as defined in claim 10, R ５５ , R ５６ , R ５９ , R ６０ Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms including 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 ６３ ~R ６８ R is defined as in claim 10, ６９ ~R ７４ R ６３ ~R ６８ It is similar to [this].

13. The catalyst for olefin polymerization according to claim 1, characterized in that the component (A-2) is a metallocene compound represented by any of the following general formulas (2-3-1) to (2-3-5). 【Chemistry 10】 [In the formula, M ５１ , X ５１ , X ５２ Q ５１ Q ５２ , R ５１ ~R ５４ , m, n, R ５５ , R ５６ , R ５９ , R ６０ , R ６３ ~R ６８ This is as defined in claim 10, R ８６ , R ８７ Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms including 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]

14. The catalyst for olefin polymerization according to claim 1, characterized in that the component (A-2) is a metallocene compound represented by the following general formula (2-4). 【Chemistry 11】 [In formula (2-4), M ５１ , X ５１ , X ５２ Q ５１ Q ５２ , R ５１ ~R ５４ m and n are as defined in claim 10, R ５５ ~R ６０ , R ６３ ~R ６８ Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms including 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 R ５５ ~R ５８ R may be bonded to adjacent substituents, including the carbon atom to which they are bonded, forming an aliphatic ring. ６３ ~R ６８ The substituents may be bonded to each other by adjacent substituents, including the carbon atom to which they are bonded, to form a ring.

15. The catalyst for olefin polymerization according to claim 1, further characterized by comprising the following component (C). Component (C): Particulate carrier

16. The catalyst for olefin polymerization according to claim 1, further characterized by comprising the following component (D). Component (D): Organoaluminum compound

17. A method for producing an olefin polymer, characterized by polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst according to any one of claims 1 to 16.

18. The method for producing an olefin-based polymer according to claim 17, characterized in that the olefin is ethylene.

19. The method for producing an olefin polymer according to claim 17, characterized in that the polymer obtained satisfies the following conditions (i) to (iii). Condition (i): MFR is between 0.001 and 1000 g / 10 min. Condition (ii): Density of 0.895–0.975 g / cm³ ３ That is the case. Condition (iii): At least one of the following conditions (iii-1), (iii-2), (iii-3), and (iii-4) must be satisfied; Condition (iii-1): The molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) using weight-average molecular weight (Mw) and number-average molecular weight (Mn) is 3.5 or greater and 100 or less. Condition (iii-2): The lowest value (g) of the branching index g' between a molecular weight of 100,000 and 1,000,000, measured by a GPC measuring device combining a differential refractometer, viscosity detector, and light scattering detector. Ｌ The value is between 0.20 and 0.

98. Condition (iii-3): Melt flow rate (MFR) at a temperature of 190°C and a load of 10 kg １０ｋｇ ) and 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, is between 6.5 and 100. Condition (iii-4): The 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 is 15 or more and 1000 or less.

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