Method for producing ethylene-α-olefin copolymer

Abstract

To provide a method for producing an ethylene-α-olefin copolymer with a large number of long-chain branched structures, employing a catalyst that contains a bridged metallocene compound.SOLUTION: Provided is a method for producing an ethylene-α-olefin copolymer, meeting the following condition (I) or (II), the method including copolymerizing ethylene with an α-olefin having from 3 to 20 carbon atoms under the presence of an olefin polymerization catalyst containing a specific bridged metallocene compound. Condition (I): the formula (1), I10 / I2+0.869×ln(I2)≥9.0, being satisfied, and Condition (II): I2 being 2.0-100 g / 10 min and I10 / I2 being at least 7.0, where I2: melt flow rate (MFR) of the copolymer at 190°C under 2160 g load and I10: MFR of the copolymer at 190°C under 10 kg load.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing an ethylene-α-olefin copolymer. [Background technology]

[0002] In recent years, metallocene compounds have become well known as homogeneous catalysts for olefin polymerization. Since the isotactic polymerization of α-olefins was reported by W. Kaminsky et al. (Non-Patent Document 1), much research has been conducted on methods for polymerizing olefins using metallocene compounds, particularly methods for stereoregularly polymerizing α-olefins.

[0003] Conventional metallocene compounds, which are single-site catalysts, are generally advantageous for producing α-olefin polymers with narrow molecular weight distributions and uniform composition distributions. However, one of the issues is that this uniformity results in poor processability and other properties.

[0004] To solve the above problems, efforts have been made to improve processability and physical properties by using polymerization techniques that use metallocene compounds that can form long-chain branched structures in polymers, or by broadening the molecular weight distribution and composition distribution by mixing different polymers or using several types of catalysts (e.g., Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2015 / 152266 [Patent Document 2] Special Publication No. 2006-509904 [Non-patent literature]

[0006] [Non-Patent Document 1] Angew. Chem. Int. Ed. Engl., 24, 507 (1985) Summary of the Invention [Problem to be solved by the invention]

[0007] Ethylene-α-olefin copolymers with long-chain branching structures are also desired to further improve processability and other properties.

[0008] An object of the present invention is to provide a process for producing an ethylene-α-olefin copolymer having a large amount of long chain branches using a catalyst containing a bridged metallocene compound. [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by the following configuration examples, and have thus completed the present invention. A configuration example of the present invention is as follows.

[0010] [1] A bridged metallocene compound (A) represented by the following formula [I], Organometallic compound (B-1), Organoaluminum oxy compound (B-2), and A compound (B-3) that reacts with the bridged metallocene compound (A) to form an ion pair. At least one compound (B) selected from the group consisting of A method for producing an ethylene-α-olefin copolymer, comprising a step [P] of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing The MFR of the ethylene-α-olefin copolymer measured in accordance with JIS K 7210:1999 at 190°C under a load of 2160 g is defined as I2 (g / 10 min), and the MFR measured in accordance with JIS K 7210:1999 at 190°C under a load of 10 kg is defined as I 10 (g / 10 min), the following formula (1) is satisfied: I 10 / I2+0.869×ln(I2) ≧ 9.0 …(1)

[0011] [ka] [In formula [I], Y independently represents a carbon atom, a silicon atom, a germanium atom, or a tin atom; M is a titanium atom, a zirconium atom, or a hafnium atom; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, a substituted aromatic group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and may be the same or different, Adjacent substituents R1 to R6 may be bonded to each other to form a ring; A and B each independently represent a sulfur atom, an oxygen atom, or CR 9 and R 9 represents an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, a substituted aromatic group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group; when A is a sulfur atom or an oxygen atom, B is CR 9 and when B is a sulfur atom or an oxygen atom, A is CR 9 and the ring containing A and B has a double bond at any available position; Q independently represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair; n is an integer from 1 to 4, j is an integer from 1 to 4.

[0012] [2] A bridged metallocene compound (A) represented by the following formula [I], Organometallic compound (B-1), Organoaluminum oxy compound (B-2), and A compound (B-3) that reacts with the bridged metallocene compound (A) to form an ion pair. At least one compound (B) selected from the group consisting of A method for producing an ethylene-α-olefin copolymer, comprising a step [P] of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing The MFR of the ethylene-α-olefin copolymer measured in accordance with JIS K 7210:1999 at 190°C under a load of 2160 g is defined as I2 (g / 10 min), and the MFR measured in accordance with JIS K 7210:1999 at 190°C under a load of 10 kg is defined as I 10 (g / 10 min), I2 is 2.0 to 100 g / 10 min, and I 10 A method for producing an ethylene-α-olefin copolymer, wherein / I2 is 7.0 or more.

[0013] [ka] [In formula [I], Y independently represents a carbon atom, a silicon atom, a germanium atom, or a tin atom; M is a titanium atom, a zirconium atom, or a hafnium atom; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, a substituted aromatic group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and may be the same or different, Adjacent substituents R1 to R6 may be bonded to each other to form a ring; A and B each independently represent a sulfur atom, an oxygen atom, or CR 9 and R 9represents an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, a substituted aromatic group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group; when A is a sulfur atom or an oxygen atom, B is CR 9 and when B is a sulfur atom or an oxygen atom, A is CR 9 and the ring containing A and B has a double bond at any available position; Q independently represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair; n is an integer from 1 to 4, j is an integer from 1 to 4.

[0014] [3] The method for producing an ethylene-α-olefin copolymer according to [1], wherein the ethylene-α-olefin copolymer has an I2 of 2.0 g / 10 min or more. [4] I of the ethylene-α-olefin copolymer 10 The method for producing an ethylene / α-olefin copolymer according to any one of [1] to [3], wherein the viscosity is 20 g / 10 min or more. [5] The method for producing an ethylene / α-olefin copolymer according to any one of [1] to [4], wherein the ethylene / α-olefin copolymer has a double bond content of 0.7 bonds / 1000C or more. [6] The method for producing an ethylene-α-olefin copolymer according to any one of [1] to [5], wherein the ethylene-α-olefin copolymer has a molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), of 2.2 or more as measured by gel permeation chromatography (GPC).

[0015] [7] The method for producing an ethylene / α-olefin copolymer according to any one of [1] to [6], wherein n in the formula [I] is 1. [8] R in the formula [I] 1 , R 2 , R 3 and R 4 The method for producing an ethylene-α-olefin copolymer according to [7], wherein all of are hydrogen atoms. [9] The method for producing an ethylene-α-olefin copolymer according to [8], wherein Y in the formula [I] is a carbon atom or a silicon atom.

[10] The method for producing an ethylene-α-olefin copolymer according to [9], wherein A or B in the formula [I] is a sulfur atom, and the other is CH.

[11] R in the formula [I] 5 and R 6 is a group selected from the group consisting of aromatic groups and substituted aromatic groups.

[0016]

[12] R in the formula [I] 5 and R 6 is a substituted aromatic group in which one or more hydrogen atoms of the aromatic group are substituted with an electron-donating substituent having a Hammett's rule substituent constant σ of −0.2 or less, and when the aromatic group has a plurality of electron-donating substituents, the respective electron-donating substituents may be the same or different and may have a substituent other than the electron-donating substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and when the aromatic group has a plurality of substituents, the respective substituents may be the same or different.

[13] R in the formula [I] 5 and R 6 is a substituted aromatic group containing an oxygen-containing group as the electron-donating substituent.

[14] The method for producing an ethylene / α-olefin copolymer according to any one of [1] to

[13] , wherein M in the formula [I] is a zirconium atom or a hafnium atom.

[0017]

[15] The method for producing an ethylene / α-olefin copolymer according to any one of [1] to

[14] , wherein the α-olefin is an α-olefin having 3 to 10 carbon atoms.

[16] The method for producing an ethylene-α-olefin copolymer according to any one of [1] to

[15] , wherein the α-olefin is propylene or 1-butene.

[17] The method for producing an ethylene / α-olefin copolymer according to any one of [1] to

[16] , wherein the copolymerization in the step [P] is carried out at a temperature of 100 to 130°C.

[18] The method for producing an ethylene-α-olefin copolymer according to any one of [1] to

[17] , wherein the step [P] is a step of copolymerizing the ethylene-α-olefin copolymer so that the proportion of structural units derived from ethylene in the ethylene-α-olefin copolymer is 70 mol % or more based on all structural units. [Effects of the Invention]

[0018] According to the present invention, an ethylene-α-olefin copolymer having a large number of long chain branches can be produced. According to one embodiment of the present invention, it is possible to produce a sufficiently large number of long chain branch structures in a homogeneous catalyst such as a metallocene compound, even without using a support which is generally considered to be advantageous for producing long chain branches. DETAILED DESCRIPTION OF THE INVENTION

[0019] In this specification, the symbol "to" indicating a numerical range, for example "M to N", means "M or more and N or less" unless otherwise specified. In this specification, when an olefin constituting a certain copolymer is represented by M, the expression "structural unit derived from M" may be used, which refers to a "structural unit corresponding to M," i.e., a structural unit having a pair of bonds formed by opening the π bond constituting the double bond of M.

[0020] <Production method of ethylene-α-olefin copolymer> The method for producing an ethylene-α-olefin copolymer according to the present invention (hereinafter also referred to as "the present production method") is a method for producing an ethylene-α-olefin copolymer that satisfies the following requirement (I) or (II), and includes a step [P] of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst described below.

[0021] Requirement (I): In accordance with JIS K 7210:1999, the MFR measured under the conditions of 190°C and 2160g load is I2 (g / 10min), and in accordance with JIS K 7210:1999, the MFR measured under the conditions of 190°C and 10kg load is I 10 (g / 10 min), the following formula (1) is satisfied. I 10 / I2+0.869×ln(I2) ≧ 9.0 …(1)

[0022] Requirement (II): In accordance with JIS K 7210:1999, the MFR measured under the conditions of 190°C and 2160g load is I2 (g / 10min), and the MFR measured under the conditions of 190°C and 10kg load is I 10 (g / 10 min), I2 is 2.0 to 100 g / 10 min, and I 10 / I2 is 7.0 or higher.

[0023] In general, I 10 The lower the I2 value of the copolymer, the higher the I2 value tends to be. Therefore, copolymers with low I2 values ​​can be easily made to have high I 10 While copolymers with high I2 values ​​can be obtained, copolymers with high I2 values ​​have high I 10 On the other hand, according to the present invention, it is not easy to obtain a copolymer having a high I2 value that satisfies the above requirements (I) and / or (II). 10 It is possible to produce ethylene-α-olefin copolymers with high I2 values. Ethylene-α-olefin copolymers satisfying the above requirements (I) and / or (II) can be produced, for example, by using a catalyst that easily introduces long-chain branched structures during copolymerization, or by controlling the polymerization temperature within a specific range during copolymerization. In particular, the present invention makes it easy to produce ethylene-α-olefin copolymers having desired physical properties even when the polymerization temperature is low (e.g., 130°C or lower).

[0024] The present production method is preferably a method for producing an ethylene-α-olefin copolymer that satisfies the above requirements (I) and (II). An ethylene-α-olefin copolymer satisfying the above requirement (I) is hereinafter also referred to as "copolymer (i)," and an ethylene-α-olefin copolymer satisfying the above requirement (II) is hereinafter also referred to as "copolymer (ii)." In the following, the copolymer (i) and the copolymer (ii) are collectively referred to as "the copolymer."

[0025] <Olefin polymerization catalyst> The olefin polymerization catalyst contains a bridged metallocene compound (A) and a compound (B), which will be described later. The bridged metallocene compound (A) used in the olefin polymerization catalyst may be one type or two or more types, and the compound (B) used in the olefin polymerization catalyst may be one type or two or more types. By copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms using the olefin polymerization catalyst, it is possible to obtain a copolymer having a high I2 value and a low I 10 It was found that ethylene-α-olefin copolymers with high I / I2 values ​​can be easily produced. 10 / I2 is a value that is considered to be one of the indicators of the degree of long chain branching of a polymer, and copolymers with high I 10 / I2 value suggests that the polymer has a large amount of long-chain branched structure. The reason why the use of the olefin polymerization catalyst makes the resulting ethylene-α-olefin copolymer more likely to have a long-chain branched structure is thought to be that the electron density of the central metal is adjusted by the electron-rich ligand such as the bridged metallocene compound (A) (particularly the bridged metallocene compound (A-4) described below), which suppresses the generation of saturated terminal polymers due to the reaction of hydrogen during polymerization and relatively promotes the coordination and insertion of macromers.

[0026] [Bridged metallocene compound (A)] The bridged metallocene compound (A) (hereinafter also referred to as "component (A)") is represented by the following formula [I].

[0027] [ka]

[0028] <Y> Y is independently selected from carbon atoms, silicon atoms, germanium atoms and tin atoms, and is preferably a carbon atom or a silicon atom, more preferably a carbon atom. When n is an integer of 2 or more, multiple Ys may be the same or different.

[0029] <M> M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom, more preferably a zirconium atom.

[0030] <R 1 ~R 8 〉 R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8are each independently an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, a substituted aromatic group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and may be the same or different. 1 From R 6 Adjacent substituents up to R may be bonded to each other to form a ring, or may not be bonded to each other. 1 and R 5 or R 6 It is preferred that the group does not form a ring. When n is an integer of 2 or more, multiple R 5 may be the same or different, and multiple R 6 may be the same or different.

[0031] Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, a linear unsaturated hydrocarbon group having 2 to 20 carbon atoms, and a cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms. 1 From R 6 When adjacent substituents up to R are bonded to each other to form a ring, 1 From R 6 Examples of the structure of the portion where adjacent substituents up to are bonded to each other include an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 20 carbon atoms.

[0032] Examples of alkyl groups having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decanyl, and branched saturated hydrocarbon groups such as isopropyl, isobutyl, s-butyl, tert-butyl, tert-amyl, neopentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-dipropylbutyl, 1,1-dimethyl-2-methylpropyl, and 1-methyl-1-isopropyl-2-methylpropyl. The alkyl group preferably has 1 to 6 carbon atoms.

[0033] Examples of cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornenyl, 1-adamantyl, and 2-adamantyl; groups in which at least one hydrogen atom of a cyclic saturated hydrocarbon group such as a 3-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-cyclohexylcyclohexyl, or 4-phenylcyclohexyl group is replaced with a hydrocarbon group having 1 to 17 carbon atoms; and groups in which at least one hydrogen atom of a linear or branched saturated hydrocarbon group such as a cyclopropylmethyl group is replaced with a cyclic saturated hydrocarbon group having 3 to 19 carbon atoms. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 5 to 11.

[0034] Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), and 1-methylethenyl group (isopropenyl group), and alkynyl groups such as ethynyl group, 1-propynyl group, and 2-propynyl group (propargyl group). The number of carbon atoms in the chain unsaturated hydrocarbon group is preferably 2 to 4.

[0035] Examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclic unsaturated hydrocarbon groups such as cyclopentadienyl, norbornyl, phenyl, naphthyl, indenyl, azulenyl, phenanthryl, and anthracenyl; groups in which at least one hydrogen atom of a cyclic unsaturated hydrocarbon group has been replaced with a hydrocarbon group having 1 to 15 carbon atoms, such as 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 4-ethylphenyl, 4-tert-butylphenyl, 4-cyclohexylphenyl, biphenylyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, and 2,4,6-trimethylphenyl (mesityl); and groups in which at least one hydrogen atom of a linear or branched saturated hydrocarbon group, such as a benzyl or cumyl group, has been replaced with a cyclic unsaturated hydrocarbon group having 5 to 19 carbon atoms. The number of carbon atoms in the cyclic unsaturated hydrocarbon group is preferably 6 to 10.

[0036] Examples of alkylene groups having 1 to 20 carbon atoms include methylene, ethylene, dimethylmethylene (isopropylidene), ethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, and n-propylene. The alkylene group preferably has 1 to 6 carbon atoms.

[0037] Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, and a 4,4'-biphenylylene group. The arylene group preferably has 6 to 12 carbon atoms.

[0038] Examples of the aromatic group include, but are not limited to, the examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, and include substituents derived from aromatic compounds such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, a phenanthrenyl group, a tetracenyl group, a chrysenyl group, a pyrenyl group, an indenyl group, an azulenyl group, a pyrrolyl group, a pyridyl group, a furanyl group, and a thiophenyl group. The aromatic group is preferably a phenyl group or a 2-naphthyl group.

[0039] Examples of aromatic compounds include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene.

[0040] The substituted aromatic group partially overlaps with the examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, but examples include groups in which one or more hydrogen atoms of the aromatic group are substituted with a substituent selected from hydrocarbon groups having 1 to 20 carbon atoms, aromatic groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups, and specific examples include a 3-methylphenyl group (m-tolyl group), a 4-methylphenyl group (p-tolyl group), a 3-ethylphenyl group, a 4-ethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a biphenylyl group, a 4-(trimethylsilyl)phenyl group, a 4-amino ... Examples of the substituted aromatic group include a 4-(dimethylamino)phenyl group, a 4-(diethylamino)phenyl group, a 4-morpholinylphenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-phenoxyphenyl group, a 3,4-dimethoxyphenyl group, a 3,5-dimethoxyphenyl group, a 3-methyl-4-methoxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3-(trifluoromethyl)phenyl group, a 4-(trifluoromethyl)phenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 5-methylnaphthyl group, and a 2-(6-methyl)pyridyl group. In addition, examples of the substituted aromatic group include an "electron-donating group-containing substituted aromatic group" described later.

[0041] Examples of the silicon-containing group include alkylsilyl groups such as trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, and triisopropylsilyl; arylsilyl groups such as dimethylphenylsilyl, methyldiphenylsilyl, and tert-butyldiphenylsilyl; pentamethyldisilanyl; and trimethylsilylmethyl. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

[0042] Examples of the nitrogen-containing group include an amino group, a nitro group, an N-morpholinyl group, and a dimethylamino group, which is a group in which at least one =CH- structure in the hydrocarbon group or silicon-containing group having 1 to 20 carbon atoms is replaced with a nitrogen atom, a group in which at least one -CH2- structure is replaced with a nitrogen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, or a group in which at least one -CH3 structure is replaced with a nitrogen atom or a nitrile group bonded to a hydrocarbon group having 1 to 20 carbon atoms, such as a dimethylamino group, a diethylamino group, a dimethylaminomethyl group, a cyano group, a pyrrolidinyl group, a piperidinyl group, or a pyridinyl group. Preferred nitrogen-containing groups are a dimethylamino group and an N-morpholinyl group.

[0043] Examples of the oxygen-containing group include a hydroxyl group, a group in which at least one -CH2- structure in the hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, or nitrogen-containing group described above is replaced with an oxygen atom or a carbonyl group, or a group in which at least one -CH3 structure is replaced with an oxygen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, such as a methoxy group, ethoxy group, tert-butoxy group, phenoxy group, trimethylsiloxy group, methoxyethoxy group, hydroxymethyl group, methoxymethyl group, ethoxymethyl group, tert-butoxymethyl group, 1- Examples of the oxygen-containing group include a hydroxyethyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, an n-2-oxabutylene group, an n-2-oxapentylene group, an n-3-oxapentylene group, an aldehyde group, an acetyl group, a propionyl group, a benzoyl group, a trimethylsilylcarbonyl group, a carbamoyl group, a methylaminocarbonyl group, a carboxy group, a methoxycarbonyl group, a carboxymethyl group, an ethoxymethyl group, a carbamoylmethyl group, a furanyl group, and a pyranyl group. As the oxygen-containing group, a methoxy group is preferred.

[0044] Examples of the halogen atom include atoms of Group 17 elements, such as fluorine atom, chlorine atom, bromine atom, and iodine atom.

[0045] Examples of the halogen-containing group include a trifluoromethyl group, a tribromomethyl group, a pentafluoroethyl group, and a pentafluorophenyl group, which are groups in which at least one hydrogen atom in the hydrocarbon group, silicon-containing group, nitrogen-containing group, or oxygen-containing group having 1 to 20 carbon atoms is substituted with a halogen atom.

[0046] A and B each independently represent a sulfur atom, an oxygen atom, or CR 9 and R 9represents an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, a substituted aromatic group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group; when A is a sulfur atom or an oxygen atom, B is CR 9 and when B is a sulfur atom or an oxygen atom, A is CR 9 In a preferred embodiment, A or B is a sulfur atom and the other is CH. The ring containing A and B has a double bond at any possible position. The two As contained in formula [I] may be different but are preferably the same, and the two Bs contained in formula [I] may be different but are preferably the same.

[0047] Examples of the hydrocarbon group having 1 to 20 carbon atoms, aromatic group, substituted aromatic group, silicon-containing group, nitrogen-containing group, oxygen-containing group, halogen atom, and halogen-containing group in A and B include the same atoms and substituents as the specific examples of these atoms and substituents described above.

[0048] Q Q is independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. When j is an integer of 2 or more, multiple Qs may be the same or different.

[0049] Examples of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms include the same atoms or substituents as those mentioned above. When Q is a halogen atom, it is preferably a chlorine atom. When Q is a hydrocarbon group having 1 to 20 carbon atoms, it is preferable that the hydrocarbon group has 1 to 7 carbon atoms.

[0050] Examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy, and phenoxy groups, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.

[0051] Examples of neutral ligands capable of coordinating with lone electron pairs include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, and ether compounds such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0052] 〈n and j〉 n is an integer of 1 to 4, and is preferably 1. j is an integer of 1 to 4, and is preferably 2.

[0053] As mentioned above, in the component (A), n is preferably 1. Such a bridged metallocene compound (A-1) is represented by the following formula [V].

[0054] [ka] [In formula [V], Y, M, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , A, B, Q and j have the same meanings as the same symbols in formula [I].

[0055] The bridged metallocene compound (A-1) has the advantage that the production process is simpler and the production cost is reduced compared to the compound in the formula [I] where n is an integer of 2 to 4. Consequently, the use of this bridged metallocene compound (A-1) has the advantage of reducing the production cost of an ethylene-α-olefin copolymer. Furthermore, when ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (A-1), the amount of long-chain branched structures produced in the resulting ethylene-α-olefin copolymer is improved.

[0056] In the bridged metallocene compound (A-1) represented by the formula [V], R 1 , R 2 , R3 , and R 4 are preferably all hydrogen atoms. Such a bridged metallocene compound (A-2) is represented by the following formula [VI].

[0057] [ka] [In formula [VI], Y, M, R 5 , R 6 , R 7 , R 8 , A, B, Q and j have the same meanings as the same symbols in formula [I].

[0058] In the bridged metallocene compound (A-2) represented by the formula [VI], Y is preferably a carbon atom or a silicon atom, more preferably a carbon atom. The bridged metallocene compound (A-3) in which Y is a carbon atom is represented by the following formula [VII].

[0059] [ka] [In formula [VII], M, R 5 , R 6 , R 7 , R 8 , A, B, Q and j have the same meanings as the same symbols in formula [I].

[0060] In the bridged metallocene compound (A-3) represented by the formula [VII], A is preferably a sulfur atom and B is preferably CH. Such a bridged metallocene compound (A-4) is represented by the following formula [VIII]. In addition, in the bridged metallocene compound (A-2), in the bridged metallocene compound (A-6) in which Y is a silicon atom, A is preferably a sulfur atom and B is preferably CH.

[0061] [ka] [In formula [VIII], M, R 5 , R 6 , R 7 , R8 , Q and j have the same meanings as the same symbols in formula [I].

[0062] The bridged metallocene compound (A-4) has an advantage over the compound of formula [VII] in that the production process for the dithiophene moiety is well established, simplifying the production process and reducing production costs. Consequently, the use of this bridged metallocene compound (A-4) offers the advantage of reducing the production costs of ethylene-α-olefin copolymers. Furthermore, when ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (A-4), the bridged metallocene compound (A-4) is thermally stable, resulting in improved polymerization activity at high temperatures (e.g., 100°C or higher).

[0063] The bridged metallocene compound (A-4) can be synthesized by a simple method such as that shown in the following formula [IX]: In the following formula [IX], Q of the bridged metallocene compound (A-4) represented by the formula [VIII] is a chlorine atom, and j is 2.

[0064] [ka] [In formula [IX], M, R 5 , R 6 , R 7 , and R 8 has the same meaning as the same symbol in the formula [I].

[0065] formula R 5 -C(=O)-R 6 Various ketones represented by the formula (I) are readily available commercially from general reagent manufacturers. Even if such ketones are not commercially available, they can be easily synthesized, for example, by the method of Olah et al. (Heterocycles, 40, 79 (1995)). Therefore, the formula R 5 -C(=O)-R 6By using a ketone represented by the formula (A-4), the bridged metallocene compound (A-4) can be produced in a simpler and easier process than a compound in which Y in formula [V] is selected from the group consisting of a silicon atom, a germanium atom, and a tin atom, further reducing the production cost, and thus using this bridged metallocene compound has the advantage of reducing the production cost of an ethylene-α-olefin copolymer. Furthermore, when ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (A-4), the resulting ethylene-α-olefin copolymer has an improved yield of long-chain branched structures.

[0066] In the bridged metallocene compound (A-4) represented by the formula [VIII], R 5 and R 6 is preferably a group selected from the group consisting of aromatic groups and substituted aromatic groups. R 5 and R 6 By selecting the bridged metallocene compound in this manner, the synthesis process of the bridged metallocene compound is simplified, further reducing the production cost, and the use of this bridged metallocene compound advantageously reduces the production cost of the ethylene-α-olefin copolymer. Furthermore, when ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized in the presence of an olefin polymerization catalyst containing such a bridged metallocene compound, the polymerization activity is further improved and the yield of long-chain branched structures in the resulting ethylene-α-olefin copolymer is increased.

[0067] In the bridged metallocene compound (A-4) represented by the formula [VIII], R 5 and R 6 and are more preferably the same substituted aromatic group. When ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound, there is an advantage in that the yield of long chain branched structures in the resulting ethylene-α-olefin copolymer is improved.

[0068] In the bridged metallocene compound (A-4) represented by the formula [VIII], R 5 and R 6 is preferably a substituted aromatic group in which one or more hydrogen atoms of the aromatic group are substituted with an electron-donating substituent having a Hammett's rule substituent constant σ of −0.2 or less, and when a plurality of electron-donating substituents are present, the respective electron-donating substituents may be the same or different, and may also have a substituent other than the electron-donating substituent selected from a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and when a plurality of such substituents are present, the respective substituents may be the same or different (hereinafter also referred to as an “electron-donating group-containing substituted aromatic group”). When ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized in the presence of an olefin polymerization catalyst containing such a bridged metallocene compound, the advantage of improving the yield of long-chain branched structures in the resulting ethylene-α-olefin copolymer is obtained.

[0069] Electron-donating groups with a Hammett's rule substituent constant σ of -0.2 or less are defined and exemplified as follows: Hammett's rule is an empirical rule proposed by L.P. Hammett in 1935 to quantitatively discuss the influence of substituents on the reaction or equilibrium of benzene derivatives, and is now widely recognized as valid. The substituent constants calculated by Hammett's rule include σp when substituted at the para position of the benzene ring and σm when substituted at the meta position, and these values ​​can be found in many general literature.

[0070] For example, a wide range of substituents are described in detail in the literature by Hansch and Taft [Chem. Rev., 91, 165 (1991)]. However, the values ​​of σp and σm described in these literature may differ slightly depending on the literature, even for the same substituent. In order to avoid confusion caused by such a situation, in the present invention, the values ​​described in Table 1 (pages 168-175) of the literature by Hansch and Taft are defined as the Hammett's rule substituent constants σp and σm for as many substituents as possible.

[0071] In the present invention, an electron-donating group having a Hammett's rule substituent constant σ of −0.2 or less refers to an electron-donating group having a σp of −0.2 or less when the electron-donating group is substituted at the para-position (4-position) of a phenyl group, an electron-donating group having a σm of −0.2 or less when the electron-donating group is substituted at the meta-position (3-position) of a phenyl group, and an electron-donating group having a σp of −0.2 or less when the electron-donating group is substituted at the ortho-position (2-position) of a phenyl group or at any position of an aromatic group other than a phenyl group.

[0072] Examples of electron-donating substituents having a Hammett's substituent constant σp or σm of −0.2 or less include nitrogen-containing groups such as p-amino group (4-amino group), p-dimethylamino group (4-dimethylamino group), p-diethylamino group (4-diethylamino group), and m-diethylamino group (3-diethylamino group), oxygen-containing groups such as p-methoxy group (4-methoxy group) and p-ethoxy group (4-ethoxy group), tertiary hydrocarbon groups such as p-tert-butyl group (4-tert-butyl group), and silicon-containing groups such as p-trimethylsiloxy group (4-trimethylsiloxy group).

[0073] The electron-donating substituents having a Hammett's rule substituent constant σp or σm of -0.2 or less as defined herein are not limited to those listed in Table 1 (pages 168-175) of the above-mentioned document by Hansch and Taft. Substituents not listed in the document, but which can have a Hammett's rule substituent constant σp or σm of -0.2 or less as measured according to Hammett's rule, are also included in the electron-donating groups having a Hammett's rule substituent constant σp or σm of -0.2 or less as defined herein. Examples of such substituents include a pN-morpholinyl group (4-N-morpholinyl group) and an mN-morpholinyl group (3-N-morpholinyl group).

[0074] When an electron-donating group-containing substituted aromatic group is substituted with a plurality of electron-donating substituents, the respective electron-donating substituents may be the same or different, and the group may be substituted with a substituent selected from a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, in addition to the electron-donating substituent. When the aromatic group is substituted with a plurality of substituents, the respective substituents may be the same or different, but it is preferable that the sum of the substituent constants σ of the Hammett's rule of the electron-donating substituents and the respective substituents contained in one substituted aromatic group is −0.15 or less.

[0075] Examples of the electron-donating group-containing substituted aromatic group include an m,p-dimethoxyphenyl group (a 3,4-dimethoxyphenyl group), a p-(dimethylamino)-m-methoxyphenyl group (a 4-(dimethylamino)-3-methoxyphenyl group), a p-(dimethylamino)-m-methylphenyl group (a 4-(dimethylamino)-3-methylphenyl group), a p-methoxy-m-methylphenyl group (a 4-methoxy-3-methylphenyl group), and a p-methoxy-m,m-dimethylphenyl group (a 4-methoxy-3,5-dimethylphenyl group).

[0076] Examples of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group, the oxygen-containing group, the halogen atom, and the halogen-containing group that the electron-donating group-containing substituted aromatic group may have include the same atoms or substituents as the specific examples of these atoms or substituents described above.

[0077] In the bridged metallocene compound (A-4) represented by the formula [VIII], R 5 and R 6 When ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized in the presence of an olefin polymerization catalyst containing a bridged metallocene compound (A-4) in which the substituted aromatic group containing an electron-donating group is copolymerized, the yield of long-chain branched structures in the resulting ethylene-α-olefin copolymer is improved.

[0078] In the bridged metallocene compound (A-4) represented by the formula [VIII], R 5 and R6 The electron-donating substituent contained in is more preferably a group selected from a nitrogen-containing group and an oxygen-containing group, and even more preferably an oxygen-containing group. These substituents have a particularly low σ in Hammett's rule and are effective in increasing the amount of long-chain branched structures produced in the copolymer produced during polymerization at high temperatures (e.g., 100°C or higher).

[0079] In the bridged metallocene compound (A-4) represented by the formula [VIII], R 5 and R 6 is more preferably a substituted phenyl group containing a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent, and even more preferably a substituted phenyl group containing an oxygen-containing group. When such a compound is synthesized, for example, according to the method of formula [IX], various benzophenone-based compounds serving as raw materials are commercially available from general reagent manufacturers, making it easy to obtain the raw materials, simplifying the production process, and further reducing production costs. Consequently, the use of this bridged metallocene compound offers the advantage of reducing the production costs of ethylene-α-olefin copolymers.

[0080] Examples of the substituted phenyl group containing a group selected from the group consisting of a nitrogen-containing group and an oxygen-containing group include an o-aminophenyl group (2-aminophenyl group), a p-aminophenyl group (4-aminophenyl group), an o-(dimethylamino)phenyl group (2-(dimethylamino)phenyl group), a p-(dimethylamino)phenyl group (4-(dimethylamino)phenyl group), an o-(diethylamino)phenyl group (2-(diethylamino)phenyl group), a p-(diethylamino)phenyl group (4-(diethylamino)phenyl group), an m-(diethylamino)phenyl group (3-(diethylamino)phenyl group), an o-methoxyphenyl group (2-methoxyphenyl group), a p-methoxyphenyl group (4-methoxyphenyl group), an o-ethoxyphenyl group (2-ethoxyphenyl group), a p-ethoxyphenyl group (4 -ethoxyphenyl group), oN-morpholinylphenyl group (2-N-morpholinylphenyl group), pN-morpholinylphenyl group (4-N-morpholinylphenyl group), mN-morpholinylphenyl group (3-N-morpholinylphenyl group), o,p-dimethoxyphenyl group (2,4-dimethoxyphenyl group), m,p-dimethoxyphenyl group (3,4-dimethoxyphenyl group), p-(dimethylamino)-m-methoxyphenyl group (4-(dimethylamino)-3-methoxyphenyl group), p-(dimethylamino)-m-methylphenyl group (4-(dimethylamino)-3-methylphenyl group), p-methoxy-m-methylphenyl group (4-methoxy-3-methylphenyl group), and p-methoxy-m,m-dimethylphenyl group (4-methoxy-3,5-dimethylphenyl group).

[0081] In the bridged metallocene compound (A-4) represented by the formula [VIII], R 5 and R 6is more preferably a substituted phenyl group containing an oxygen-containing group as the electron-donating substituent at the meta-position and / or para-position relative to the bond to the carbon atom represented by Y. For example, when synthesis is performed according to the method represented by formula [IX], synthesis is easier than when the oxygen-containing group is substituted at the ortho-position, the production process is simplified, and production costs are reduced. Consequently, use of this bridged metallocene compound offers the advantage of reducing the production costs of ethylene-α-olefin copolymers.

[0082] In the bridged metallocene compound (A-4) represented by the formula [VIII], R 5 and R 6 is preferably a bridged metallocene compound (A-5) in which Y is a substituted phenyl group containing an oxygen-containing group as the electron-donating substituent at the meta-position and / or para-position relative to the bond to the carbon atom, and the oxygen-containing group is more preferably a group represented by the following formula [III]: R 10 -O-* …[III] [In formula [III], R 10 represents an atom or substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group, and * represents a bond to a phenyl group.

[0083] R 10 Examples of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group and the halogen-containing group as the substituents include the same substituents as those given above as specific examples of these substituents. The bridged metallocene compound (A-5) includes a compound represented by the following formula [X].

[0084] [ka] [In the formula [X], M, R 7 , R 8 , Q and j have the same meanings as those in the formula [I]. 10 R independently has the same meaning as the corresponding symbol in the formula [III]. 11are independently an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group. OR 10 When there are a plurality of groups, they may be the same or different, n is an integer of 1 to 3, and m is an integer of 0 to 4.

[0085] In the bridged metallocene compound (A) represented by formula [I], the bridged metallocene compound (A-1) represented by formula [V], the bridged metallocene compound (A-2) represented by formula [VI], the bridged metallocene compound (A-3) represented by formula [VII], the bridged metallocene compound (A-4) represented by formula [VIII], the bridged metallocene compound (A-5) represented by formula [X], and the bridged metallocene compound (A-6), M is more preferably a zirconium atom. When ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound in which M is a zirconium atom, an advantage can be obtained in that the yield of long-chain branched structures in the resulting ethylene-α-olefin copolymer is improved.

[0086] (Examples of component (A)) Specific examples of component (A) include: [Dimethylmethylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [diethylmethylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [di-n-butylmethylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [dicyclopentylmethylene(η 5 -cyclopentadienyl)(η 5-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [dicyclohexylmethylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [Cyclopentylidene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [cyclohexylidene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [Diphenylmethylene (η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [di-1-naphthylmethylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [di-2-naphthylmethylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(3-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(3,4-dimethylphenyl)methylene(η5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-n-hexylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-cyclohexylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-tert-butylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(3-methoxyphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-methoxyphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(3,4-dimethoxyphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-methoxy-3-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-methoxy-3,4-dimethylphenyl)methylene(η 5 -cyclopentadienyl)(η5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-ethoxyphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-phenoxyphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis{4-(trimethylsiloxy)phenyl}methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis{3-(dimethylamino)phenyl}methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis{4-(dimethylamino)phenyl}methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-N-morpholinylphenyl)(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis{4-(trimethylsilyl)phenyl}methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(3-chlorophenyl)methylene(η 5 -cyclopentadienyl)(η 5-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-chlorophenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(3-fluorophenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-fluorophenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis{3-(trifluoromethyl)phenyl}methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis{4-(trifluoromethyl)phenyl}methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [Methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [methyl(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [methyl(4-methoxyphenyl)methylene(η 5 -cyclopentadienyl)(η 5-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [methyl{4-(dimethylamino)phenyl}methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [methyl(4-N-morpholinylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [Dimethylsilylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [diethylsilylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [dicyclohexylsilylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [diphenylsilylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [di(4-methylphenyl)silylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [Dimethylgermylene(η 5 -cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [diphenylgermylene(η 5-cyclopentadienyl)(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [1-(η 5 -cyclopentadienyl)-2-(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))ethylene]zirconium dichloride, [1-(η 5 -cyclopentadienyl)-3-(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))propylene]zirconium dichloride, [1-(η 5 -cyclopentadienyl)-2-(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))-1,1,2,2-tetramethylsilylene]zirconium dichloride, [1-(η 5 -cyclopentadienyl)-2-(η 5 -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))phenylene]zirconium dichloride, and Compounds in which the zirconium atom of these compounds is replaced with a hafnium atom or compounds in which the chloro ligand is replaced with a methyl group is exemplified.

[0087] [Compound (B)] Compound (B) (hereinafter also referred to as "component (B)") is an organometallic compound (B-1) (hereinafter also referred to as "component (B-1)"), an organoaluminum oxy-compound (B-2) (hereinafter also referred to as "component (B-2)"), and The component (B-3) is at least one compound selected from the group consisting of compounds (B-3) (hereinafter also referred to as "component (B-3)") that react with the transition metal compound (A) to form an ion pair.

[0088] ·Component (B-1) Component (B-1) is not particularly limited as long as it is a compound other than component (B-2), but it is preferably at least one compound selected from the group consisting of an organoaluminum compound (B-1a) represented by the following formula (B-1a), a compound (B-1b) of a Group 1 metal and aluminum represented by the following formula (B-1b), and a compound (B-1c) of a Group 2 or Group 12 metal represented by the following formula (B-1c). Among these, the compound (B-1a) is preferred. Component (B-1) may be used alone or in combination of two or more.

[0089] R a m Al(OR b ) n H p X q …(B-1a) 〔In the formula (B-1a), R a and R b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X independently represents a halogen atom, m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3.〕

[0090] Examples of the compound (B-1a) include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, and tricycloalkylaluminum.

[0091] M a AlR a 4 …(B-1b) 〔In the formula (B-1b), M a represents Li, Na, or K, and R a each independently represents a hydrocarbon group having 1 to 15 (preferably 1 to 4) carbon atoms.〕

[0092] Examples of the compound (B-1b) include, for example, LiAl(C2H5)4, LiAl(C7H 15)4 can be mentioned.

[0093] R a r M b R b s X t …(B-1c) [In formula (B-1c), R a and R b each independently represents a hydrocarbon group having 1 to 15 carbon atoms, and may be the same or different; M b is selected from Mg, Zn and Cd, X represents a halogen atom, and r is 0. <r≦2、sは0≦s≦1、tは0≦t≦1であり、かつr+s+t=2である。〕

[0094] Examples of the compound (B-1c) include dimethyl magnesium, diethyl magnesium, di-n-butyl magnesium, ethyl-n-butyl magnesium, diphenyl magnesium, dimethyl zinc, diethyl zinc, di-n-butyl zinc, and diphenyl zinc.

[0095] ·Component (B-2) Component (B-2) may be, for example, a conventionally known aluminoxane, or an organoaluminum oxy compound that is insoluble or slightly soluble in benzene, as exemplified in JP-A-2-78687. Conventionally known aluminoxanes can be produced, for example, by the following methods (1) to (4), and are usually obtained as a solution in a hydrocarbon solvent. The component (B-2) may be used alone or in combination of two or more.

[0096] (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or water of crystallization with the organoaluminum compound.

[0097] (2) A method in which water, ice or water vapor is directly reacted with an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.

[0098] (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0099] (4) A method in which an organoaluminum such as trialkylaluminum is reacted with an organic compound having a carbon-oxygen bond such as a tertiary alcohol, a ketone, or a carboxylic acid, and the resulting compound is subjected to a non-hydrolytic conversion such as thermal decomposition reaction.

[0100] The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed from the recovered aluminoxane solution by distillation or the like, the aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0101] Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the compound (B-1a) above. Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

[0102] Other examples of component (B-2) include modified methylaluminoxane. Modified methylaluminoxane is an aluminoxane prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such compounds are commonly referred to as MMAO. MMAO can be prepared by the methods described in U.S. Patent Nos. 4,960,878 and 5,041,584. Tosoh Finechem Corporation and other companies also produce MMAO and TMAO, which are prepared using trimethylaluminum and triisobutylaluminum.

[0103] Such MMAO is an aluminoxane with improved solubility in various solvents and improved storage stability. Specifically, unlike the organoaluminum oxy compounds mentioned above, which are insoluble or poorly soluble in benzene, MMAO is characterized by its solubility in aliphatic hydrocarbons and alicyclic hydrocarbons.

[0104] Further examples of component (B-2) include organoaluminum oxy compounds containing a boron atom, halogen-containing aluminoxanes such as those exemplified in WO 2005 / 066191 and WO 2007 / 131010, and ionic aluminoxanes such as those exemplified in WO 2003 / 082879.

[0105] ·Component (B-3) Examples of component (B-3) include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Patent No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds. The component (B-3) may be used alone or in combination of two or more.

[0106] As the component (B-3), a compound represented by the following formula (B-3a) is preferred.

[0107] [ka] [In formula (B-3a), R e+ For example, H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. f ~R i are each independently an organic group, preferably an aryl group.

[0108] Examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation, and tris(dimethylphenyl)carbenium cation.

[0109] Examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.

[0110] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation, and tris(dimethylphenyl)phosphonium cation.

[0111] R e+As the cation, for example, a carbenium cation or an ammonium cation is preferred, and a triphenylcarbenium cation, an N,N-dimethylanilinium cation or an N,N-diethylanilinium cation is particularly preferred.

[0112] R e+ is a carbenium cation, examples of the compound represented by formula (B-3a) include triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(3,5-ditrifluoromethylphenyl)borate, tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate, and tris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl)borate.

[0113] R e+ Examples of the compound represented by formula (B-3a) in which is an ammonium cation include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, and dialkylammonium salts.

[0114] Examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis(o-tolyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(4-trifluoromethylphenyl)borate, and tri(n-butyl)ammonium tetrakis(4-trifluoromethylphenyl)borate. dioctadecylmethylammonium tetrakis(3,5-ditrifluoromethylphenyl)borate, tri(n-butyl)ammonium tetrakis(o-tolyl)borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis(p-tolyl)borate, dioctadecylmethylammonium tetrakis(o-tolyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(4-trifluoromethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-ditrifluoromethylphenyl)borate, and dioctadecylmethylammonium.

[0115] Examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-2,4,6-pentamethylanilinium tetraphenylborate, and N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate.

[0116] Examples of the dialkylammonium salt include di(isopropyl)ammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

[0117] As the component (B-3), ionic compounds disclosed in JP-A-2004-51676 can also be used without any restrictions.

[0118] [Carrier (C)] The olefin polymerization catalyst may further contain a support (C) (hereinafter also referred to as "component (C)"), if necessary. Examples of component (C) include inorganic or organic compounds, and granular or particulate solids. As described above, in the present invention, it is possible to generate a sufficiently large number of long chain branched structures without using component (C), and therefore it is preferable not to use component (C). Examples of component (C) include carriers described in JP-A-2019-172794. The component (C) may be used alone or in combination of two or more.

[0119] [Organic compound component (D)] The olefin polymerization catalyst may further contain, as necessary, an organic compound component (D) (hereinafter also referred to as "component (D)"). Component (D) is used for the purposes of improving polymerization performance and the physical properties of the produced polymer. Examples of component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates. The component (D) may be used alone or in combination of two or more.

[0120] [Method of use and order of addition of components constituting the olefin polymerization catalyst] When carrying out the step [P], the method of using the components constituting the olefin polymerization catalyst, the order of addition, etc. may be selected arbitrarily, but examples thereof include the following methods. (1) A method in which component (A) and component (B) are added to a polymerization reactor in any order. (2) A method in which a catalyst component in which component (A) is supported on component (C) and component (B) are added to a polymerization vessel in any order. (3) A method in which a catalyst component in which component (B) is supported on component (C) and component (A) are added to a polymerization reactor in any order. (4) A method in which a catalyst component in which component (A) and component (B) are supported on component (C) is added to a polymerization reactor.

[0121] In each of the above methods (1) to (3), at least two of the catalyst components may be contacted in advance. In each of the above methods (1) to (4), component (D) may also be used. In the above methods (3) and (4) in which component (B) is supported, unsupported component (B) may be added in any order, if necessary. In this case, the supported component (B) and the optionally added component (B) may be the same or different. Furthermore, the solid catalyst component in which component (A) is supported on component (C) and the solid catalyst component in which components (A) and (B) are supported on component (C) may be prepolymerized with an olefin, or the prepolymerized solid catalyst component may have further catalyst components supported thereon.

[0122] <Process [P]> This production method includes a step [P] of copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of the above-mentioned olefin polymerization catalyst. Furthermore, the phrase "copolymerizing ethylene with an α-olefin in the presence of an olefin polymerization catalyst" encompasses embodiments in which each component of the olefin polymerization catalyst is added to a polymerization vessel by any method, and ethylene and an α-olefin are copolymerized, such as the above-mentioned methods (1) to (4).

[0123] The copolymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. In the liquid phase polymerization method, it is preferable to use an inert hydrocarbon medium. Examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more. Also, a so-called bulk polymerization method can be used in which the liquefied olefin to be supplied to the copolymerization itself is used as a solvent.

[0124] When the copolymerization is carried out, the amounts of the components that can constitute the olefin polymerization catalyst are preferably as follows:

[0125] Component (A) is usually 1 x 10 per liter of reaction volume. -10 ~1×10 -2 mol, preferably 1 x 10 -8 ~1×10 -3 It is used in molar amounts.

[0126] When component (B-1) is used, component (B-1) can be used in an amount such that the molar ratio of component (B-1) to the total transition metal atoms (M) in component (A) [(B-1) / M] is preferably 1 to 50,000, more preferably 10 to 20,000, and even more preferably 50 to 10,000.

[0127] When component (B-2) is used, component (B-2) can be used in an amount such that the molar ratio [Al / M] of aluminum atoms (Al) in component (B-2) to the total transition metal atoms (M) in component (A) is preferably 10 to 5,000, more preferably 20 to 2,000.

[0128] When component (B-3) is used, component (B-3) can be used in an amount such that the molar ratio of component (B-3) to the total transition metal atoms (M) in component (A) [(B-3) / M] is preferably 1 to 1000, more preferably 1 to 200.

[0129] When component (C) is used, component (C) can be used in an amount such that the mass ratio of component (A) to component (C) [(A) / (C)] is usually 0.0001 to 1, preferably 0.0005 to 0.5, and more preferably 0.001 to 0.1.

[0130] When component (D) is used, When component (B) is component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5, When component (B) is component (B-2), the molar ratio [(D) / (B-2)] is usually 0.005 to 2, preferably 0.01 to 1, When component (B) is component (B-3), component (D) can be used in an amount such that the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5.

[0131] In the present production method, the temperature during copolymerization in the step [P] is preferably 100 to 130°C, more preferably 105 to 125°C. By controlling the polymerization temperature during copolymerization within the above range, an ethylene-α-olefin copolymer satisfying the above requirements (I) and / or (II) can be easily produced. Furthermore, by controlling the polymerization temperature during copolymerization within the above range, a decrease in the activity of the olefin polymerization catalyst can be suppressed, which brings about significant advantages in terms of cost and polymer design when producing an ethylene-α-olefin copolymer.

[0132] In this production method, the polymerization pressure during copolymerization in step [P] is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure, and the polymerization time is usually 1 hour or less, preferably 40 minutes or less, more preferably 30 minutes or less, preferably 5 to 20 minutes. The copolymerization reaction can be carried out in any of batch, semi-continuous and continuous systems. Furthermore, the copolymerization can be carried out in two or more stages with different reaction conditions.

[0133] The molecular weight of the resulting ethylene-α-olefin copolymer can be controlled by adding hydrogen or other additives to the polymerization system, by changing the polymerization temperature, or by adjusting the amount of component (B) used. In particular, hydrogen can be said to be a preferred additive because it can improve the polymerization activity of the catalyst and increase or decrease the molecular weight of the polymer. When hydrogen is added to the system, the molar ratio of hydrogen (H2) to ethylene (moles of hydrogen / moles of ethylene) is preferably less than 0.020, more preferably 0.001 or more and less than 0.020.

[0134] When the polymerization temperature is within the above range, the effect of improving the polymerization activity by supplying hydrogen gas to the polymerization system is large, whereas when the polymerization temperature is lower than the above range, the effect of improving the polymerization activity by supplying hydrogen gas to the polymerization system is small. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system can also be adjusted by performing a reaction that produces or consumes hydrogen within the system, by separating hydrogen using a membrane, or by releasing a portion of the hydrogen-containing gas outside the system.

[0135] The ethylene-α-olefin copolymer obtained by this production method may be subjected to known post-treatment steps such as a catalyst deactivation step, a catalyst residue removal step, and a drying step, if necessary, after synthesis by the above-mentioned method.

[0136] [α-Olefin] In this production method, the α-olefin supplied to the polymerization reaction is an α-olefin having 3 to 20 carbon atoms. One or more of the α-olefins may be used.

[0137] As the α-olefin, an α-olefin having 3 to 10 carbon atoms is particularly preferred. The α-olefin may be a linear or branched α-olefin. Examples of linear or branched α-olefins include propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.

[0138] At least one of the α-olefins supplied is preferably propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene or 1-decene, more preferably propylene, 1-butene or 4-methyl-1-pentene, and particularly preferably propylene or 1-butene.

[0139] Ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized in such a ratio that the proportion of structural units derived from ethylene in the resulting ethylene-α-olefin copolymer is preferably 70 mol % or more, more preferably 75 mol % or more, and even more preferably 80 mol % or more, based on the total structural units of the copolymer. The amount of each component fed in step [P] is appropriately set depending on the proportion of structural units in the target ethylene-α-olefin copolymer.

[0140] <This copolymer> The melt flow rate (MFR) I2 (g / 10 min) of copolymer (i), measured in accordance with JIS K 7210:1999 at 190°C under a load of 2160 g, is preferably 2.0 g / 10 min or more, more preferably 2.5 g / 10 min or more, and is preferably 100 g / 10 min or less, more preferably 80 g / 10 min or less, even more preferably 60 g / 10 min or less, and particularly preferably 40 g / 10 min or less. Furthermore, I2 (g / 10 min) of the copolymer (ii) is 2.0 g / 10 min or more, preferably 2.5 g / 10 min or more, and 100 g / 10 min or less, preferably 80 g / 10 min or less, more preferably 60 g / 10 min or less, and even more preferably 40 g / 10 min or less.

[0141] The MFR of this copolymer is measured at 190°C under a 10 kg load in accordance with JIS K 7210:1999. 10 (g / 10 min) is preferably 20 g / 10 min or more, more preferably 25 g / 10 min or more, and is usually 300 g / 10 min or less, preferably 250 g / 10 min or less, more preferably 200 g / 10 min or less, and even more preferably 180 g / 10 min or less.

[0142] The copolymer (i) satisfies the following formula (1), preferably the following formula (2), and more preferably the following formula (3). Furthermore, the copolymer (ii) preferably satisfies the following formula (1), more preferably satisfies the following formula (2), and further preferably satisfies the following formula (3). I 10 / I2+0.869×ln(I2) ≧ 9.0 …(1) I 10 / I2+0.869×ln(I2) ≧ 9.5 …(2) I 10 / I2+0.869×ln(I2) ≧ 10.0 …(3) "I" in the above formulas (1) to (3) 10 / I2+0.869×ln(I2)” is usually 54.0 or less, preferably 40.0 or less, more preferably 30.0 or less, even more preferably 20.0 or less, and particularly preferably 15.0 or less.

[0143] Copolymer (i) I 10 / I2 is preferably 7.0 or more, more preferably 7.2 or more, and even more preferably 7.5 or more, and is usually 50 or less, and preferably 20 or less. Also, I of copolymer (ii) 10 / I2 is 7.0 or more, preferably 7.2 or more, more preferably 7.5 or more, and is usually 50 or less, preferably 20 or less.

[0144] The copolymer, 1 The amount of double bonds (total amount of vinyl double bonds, vinylidene double bonds, di-substituted olefin double bonds, and tri-substituted olefin double bonds) per 1000 carbon atoms (1000C) determined by H-NMR is preferably 0.7 or more, more preferably 0.75 or more, and even more preferably 0.8 or more. There is no particular upper limit to the amount of double bonds, but it is usually 2. The copolymer having the double bond content within the above range is usually crosslinkable, and when the double bond content is within the above range, crosslinking is facilitated, making it possible to easily obtain molded articles and crosslinked foams that are excellent in compression set and mechanical strength. A specific method for measuring the amount of double bonds will be described in detail in the Examples below.

[0145] The molecular weight distribution (Mw / Mn), which is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) of the copolymer measured by gel permeation chromatography (GPC), is preferably 2.2 or more, more preferably 2.3 or more, and even more preferably 2.4 or more. There is no particular upper limit to Mw / Mn, but it is usually 3.5. The present copolymer having a molecular weight distribution within the above range has good processability.

[0146] Mw is preferably 30,000 to 500,000, more preferably 50,000 to 300,000, still more preferably 70,000 to 200,000, and particularly preferably 100,000 to 180,000. Mn is preferably 25,000 to 150,000, more preferably 30,000 to 100,000, still more preferably 35,000 to 75,000, and particularly preferably 37,000 to 65,000. Specific methods for measuring Mw, Mn and Mw / Mn will be described in detail in the examples below.

[0147] The density measured at 23°C in accordance with ASTM D1505 is preferably 854 to 888 kg / m 3 , more preferably 857 to 885 kg / m 3 , more preferably 860 to 882 kg / m 3 , particularly preferably 863 to 880 kg / m 3 is. [Example]

[0148] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0149] [Ethylene content] The ethylene content in ethylene-α-olefin copolymer is 13 C-NMR measurements were performed, and the values ​​were calculated by analyzing the obtained spectra. Equipment: Bruker BioSpin AVANCE IIIcryo-500 nuclear magnetic resonance spectrometer Measurement nuclei: 13 C(125MHz) Measurement mode: Single pulse proton broadband decoupling Pulse width: 45° (5.00 μsec) Number of points: 64 x 103 Measurement range: 250 ppm (-55 to 195 ppm) Repeat time: 5.5 seconds Number of times accumulated: 128 Measurement solvent: orthodichlorobenzene / benzene-d6 (4 / 1 [v / v]) Sample concentration: ca. 60 mg / 0.6 mL Measurement temperature: 120℃ Window function: exponential (BF: 1.0 Hz) Chemical shift reference: δδ signal (29.73 ppm)

[0150] 〔density〕 Density of ethylene-α-olefin copolymer (kg / m 3 ) was measured at 23°C in accordance with ASTM D1505.

[0151] [Melt flow rate (MFR)] The MFR (g / 10 min) of ethylene-α-olefin copolymer was measured at 190°C in accordance with JIS K 7210:1999. The measured value under a 2160g load was I2, and the measured value under a 10kg load was I. 10 It was decided.

[0152] [Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of ethylene-α-olefin copolymers are values ​​measured by GPC and converted into polystyrene equivalents. The measurement equipment and conditions are as follows. The molecular weight was calculated based on a calibration curve prepared using commercially available monodisperse polystyrene. Apparatus: Gel permeation chromatograph Alliance GP2000 (Waters) Analysis device: Empower2 (Waters) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (both 7.5 mm I.D. x 30 cm, manufactured by Tosoh Corporation) Column temperature: 140℃ Mobile phase: o-dichlorobenzene (containing 0.025% BHT) Detector: Differential refractometer (RI) Flow rate: 1.0mL / min Injection volume: 400μL Sampling time interval: 1s Column calibration: Monodisperse polystyrene (Tosoh Corporation) Molecular weight conversion: Old EPR conversion / calibration method taking viscosity into account

[0153] [Double bond amount] The amount of double bonds in ethylene-α-olefin copolymers is determined under the following conditions: 1 H-NMR measurements were performed, and the resulting spectra were analyzed to calculate the values. Equipment: Bruker BioSpin AVANCE IIIcryo-500 nuclear magnetic resonance spectrometer Measurement nuclei: 1 H(500MHz) Measurement mode: wetdc (WET offset: 1.2 ppm) Pulse width: 90° Number of points: 32 x 103 Measurement range: 20 ppm (-9 to 11 ppm) Repeat time: 7.0 seconds Number of times accumulated: 128 Measurement solvent: 2.5 mM Cr(acac)3 in orthodichlorobenzene-d4 Sample concentration: ca. 20 mg / 0.6 mL Measurement temperature: 120℃ Window function: exponential (BF: 1.0 Hz) Chemical shift standard: orthodichlorobenzene (7.1 ppm)

[0154] Here, the signals derived from double bonds observed are those of the vinyl double bond, vinylidene double bond, di-substituted olefin double bond, and tri-substituted olefin double bond shown below. The amount of double bonds was quantified from the integrated intensity of each signal. The main chain methylene signal of ethylene-α-olefin copolymer was used as the chemical shift reference (1.2 ppm).

[0155] [ka] [In each formula, * represents a bond to an atom other than a hydrogen atom.]

[0156] The peaks of the hydrogen atoms a to e are observed near the following positions. Hydrogen atom a peak: 4.60 ppm Hydrogen atom b peak: 4.85 ppm Hydrogen atom c peak: 5.10 ppm Hydrogen atom d peak: 5.25 ppm Hydrogen atom e peak: 5.70 ppm

[0157] The quantitative formula for the amount of double bonds is as follows: Amount of vinyl double bonds = {(integrated intensity of signal b) + (integrated intensity of signal e)} / 3 Amount of vinylidene double bonds = (integrated intensity of signal a) / 2 Amount of disubstituted olefinic double bonds = (integral intensity of signal d) / 2 Amount of trisubstituted olefinic double bonds = (integrated intensity of signal c) From these results, the amount of double bonds of each type (vinyl type, vinylidene type, di-substituted olefin type, tri-substituted olefin type) per 1000 carbon atoms (1000C) of ethylene-α-olefin copolymer was calculated.

[0158] [Identification of transition metal compounds] The structure of the transition metal compound (metallocene compound) obtained in the synthesis example is 270MHz 1 The determination was performed using H-NMR (JEOL Ltd., GSH-270) and FD-MS (JEOL Ltd., JMS-T100GC).

[0159] [Synthesis Example 1] A compound represented by the following formula (A1): [bis(4-methoxyphenyl)methylene(η 5 -cyclopentadienyl)(η 5 Synthesis of -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride (bridged metallocene compound (A1))

[0160] [ka]

[0161] (1) Synthesis of bis(4-methoxyphenyl)(cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)methane Under a nitrogen atmosphere, a 100 mL three-neck flask was charged with 30 mL of dehydrated cyclopentyl methyl ether and 2.29 g (11.1 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b']-dithiophene. To this solution, 7.16 mL (11.1 mmol) of a 1.55 M n-butyllithium hexane solution was added dropwise over 5 minutes in an ice-water bath, followed by stirring at room temperature for 1 hour. Then, 2.90 g (10.0 mmol) of 6,6-bis(4-methylphenyl)fulvene was added and stirred at room temperature for 15 hours. Saturated aqueous ammonium chloride was added to the resulting reaction solution, the organic layer was separated, and the aqueous layer was extracted with 300 mL of methylene chloride. The extract was then combined with the organic layer and washed with water and saturated aqueous sodium chloride, respectively. The mixture was then dried over magnesium sulfate, and the solvent was evaporated. The obtained solid was washed with diethyl ether to obtain bis(4-methoxyphenyl)(cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)methane as a white powder. The yield was 1.94 g, and the yield was 63%. Bis(4-methoxyphenyl)(cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)methane was identified by FD-MS spectroscopy. The measured values ​​are shown below. FD-MS spectrum: M / z 497 (M + )

[0162] (2) Synthesis of bridged metallocene compound (A1) Under a nitrogen atmosphere, a 100 mL Schlenk tube was charged with 0.497 g (1.00 mmol) of bis(4-methoxyphenyl)(cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)methane, 144 mg (2.00 mmol) of dehydrated tetrahydrofuran, and 30 mL of dehydrated toluene. After cooling the Schlenk tube in a dry ice / acetone bath, 1.29 mL (2.0 mmol) of a 1.55 M n-butyllithium hexane solution was added dropwise over 10 minutes. The mixture was then warmed to room temperature and stirred for 4 hours. After cooling in a dry ice / acetone bath, 0.233 g (1.00 mmol) of zirconium tetrachloride was added and reacted at room temperature for 17 hours. After distilling off the solvent, approximately 15 mL of dehydrated dichloromethane was added to extract the soluble matter. The resulting solution was concentrated, and 5 mL of dehydrated diethyl ether and 2 mL of dehydrated hexane were added thereto. The precipitated solid was collected by filtration to obtain a bridged metallocene compound (A1) as an orange powder. The yield was 0.350 g, and the yield was 53%. The bridged metallocene compound (A1) can be identified by 1 The results were obtained by H-NMR spectroscopy and FD-MS spectroscopy. 1H-NMR spectrum (270MHz, C6D6): δ / ppm 7.46 (d, J=8.9Hz, 4H), 6.81 (d, J=8.9Hz, 4H), 6.72 (d, J=1.3Hz, 2H), 6.41 (d, J=2.6Hz, 2H), 5.89(d, J=2.6Hz, 2H), 3.28(s, 6H), 2.19(d, J=1.3Hz, 6H) FD-MS spectrum: M / z 656 (M + )

[0163] [Comparative Synthesis Example 1] Synthesis of ethylene(cyclopentadienyl)(1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenz[b,h]-fluorenyl)zirconium dichloride (bridged metallocene compound (a1)) represented by the following formula (a1):

[0164] [ka]

[0165] A bridged metallocene compound (a1) was synthesized by the method described in JP-A-2004-175707.

[0166] [Example 1] A 2-L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 490 mL of hexane and 610 mL of 1-butene. The system temperature was raised to 115°C, and ethylene was introduced to adjust the total pressure to 3.0 MPa-G. Next, 0.2 mmol of triisobutylaluminum (TIBAL) was introduced into the autoclave using nitrogen. A premixed catalyst consisting of 0.0002 mmol of bridged metallocene compound (A1) and 0.1 mmol (Al atom equivalent) of MMAO (Tosoh Finechem Corporation) mixed for 15 minutes at room temperature was introduced using nitrogen. The agitator speed was increased to 250 rpm to initiate polymerization. Subsequently, ethylene alone was continuously introduced to maintain the total pressure at 3.0 MPa-G, and polymerization was carried out for 9 minutes at 115°C. The polymerization was then terminated by adding a small amount of methanol to the system, after which unreacted ethylene and 1-butene were purged. The resulting polymer solution was poured into a large excess of a methanol / acetone mixture to precipitate the polymer. The precipitated polymer was recovered by filtration and dried overnight under reduced pressure at 120°C. The ethylene content was 82 mol% and the density was 867 kg / m 3 ,I2:2.74g / 10min,I 10 :26g / 10min, I 10 The obtained 14.35 g of ethylene-1-butene copolymer had a molecular weight distribution (Mw / Mn) of 9.5, Mw of 160,000, Mn of 61,700, a molecular weight distribution (Mw / Mn) of 2.59, and a double bond content of 1.0 / 1000C (vinyl double bonds: 0.1 / 1000C, vinylidene double bonds: 0.2 / 1000C, di-substituted olefin double bonds: 0.3 / 1000C, tri-substituted olefin double bonds: 0.4 / 1000C). The polymerization activity was 480 kg / mmol-Zr h.

[0167] [Example 2] Polymerization was carried out in the same manner as in Example 1, except that the operation of charging 490 mL of hexane and 610 mL of 1-butene in Example 1 was changed to the operation of charging 540 mL of hexane, 560 mL of 1-butene, and 500 mL of hydrogen. The polymerization results are shown in Table 1.

[0168] [Example 3] A 2-L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 900 mL of hexane and 200 mL of propylene. The system temperature was raised to 115°C, and ethylene was introduced to adjust the total pressure to 3.0 MPa-G. Next, 0.2 mmol of triisobutylaluminum (TIBAL) was introduced into the autoclave using nitrogen. A premixed catalyst consisting of 0.0004 mmol of bridged metallocene compound (A1) and 0.2 mmol (Al atom equivalent) of MMAO (Tosoh Finechem Corporation) mixed for 15 minutes at room temperature was introduced using nitrogen. The agitation speed was increased to 250 rpm to initiate polymerization. Subsequently, ethylene alone was continuously introduced to maintain the total pressure at 3.0 MPa-G, and polymerization was carried out for 9 minutes at 115°C. The polymerization was then terminated by adding a small amount of methanol to the system, after which unreacted ethylene and propylene were purged. The resulting polymer solution was poured into a large excess of a methanol / acetone mixture to precipitate the polymer. The precipitated polymer was recovered by filtration and dried overnight under reduced pressure at 120°C. The ethylene content was 82 mol% and the density was 879 kg / m 3 ,I2:8.7g / 10min,I 10 :73g / 10min, I 10 The polymerization yield was 22.8 g of ethylene-propylene copolymer with a polymerization activity of 380 kg / mmol-Zr·h. The copolymer had a molecular weight distribution (Mw / Mn) of 2.71, a molecular weight of 117,000, a molecular weight of 43,100, and a double bond content of 0.8 to less than 0.9 per 1000 carbon atoms (vinyl double bonds: 0.1 per 1000 carbon atoms, vinylidene double bonds: 0.5 per 1000 carbon atoms, di-substituted olefin double bonds: less than 0.1 per 1000 carbon atoms, and tri-substituted olefin double bonds: 0.2 per 1000 carbon atoms).

[0169] [Example 4] Polymerization was carried out in the same manner as in Example 3, except that the operation of charging 900 mL of hexane, 200 mL of propylene, 0.0004 mmol of the bridged metallocene compound (A1), and 0.2 mmol of MMAO was changed to the operation of charging 850 mL of hexane, 250 mL of propylene, 0.0003 mmol of the bridged metallocene compound (A1), and 0.15 mmol of MMAO. The polymerization results are shown in Table 2.

[0170] [Comparative Example 1] A 2-L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 390 mL of hexane, 710 mL of 1-butene, and 500 mL of hydrogen. The system temperature was raised to 115 °C, and ethylene was introduced to adjust the total pressure to 3.0 MPa-G. Next, 0.2 mmol of TIBAL was introduced into the autoclave under pressure using nitrogen. A premixed catalyst consisting of 0.00015 mmol of bridged metallocene compound (a1) and 0.075 mmol (Al atom equivalent) of MMAO (Tosoh Finechem Corporation) was introduced under pressure using nitrogen. Polymerization was initiated by increasing the agitation speed to 250 rpm. Subsequently, ethylene alone was continuously introduced to maintain the total pressure at 3.0 MPa-G, and polymerization was carried out for 9 minutes at 115 °C. The polymerization was terminated by adding a small amount of methanol to the system, and unreacted ethylene, 1-butene, and hydrogen were purged. The polymer solution was poured into a large excess of a methanol / acetone mixed solution to precipitate the polymer. The polymer was recovered by filtration and dried overnight under reduced pressure at 120°C. The ethylene content was 85 mol% and the density was 873 kg / m 3 ,I2:5.0g / 10min,I 10 :34g / 10min, I 10The obtained 16.28 g of ethylene-1-butene copolymer had a polymerization activity of 727 kg / mmol-Zr·h. The polymerization activity was 727 kg / mmol-Zr·h. The polymerization yield was 16.28 g. The polymerization yield was 16.28 g of ethylene-1-butene copolymer with a molecular weight of 6.8, Mw of 140,000, Mn of 65,600, molecular weight distribution (Mw / Mn) of 2.13, and double bond content of 0.6 to less than 0.7 per 1000 carbon atoms (vinyl double bonds: 0.1 per 1000 carbon atoms, vinylidene double bonds: less than 0.1 per 1000 carbon atoms, di-substituted olefin double bonds: 0.2 per 1000 carbon atoms, tri-substituted olefin double bonds: 0.3 per 1000 carbon atoms).

[0171] Comparative Example 2 Polymerization was carried out in the same manner as in Comparative Example 1, except that the amount of hydrogen used was changed to 650 mL. The polymerization results are shown in Table 1.

[0172] Comparative Example 3 A 2-L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 850 mL of hexane, 250 mL of propylene, and 500 mL of hydrogen. The system temperature was raised to 115°C, and then ethylene was introduced to adjust the total pressure to 3.0 MPa-G. Next, 0.2 mmol of TIBAL was introduced into the autoclave using nitrogen. A premixed catalyst consisting of 0.0003 mmol of bridged metallocene compound (a1) and 0.15 mmol (Al atom equivalent) of MMAO (Tosoh Finechem Corporation) mixed for 15 minutes at room temperature was introduced using nitrogen. The agitation speed was increased to 250 rpm to initiate polymerization. Subsequently, ethylene alone was continuously introduced, maintaining the total pressure at 3.0 MPa-G. Polymerization was continued for 9 minutes at 115°C. The polymerization was terminated by adding a small amount of methanol to the system, and unreacted ethylene, propylene, and hydrogen were purged. The resulting polymer solution was poured into a large excess of a methanol / acetone mixture to precipitate the polymer. The polymer was recovered by filtration and dried overnight under reduced pressure at 120°C, and had an ethylene content of 79 mol% and a density of 868 kg / m 3 ,I2:5.0g / 10min,I 10 :32g / 10min, I 10The yield was 9.96 g of ethylene-propylene copolymer with a molecular weight of 6.4, Mw of 149,000, Mn of 67,200, molecular weight distribution (Mw / Mn) of 2.22, and double bond content of 0.3 per 1000 carbon atoms (vinyl double bonds: 0.1 per 1000 carbon atoms, vinylidene double bonds: 0.1 per 1000 carbon atoms, di-substituted olefin double bonds: 0 per 1000 carbon atoms (not detected), tri-substituted olefin double bonds: 0.1 per 1000 carbon atoms). The polymerization activity was 220 kg / mmol-Zr h.

[0173] Comparative Example 4 Polymerization was carried out in the same manner as in Comparative Example 3, except that the amount of hydrogen used was changed to 700 mL. The polymerization results are shown in Table 2.

[0174] [Table 1]

[0175] [Table 2]

Claims

1. a bridged metallocene compound (A) represented by the following formula [I]; organometallic compound (B-1), an organoaluminum oxy compound (B-2), and Compound (B-3) that reacts with bridged metallocene compound (A) to form an ion pair At least one compound (B) selected from the group consisting of A method for producing an ethylene / α-olefin copolymer, comprising a step [P] of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing The MFR of the ethylene-α-olefin copolymer measured in accordance with JIS K 7210:1999 under conditions of 190°C and a load of 2160 g is expressed as I ２ (g / 10 min), and the MFR measured in accordance with JIS K 7210:1999 under the conditions of 190°C and a 10 kg load is I １０ (g / 10 min), the following formula (1) is satisfied: I １０ / I ２ +0.869×ln(I ２ ) ≧ 9.0 …(1) 【Chemical 1】 [In formula [I], Y independently represents a carbon atom, a silicon atom, a germanium atom, or a tin atom; M is a titanium atom, a zirconium atom, or a hafnium atom; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ and R ８ each independently represents an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, a substituted aromatic group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and may be the same or different, R １ From R ６ Adjacent substituents up to may be bonded to each other to form a ring, A and B each independently represent a sulfur atom, an oxygen atom, or CR ９ and R ９ represents an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, a substituted aromatic group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group; when A is a sulfur atom or an oxygen atom, B is CR ９ and when B is a sulfur atom or an oxygen atom, A is CR ９ and the ring containing A and B has a double bond at any available position; Q independently represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair; n is an integer from 1 to 4, j is an integer from 1 to 4.

2. a bridged metallocene compound (A) represented by the following formula [I]; organometallic compound (B-1), an organoaluminum oxy compound (B-2), and Compound (B-3) that reacts with bridged metallocene compound (A) to form an ion pair At least one compound (B) selected from the group consisting of A method for producing an ethylene / α-olefin copolymer, comprising a step [P] of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing The MFR of the ethylene-α-olefin copolymer measured in accordance with JIS K 7210:1999 under conditions of 190°C and a load of 2160 g is expressed as I ２ (g / 10 min), and the MFR measured in accordance with JIS K 7210:1999 under the conditions of 190°C and a 10 kg load is I １０ (g / 10 min), I ２ is 2.0 to 100 g / 10 min, and I １０ / I ２ A method for producing an ethylene / α-olefin copolymer, wherein the modulus of elasticity is 7.0 or more. 【Chemistry 2】 [In formula [I], Y independently represents a carbon atom, a silicon atom, a germanium atom, or a tin atom; M is a titanium atom, a zirconium atom, or a hafnium atom; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ and R ８ each independently represents an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, a substituted aromatic group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and may be the same or different, R １ From R ６ Adjacent substituents up to may be bonded to each other to form a ring, A and B each independently represent a sulfur atom, an oxygen atom, or CR ９ and R ９ represents an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, a substituted aromatic group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group; when A is a sulfur atom or an oxygen atom, B is CR ９ and when B is a sulfur atom or an oxygen atom, A is CR ９ and the ring containing A and B has a double bond at any available position; Q independently represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair; n is an integer from 1 to 4, j is an integer from 1 to 4.

3. The ethylene-α-olefin copolymer I ２ The method for producing an ethylene / α-olefin copolymer according to claim 1, wherein the elongation coefficient is 2.0 g / 10 min or more.

4. The ethylene-α-olefin copolymer I １０ The method for producing an ethylene / α-olefin copolymer according to claim 1 or 2, wherein the elongation coefficient is 20 g / 10 min or more.

5. 3. The method for producing an ethylene / α-olefin copolymer according to claim 1, wherein the ethylene / α-olefin copolymer has a double bond content of 0.7 / 1000C or more.

6. 3. The method for producing an ethylene / α-olefin copolymer according to claim 1 or 2, wherein the ethylene / α-olefin copolymer has a molecular weight distribution (Mw / Mn) of 2.2 or more, which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) as measured by gel permeation chromatography (GPC).

7. The method for producing an ethylene / α-olefin copolymer according to claim 1 or 2, wherein n in formula [I] is 1.

8. R in the formula [I] １ , R ２ , R ３ and R ４ The method for producing an ethylene / α-olefin copolymer according to claim 7, wherein all of are hydrogen atoms.

9. The method for producing an ethylene / α-olefin copolymer according to claim 8, wherein Y in the formula [I] is a carbon atom or a silicon atom.

10. 10. The method for producing an ethylene / α-olefin copolymer according to claim 9, wherein A or B in the formula [I] is a sulfur atom, and the other is CH.

11. R in the formula [I] ５ and R ６ The method for producing an ethylene / α-olefin copolymer according to claim 10, wherein is a group selected from the group consisting of aromatic groups and substituted aromatic groups.

12. R in the formula [I] ５ and R ６ is a substituted aromatic group in which one or more hydrogen atoms of the aromatic group are substituted with an electron-donating substituent having a Hammett's rule substituent constant σ of −0.2 or less, and when the aromatic group has a plurality of electron-donating substituents, the respective electron-donating substituents may be the same or different and may have a substituent other than the electron-donating substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and when the aromatic group has a plurality of substituents, the respective substituents may be the same or different.

13. R in the formula [I] ５ and R ６ The method for producing an ethylene / α-olefin copolymer according to claim 12, wherein the electron-donating substituent is a substituted aromatic group containing an oxygen-containing group.

14. 3. The method for producing an ethylene / α-olefin copolymer according to claim 1, wherein M in the formula [I] is a zirconium atom or a hafnium atom.

15. The method for producing an ethylene / α-olefin copolymer according to claim 1 or 2, wherein the α-olefin is an α-olefin having 3 to 10 carbon atoms.

16. 3. The method for producing an ethylene / α-olefin copolymer according to claim 1, wherein the α-olefin is propylene or 1-butene.

17. The method for producing an ethylene / α-olefin copolymer according to claim 1 or 2, wherein the copolymerization temperature in the step [P] is 100 to 130°C.

18. The method for producing an ethylene / α-olefin copolymer according to claim 1 or 2, wherein the step [P] is a step of copolymerizing the ethylene / α-olefin copolymer so that the proportion of structural units derived from ethylene in the ethylene / α-olefin copolymer is 70 mol % or more based on all structural units.

Images