Transition metal compounds, catalysts for olefin polymerization, and methods for producing olefin copolymers

Abstract

This invention provides transition metal compounds that can be produced with high productivity under high-temperature conditions. [Solution] A transition metal compound (A) represented by the following general formula [I]. JPEG2026091635000017.jpg71160 (In the formula, R 1 (It is an adamantyl group derivative.)

Description

[Technical Field]

[0001] The present invention relates to transition metal compounds, catalysts for olefin polymerization, and methods for producing olefin copolymers. [Background technology]

[0002] In recent years, metallocene compounds have become well known as homogeneous catalysts for olefin polymerization. Regarding methods for polymerizing olefins using metallocene compounds (particularly methods for polymerizing α-olefins), since the isotactic polymerization was reported by W. Kaminsky et al., many improvement studies have been conducted from the perspective of further improving stereoregularity and polymerization activity (Non-Patent Literature 1).

[0003] In the polymerization of α-olefins using metallocene compounds, it is known that introducing substituents to the cyclopentadienyl ring of the metallocene compound ligand or crosslinking two cyclopentadienyl rings can significantly alter the stereoregularity and molecular weight of the resulting olefin (co)polymer.

[0004] For example, when a metallocene compound having a ligand in which a cyclopentadienyl ring and a fluorenyl ring are crosslinked is used as a polymerization catalyst for propylene, from the viewpoint of stereoregularity of the polymer, syndiotactic polypropylene is obtained from dimethylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride (Non-Patent Literature 2), hemiisotactic polypropylene is obtained from dimethylmethylene(3-methylcyclopentadienyl)(fluorenyl)zirconium dichloride, in which a methyl group is introduced at the 3-position of the cyclopentadienyl ring (Patent Literature 1), and similarly, isotactic polypropylene is obtained from dimethylmethylene(3-tert-butylcyclopentadienyl)(fluorenyl)zirconium dichloride, in which a tert-butyl group is introduced (Patent Literature 2).

[0005] In recent years, in order to enable the industrial production of these olefin(co)polymers, there has been a demand for the ability to produce olefin(co)polymers with desired physical properties (e.g., melting point, molecular weight, molecular weight distribution, monomer composition) at temperatures above room temperature, preferably above room temperature. For example, by having specific substituents on the cyclopentadienyl ring and / or fluorenyl ring of a metallocene compound, catalysts for olefin polymerization containing the metallocene compound have been disclosed to produce olefin (co)polymers with characteristics such as high molecular weight and high melting point, even under high-temperature conditions advantageous in industrial production methods (Patent Documents 3-5). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 3-193796 [Patent Document 2] Japanese Patent Application Publication No. 6-122718 [Patent Document 3] International Publication No. 2014 / 142111 [Patent Document 4] Japanese Patent Publication No. 2016-164264 [Patent Document 5] International Publication No. 2019 / 188644 [Non-patent literature]

[0007] [Non-Patent Document 1] Angew. Chem. Int. Ed. Engl., 24, 507 (1985) [Non-Patent Document 2] J. Am. Chem. Soc.,110,6255 (1988) [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] However, the development of a polymerization catalyst that can produce an olefin copolymer having a desired monomer composition with high polymerization activity is not yet sufficient. Therefore, a manufacturing method and an olefin polymerization catalyst that can obtain a copolymer having a desired monomer composition with high productivity have been strongly desired.

[0009] The present invention has been made to solve the above problems, and an object thereof is to produce an olefin copolymer having a desired monomer composition with high productivity even under high-temperature conditions advantageous in an industrial production method. It is to provide a transition metal compound, an olefin polymerization catalyst, and a method for producing the olefin copolymer.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that it can be solved by a transition metal compound having a specific substituent, and completed the present invention. The gist of the present invention is as follows.

[0011] [1] A transition metal compound (A) represented by the following general formula [I].

[0012]

Chemical formula

[0013] [2] The transition metal compound (A) described in [1], wherein Z is an oxygen atom in the general formula [I]. [3] In the above general formula [I], R 3 and R 6 A transition metal compound (A) according to either [1] or [2], wherein is a hydrogen atom. [4] In the above general formula [I], R 4 and R 5 A transition metal compound (A) described in any of [1] to [3], wherein the atom is a hydrogen atom. [5] In the above general formula [I], R 12 A transition metal compound (A) according to any of [1] to [4], wherein is a hydrocarbon group having 1 to 20 carbon atoms.

[0014] [6] In the above general formula [I], R 8 ~R 11 However, each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 8 ~R 11 The transition metal compound (A) described in any of [1] to [5], wherein adjacent substituents may bond to each other to form a ring. [7] In the above general formula [I], R 10 and R 11 A transition metal compound (A) described in [6], wherein is a hydrogen atom. [8] In the above general formula [I], R 8 and R 9A transition metal compound (A) as described in [6] or [7], wherein is a hydrocarbon group having 1 to 20 carbon atoms. [9] A transition metal compound (A) according to any of [1] to [8], wherein n is 1 in the general formula [I].

[0015]

[10] A transition metal compound (A) described in any of [1] to [9], Organoaluminum oxy compounds (b-1), Compound (b-2) that reacts with transition metal compound (A) to form an ion pair, and Organoaluminum compounds (b-3) At least one compound (B) selected from and A catalyst for olefin polymerization containing [specific component].

[0016] A method for producing an olefin copolymer, comprising the step of copolymerizing a monomer containing 1-butene and at least one olefin selected from α-olefins having 3 to 20 carbon atoms other than 1-butene, in the presence of the olefin polymerization catalyst described in

[10] and under polymerization temperature conditions of 50 to 200°C.

[12] The method for producing an olefin copolymer according to

[11] , wherein at least one olefin selected from α-olefins having 3 to 20 carbon atoms other than 1-butene is propylene.

[13] A method for producing an olefin copolymer according to

[11] or

[12] , wherein the olefin copolymer has a content of 1-butene-derived structural units of 50.0 to 92.0 mol%, and the total content (K) of structural units derived from at least one olefin selected from α-olefins having 3 to 20 carbon atoms other than 1-butene is 8.0 to 50.0 mol% (provided that the sum of the content of 1-butene-derived structural units and the total content (K) is 100 mol%).

[14] A method for producing an olefin copolymer according to

[12] , wherein, in the step of copolymerizing the monomer, hydrogen is supplied to the polymerization reaction system continuously or intermittently to copolymerize in the presence of hydrogen, the amount of hydrogen supplied is 0.00001 to 100 NL per mole of olefin, and the polymerization pressure is a total pressure of 0.1 to 3.0 MPa gauge pressure, and the olefin polymerization activity is 50 to 1,000,000 kg / mmol-M / h (where M is the same as M in the general formula [I] above). [Effects of the Invention]

[0017] According to the present invention, olefin copolymers having a desired monomer composition can be produced with high productivity even under high-temperature conditions that are advantageous in industrial manufacturing processes. [Modes for carrying out the invention]

[0018] In this specification, the "~" symbol indicating a numerical range, for example, "M~N", means "M or greater, and N or less" unless otherwise specified. In this specification, when M is an olefin constituting a copolymer, the expression "structural unit derived from M" is sometimes used. This refers to the "structural unit corresponding to M," that is, a structural unit having a pair of bonding hands that is formed when the π bond constituting the double bond of M opens. The technical scope of the present invention is not limited to the following embodiments.

[0019] ≪Transition metal compound (A)≫ The transition metal compound (A) according to the present invention is represented by the following general formula [I]. By using an olefin polymerization catalyst containing the transition metal compound (A), olefin copolymers can be efficiently produced when polymerizing α-olefins such as propylene or 1-butene. That is, the transition metal compound (A) can be suitably used as a catalyst component for olefin polymerization to produce olefin copolymers (e.g., 1-butene copolymers).

[0020] [ka]

[0021] <R 1 > In the above general formula [I], R 1 It is an adamantyl group derivative. Examples of the adamantyl group derivatives include 1-adamantyl group, 2-adamantyl group, 3,5-dimethyl-1-adamantyl group, or 3,5,7-trimethyl-1-adamantyl group, with 1-adamantyl group, 3,5-dimethyl-1-adamantyl group, or 3,5,7-trimethyl-1-adamantyl group being preferred, and 1-adamantyl group being more preferred.

[0022] R 1 However, because it is an adamantyl group derivative, it is preferable from the viewpoint of efficiently obtaining the resulting olefin copolymer. 1 Due to its three-dimensional bulk, it is thought that counter anions have difficulty approaching the metallocene cation derived from general formula [I], which is presumed to be the active species. Therefore, (1) the coordination space of the metallocene cation expands, making it easier for monomers to approach the metallocene cation, and (2) the Lewis acidity of the metallocene cation improves, increasing its reactivity with olefins, thus improving catalytic activity.

[0023] <R 2 and R 7 > In the above general formula [I], R 2 and R 7 Each of them is independently, ZR 13 This substituent is represented by [formula]. Z is either an oxygen atom or a sulfur atom, with an oxygen atom being preferred. R 13 This is a group that is bonded to the fluorenyl ligand via Z. 13 These are hydrocarbon groups with 1 to 20 carbon atoms. R 2 and R 7These may be the same or different, but from the viewpoint of the ease of manufacturing the transition metal compound (A), R 2 and R 7 However, it is preferable that the substituents are the same.

[0024] Examples of hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms, saturated alicyclic groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10.

[0025] Examples of alkyl groups having 1 to 20 carbon atoms include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decanyl group; and branched alkyl groups such as iso-propyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, and 1-methyl-1-isopropyl-2-methylpropyl group.

[0026] Examples of saturated alicyclic groups having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; and alicyclic polycyclic groups such as norbornyl and adamantyl groups.

[0027] Examples of aryl groups having 6 to 20 carbon atoms include unsubstituted aryl groups such as phenyl, naphthyl, phenanthryl, anthracenyl, and biphenyl groups; and alkylaryl groups such as o-tolyl, m-tolyl, p-tolyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, and xylyl groups.

[0028] Examples of aralkyl groups having 7 to 20 carbon atoms include unsubstituted aralkyl groups such as benzyl group, cumyl group, α-phenethyl group, β-phenethyl group, diphenylmethyl group, naphthylmethyl group, and neophyll group; and alkyl aralkyl groups such as o-methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group, ethylbenzyl group, n-propylbenzyl group, iso-propylbenzyl group, n-butylbenzyl group, sec-butylbenzyl group, and tert-butylbenzyl group.

[0029] R 13 Preferred members include branched alkyl groups, cycloalkyl groups, and alicyclic polycyclic groups; branched alkyl groups and cycloalkyl groups are more preferred; and branched alkyl groups such as iso-propyl groups and tert-butyl groups are even more preferred.

[0030] R 2 and R 7 However, ZR 13 The substituent represented by R is preferable from the viewpoint of improving the melting point, monomer composition, and polymerization activity of the resulting olefin copolymer. 2 and R 7 It is thought that the Z component present in ZR changes the charge state of the central metal M, thereby improving the stereoregularity of the olefin. 13 Due to its three-dimensional bulk, the R 1 Similarly, the reactivity with olefins is increased, which is thought to improve catalytic activity. In addition to the above effect, the electronic effect of oxygen or sulfur atoms improves the coordination and insertion rate of comonomers such as propylene, making it easier to obtain copolymers with the desired comonomer composition.

[0031] <R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 and R 12 > R 3 , R 4 , R 5 , R6 , R 8 , R 9 , R 10 , R 11 and R 12 Each of these is independently selected from the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and each may be the same or different, R 3 ~R 6 and R 8 ~R 12 Adjacent substituents may bond to each other to form a ring.

[0032] The number of carbon atoms in the hydrocarbon group is preferably 1 to 20, and more preferably 1 to 10. Examples of hydrocarbon groups include alkyl groups with 1 to 20 carbon atoms, saturated alicyclic groups with 3 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, and aralkyl groups with 7 to 20 carbon atoms. A specific example is R 13 Examples of hydrocarbon groups with 1 to 20 carbon atoms include those similar to those listed in the examples of hydrocarbon groups with 1 to 20 carbon atoms.

[0033] Examples of silicon-containing groups include alkylsilyl groups such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, and dimethyl-tert-butylsilyl group; and arylsilyl groups such as dimethylphenylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group.

[0034] Examples of nitrogen-containing groups include amino groups, nitro groups, and N-morpholinyl groups, as well as the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms or silicon-containing groups, specifically groups in which the =CH- structural unit is replaced by a nitrogen atom, a -CH2- structural unit is replaced by a nitrogen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, or a -CH3 structural unit is replaced by a nitrogen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms or a nitrile group, such as dimethylaminomethyl groups, cyano groups, pyrrolidinyl groups, piperidinyl groups, and pyridinyl groups.

[0035] Oxygen-containing groups include hydroxyl groups, as well as the aforementioned hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, or nitrogen-containing groups in which the -CH2- structural unit is replaced by an oxygen atom or a carbonyl group, or in which the -CH3 structural unit is replaced by an oxygen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, such as trimethylsiloxy groups, methoxyethoxy groups, hydroxymethyl groups, methoxymethyl groups, ethoxymethyl groups, tert-butoxymethyl groups, 1-hydroxyethyl groups, and 1-methoxyethoxy groups. Examples include 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, methylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl group, carboxyl group, methoxycarbonyl group, carboxymethyl group, ethocarboxymethyl group, carbamoylmethyl group, furanyl group, and pyranyl group.

[0036] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, which are elements of Group 17.

[0037] Examples of halogen-containing hydrocarbon groups include groups in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom. Specifically, halogen-substituted alkyl groups such as fluoroalkyl groups such as trifluoromethyl groups; fluoroaryl groups such as pentafluorophenyl groups; chloroaryl groups such as o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, and chloronaphthyl groups; bromoaryl groups such as o-bromophenyl, m-bromophenyl, p-bromophenyl, and bromonaphthyl groups; halogen substituents of the unsubstituted aryl groups such as o-iodophenyl, m-iodophenyl, p-iodophenyl, and iodoaryl groups such as iodonaphthyl groups; fluoroalkylaryl groups such as trifluoromethylphenyl groups; bromomethylphenyl groups; dibro Examples of halogen-substituted aryl groups include halogen substituents of alkylaryl groups such as bromoalkylaryl groups such as momethylphenyl group and iodoalkylaryl groups such as iodomethylphenyl group and diiodomethylphenyl group; chloroaralkyl groups such as o-chlorobenzyl group, m-chlorobenzyl group, p-chlorobenzyl group, and chlorophenethyl group; bromoalkyl groups such as o-bromobenzyl group, m-bromobenzyl group, p-bromobenzyl group, and bromophenethyl group; and halogen-substituted aralkyl groups such as halogen substituents of unsubstituted aralkyl groups such as o-iodobenzyl group, m-iodobenzyl group, p-iodobenzyl group, and iodophenethyl group.

[0038] In general formula [I], the presence of hydrogen atoms at positions 1 and 8 of the fluorenyl moiety allows for the efficient production of the resulting olefin copolymer.

[0039] R 2 and R 7 As described above, each is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably an ethyl group, an iso-propyl group, or a tert-butyl group, and even more preferably an iso-propyl group. 2 and R 7Since it is the said group, it is preferable from the viewpoint of easily obtaining an olefin copolymer having a high melting point.

[0040] R 3 and R 6 are preferably hydrogen atoms. Since R 3 and R 6 are hydrogen atoms, it is preferable from the viewpoints of efficiently obtaining the produced olefin copolymer and the melt fluidity of the produced olefin copolymer.

[0041] R 4 and R 5 are each independently preferably a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, more preferably a hydrogen atom, a methyl group, an ethyl group, a chlorine atom, a bromine atom or a fluorine atom, and even more preferably a hydrogen atom. Since R 4 and R 5 are the said groups, it is preferable from the viewpoint of efficiently obtaining the produced olefin copolymer.

[0042] R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, even more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a phenyl group, and particularly preferably a methyl group. Since R 12 is the said group, it is preferable from the viewpoint of efficiently obtaining the produced olefin copolymer. 3]

[0043] R 8 , R 9 , R 10 and R 11 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a cyclohexyl group, and even more preferably a hydrogen atom, a methyl group, or an isopropyl group. In general formula [I], R 8 and R 9Each of these is preferably an independent hydrocarbon group having 1 to 20 carbon atoms. 10 and R 11 It is preferable that it is a hydrogen atom.

[0044] Also, R 8 ~R 11 Adjacent substituents may bond to each other to form a ring, and in another preferred embodiment of the present invention, R 9 and R 10 Groups that bond to each other and form cyclopentane rings, or R 9 and R 10 Preferably, the groups are bonded to each other and form a cyclohexane ring, R 9 and R 10 It is more preferable that the groups bond to each other and form a cyclohexane ring.

[0045] Here, in a preferred embodiment of the present invention, R 8 and R 9 R is a hydrocarbon group, and more preferably a hydrocarbon group having 1 to 20 carbon atoms. Also, in one preferred embodiment of the present invention, 10 and R 11 It is a hydrogen atom.

[0046] <n, M, Q, and j> n is an integer from 1 to 3, preferably 1 or 2, and more preferably 1. The above values ​​for n are preferable from the viewpoint of efficiently obtaining the resulting olefin copolymer.

[0047] M is a group 4 transition metal, i.e., a titanium atom, a zirconium atom, or a hafnium atom, preferably a zirconium atom or a hafnium atom, more preferably a zirconium atom.

[0048] Q is independently a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can coordinate with a lone pair of electrons. If j is an integer greater than or equal to 2, multiple Qs may be the same or different.

[0049] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, which are elements of Group 17.

[0050] In Q, alkyl groups having 1 to 10 carbon atoms and cycloalkyl groups having 3 to 10 carbon atoms are preferred as hydrocarbon groups. More preferably, the hydrocarbon group has 5 carbon atoms or less.

[0051] Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1,1,3-trimethylbutyl group, and neopentyl group.

[0052] Examples of cycloalkyl groups having 3 to 10 carbon atoms include cyclohexylmethyl, cyclohexyl, and 1-methyl-1-cyclohexyl groups.

[0053] Examples of anionic ligands include alkoxy groups such as methoxy groups and tert-butoxy groups; aryloxy groups such as phenoxy groups; carboxylate groups such as acetate groups and benzoate groups; and sulfonate groups such as mesylate groups and tosylate groups.

[0054] Examples of neutral ligands that can coordinate with a lone pair of electrons include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ethers such as tetrahydrofuran (THF), diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0055] Q is preferably a halogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a halogen atom or an alkyl group having 1 to 5 carbon atoms. If Q is a halogen atom, it is preferably a chlorine atom.

[0056] j is an integer between 1 and 4, preferably 2.

[0057] <Examples of transition metal compounds (A)> Specific examples of transition metal compounds (A) are shown, but this does not particularly limit the scope of the present invention.

[0058] For the sake of explanation, the MQ of metallocene compounds j If we divide the ligand structure, excluding the (metal portion), into two parts—the cyclopentadienyl derivative portion and the fluorenyl portion—and represent the fluorenyl portion as "Flu," then the cyclopentadienyl derivative portion will have the following structures: (i) (n=1), (ii) (n=2), and (iii) (n=3).

[0059] [ka]

[0060] The structure formed by the bonding of two substituents is as follows: (i-1)(R 11 and R 12 (These two elements bond to each other to form a cyclopentane ring), structure (i-2)(R 11 and R 12 An example is when two elements bond to each other to form a cyclohexane ring.

[0061] [ka]

[0062] MQ of metallocene compounds j The ligand structure with the (metal part) removed is R 1 The compound is divided into three parts: the adamantyl group derivative (α), the cyclopentadienyl derivative (β), and the fluorenyl part (γ). Specific examples of each substructure are shown in Tables 1-3. Note that in Table 2, "Adm" is R 1In Table 3, "Cp" represents the adamantyl group derivative portion, "Flu" represents the fluorenyl portion, and "Cp" represents the cyclopentadienyl derivative portion.

[0063] [Table 1]

[0064] [Table 2]

[0065] [Table 3]

[0066] According to the table above, the ligand structure consists of a combination of α1, β5, and γ1, and the metallic part is MQ j In the case of ZrCl2, the following metallocene compound is given as an example.

[0067] [ka]

[0068] MQ j Specific examples include ZrCl2, ZrBr2, ZrMe2, Zr(OTs)2, Zr(OMs)2, Zr(OTf)2, TiCl2, TiBr2, TiMe2, Ti(OTs)2, Ti(OMs)2, Ti(OTf)2, HfCl2, HfBr2, HfMe2, Hf(OTs)2, Hf(OMs)2, Hf(OTf)2, etc. Ts represents a p-toluenesulfonyl group, Ms represents a methanesulfonyl group, and Tf represents a trifluoromethanesulfonyl group.

[0069] The aforementioned MQ j Compounds obtained by replacing "zirconium" in the example compounds with "hafnium" or "titanium," and metallocene compounds obtained by replacing "dichloride" with "dimethyl" or "methyl ethyl," are also included in transition metal compounds (A).

[0070] ≪Catalyst for olefin polymerization≫ The catalyst for olefin polymerization according to the present invention (hereinafter also referred to as "this olefin polymerization catalyst") contains a transition metal compound (A) and a compound (B) described later. The transition metal compound (A) used in this olefin polymerization catalyst may be one or more, and the compound (B) used in the olefin polymerization catalyst may be one or more.

[0071] <Compound (B)> Compound (B) is at least one compound selected from organoaluminum oxy compounds (b-1), compounds (b-2) that react with transition metal compounds (A) to form ion pairs, and organoaluminum compounds (b-3). Among these, organoaluminum oxy compound (b-1) is preferred from the viewpoint of efficiently obtaining the resulting olefin copolymer.

[0072] <Organoaluminum oxy compounds (b-1)> Examples of organoaluminum oxy compounds (b-1) include conventionally known aluminoxanes such as compounds represented by the following general formula [B1] and compounds represented by the general formula [B2], modified methylaluminoxanes having the structure represented by the following general formula [B3], and boron-containing organoaluminum oxy compounds represented by the following general formula [B4]. The organoaluminum oxy compound (b-1) may be used alone or in combination of two or more types.

[0073] [ka]

[0074] In formulas [B1] and [B2], R is a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group, and n is an integer of 2 or more, preferably 3 or more, and more preferably 10 or more.

[0075] [ka]

[0076] In formula [B3], R is a hydrocarbon group having 2 to 10 carbon atoms, and m and n are each independent integers greater than or equal to 2. Multiple R groups may be identical or different from one another.

[0077] Modified methyl aluminoxanes having the structure represented by formula [B3] can be prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Modified methyl aluminoxanes having the structure represented by formula [B3] are generally called MMAO (modified methyl aluminoxane). Specifically, MMAO can be prepared by the methods described in U.S. Patent No. 4,960,878 and U.S. Patent No. 5,041,584.

[0078] Furthermore, Tosoh Finechem Co., Ltd. and others also commercially produce methylaluminoxanes modified using trimethylaluminum and triisobutylaluminum (i.e., R in formula [B3] is an isobutyl group) under the names MMAO and TMAO.

[0079] MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, unlike compounds that are insoluble or poorly soluble in benzene, such as those represented by general formulas [B1] or [B2], MMAO is soluble in aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0080] [ka]

[0081] In formula [B4], R c R is a hydrocarbon group with 1 to 10 carbon atoms. There are multiple R groups. d Each of these is independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0082] Furthermore, benzene-insoluble or sparingly soluble organoaluminum oxy compounds, such as those exemplified in Japanese Patent Publication No. 2-78687, organoaluminum oxy compounds described in Japanese Patent Publication No. 2-167305, and aluminoxanes having two or more alkyl groups, as described in Japanese Patent Publication No. 2-24701 and Japanese Patent Publication No. 3-103407, can also be suitably used.

[0083] Furthermore, the aforementioned "benzene-insoluble or sparingly soluble" organoaluminum oxy compounds refer to organoaluminum oxy compounds that are insoluble or sparingly soluble in benzene, such that the amount of the compound that dissolves in benzene at 60°C is usually 10% by mass or less, preferably 5% by mass or less, and particularly preferably 2% by mass or less, in terms of Al atoms.

[0084] <Compounds (b-2) that react with transition metal compounds (A) to form ion pairs> Examples of compounds (b-2) that react with transition metal compounds (A) to form ion pairs (hereinafter also referred to as "ionic compounds (b-2)") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Publication No. 3-179005, Japanese Patent Publication No. 3-179006, Japanese Patent Publication No. 3-207703, Japanese Patent Publication No. 3-207704, Japanese Patent Publication No. 2004-51676, and U.S. Patent No. 5321106, etc. Furthermore, heteropoly compounds and isopoly compounds are also examples. The ionic compound (b-2) may be used alone or in combination of two or more types.

[0085] As the ionic compound (b-2), a compound represented by the following general formula [B5] is preferred.

[0086] [ka]

[0087] In formula [B5], R e+ H+ Examples include oxonium cations, carbenium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, and ferrocenium cations having transition metals. f , R g , R h and R i Each of these independently represents an organic group, preferably an aryl group, or a halogen-substituted aryl group.

[0088] Examples of carbenium cations include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation, and tris(dimethylphenyl)carbenium cation.

[0089] 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.

[0090] Examples of phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation, and tris(dimethylphenyl)phosphonium cation.

[0091] R e+ Preferred cations include carbenium cations and ammonium cations, with triphenylcarbenium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations being particularly preferred.

[0092] Re+ Examples of compounds represented by formula [B5] when is a carbenium cation salt include triphenylcarbenium tetraphenyl borate, 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.

[0093] R e+ Examples of ammonium salts where the ammonium cation is trialkylammonium salts, N,N-dialkylanilinium salts, and dialkylammonium salts are examples of ammonium salts.

[0094] The compounds represented by formula [B5] when they are trialkylammonium salts include, specifically, triethylammonium tetraphenyl borate, tripropylammonium tetraphenyl borate, tri(n-butyl)ammonium tetraphenyl borate, 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 Examples include (n-butyl)ammonium tetrakis(3,5-ditrifluoromethylphenyl) borate, tri(n-butyl)ammonium tetrakis(o-tolyl) borate, dioctadecylmethylammonium tetraphenyl borate, 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.

[0095] Examples of the compound represented by the formula [B5] in the case of an N,N-dialkylanilinium salt include specifically 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.

[0096] Examples of the compound represented by the formula [B5] in the case of a dialkylammonium salt include specifically diisopropylammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

[0097] (Organic aluminum compound (b-3)) Examples of the organic aluminum compound (b-3) include an organic aluminum compound represented by the following general formula [B6] and a complex alkylated product of a Group 1 metal of the periodic table and aluminum represented by the following general formula [B7]. The organic aluminum compound (b-3) may be used alone or in combination of two or more.

[0098] R a m Al(OR b ) n H p X q …[B6] In the formula [B6], R a and R b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is independently a halogen atom, m is 0 < m ≦ 3, n is 0 ≦ n < 3, p is 0 ≦ p < 3, q is 0 ≦ q < 3, and m + n + p + q = 3.

[0099] M 2 AlR a 4…[B7] In formula [B7], M 2 R is Li, Na or K, and there are multiple R a These are independently hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

[0100] Organoaluminum compounds represented by general formula [B6] include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, and trioctylaluminum; tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride; and general formula (i-C4H9) x Al y (C5H 10 ) z Alkenyl aluminum such as isoprenyl aluminum (wherein x, y, and z are positive numbers and z ≤ 2x); alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; general formula R a 2.5 Al(OR b ) 0.5 (In the formula, R a and R bR in the above formula [B6] is a and R b Examples include partially alkoxylated alkylaluminum having an average composition represented by ); alkylaluminum allyloxides such as diethylaluminum phenoxide and diethylaluminum (2,6-ditert-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; partially halogenated alkylaluminum such as alkylaluminum dihalides such as ethylaluminum dichloride; partially hydrogenated alkylaluminum such as dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, and alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; and partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

[0101] Examples of complex alkylates of Group 1 metals of the periodic table represented by general formula [B7] and aluminum include LiAl(C2H5)4 and LiAl(C7H 15 )4 is given as an example. Compounds similar to the aforementioned complex alkylates can also be used, and examples include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. An example of such a compound is (C2H5)2AlN(C2H5)Al(C2H5)2.

[0102] As for the organoaluminum compound (b-3), trimethylaluminum and triisobutylaluminum are preferred due to their availability.

[0103] <Carrier (C)> This olefin polymerization catalyst may further contain a support (C) as needed. Examples of the support (C) include inorganic or organic compounds, which may be in the form of granular or particulate solids. The carrier (C) may be used alone or in combination of two or more types.

[0104] (Inorganic compound) Examples of inorganic compounds include porous oxides, inorganic halides, clay minerals, clay (usually composed mainly of these clay minerals), and ion-exchangeable layered compounds (most clay minerals are ion-exchangeable layered compounds). Examples of porous oxides include SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, and ThO2; and composites or mixtures containing these oxides. Examples of composites or mixtures include natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, and SiO2-TiO2-MgO. Among these, porous oxides with either or both of SiO2 and Al2O3 as the main components are particularly noteworthy. It is preferable.

[0105] Porous oxides vary in properties depending on the type and manufacturing method, but their particle size is preferably in the range of 10 to 300 μm, more preferably 20 to 200 μm; and their specific surface area is preferably 50 to 1000 m². 2 / g, more comfortably 100-700m 2 It is in the range of / g; the pore volume is preferably 0.3-3.0 cm³. 3 It is in the range of / g. Such porous oxides are used after being calcined at 100-1000°C, preferably 150-700°C, as needed.

[0106] Examples of inorganic halides include MgCl2, MgBr2, MnCl2, and MnBr2. These inorganic halides may be used as is, or they may be used after being ground using a ball mill or vibration mill. Alternatively, the inorganic halides may be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

[0107] As for clay, clay minerals, and ion-exchangeable layered compounds, not only naturally occurring materials but also artificially synthesized materials can be used. Ion-exchangeable layered compounds are compounds that have a crystalline structure in which planes formed by ionic bonds are stacked parallel to each other with weak bonding forces, and are compounds in which the contained ions can be exchanged.

[0108] Specifically, examples of clays and clay minerals include kaolin, bentonite, kibushi clay, gylome clay, allophane, hisingerite, pyrophyllite, synthetic mica (unmo group), montmorillonite group, vermiculite, lyokdiite group, palygorskite, kaolinite, nacrite, dickite, hectorite, teniolite, and halloysite; examples of ion-exchangeable layered compounds include ionic crystalline compounds having layered crystal structures such as hexagonal close-packed type, antimony type, CdCl2 type, and CdI2 type. Specifically, examples of ion-exchangeable layered compounds include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O.

[0109] It is also preferable to subject clay and clay minerals to chemical treatment. Chemical treatments can include surface treatments to remove impurities adhering to the surface, and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment.

[0110] Furthermore, ion-exchangeable layered compounds can be modified by utilizing their ion-exchange properties to exchange the exchangeable ions between layers with other large, bulky ions, thereby creating layered compounds with expanded interlayers. These bulky ions play a supporting role in the layered structure and are usually called pillars. For example, oxide pillars can be formed between layers of a layered compound by intercalating the following metal hydroxide ions and then heating and dehydrating the compound. The process of introducing another substance between layers of a layered compound in this way is called intercalation.

[0111] Interpolated guest compounds include cationic inorganic compounds such as TiCl4 and ZrCl4; metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.); [Al 13 O4(OH) 24 ] 7+ [Zr4(OH) 14 ] 2+ [Fe3O(OCOCH3)6] + Examples of metal hydroxide ions include the following. These guest compounds may be used individually or in combination of two or more.

[0112] Furthermore, when intercalating guest compounds, polymers obtained by hydrolysis and polycondensation of metal alkoxides such as Si(OR)4, Al(OR)3, and Ge(OR)4 (where R is a hydrocarbon group, etc.), as well as colloidal inorganic compounds such as SiO2, can also be included. Among inorganic compounds, clay minerals and clays are preferred, with montmorillonites, vermiculites, hectorites, teniolites, and synthetic micas being particularly preferred.

[0113] (organic compound) Examples of organic compounds include granular or particulate solids with particle sizes ranging from 10 to 300 μm. Specifically, examples include (co)polymers synthesized primarily from α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene; (co)polymers synthesized primarily from vinylcyclohexane and styrene; and modified forms of these (co)polymers.

[0114] <Organic compound component (D)> This olefin polymerization catalyst may further contain an organic compound component (D) as needed. The organic compound component (D) is used to improve the polymerization performance in the α-olefin polymerization reaction and the physical properties of the olefin copolymer. Examples of organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates. The organic compound component (D) may be used alone or in combination of two or more types.

[0115] <How to use and the order of addition for each ingredient> The method of use and the order of addition of each component constituting the olefin polymerization catalyst during olefin polymerization can be arbitrarily selected, but the following methods are examples. Hereinafter, the transition metal compound (A), compound (B), support (C), and organic compound component (D) will also be referred to as "components (A) to (D)," respectively.

[0116] (1) A method of adding a transition metal compound (A) alone to a polymerizer. (2) A method of adding transition metal compound (A) and compound (B) to a polymerizer in any order. (3) A method of adding a catalyst component in which a transition metal compound (A) is supported on a support (C), and compound (B) to a polymerizer in any order. (4) A method of adding a catalyst component in which compound (B) is supported on a support (C), and a transition metal compound (A) to a polymerizer in any order. (5) A method of adding a catalyst component, in which a transition metal compound (A) and a compound (B) are supported on a support (C), to a polymerizer. (6) A method of adding a catalyst component, in which a transition metal compound (A) and compound (B) are supported on a support (C), and compound (B) to a polymerizer in any order. In this case, compound (B) may be the same or different. (7) A method of adding a catalyst component in which compound (B) is supported on a support (C), and a transition metal compound (A) to a polymerizer in any order. (8) A method of adding a catalyst component in which compound (B) is supported on a support (C), a transition metal compound (A), and compound (B) to a polymerizer in any order. In this case, compound (B) may be the same or different. (9) A method of adding a component in which a transition metal compound (A) is supported on a support (C), and a component in which compound (B) is supported on a support (C), to a polymerizer in any order. (10) A method of adding a component in which a transition metal compound (A) is supported on a support (C), a component in which compound (B) is supported on a support (C), and compound (B) to a polymerizer in any sequence. In this case, compound (B) may be the same or different. (11) A method for adding a transition metal compound (A), a compound (B), and an organic compound component (D) to a polymerizer in any order. (12) A method of adding a component in which compound (B) and an organic compound component (D) have been brought into contact beforehand, and a transition metal compound (A), to a polymerizer in any order. (13) A method of adding a component in which compound (B) and an organic compound component (D) are supported on a carrier (C), and a transition metal compound (A) to a polymerizer in any order. (14) A method of adding a catalyst component, which consists of a transition metal compound (A) and a compound (B) in prior contact, and an organic compound component (D) to a polymerizer in any order. (15) A method of adding a catalyst component in which a transition metal compound (A) and compound (B) have been brought into contact beforehand, and compound (B) to a polymerizer in any order. In this case, compound (B) may be the same or different. (16) A method of adding a catalyst component in which a transition metal compound (A) and compound (B) have been brought into contact beforehand, and compound (B) and organic compound component (D) to a polymerizer in any order. In this case, compound (B) may be the same or different. (17) A method of adding a catalyst component in which a transition metal compound (A) and compound (B) have been brought into contact beforehand, and a component in which compound (B) and organic compound component (D) have been brought into contact beforehand, to a polymerizer in any order. In this case, compound (B) may be the same or different. (18) A method of adding a component in which a transition metal compound (A) is supported on a carrier (C), a compound (B), and an organic compound component (D) to a polymerizer in any order. (19) A method of adding a component in which a transition metal compound (A) is supported on a support (C), and a component in which a compound (B) and an organic compound component (D) have been brought into contact beforehand, to a polymerizer in any order. (20) A method of adding a catalyst component to a polymerizer, in which a transition metal compound (A), a compound (B), and an organic compound component (D) have been brought into contact in any order beforehand. (21) A catalyst component obtained by contacting a transition metal compound (A), a compound (B), and an organic compound component (D) in any order beforehand, and a method of adding compound (B) to a polymerizer in any order. In this case, compound (B) may be the same or different. (22) A method of adding a catalyst, in which a transition metal compound (A), a compound (B), and an organic compound component (D) are supported on a support (C), to a polymerizer. (23) A method of adding a catalyst component, in which a transition metal compound (A), a compound (B), and an organic compound component (D) are supported on a carrier (C), and compound (B) to a polymerizer in any order. In this case, compound (B) may be the same or different.

[0117] The compound (B) may be one type or two or more types. The solid catalyst component in which the transition metal compound (A) is supported on the support (C), and the solid catalyst component in which the transition metal compound (A) and compound (B) are supported on the support (C), may have an olefin prepolymerized, and further catalyst components may be supported on the prepolymerized solid catalyst component.

[0118] ≪Method for producing olefin copolymers≫ The present invention's method for producing olefin copolymers (hereinafter also referred to as "this production method") comprises the step of polymerizing a monomer containing 1-butene and at least one olefin selected from α-olefins having 3 to 20 carbon atoms other than 1-butene (hereinafter also referred to as "olefin A") in the presence of this olefin polymerization catalyst and under polymerization temperature conditions of 50 to 200°C.

[0119] Here, "polymerization" is used to refer collectively to both homopolymerization and copolymerization. Furthermore, "polymerizing a monomer containing 1-butene and olefin A in the presence of an olefin polymerization catalyst" includes methods such as those described in (1) to (23) above, in which each component of the olefin polymerization catalyst is added to the polymerizer by any method to polymerize the monomer containing 1-butene and olefin A.

[0120] As described above, olefin A is at least one olefin selected from α-olefins having 3 to 20 carbon atoms other than 1-butene, preferably at least one olefin selected from α-olefins having 3 to 10 carbon atoms other than 1-butene, and more preferably propylene.

[0121] In this manufacturing method, olefin polymerization 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 liquid-phase polymerization, it is preferable to use an inert hydrocarbon medium. Examples of such inert hydrocarbon mediums 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 a mixture of two or more types. Alternatively, a so-called bulk polymerization method can be used, in which the liquefied olefin itself, which can be supplied for polymerization, is used as the solvent.

[0122] In this manufacturing method, when carrying out olefin polymerization, the amounts used for each component that can constitute the olefin polymerization catalyst are preferably as follows. Hereinafter, the organoaluminum oxy compound (b-1), the compound (b-2) that reacts with the transition metal compound (A) to form an ion pair, and the organoaluminum compound (b-3) will also be referred to as "components (b-1) to (b-3)," respectively.

[0123] (1) Component (A) is typically 1 × 10 per liter of reaction volume. -9 ~1 × 10 -1 Moles, preferably 1 × 10⁻⁶ -8 ~1 × 10 -2 It is used in quantities that equal moles.

[0124] (2) When component (b-1) is used, component (b-1) is used in such an amount that the molar ratio [Al / M] of aluminum atoms (Al) in component (b-1) to all transition metal atoms (M) in component (A) is usually 0.01 to 5000, preferably 0.05 to 2000, more preferably 100 to 1000, even more preferably 250 to 750, and particularly preferably 400 to 600.

[0125] (3) When component (b-2) is used, it is used in an amount such that the molar ratio of component (b-2) to the total transition metal atoms (M) in component (A) [(b-2) / M] is usually 1 to 10, preferably 1 to 5.

[0126] (4) When component (b-3) is used, component (b-3) is 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 usually 10 to 5000, preferably 20 to 2000.

[0127] (5) 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.

[0128] (6) When using component (D), When component (B) is component (b-1), the amount is such that the molar ratio [(D) / (b-1)] is usually 0.001 to 10, preferably 0.005 to 5, more preferably 0.010 to 0.050, even more preferably 0.015 to 0.040, and particularly preferably 0.020 to 0.030. When component (B) is component (b-2), the amount is such that the molar ratio [(D) / (b-2)] is usually 0.01 to 10, preferably 0.1 to 5. 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 2, preferably 0.005 to 1.

[0129] In this manufacturing method, the polymerization temperature of the olefin is preferably 50 to 200°C, more preferably 50 to 180°C, even more preferably 50 to 150°C, and particularly preferably 50 to 100°C (in other words, particularly preferably a temperature at which industrialization is possible). The polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization time is usually 1 hour or less, preferably 40 minutes or less, more preferably 30 minutes or less, and preferably 5 to 20 minutes.

[0130] Polymerization can be carried out using batch, semi-continuous, or continuous methods. Furthermore, polymerization can be divided into two or more stages with different reaction conditions. The molecular weight of the resulting olefin copolymer can be adjusted by the presence of hydrogen or other elements in the polymerization system, by changing the polymerization temperature, or by the amount of component (B) used.

[0131] In this manufacturing method, it is preferable to continuously or intermittently supply hydrogen to the polymerization reaction system and copolymerize in the presence of hydrogen. Copolymerizing in the presence of hydrogen has the effect of improving the polymerization activity of the catalyst and increasing or decreasing the molecular weight of the polymer.

[0132] When hydrogen is supplied into the system, the amount of hydrogen supplied is 0.00001 to 100 NL per mole of olefin, more preferably 0.0001 to 10 NL, and even more preferably 0.0002 to 1 NL. The olefin in "per mole of olefin" includes 1-butene and olefin A.

[0133] In addition to supplying hydrogen from outside the system, the hydrogen concentration within the system can also be adjusted by carrying out reactions that generate or consume hydrogen within the system, by separating hydrogen using membranes, or by releasing some of the hydrogen-containing gases outside the system.

[0134] When hydrogen is supplied into the system, the polymerization pressure is preferably 0.1 to 3.0 MPa total pressure gauge pressure, more preferably 0.2 to 2.0 MPa total pressure gauge pressure, and even more preferably 0.3 to 1.5 MPa total pressure gauge pressure.

[0135] The olefin copolymer obtained by this manufacturing method may be subjected to post-treatment steps such as known catalyst deactivation, catalyst residue removal, and drying steps, as needed, after synthesis by the above method.

[0136] This manufacturing method makes it possible to produce olefin copolymers, such as propylene polymers, that have a high molecular weight while maintaining high catalytic activity.

[0137] <Olefin> In this manufacturing method, the olefins supplied to the polymerization reaction are 1-butene and olefin A (at least one olefin selected from α-olefins with 3 to 20 carbon atoms other than 1-butene). Olefin A may be used alone or in combination of two or more types.

[0138] Examples of olefin A include linear or branched α-olefins. Examples of linear or branched α-olefins include propylene, 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-octadecene, and 1-icosene. Preferably, olefin A is at least one selected from α-olefins having 3 to 10 carbon atoms, with propylene being more preferred.

[0139] Furthermore, without departing from the spirit of the present invention, polymerization can be carried out in the polymerization reaction system with at least one selected from cyclic olefins, olefins having polar groups, terminally hydroxylated vinyl compounds, and aromatic vinyl compounds. Polyenes can also be used in combination. Furthermore, without departing from the spirit of the present invention, other components such as vinylcyclohexane may be copolymerized.

[0140] Examples of cyclic olefins include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0141] Examples of olefins having polar groups include α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid anhydride, and metal salts thereof such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts, calcium salts, and aluminum salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert acrylate Examples include α,β-unsaturated carboxylic acid esters such as -butyl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; and unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconic acid ester.

[0142] Examples of terminal vinyl hydroxylated compounds include linear terminal vinyl hydroxylated compounds such as 1-butene hydroxide, 1-pentene hydroxide, 1-hexene hydroxide, 1-octene hydroxide, 1-decene hydroxide, 1-undecene hydroxide, 1-dodecene hydroxide, 1-tetradecene hydroxide, 1-hexadecene hydroxide, 1-octadecene hydroxide, and 1-eicosene hydroxide; and 3-methyl hydroxide. Examples include branched vinyl-terminated compounds such as ru-1-butene, 3-methyl-1-pentene hydroxide, 4-methyl-1-pentene hydroxide, 3-ethyl-1-pentene hydroxide, 4,4-dimethyl-1-pentene hydroxide, 4-methyl-1-hexene hydroxide, 4,4-dimethyl-1-hexene hydroxide, 4-ethyl-1-hexene hydroxide, and 3-ethyl-1-hexene hydroxide.

[0143] Examples of aromatic vinyl compounds include styrene; mono- or polyalkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene; functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, vinyl methyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, and divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, and α-methylstyrene.

[0144] The polyene is preferably selected from dienes and trienes. It is also a preferred embodiment to use the polyene in an amount of 0.0001 to 1 mol% relative to the total olefin supplied to the polymerization reaction.

[0145] Examples of dienes include α,ω-nonconjugated dienes such as 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, and 1,9-decadiene; nonconjugated dienes such as ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, and 4-ethylidene-8-methyl-1,7-nonadiene; and conjugated dienes such as butadiene and isoprene. Among these, α,ω-nonconjugated dienes and dienes having a norbornene skeleton are preferred.

[0146] Examples of trienes include 6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene, 5,9-dimethyl-1,4,8-decatriene, 6,9-dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, 4-ethylidene-1,6,-octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadienene (EMND), and 7-methyl-4-ethylidene-1,6-nonadienene. Examples include non-conjugated trienes such as 7-ethyl-4-ethylidene-1,6-nonadien, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadien, 4-ethylidene-1,6-decadien, 7-methyl-4-ethylidene-1,6-decadien, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylidene-1,7-nonadien, 8-methyl-4-ethylidene-1,7-nonadien, and 4-ethylidene-1,7-undecanediene; and conjugated triidines such as 1,3,5-hexatriene. Among these, non-conjugated trienes having a double bond at the terminal, 4,8-methyl-1,4,8-decatriene, and 4-ethylidene-8-methyl-1,7-nonadiene (EMND) are preferred.

[0147] Dienes or trienes may be used individually or in combination of two or more. Dienes and trienes may also be used in combination. Among polyenes, α,ω-non-conjugated dienes and polyenes having a norbornene skeleton are particularly preferred.

[0148] In this manufacturing method, the olefin A supplied to the polymerization reaction system is propylene, and in the step of copolymerizing the monomer, hydrogen is supplied to the polymerization reaction system continuously or intermittently to copolymerize in the presence of hydrogen, and when the amount of hydrogen supplied is within the above range and the polymerization pressure is within the above range, the olefin polymerization activity is preferably 50 to 1,000,000 kg / mmol-M / hr (where M is the same as M in the above general formula [I]), more preferably 60 to 100,000 kg / mmol-M / hr, even more preferably 70 to 10,000 kg / mmol-M / hr, and particularly preferably 80 to 1,000 kg / mmol-M / hr.

[0149] <Olefin copolymer> The olefin copolymer obtained by this manufacturing method is preferably a 1-butene / α-olefin copolymer such as 1-butene / propylene copolymer, 1-butene / 1-octene copolymer, 1-butene / 1-hexene copolymer, 1-butene / 4-methyl-1-pentene copolymer, 1-butene / propylene / 1-octene copolymer, 1-butene / propylene / 1-hexene copolymer, or 1-butene / propylene / 4-methyl-1-pentene copolymer. Alternatively, a so-called block copolymer (impact copolymer) obtained by mixing or continuously producing two or more polymers selected from these polymers may also be used.

[0150] In this specification, in olefin copolymers (A / B copolymers and B / A copolymers) having structural units derived from two monomers (monomer A and monomer B), copolymers where [content of structural units derived from monomer A (mol%)] > [content of structural units derived from monomer B (mol%)] are included in A / B copolymers. On the other hand, copolymers where [content of structural units derived from monomer A (mol%)] < [content of structural units derived from monomer B (mol%)] are included in B / A copolymers. Copolymers where [content of structural units derived from monomer A (mol%)] = [content of structural units derived from monomer B (mol%)] are included in both A / B copolymers and B / A copolymers. Furthermore, olefin copolymers having structural units derived from three or more monomers are distinguished in the same way.

[0151] The olefin copolymer obtained by this manufacturing method is most preferably a 1-butene homopolymer consisting only of structural units derived from 1-butene, or a 1-butene / propylene copolymer consisting only of structural units derived from 1-butene and structural units derived from propylene.

[0152] In the 1-butene / α-olefin copolymer, the content of structural units derived from 1-butene is preferably 50.0 to 92.0 mol%, more preferably 70.0 to 91.8 mol%, even more preferably 80.0 to 91.5 mol%, and particularly preferably 85.0 to 91.5 mol%, and the total content (K) of structural units derived from at least one olefin selected from α-olefins having 3 to 20 carbon atoms other than 1-butene is preferably 8.0 to 50.0 mol%, more preferably 8.2 to 30.0 mol%, even more preferably 8.5 to 20.0 mol%, and particularly preferably 8.5 to 15.0 mol% (provided that the sum of the content of structural units derived from 1-butene and the total content (K) is 100 mol%). If the total content (K) is below the lower limit, the compatibility with polymers such as polypropylene may decrease, and if the total content (K) exceeds the upper limit, the melting point may decrease, so it is preferable to keep it within the above range.

[0153] The olefin copolymer may contain other structural units other than the α-olefin, as long as they do not impair the effects of the present invention. The monomer content in olefin copolymers can be measured by nuclear magnetic resonance spectroscopy, or by infrared spectroscopy if a reference substance is available.

[0154] The melting point (Tm) of the olefin copolymer obtained by this manufacturing method, as determined by DSC, is preferably 90 to 150°C, more preferably 90 to 140°C, even more preferably 95 to 130°C, and particularly preferably 100 to 120°C. Olefin copolymers with a melting point (Tm) within the above range exhibit high stereoregularity, which leads to faster crystallization and is advantageous for molding. The specific method for measuring the melting point (Tm) will be described in detail in the examples below.

[0155] The molecular weight distribution (Mw / Mn) of the olefin copolymer obtained by this manufacturing method, measured by gel permeation chromatography (GPC) and calculated on a polystyrene basis, is preferably 1.6 to 5.0, more preferably 1.8 to 3.0, and even more preferably 2.0 to 2.4.

[0156] The intrinsic viscosity [η] of the olefin copolymer obtained by this manufacturing method is preferably 0.5 to 10.0 dl / g, more preferably 0.7 to 5.0 dl / g, even more preferably 0.9 to 2.5 dl / g, and preferably 1.0 to 2.0 dl / g. The specific method for measuring the intrinsic viscosity [η] will be described in detail in the examples below. [Examples]

[0157] The present invention will be described in more detail below based on examples, but the present invention is not limited in any way to these examples.

[0158] [Melting point (Tm)] The melting point (Tm) of the olefin copolymer was measured using a Hitachi High-Tech Science Corporation DSC 7020 as follows. Under a nitrogen atmosphere (20 mL / min), the sample (approximately 5 mg) was (1) heated to 230°C and held at 230°C for 3 minutes, (2) cooled to 30°C at 10°C / min and held at 30°C for 1 minute, and then (3) heated to 230°C at 10°C / min. The melting point (Tm) was calculated from the peak of the crystal melting peak during the heating process in (3), and the crystallization temperature (Tc) was calculated from the peak of the crystallization peak during the cooling process in (2). In the case of the olefin copolymers described in the examples and comparative examples, if multiple crystal melting peaks were observed (for example, a low-temperature peak Tm1 and a high-temperature peak Tm2), the high-temperature peak was defined as the melting point (Tm) of the olefin copolymer.

[0159] [Quantitative determination of comonomer content] (FT-IR measurement) For FT-IR, the 1-butene / propylene copolymer obtained in the examples and comparative examples was heated to 135°C, dissolved and stretched using a hot press, and then cooled under pressure at room temperature. The resulting film was used as the measurement sample, and the propylene-derived structural unit content was measured using a calibration curve. The 1-butene / propylene copolymer samples for calibration curve creation are as follows: 13 C-NMR measurement 1 The comonomer content was determined by 1H-NMR measurement. A calibration curve was obtained by selecting the peak intensity ratios of two specific absorption wavenumbers that showed a linear or nearly linear relationship with the propylene structural unit content data from these samples, and then graphing these relationships.

[0160] ( 13 C-NMR measurement) Using o-dichlorobenzene / benzene-d6 (4 / 1 {vol / vol%}) as the measurement solvent, under the following conditions: measurement temperature 120°C, spectral width 250 ppm, pulse repetition time 5.5 seconds, pulse width 4.7 μs (45° pulse) (100 MHz, JEOL ECX400P), or under the following conditions: measurement temperature 120°C, spectral width 250 ppm, pulse repetition time 5.5 seconds, pulse width 5.0 μs (45° pulse) (125 MHz, Bruker BioSpin, AVANCE III CRYO-500). 13¹³C-NMR spectra were measured, various signals were assigned using conventional methods, and the comonomer content of the 1-butene / propylene copolymer for calibration curve construction was quantified based on the integrated signal intensity.

[0161] ( 1 H-NMR measurement) The measurement was performed using o-dichlorobenzene d4 as the solvent, under the following conditions: measurement temperature 120°C, spectral width 250 ppm, pulse repetition time 7.0 seconds, and pulse width 5.0 μs (45° pulse) (500 MHz, Bruker BioSpin, AVANCE III CRYO-500). 1 1H-NMR measurements were performed. Various signals, such as methyl groups, were assigned using conventional methods, and the comonomer content of the 1-butene / propylene copolymer for calibration curve construction was quantified based on the integrated signal intensity.

[0162] [Intrinsic viscosity [η]] The intrinsic viscosity [η] of the olefin copolymers obtained in the examples and comparative examples is measured at 135°C using decalin solvent. Specifically, a granulated pellet of the olefin copolymer (approximately 20 mg) is dissolved in decalin solvent (15 mL), and the specific viscosity ηsp is measured in an oil bath at 135°C. After diluting this decalin solution by adding decalin solvent (5 mL), the specific viscosity ηsp is measured again in the same manner. This dilution procedure is repeated two more times, and the value of ηsp / C when the concentration of the olefin copolymer (C) is extrapolated to 0 is taken as the intrinsic viscosity [η] of the olefin copolymer. Intrinsic viscosity [η]=lim(ηsp / C) (C→0)

[0163] [Identification of metallocene compounds] The structure of the transition metal compound obtained in the synthesis example is 400MHz 1 The determination was made using 1H-NMR (ECZ400S, JEOL Ltd.) and FD-MS (SX-102A, JEOL Ltd.).

[0164] [Examples of metallocene compound synthesis] The transition metal compounds used in this embodiment can also be synthesized by the methods described in the following patent publications. Specifically, these include JP 2000-212194, JP 2004-168744, JP 2004-189666, JP 2004-161957, JP 2007-302854, JP 2007-302853, JP 2016-164264, and International Publication No. 01 / 027124. Specifically, they were synthesized by the method described in the synthesis example below.

[0165] [Synthesis Example 1] Synthesis of transition metal compound (a) represented by the following formula

[0166] [ka]

[0167] (Composition of ligand (a-1)) Under a nitrogen atmosphere, 0.70 g (2.48 mmol) of 2,7-diisopropoxy-9H-fluorene and 30 ml of tert-butylmethyl ether were placed in a flask, and 1.70 ml of n-butyllithium (hexane solution; 2.73 mmol) was added while cooling to 0°C. The mixture was stirred at 50°C for 14 hours, then cooled again to 0°C, and 0.77 g (2.74 mmol) of 5-adamantyl-1,1-dimethyl-3-methyl-1,2-dihydropentalene was added, and the mixture was stirred at room temperature for 19 hours. After stirring, 1N HCl aqueous solution was added to separate the organic phase. The separated organic phase was washed with water and saturated sodium chloride aqueous solution. After drying with magnesium sulfate, crystals were precipitated with methanol / hexane. The obtained crystals were washed with hexane, and 1.01 g (yield 72%) of the target product was obtained as white crystals. The formation of the target product was confirmed by FD-MS measurement. FD-MS: m / Z = 562.4(M + ) 1 ¹H-NMR measurement confirmed that the white crystal was a mixture of multiple isomers. The compound obtained in this manner was used as ligand (a-1) in subsequent steps.

[0168] (Synthesis of transition metal compound (a)) Under a nitrogen atmosphere, 1.01 g (1.79 mmol) of ligand (a-1), 0.47 g (3.95 mmol) of α-methylstyrene, 1.81 g (17.9 mmol) of cyclopentyl methyl ether, and 25 ml of hexane were placed in a Schlenk flask. While cooling to 0°C, 2.50 ml of n-butyllithium (hexane solution; 3.95 mmol) was added. After stirring at 60°C for 4 hours, the solution was concentrated under reduced pressure and 50 ml of diethyl ether was added. The resulting solution was cooled to -78°C, 0.39 g (1.69 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 18 hours while returning to room temperature. The solvent was removed by distillation, and the soluble components were extracted with toluene. The resulting solution was concentrated, dissolved in hexane, and recrystallized. The precipitated solid was recovered by filtration, washed with hexane, and dried under reduced pressure to obtain 0.35 g (yield 27%) of the target product as orange crystals. 1 The formation of the target product was confirmed by 1H-NMR and FD-MS measurements. 1 H-NMR(400MHz, CDCl3):δ / ppm 7.88(dd,J=9.2,2.0Hz,2H),7.28(d,J=2.0Hz,1H),7.19(dd,J=9.2,2.0Hz,1H),7.09(dd,J=9.2,2.0H z,1H),7.06(d,J=2.0Hz,1H),6.10(d,J=2.0Hz,1H),5.28(d,J=1.6Hz,1H),4.64-4.57(m,2H),3.87(d, J=14.8Hz,1H),2.59(d,J=2.6Hz,1H),2.29(s,3H),1.89(brs,3H),1.82-1.73(m,6H),1.67(brs,6H), 1.38(d,J=3.6Hz,3H),1.37(s,3H),1.34(d,J=6.0Hz,3H),1.34(d,J=6.0Hz,3H),1.30(d,J=6.0Hz,3H) FD-MS: m / Z = 722.2(M + ) In the following examples, the compound obtained in this manner was used as "transition metal compound (a)".

[0169] [Other transition metal compounds] In addition to the transition metal compound (a) obtained in the above synthesis example, a transition metal compound (e) represented by the following formula was used. Unlike the aforementioned transition metal compound (a), this transition metal compound (e) has R in the general formula [I] above. 1 It is not an adamantyl group derivative, R 2 and R 7 ZR 13 It is a transition metal compound that does not contain [unclear].

[0170] [ka]

[0171] [Example 1] Under a nitrogen atmosphere, 0.0064 mmol of transition metal compound (a) was placed in a Schlenk tube as transition metal compound (A), dissolved in 5.0 mL of heptane, and then 0.80 mL of a suspension of modified methylaluminoxane (trade name: TMAO341, manufactured by Tosoh Finechem Co., Ltd.) (n-hexane solvent, 4.00 M in terms of aluminum atoms, 1.2 mmol) was added. The mixture was stirred at room temperature for 30 minutes to prepare a catalyst solution with a transition metal compound (a) concentration of 0.0001 M. In a 1.5 L stainless steel autoclave that had been thoroughly purged with nitrogen, 5.0 mL (0.05 M, 0.125 mmol) of triisobutylaluminum n-heptane solution and 300 mL of n-heptane as the polymerization solvent were added and stirred at 850 rpm. After adding 120 g of 1-butene to this solution, 31 mL of hydrogen (0.013 NL per mole of olefin (1-butene and propylene)) was charged, and the solution was heated to 60°C. Then, propylene was charged in at a partial pressure of 0.07 MPa gauge pressure. At this time, the pressure inside the polymerization vessel (total polymerization pressure) was 0.49 MPa gauge pressure. 0.5 mL (1.0 μmol of transition metal compound (a)) of the catalyst solution was charged into the autoclave, pumped, and polymerization was initiated. After the initiation of polymerization, n-heptane was charged into the catalyst pot and pumped. After polymerization at 60 °C for 20 minutes, 5 mL of methanol was added to stop the polymerization. The polymerization solution taken out from the cooled / depressurized autoclave was poured into 1.5 L of an acetone / methanol mixed solvent (volume ratio 1:1), and the polymer was precipitated and recovered by filtration. The obtained polymer was dried under reduced pressure at 150 °C for 10 hours to obtain 28.2 g of a 1-butene / propylene copolymer. The polymerization activity was 84.5 kg / mmol-Zr / hr, and the obtained 1-butene / propylene copolymer had a 1-butene content of 91.3 mol% and a propylene content of 8.7 mol%, an intrinsic viscosity [η] of 1.21 dL / g, and a melting point (Tm) of 101.0 °C.

[0172] [Comparative Example 1] A catalyst solution was prepared and olefin polymerization was carried out in the same manner as in Example 1, except that the transition metal compound (a) used was replaced with the transition metal compound (e). The catalyst activity was 38.9 kg / mmol-Zr / hr, and the obtained 1-butene / propylene copolymer had a 1-butene content of 92.3 mol% and a propylene content of 7.7 mol%, an intrinsic viscosity [η] of 1.66 dL / g, and a melting point (Tm) of 103.6 °C.

[0173] For Example 1 and Comparative Example 1, the physical properties of the obtained 1-butene / propylene copolymer are shown in Table 4. Here, the symbols described in the column of "transition metal compound" in Table 4 are based on the symbols of the transition metal compounds used in the preparation of the catalyst. Also, for [η], the value shown in Table 4 is the value expressed with three significant figures. In Table 4, the unit of "polymerization activity (kg / mmol-M / hr)" means "polymerization activity (kg / mmol-Zr / hr)" when Zr is used as the transition metal M constituting the catalyst.

[0174]

Table 4

Claims

1. A transition metal compound (A) represented by the following general formula [I]. 【Chemistry 1】 (In the formula, R 1 is an adamantyl group derivative, R 2 and R 7 are each independently a substituent represented by ZR 13 (where Z is an oxygen atom or a sulfur atom, R 13 is a hydrocarbon group having 1 to 20 carbon atoms, and is bonded to a fluorenyl ligand via Z.)), and R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different from each other. Among R 3 to R 6 and R 8 to R 12 , adjacent substituents may be bonded to each other to form a ring. n is an integer of 1 to 3, M is a Group 4 transition metal, Q is independently a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons, and j is an integer of 1 to 4.)

2. The transition metal compound (A) according to claim 1, wherein Z is an oxygen atom in the general formula [I].

3. In the above general formula [I], R 3 and R 6 The transition metal compound (A) according to claim 1, wherein is a hydrogen atom.

4. In the above general formula [I], R 4 and R 5 The transition metal compound (A) according to claim 1, wherein is a hydrogen atom.

5. In the above general formula [I], R 12 The transition metal compound (A) according to claim 1, wherein is a hydrocarbon group having 1 to 20 carbon atoms.

6. In the above general formula [I], R 8 ~R 11 However, each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 8 ~R 11 The transition metal compound (A) according to claim 1, wherein adjacent substituents may bond to each other to form a ring.

7. In the above general formula [I], R 10 and R 11 The transition metal compound (A) according to claim 6, wherein is a hydrogen atom.

8. In the above general formula [I], R 8 and R 9 The transition metal compound (A) according to claim 6, wherein is a hydrocarbon group having 1 to 20 carbon atoms.

9. The transition metal compound (A) according to claim 1, wherein n is 1 in the general formula [I].

10. The transition metal compound (A) described in claim 1, Organoaluminum oxy compound (b-1), A compound (b-2) that reacts with a transition metal compound (A) to form an ion pair, and Organoaluminum compounds (b-3) At least one compound (B) selected from and A catalyst for olefin polymerization containing [specific component].

11. A method for producing an olefin copolymer, comprising the step of copolymerizing a monomer containing 1-butene and at least one olefin selected from α-olefins having 3 to 20 carbon atoms other than 1-butene, in the presence of the olefin polymerization catalyst described in claim 10, under polymerization temperature conditions of 50 to 200°C.

12. The method for producing an olefin copolymer according to claim 11, wherein at least one olefin selected from α-olefins having 3 to 20 carbon atoms other than 1-butene is propylene.

13. A method for producing an olefin copolymer according to claim 11, wherein the olefin copolymer contains 50.0 to 92.0 mol% of structural units derived from 1-butene, and the total content (K) of structural units derived from at least one olefin selected from α-olefins having 3 to 20 carbon atoms other than 1-butene is 8.0 to 50.0 mol% (provided that the sum of the content of structural units derived from 1-butene and the total content (K) is 100 mol%).

14. A method for producing an olefin copolymer according to claim 12, wherein, in the step of copolymerizing the monomer, hydrogen is continuously or intermittently supplied to the polymerization reaction system to copolymerize in the presence of hydrogen, the amount of hydrogen supplied is 0.00001 to 100 NL per mole of olefin, and the polymerization pressure is a total pressure of 0.1 to 3.0 MPa gauge pressure, and the olefin polymerization activity is 50 to 1,000,000 kg / mol-M / h (where M is the same as M in the general formula [I] above).

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