Transition metal compound, olefin polymerization catalyst, and method for producing olefin polymer

Abstract

To provide, e.g., a transition metal compound capable of producing an olefin polymer having a high molecular weight and a high melting point, even under high-temperature conditions that are advantageous in industrial production methods.SOLUTION: A transition metal compound (A) is represented by the general formula [I] in the figure.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a transition metal compound, a catalyst for olefin polymerization, and a method for producing an olefin polymer.

Background Art

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

[0003] In the polymerization of α-olefins using metallocene compounds, it is known that the stereoregularity and molecular weight of the resulting olefin polymer change greatly by introducing substituents into the cyclopentadienyl ring of the ligand of the metallocene compound or by crosslinking two cyclopentadienyl rings.

[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 the stereoregularity of the polymer, syndiotactic polypropylene is obtained with dimethylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride (Non-Patent Document 2), hemiiotactic polypropylene is obtained with dimethylmethylene(3-methylcyclopentadienyl)(fluorenyl)zirconium dichloride in which a methyl group is introduced at the 3-position of the cyclopentadienyl ring (Patent Document 1), and similarly, isotactic polypropylene is obtained with dimethylmethylene(3-tert-butylcyclopentadienyl)(fluorenyl)zirconium dichloride in which a tert-butyl group is introduced (Patent Document 2).

[0005] From attempts to improve these metallocene compounds, relatively high melting points, which are indicators of the stereoregularity of the polymer, can be obtained, and polymers with sufficiently high molecular weights can also be obtained. Furthermore, in recent years, in order to enable the industrial production of these olefin polymers, it has been desired that olefin polymers having the above characteristics (high molecular weight and high melting point) can be produced at temperatures above room temperature, preferably at high temperatures exceeding room temperature.

[0006] For example, by having specific substituents on the cyclopentadienyl ring and / or fluorenyl ring of the metallocene compound, the olefin polymerization catalyst containing the metallocene compound has been disclosed to have characteristics such as high molecular weight and high melting point even under high temperature conditions advantageous in industrial production methods (Patent Documents 3 to 5).

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Non-Patent Documents

[0008]

Non-Patent Document 1

Non-Patent Document 2

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] However, the development of a polymerization catalyst that can produce a polymer having a sufficiently high molecular weight and a high melting point with high polymerization activity is not yet sufficient. Therefore, a production method and an olefin polymerization catalyst capable of obtaining a polymer having a high melting point and a high molecular weight have been strongly desired.

[0010] The present invention has been made to solve the above problems, and an object thereof is to provide a transition metal compound, an olefin polymerization catalyst, and a method for producing an olefin polymer, which can produce a high molecular weight and high melting point olefin polymer even under high temperature conditions advantageous in an industrial production method.

MEANS FOR SOLVING THE PROBLEMS

[0011] As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by a transition metal compound having a specific substituent, and have completed the present invention. The gist of the present invention is as follows.

[0012] [1] A transition metal compound (A) represented by the following general formula [I].

CHEMICAL

[0013] [2] The transition metal compound (A) according to [1], wherein in the general formula [I], Z is an oxygen atom. [3] The transition metal compound (A) according to [1] or [2], wherein in the general formula [I], R 13 is a hydrocarbon group having 1 to 20 carbon atoms. [4] The transition metal compound (A) according to any one of [1] to [3], wherein in the general formula [I], R 3 and R 6 are hydrogen atoms. [5] The transition metal compound (A) according to any one of [1] to [4], wherein in the general formula [I], R 4 and R 5 are hydrogen atoms. [6] The transition metal compound (A) according to any one of [1] to [5], wherein in the general formula [I], R 12 is a hydrocarbon group having 1 to 20 carbon atoms.

[0014] [7] The transition metal compound (A) according to any one of [1] to [6], wherein in the general formula [I], R 8 ~R 11 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and among R 8 ~R 11 adjacent substituents may combine with each other to form a ring. [8] In the general formula [I], R10 and R 11 The transition metal compound (A) according to [7], wherein R is a hydrogen atom. [9] In the general formula [I], R 8 and R 9 The transition metal compound (A) according to [7] or [8], wherein R and R are hydrocarbon groups having 1 to 20 carbon atoms.

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

[0015]

[11] A catalyst for olefin polymerization comprising the transition metal compound (A) according to any one of [1] to

[10] , an organoaluminum oxy compound (b-1), a compound (b-2) that reacts with the transition metal compound [A] to form an ion pair, and an organoaluminum compound (b-3) at least one compound (B) selected from A method for producing an olefin polymer, comprising a step of polymerizing a monomer containing at least one α-olefin having 3 or more carbon atoms under a polymerization temperature condition of 50 to 200 ° C. in the presence of the catalyst for olefin polymerization according to

[11] .

[0016]

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

[12] , wherein at least one of the α-olefins having 3 or more carbon atoms is propylene.

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

[12] or

[13] , wherein the intrinsic viscosity [η] of the olefin polymer determined from the following formula (1) is 1.0 to 10 dl / g.

[14] The method for producing an olefin polymer according to any one of

[12] to

[14] , wherein the melting point peak (Tm) of the olefin polymer determined by a differential scanning calorimeter (DSC) is 120 to 150 ° C. [η]=K m M a ···(1) (In the formula, M represents the molecular weight, and K m is 0.0004 and a is 0.69.)

[15] The method for producing an olefin polymer according to any one of

[12] to

[14] , wherein the melting point peak (Tm) of the olefin polymer determined by a differential scanning calorimeter (DSC) is 120 to 150 ° C. [Advantages of the Invention]

[0017] According to the present invention, a high molecular weight and high melting point olefin polymer can be produced even under high temperature conditions advantageous in industrial production methods. [Modes for Carrying Out the Invention]

[0018] In this specification, "~" indicating a numerical range means "M or more and N or less" in the case of "M~N" unless otherwise specified. In this specification, when an olefin constituting a certain copolymer is denoted as M, the expression "structural unit derived from M" may be used, which means "structural unit corresponding to M", that is, a structural unit having a pair of bonds formed by opening a π bond constituting a double bond of M. It should be noted that 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), for example, when polymerizing an α-olefin such as propylene, an olefin polymer can be efficiently produced. That is, the transition metal compound (A) can be suitably used as a catalyst component for olefin polymerization for producing an olefin polymer (for example, a propylene (co)polymer).

[0020] [Chemical Formula]

[0021] 〈R 1 〉 In the general formula [I], R 1 is an adamantyl group derivative. Examples of the adamantyl group derivative include a 1 - adamantyl group, a 2 - adamantyl group, a 3,5 - dimethyl - 1 - adamantyl group, or a 3,5,7 - trimethyl - 1 - adamantyl group. Among them, a 1 - adamantyl group, a 3,5 - dimethyl - 1 - adamantyl group, or a 3,5,7 - trimethyl - 1 - adamantyl group is preferable, and a 1 - adamantyl group is more preferable.

[0022] R 1 is preferably an adamantyl group derivative from the viewpoint of efficiently obtaining the resulting olefin polymer. R 1 、R 2 and R 7 Due to the steric bulk of, it is considered that the anion becomes less likely to approach the metallocene cation derived from the general formula [I], which is presumed to be the active species. For this reason, (1) the coordination space of the metallocene cation expands, making it easier for the monomer to approach the metallocene cation, and (2) the Lewis acidity of the metallocene cation improves, increasing the reactivity with olefins, so it is considered that the catalytic activity improves.

[0023] 〈R 2 and R 7 〉 In the general formula [I], R 2 and R 7 are each independently a substituent represented by ZR 13 . Z is an oxygen atom or a sulfur atom, and an oxygen atom is preferable. R 13 is a group bonded to the fluorenyl ligand via Z. R 13 is a 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, and a halogen - containing hydrocarbon group, and a hydrocarbon group having 1 to 20 carbon atoms is preferable. These substituents will be described in detail in the columns for the description of R 3 ~R 6 、R 8 ~R 12 below. R 2 and R 7Although they may be the same or different from each other, from the viewpoint of ease of production of the transition metal compound (A), R 2 and R 7 are preferably the same substituent.

[0024] R 2 and R 7 are preferably substituents represented by ZR 13 from the viewpoint of improving the melting point of the resulting olefin polymer. It is considered that the stereoregularity of olefins is improved by the change in the charge state of the central metal M due to Z possessed by R 2 and R 7 .

[0025] 〈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 、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 they may be the same or different from each other. Among R 3 ~R 6 and R 8 ~R 12 , adjacent substituents may combine with each other to form a ring.

[0026] The hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a saturated alicyclic group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

[0027] 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, 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, 1-methyl-1-isopropyl-2-methylpropyl group.

[0028] Examples of saturated alicyclic groups having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; and alicyclic polycyclic groups such as norbornyl group, adamantyl group.

[0029] Examples of aryl groups having 6 to 20 carbon atoms include unsubstituted aryl groups such as phenyl group, naphthyl group, phenanthryl group, anthracenyl group, biphenyl group; and alkylaryl groups such as o-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, n-propylphenyl group, iso-propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, xylyl group.

[0030] 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, neophyl group; and alkylaralkyl 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, tert-butylbenzyl group.

[0031] Examples of the silicon-containing group include alkylsilyl groups such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group; and arylsilyl groups such as dimethylphenylsilyl group, diphenylmethylsilyl group, triphenylsilyl group.

[0032] Examples of the nitrogen-containing group include amino group, nitro group, and N-morpholinyl group, and groups in which the =CH- structural unit in the above-described hydrocarbon group or silicon-containing group having 1 to 20 carbon atoms is replaced by a nitrogen atom, groups in which the -CH2- structural unit is replaced by a nitrogen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, or groups in which the -CH3 structural unit is replaced by a nitrogen atom or nitrile group bonded to a hydrocarbon group having 1 to 20 carbon atoms, such as dimethylaminomethyl group, cyano group, pyrrolidinyl group, piperidinyl group, pyridinyl group.

[0033] Examples of the oxygen-containing group include hydroxyl group, and groups in which the -CH2- structural unit in the above-described hydrocarbon group, silicon-containing group or nitrogen-containing group having 1 to 20 carbon atoms is replaced by an oxygen atom or a carbonyl group, or groups in which the -CH3 structural unit is replaced by an oxygen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, such as trimethylsiloxy group, methoxyethoxy group, hydroxymethyl group, methoxymethyl group, ethoxymethyl group, tert-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 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, trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl group, carboxy group, methoxycarbonyl group, carboxymethyl group, ethoxycarbonylmethyl group, carbamoylmethyl group, furanyl group, pyranyl group.

[0034] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, which are Group 17 elements.

[0035] Examples of the halogen-containing hydrocarbon group include groups formed by substituting at least one hydrogen atom of the hydrocarbon group with a halogen atom. Specific examples of the halogen-containing hydrocarbon group include halogen-substituted alkyl groups such as fluoroalkyl groups like the trifluoromethyl group; halogen-substituted aryl groups such as fluoroaryl groups like the pentafluorophenyl group, chloroaryl groups such as the o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, chloronaphthyl group, bromoaryl groups such as the o-bromophenyl group, m-bromophenyl group, p-bromophenyl group, bromonaphthyl group, iodoaryl groups such as the o-iodophenyl group, m-iodophenyl group, p-iodophenyl group, iodonaphthyl group, etc., which are halogen substituents of the unsubstituted aryl group; fluoroalkylaryl groups such as the trifluoromethylphenyl group, bromoalkylaryl groups such as the bromomethylphenyl group, dibromomethylphenyl group, etc., iodoalkylaryl groups such as the iodomethylphenyl group, diiodomethylphenyl group, etc., which are halogen substituents of the alkylaryl group, etc.; halogen-substituted aralkyl groups such as chloroaralkyl groups like the o-chlorobenzyl group, m-chlorobenzyl group, p-chlorobenzyl group, chlorophenethyl group, bromoaralkyl groups such as the o-bromobenzyl group, m-bromobenzyl group, p-bromobenzyl group, bromophenethyl group, iodoaralkyl groups such as the o-iodobenzyl group, m-iodobenzyl group, p-iodobenzyl group, iodophenethyl group, etc., which are halogen substituents of the unsubstituted aralkyl group.

[0036] In general formula [I], when the 1-position and 8-position of the fluorenyl moiety are hydrogen atoms, an olefin polymer can be efficiently obtained.

[0037] R 2 and R 7 are, as described above, each independently 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. R 2 and R 7It is preferable from the viewpoint of easily obtaining an olefin polymer having a high melting point by being the above group.

[0038] R 3 and R 6 are preferably hydrogen atoms. By R 3 and R 6 being hydrogen atoms, it is preferable from the viewpoints of efficiently obtaining the produced olefin polymer and the melt fluidity of the produced olefin polymer.

[0039] 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 chloro group, a bromo group or a fluoro group, and even more preferably a hydrogen atom. By R 4 and R 5 being the above group, it is preferable from the viewpoint of efficiently obtaining the produced olefin polymer.

[0040] R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a methyl group, ethyl, n-propyl, n-butyl group, or phenyl group, and particularly preferably a methyl group. By R 12 being the above group, it is preferable from the viewpoint of efficiently obtaining the produced olefin polymer.

[0041] 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 9 are each independently preferably a hydrocarbon group having 1 to 20 carbon atoms. Also, R10 and R 11 is preferably a hydrogen atom.

[0042] Also, R 8 ~R 11 Among them, adjacent substituents may be bonded to each other to form a ring. In another preferred embodiment of the present invention, R 9 and R 10 are groups that are bonded to each other to form a cyclopentane ring, or R 9 and R 10 are preferably groups that are bonded to each other to form a cyclohexane ring, and more preferably R 9 and R 10 are groups that are bonded to each other to form a cyclohexane ring.

[0043] Here, in a preferred embodiment of the present invention, R 8 and R 9 are hydrocarbon groups, and more preferably hydrocarbon groups having 1 to 20 carbon atoms. Also, in one of the preferred embodiments of the present invention, R 10 and R 11 are hydrogen atoms.

[0044] 〈n, M, Q and j〉 n is an integer from 1 to 3, preferably 1 or 2, and more preferably 1. When n is the above value, it is preferable from the viewpoint of efficiently obtaining the produced olefin polymer.

[0045] M is a Group 4 transition metal, that is, a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom, and more preferably a zirconium atom.

[0046] 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. When j is an integer of 2 or more, a plurality of Qs may be the same or different.

[0047] As the hydrocarbon group in Q, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms is preferable. The number of carbon atoms of the hydrocarbon group is more preferably 5 or less.

[0048] Examples of the alkyl group 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.

[0049] Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclohexylmethyl group, cyclohexyl group, and 1-methyl-1-cyclohexyl group.

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

[0051] Examples of the neutral ligand capable of coordinating with an unshared electron pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ethers such as tetrahydrofuran (THF), diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0052] 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. When Q is a halogen atom, it is preferably a chlorine atom.

[0053] j is an integer of 1 to 4, and preferably 2.

[0054] <Examples of the transition metal compound (A)> Specific examples of the transition metal compound (A) are shown, but the scope of the present invention is not particularly limited thereby.

[0055] For convenience in explanation, the ligand structure of the metallocene compound excluding the MQ j (metal part) is divided into two parts, a cyclopentadienyl derivative part and a fluorenyl part. When the fluorenyl part is represented by "Flu", the cyclopentadienyl derivative part has the following structures: structure (i) (n = 1), structure (ii) (n = 2), and structure (iii) (n = 3).

[0056]

Chemical formula

[0057] As the structure in which two substituents are bonded to each other, the following structures are exemplified: structure (i-1) (R 11 and R 12 are bonded to each other to form a cyclopentane ring), and structure (i-2) (R 11 and R 12 are bonded to each other to form a cyclohexane ring).

[0058]

Chemical formula

[0059] The ligand structure of the metallocene compound excluding the MQ j (metal part) is divided into three parts: the adamantyl derivative part (α) of R 1 , the cyclopentadienyl derivative part (β), and the fluorenyl part (γ). Specific examples of each partial structure are shown in Tables 1 to 3. In Table 2, "Adm" represents the adamantyl derivative part of R 1 , "Flu" represents the fluorenyl part, and in Table 3, "Cp" represents the cyclopentadienyl derivative part.

[0060]

Table 1

[0061]

Table 2

[0062]

Table 3

[0063] According to the above table, when the ligand structure consists of a combination of α1, β5, and γ1, and the metal moiety MQ j is ZrCl2, the metallocene compounds represented by the following formula are exemplified.

[0064]

Chemical formula

[0065] MQ j Specific examples of MQ 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.

[0066] The above MQ j Compounds in which "zirconium" in the exemplified compounds is replaced with "hafnium" or "titanium", or metallocene compounds in which "dichloride" is replaced with "dimethyl" or "methylethyl" are also included in the transition metal compound (A) in the same manner.

[0067] ≪Olefin polymerization catalyst≫ The olefin polymerization catalyst according to the present invention (hereinafter also referred to as "the present olefin polymerization catalyst") contains a transition metal compound (A) and a compound (B) described later. The transition metal compound (A) used in the olefin polymerization catalyst may be one kind or two or more kinds, and the compound (B) used in the olefin polymerization catalyst may be one kind or two or more kinds.

[0068] <Compound (B)> Compound (B) is at least one compound selected from an organoaluminum oxy compound (b-1), a compound (b-2) that reacts with the transition metal compound (A) to form an ion pair, and an organoaluminum compound (b-3). Among these, from the viewpoint of efficiently obtaining the produced olefin polymer, the organoaluminum oxy compound (b-1) is preferable.

[0069] 〈Organoaluminum oxy compound (b-1)〉 Examples of the organoaluminum oxy compound (b-1) include conventionally known aluminoxanes such as a compound represented by the following general formula [B1] and a compound represented by the general formula [B2], a modified methylaluminoxane having a structure represented by the following general formula [B3], and a boron-containing organoaluminum oxy compound represented by the following general formula [B4]. The organoaluminum oxy compound (b-1) may be used alone or in combination of two or more.

[0070]

Chemical formula

[0071] In the 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, more preferably 10 or more.

[0072]

Chemical formula

[0073] In formula [B3], R is a hydrocarbon group having 2 to 10 carbon atoms, and m and n are each independently an integer of 2 or more. A plurality of Rs may be the same as or different from each other.

[0074] The modified methylaluminoxane having the structure represented by formula [B3] can be prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. The modified methylaluminoxane having the structure represented by formula [B3] is generally called MMAO (modified methyl aluminoxane). MMAO can be specifically prepared by the methods described in U.S. Patent No. 4,960,878 and U.S. Patent No. 5,041,584.

[0075] In addition, modified methylaluminoxanes prepared using trimethylaluminum and triisobutylaluminum (i.e., R is an isobutyl group in formula [B3]), such as those from Tosoh Finechem Corporation, are commercially produced under the names MMAO and TMAO.

[0076] 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 compounds represented by general formula [B1] or [B2], MMAO is soluble in aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0077]

Chemical formula

[0078] In formula [B4], R c is a hydrocarbon group having 1 to 10 carbon atoms. A plurality of Rs d are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0079] Furthermore, benzene-insoluble or poorly soluble organoaluminumoxy compounds as exemplified in JP-A-2-78687, organoaluminumoxy compounds described in JP-A-2-167305, aluminoxanes having two or more alkyl groups described in JP-A-2-24701 and JP-A-3-103407 can also be preferably used.

[0080] The above-mentioned "benzene-insoluble or poorly soluble" organoaluminumoxy compound refers to an organoaluminumoxy compound that is insoluble or poorly soluble in benzene, and the dissolution amount of the compound dissolved in benzene at 60 °C is usually 10% by mass or less, preferably 5% by mass or less, particularly preferably 2% by mass or less in terms of Al atoms.

[0081] <Compound (b-2) that reacts with transition metal compound (A) to form an ion pair> Examples of the compound (b-2) that reacts with the transition metal compound (A) to form an ion pair (hereinafter also referred to as "ionic compound (b-2)") 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, JP-A-2004-51676, US Patent No. 5321106, etc. Furthermore, heteropoly compounds and isopoly compounds are also exemplified. The ionic compound (b-2) may be used alone or in combination of two or more.

[0082] As the ionic compound (b-2), a compound represented by the following general formula [B5] is preferable.

[0083] [Chemical formula]

[0084] In formula [B5], R e+ is, for example, H +, oxonium cation, carbocation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal are exemplified. R f , R g , R h and R i each independently represent an organic group, preferably an aryl group, or a halogen-substituted aryl group.

[0085] Examples of the carbocation include trisubstituted carbocations such as triphenylcarbocation, tris(methylphenyl)carbocation, and tris(dimethylphenyl)carbocation.

[0086] Examples of the ammonium cation 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.

[0087] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation, and tris(dimethylphenyl)phosphonium cation.

[0088] R e+ is preferably a carbocation or an ammonium cation, and particularly preferably triphenylcarbocation, N,N-dimethylanilinium cation, or N,N-diethylanilinium cation.

[0089] R e+Examples of the compound represented by formula [B5] when it is a carbocation salt include triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate, and tris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl)borate.

[0090] R e+ Examples of the ammonium salt when R is an ammonium cation include trialkylammonium salts, N,N-dialkylanilinium salts, and dialkylammonium salts.

[0091] Examples of the compound represented by the formula [B5] in the case of a trialkylammonium 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, tri(n-butyl)ammonium 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.

[0092] Examples of the compound represented by the formula [B5] when it is an N,N-dialkylanilinium salt include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N,2,4,6-pentamethylanilinium tetraphenylborate, and N,N,2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate.

[0093] Examples of the compound represented by the formula [B5] when it is a dialkylammonium salt include diisopropylammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

[0094] (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.

[0095] 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 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.

[0096] M 2 AlR a 4…[B7] In formula [B7], M 2 is Li, Na or K, and the plurality of R a are independently hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

[0097] Examples of the organoaluminum compound represented by the general formula [B6] include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, and trioctylaluminum; tri-branched chain alkylaluminums such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride; alkenylaluminums such as isoprenylaluminum represented by the general formula (i-C4H9) x Al y (C5H 10 ) z (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 (wherein, R a and R bis R in the formula [B6] a and R b are synonymous. Partially alkoxylated alkylaluminum having an average composition represented by); diethylaluminum phenoxide, alkylaluminum aryloxides such as diethylaluminum (2,6 - di - tert - butyl - 4 - methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; partially halogenated alkylaluminum such as ethylaluminum dichloride; partially hydrogenated alkylaluminum such as dialkylaluminum hydrides like diethylaluminum hydride, dibutylaluminum hydride, and alkylaluminum dihydrides like ethylaluminum dihydride, propylaluminum dihydride; partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide are exemplified.

[0098] Examples of the complex alkyl compound of a Group 1 metal of the periodic table and aluminum represented by the general formula [B7] include LiAl(C2H5)4, LiAl(C7H 15 )4. Compounds similar to the above complex alkyl compounds can also be used, and examples include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Such a compound is exemplified by (C2H5)2AlN(C2H5)Al(C2H5)2.

[0099] As the organoaluminum compound (b - 3), trimethylaluminum and triisobutylaluminum are preferred from the viewpoint of easy availability.

[0100] <Support (C)> This olefin polymerization catalyst may further contain a carrier (C) if necessary. Examples of the carrier (C) include inorganic compounds or organic compounds, which are granular or particulate solids. The carrier (C) may be used alone or in combination of two or more.

[0101] (Inorganic compound) Examples of the inorganic compound include porous oxides, inorganic halides, clay minerals, clays (usually composed mainly of the clay minerals), and ion-exchangeable layered compounds (most clay minerals are ion-exchangeable layered compounds). Examples of the porous oxide include SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2; composites or mixtures containing these oxides. Examples of the composites or mixtures include natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO. Among these, porous oxides mainly composed of either or both of SiO2 and Al2O3 components are preferred.

[0102] Although the properties of the porous oxide vary depending on the type and production method, the particle size is preferably in the range of 10 to 300 μm, more preferably 20 to 200 μm; the specific surface area is preferably 50 to 1000 m 2 / g, more preferably 100 to 700 m 2 / g; the pore volume is preferably in the range of 0.3 to 3.0 cm 3 / g. Such a porous oxide is used after being calcined at 100 to 1000 °C, preferably 150 to 700 °C if necessary.

[0103] Examples of the inorganic halide include MgCl2, MgBr2, MnCl2, and MnBr2. The inorganic halide may be used as it is, or after being pulverized by a ball mill or a vibration mill. Further, a component obtained by dissolving the inorganic halide in a solvent such as alcohol and then precipitating it into fine particles with a precipitant can also be used.

[0104] As for the clay, clay mineral, and ion-exchangeable layered compound, not only natural products but also synthetic products can be used. The ion-exchangeable layered compound is a compound having a crystal structure in which planes composed of ionic bonds or the like are stacked parallel to each other with a weak binding force, and is a compound in which the contained ions are exchangeable.

[0105] Specifically, examples of the clay and clay mineral include kaolin, bentonite, kibushi clay, gaylussite clay, allophane, hisingerite, pyrophyllite, synthetic mica, etc. from the umo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, dickite, hectorite, teniolite, halloysite; examples of the ion-exchangeable layered compound include ionic crystalline compounds having a layered crystal structure such as hexagonal closest packing type, antimonide type, CdCl2 type, CdI2 type. Specifically, examples of the ion-exchangeable layered compound 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, γ-Ti(NH4PO4)2·H2O.

[0106] It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any treatment such as surface treatment for removing impurities adhering to the surface and treatment that affects the crystal structure of the clay can be used. Specifically, examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment.

[0107] In addition, the ion-exchangeable layered compound may be a layered compound with expanded interlayer spaces by utilizing its ion-exchangeability to exchange the exchangeable ions between layers with another large and bulky ion. Such a bulky ion plays a pillar-like role in supporting the layered structure and is usually called a pillar. For example, by intercalating the following metal hydroxide ions between the layers of the layered compound and then heating and dehydrating, an oxide pillar (pillar) can be formed between the layers. Note that introducing another substance between the layers of the layered compound in this way is called intercalation.

[0108] Examples of guest compounds for intercalation 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.); 13 O4(OH) 24 7+ , [Zr4(OH) 14 2+ , [Fe3O(OCOCH3)6] + and other metal hydroxide ions are exemplified. These guest compounds may be used alone or in combination of two or more.

[0109] In addition, when intercalating the guest compound, polymers obtained by hydrolyzing and polycondensing metal alkoxides such as Si(OR)4, Al(OR)3, and Ge(OR)4 (where R is a hydrocarbon group, etc.), colloidal inorganic compounds such as SiO2, etc. can also coexist. Among inorganic compounds, clay minerals and clays are preferred, and montmorillonite group, vermiculite, hectorite, teniolite, and synthetic mica are particularly preferred.

[0110] (Organic compound) ​​Examples of the organic compound include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specifically, (co)polymers synthesized mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene; (co)polymers synthesized mainly from vinylcyclohexane and styrene; and modified products of these (co)polymers are exemplified.

[0111] <Organic compound component (D)> This olefin polymerization catalyst may further contain an organic compound component (D) as necessary. The organic compound component (D) is used for the purpose of improving the polymerization performance in the polymerization reaction of α-olefins and the physical properties of olefin polymers. Examples of the 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.

[0112] <Usage and addition order of each component> Regarding the usage, addition order, etc. of each component constituting the olefin polymerization catalyst during olefin polymerization, they can be arbitrarily selected, and the following methods are exemplified. Hereinafter, the transition metal compound (A), compound (B), carrier (C), and organic compound component (D) are also referred to as "components (A) to (D)", respectively.

[0113] (1) A method of adding component (A) and component (B) to the polymerization reactor in any order. (2) A method of adding the catalyst component obtained by supporting component (A) on component (C) and component (B) to the polymerization reactor in any order. (3) A method of adding the catalyst component obtained by supporting component (B) on component (C) and component (A) to the polymerization reactor in any order. (4) A method of adding the catalyst component obtained by supporting component (A) and component (B) on component (C) to the polymerization reactor.

[0114] 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 be further used. In each of the above methods (3) and (4) in which component (B) is supported, the unsupported component (B) may be further added in any order as necessary. In this case, the supported component (B) and the optionally added component (B) may be the same or different. Further, a solid catalyst component in which component (A) is supported on component (C), and a solid catalyst component in which component (A) and component (B) are supported on component (C) may be prepolymerized with an olefin, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

[0115] ≪Process for producing olefin polymer≫ The process for producing an olefin polymer of the present invention (hereinafter also referred to as "the present production process") has a monomer step containing at least one α-olefin having 3 or more carbon atoms under polymerization temperature conditions of 50 to 200°C in the presence of the present catalyst for olefin polymerization.

[0116] Here, "polymerization" is used in the general sense including homopolymerization and copolymerization. Further, "polymerizing a monomer containing at least one α-olefin having 3 or more carbon atoms in the presence of a catalyst for olefin polymerization" includes a mode in which each component of the olefin polymerization catalyst is added to a polymerization vessel by any method as in the above methods (1) to (4) to polymerize a monomer containing at least one α-olefin having 3 or more carbon atoms.

[0117] Preferably, at least one of the monomers is a monomer selected from α-olefins having 3 to 20 carbon atoms, more preferably at least one is a monomer selected from α-olefins having 3 to 10 carbon atoms, and still more preferably at least one is propylene.

[0118] Olefin polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization or 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, it is possible to use a so-called bulk polymerization method in which the liquefied olefin itself that can be supplied to the polymerization is used as a solvent.

[0119] When carrying out olefin polymerization, it is preferable that the usage amounts of the respective components that can constitute an olefin polymerization catalyst are 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) are also referred to as "components (b-1) to (b-3)", respectively.

[0120] (1) Component (A) is usually 10 -9 ~10 -1 moles, preferably 10 -8 ~10 -2 moles per liter of the reaction volume and is used in such an amount.

[0121] (2) When using component (b-1), component (b-1) is used in such an amount that the molar ratio [Al / M] of the aluminum atom (Al) in component (b-1) to all the transition metal atoms (M) in component (A) is usually 0.01 to 5000, preferably 0.05 to 2000, more preferably 100 to 1000, still more preferably 250 to 750, and particularly preferably 400 to 600.

[0122] (3) When using component (b-2), component (b-2) is used in an amount such that the molar ratio [(b-2) / M] of component (b-2) to all transition metal atoms (M) in component (A) is usually 1 to 10, preferably 1 to 5.

[0123] (4) When using component (b-3), component (b-3) is used in an amount such that the molar ratio [(b-3) / M] of component (b-3) to all transition metal atoms (M) in component (A) is usually 10 to 5000, preferably 20 to 2000.

[0124] (5) When using component (C), component (C) can be used in an amount such that the mass ratio [(A) / (C)] of component (A) to component (C) is usually 0.0001 to 1, preferably 0.0005 to 0.5, more preferably 0.001 to 0.1.

[0125] (6) When using component (D), When component (B) is component (b-1), component (D) is used in an amount 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, still more preferably 0.015 to 0.040, particularly preferably 0.020 to 0.030. When component (B) is component (b-2), component (D) is used in an amount 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.

[0126] In this production method, the polymerization temperature of the olefin is preferably 50 to 200 °C, more preferably 50 to 180 °C, still more preferably 50 to 150 °C, particularly preferably 50 to 100 °C (in other words, particularly preferably a temperature that can be industrialized). The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal 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.

[0127] The polymerization reaction can be carried out in any of the batch, semi - continuous, or continuous methods. Furthermore, the polymerization can also be carried out in two or more stages with different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen or the like in the polymerization system, by changing the polymerization temperature, or by the amount of component (B) used.

[0128] In particular, hydrogen can sometimes obtain the effects of improving the polymerization activity of the catalyst and increasing or decreasing the molecular weight of the polymer, and can be said to be a preferred additive. When adding hydrogen to the system, an appropriate amount is about 0.00001 - 100 NL per mole of olefin. The hydrogen concentration in the system can be adjusted not only by adjusting the supply amount of hydrogen, but also by carrying out a reaction that generates or consumes hydrogen in the system, by using a membrane to separate hydrogen, or by discharging a part of the gas containing hydrogen out of the system.

[0129] For the olefin polymer obtained by this production method, after synthesis by the above method, post - treatment steps such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step may be carried out as necessary.

[0130] According to this production method, it is possible to produce an olefin polymer such as a propylene polymer having a high molecular weight while maintaining high catalyst activity.

[0131] 〈Olefin〉 In this production method, the olefin supplied to the polymerization reaction is at least one olefin selected from α - olefins having 3 or more carbon atoms, preferably α - olefins having 3 - 20 carbon atoms. The α - olefins may be used alone or in combination of two or more.

[0132] Examples of the α-olefins having 3 to 20 carbon atoms include linear or branched α-olefins. Examples of the linear or branched α-olefins include propylene, 1-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-octadecene, and 1-icosene. At least one selected from α-olefins having 3 to 10 carbon atoms is more preferable, and propylene is even more preferable.

[0133] When propylene is used as the α-olefin, if necessary, at least one olefin A selected from ethylene and α-olefins having 4 to 20 carbon atoms can be used in combination. Olefin A is preferably at least one selected from ethylene and α-olefins having 4 to 10 carbon atoms, and examples thereof include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, and 1-decene. Among them, it is more preferable that it is at least one selected from ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene, and ethylene is even more preferable.

[0134] When propylene is used as the α-olefin, the usage ratio of propylene to olefin A is in terms of propylene:olefin A (molar ratio), usually 1:10 to 5000:1, preferably 1:5 to 1000:1.

[0135] In addition, at least one selected from cyclic olefins, olefins having a polar group, terminal hydroxylated vinyl compounds, and aromatic vinyl compounds can be allowed to coexist in the reaction system to proceed with the polymerization. It is also possible to use a polyene in combination. Further, within the scope not departing from the gist of the present invention, other components such as vinylcyclohexane may be copolymerized.

[0136] Examples of the cyclic olefin 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.

[0137] Examples of the olefin having a polar group include, for example, α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydride, and metal salts thereof such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts, calcium salts, and aluminum salts; α,β-unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 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 caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate; are included.

[0138] Examples of the terminal hydroxyl group-containing vinyl compounds include linear terminal hydroxyl group-containing vinyl compounds such as 1-butenol, 1-pentenol, 1-hexenol, 1-octenol, 1-decenol, 1-undecenol, 1-dodecenol, 1-tetradecenol, 1-hexadecenol, 1-octadecenol, 1-eicosanol; and branched terminal hydroxyl group-containing vinyl compounds such as 3-methyl-1-butenol, 3-methyl-1-pentenol, 4-methyl-1-pentenol, 3-ethyl-1-pentenol, 4,4-dimethyl-1-pentenol, 4-methyl-1-hexenol, 4,4-dimethyl-1-hexenol, 4-ethyl-1-hexenol, 3-ethyl-1-hexenol.

[0139] Examples of the aromatic vinyl compounds include styrene; mono- or polyalkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene.

[0140] The polyene is preferably selected from dienes and trienes. It is also a preferred embodiment to use the polyene in the range of 0.0001 to 1 mol% based on all the olefins supplied to the polymerization reaction.

[0141] Examples of the diene include α,ω-non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene; non-conjugated dienes such as ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene; and conjugated dienes such as butadiene and isoprene. Among these, α,ω-non-conjugated dienes and dienes having a norbornene skeleton are preferable.

[0142] Examples of the triene include non-conjugated trienes such as 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-nonadiene (EMND), 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylidene-1,7-nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecandiene; and conjugated trienes 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 preferable.

[0143] The diene or triene may be used alone or in combination of two or more. Further, a combination of a diene and a triene may be used. Among polyenes, α,ω-non-conjugated dienes and polyenes having a norbornene skeleton are particularly preferred.

[0144] In this production method, when at least one of the olefins supplied to the polymerization reaction is propylene, the olefin polymerization activity under hydrogen-free conditions is preferably 20 to 1,000,000 kg / mmol-M / hr, and more preferably 25 to 100,000 kg / mmol-M / hr.

[0145] 〈Olefin Polymer〉 The olefin polymer obtained by this production method is a propylene homopolymer; propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer, propylene / 1-octene copolymer, propylene / 1-hexene copolymer, propylene / 4-methyl-1-pentene copolymer, propylene / ethylene / 1-octene copolymer, propylene / ethylene / 1-hexene copolymer, propylene / ethylene / 4-methyl-1-pentene copolymer and other propylene / α-olefin copolymers (preferably the olefin A) ethylene homopolymer; ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / 1-octene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / propylene / 1-octene copolymer, ethylene / propylene / 1-hexene copolymer, ethylene / propylene / 4-methyl-1-pentene copolymer and other ethylene / α-olefin copolymers are preferred. Further, a so-called block copolymer (impact copolymer) obtained by mixing or continuously producing two or more selected from these polymers may also be used.

[0146] The olefin polymer obtained by this production method is most preferably a propylene homopolymer consisting essentially of only propylene-derived structural units, a propylene / ethylene copolymer consisting essentially of only propylene-derived structural units and ethylene-derived structural units, or an ethylene / 1-butene copolymer consisting essentially of only ethylene-derived structural units and 1-butene-derived structural units.

[0147] Here, "substantially" means that in the propylene polymer, the proportion of propylene-derived structural units is 95% by mass or more; in the propylene / ethylene copolymer, the total proportion of propylene-derived structural units and ethylene-derived structural units is 95% by mass or more; and in the ethylene / 1-butene copolymer, the total proportion of ethylene-derived structural units and 1-butene-derived structural units is 95% by mass or more.

[0148] In the case of a propylene / α-olefin copolymer, when the total of the content of propylene-derived structural units and the content of structural units derived from monomers other than propylene (particularly, the structural units derived from the olefin A) is 100 mol%, the propylene / α-olefin copolymer preferably contains propylene-derived structural units in the range of 50 to 100 mol%, preferably 80 to 99.5 mol%, more preferably 90 to 99 mol%, and contains a total of 0 to 50 mol%, 0.5 to 20 mol%, more preferably 1 to 10 mol% of structural units derived from monomers other than propylene (particularly, the structural units derived from the olefin A).

[0149] In the case of an ethylene / α-olefin copolymer, when the total of the content of ethylene-derived structural units and the content of structural units derived from monomers other than ethylene is 100 mol%, the ethylene / α-olefin copolymer preferably contains ethylene-derived structural units in the range of 50 to 100 mol%, preferably 80 to 99.5 mol%, more preferably 90 to 99 mol%, and contains a total of 0 to 50 mol%, 0.5 to 20 mol%, more preferably 1 to 10 mol% of structural units derived from monomers other than ethylene.

[0150] Propylene / α-olefin copolymers in which the constituent units derived from monomers other than propylene, particularly the constituent units derived from the olefin A, are within the above range are excellent in moldability. Also, other constituent units may be included as long as the effects of the present invention are not impaired. The content of the monomers contained in the olefin polymer can be measured by nuclear magnetic resonance spectroscopy or, when there is a reference substance, by infrared spectroscopy or the like.

[0151] The melting point (Tm) determined by DSC of the olefin polymer obtained by this production method is preferably 120 to 150 °C, more preferably 125 to 150 °C, and even more preferably 130 to 150 °C. Since the olefin polymer having a melting point (Tm) within the above range has high stereoregularity, crystallization is fast, which is advantageous for molding.

[0152] The crystallization temperature (Tc) determined by DSC of the olefin polymer obtained by this production method is preferably 85 to 130 °C, more preferably 95 to 120 °C, and even more preferably 100 to 115 °C. Specific methods for measuring the melting point (Tm) and the crystallization temperature (Tc) will be described in detail in the examples described later.

[0153] The weight average molecular weight (Mw) obtained by measurement by gel permeation chromatography (GPC) of the olefin polymer obtained by this production method and converted to polystyrene is preferably 50,000 to 800,000, more preferably 100,000 to 700,000, and even more preferably 150,000 to 600,000. It can be said that the olefin polymer having Mw within the above range has high toughness.

[0154] The molecular weight distribution (Mw / Mn) obtained by measurement by gel permeation chromatography (GPC) of the olefin polymer obtained by this production method and converted to polystyrene is preferably 1.6 to 5.0, more preferably 1.8 to 3.0, and even more preferably 2.0 to 2.4.

[0155] The intrinsic viscosity [η] determined from the following formula (1) of the olefin polymer obtained by this production method is preferably 1.0 to 10 dl / g, more preferably 1.2 to 7 dl / g, and still more preferably 1.4 to 5 dl / g. Formula (1) is called the Mark-Houwink (M-H) formula, and K m represents the solvent constant and M represents the molecular weight. [η]=K m M a ···(1) (In the formula, K m is 0.0004 and a is 0.69.)

Examples

[0156] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples at all.

[0157] 〔Melting point (Tm), crystallization temperature (Tc)〕 The melting point (Tm) or crystallization temperature (Tc) of the olefin polymer was measured as follows using DSC 7020 manufactured by Hitachi High-Tech Sciences Corporation. Under a nitrogen atmosphere (20 mL / min), the sample (about 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 top of the crystal melting peak in the heating process of (3), and the crystallization temperature (Tc) was calculated from the peak top of the crystallization peak in the cooling process of (2). In the olefin polymers described in the examples and comparative examples, when 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 polymer.

[0158] 〔Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)〕 The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. The separation columns were two TSKgel GNH6-HT and two TSKgel GNH6-HTL, both with a column size of 7.5 mm in diameter and 300 mm in length. The column temperature was 140 °C. As the mobile phase, o-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Corporation) and 0.025 wt% of BHT (manufactured by Takeda Pharmaceutical Company Limited) as an antioxidant were used. The mobile phase was moved at 1.0 mL / min, the sample concentration was 15 mg / 10 mL, the sample injection volume was 500 microliters, and a differential refractometer was used as the detector. Standard polystyrene was manufactured by Tosoh Corporation for Mw < 1000 and Mw > 4×10 6 and was manufactured by Pressure Chemical Company for 1000 ≤ Mw ≤ 4×10 6 . The molecular weight distribution and various average molecular weights were calculated as polypropylene molecular weight conversions according to the general calibration procedure.

[0159] [Intrinsic viscosity [η]] The intrinsic viscosity [η] of the olefin polymers obtained in Examples 1 to 3 was determined from the value of the molecular weight M by the following formula (1). This formula is called the Mark-Houwink (M-H) formula, where K m is the solvent constant and M is the molecular weight. [η] = K m M a ···(1) (In the formula, K m is 0.0004, a is 0.69, and M is the weight-average molecular weight Mw.)

[0160] The intrinsic viscosity [η] of the olefin polymers obtained in Comparative Examples 1 to 3 is a value measured at 135 °C using a decalin solvent. That is, the granulated pellets (about 20 mg) of the olefin polymer are dissolved in a decalin solvent (15 mL), and the specific viscosity ηsp is measured in an oil bath at 135 °C. After adding and diluting the decalin solution with a decalin solvent (5 mL), the specific viscosity ηsp is measured in the same manner as above. This dilution operation is repeated two more times, and the value of ηsp / C when extrapolating the concentration (C) of the olefin polymer to 0 is defined as the intrinsic viscosity [η] of the olefin polymer. Intrinsic viscosity [η] = lim(ηsp / C) (C → 0)

[0161] 〔Identification of the target substance〕 The structure of the transition metal compound obtained in the synthesis example was determined using 400 MHz 1 1H-NMR (JEOL ECZ400S) and FD-MS (JEOL SX-102A).

[0162] 〔Synthesis example of metallocene compound〕 The metallocene compound used in this example can also be synthesized by the methods described in the following patent publications. Specifically, JP-A-2000-212194, JP-A-2004-168744, JP-A-2004-189666, JP-A-2004-161957, JP-A-2007-302854, JP-A-2007-302853, JP-A-2016-164264, WO 01 / 027124 pamphlet, etc.

[0163] [Synthesis Example 1] Synthesis of the transition metal compound (a) represented by the following formula

[0164]

Chemical formula

[0165] (Synthesis 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-butyl methyl ether were placed in a flask, and 1.70 ml (hexane solution; 2.73 mmol) of n-butyllithium was added while cooling to 0 °C. The mixture was stirred at 50 °C for 14 hours, cooled again to 0 °C, then 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 aqueous HCl solution was added, and the organic layer was separated. The separated organic layer was washed with water and saturated aqueous sodium chloride solution. After drying over magnesium sulfate, crystals were precipitated with methanol / hexane. The obtained crystals were washed with hexane to obtain 1.01 g (yield 72%) of the target product as white crystals. The formation of the target product was confirmed by FD-MS measurement. FD-MS: m / Z = 562.4 (M + ) 1 By 1H-NMR measurement, it was confirmed that the white crystals were a mixture of multiple isomers. In the subsequent steps, the compound thus obtained was used as the ligand (a-1).

[0166] (Synthesis of transition metal compound (a)) Under a nitrogen atmosphere, 1.01 g (1.79 mmol) of the 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, and 2.50 ml (hexane solution; 3.95 mmol) of n-butyllithium was added while cooling to 0 °C. After stirring at 60 °C for 4 hours, concentration under reduced pressure was performed and 50 ml of diethyl ether was added. The obtained solution was cooled to -78 °C, 0.39 g (1.69 mmol) of zirconium tetrachloride was charged, and the mixture was stirred for 18 hours while returning to room temperature. The solvent was distilled off, and the soluble component was extracted with toluene. The obtained 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 measurement and FD-MS measurement. 1 1H-NMR (400 MHz, CDCl3): δ / ppm 7.88 (dd, J = 9.2, 2.0 Hz, 2H), 7.28 (d, J = 2.0 Hz, 1H), 7.19 (dd, J = 9.2, 2.0 Hz, 1H), 7.09 (dd, J = 9.2, 2.0 Hz, 1H), 7.06 (d, J = 2.0 Hz, 1H), 6.10 (d, J = 2.0 Hz, 1H), 5.28 (d, J = 1.6 Hz, 1H), 4.64 - 4.57 (m, 2H), 3.87 (d, J = 14.8 Hz, 1H), 2.59 (d, J = 2.6 Hz, 1H), 2.29 (s, 3H), 1.89 (brs, 3H), 1.82 - 1.73 (m, 6H), 1.67 (brs, 6H), 1.38 (d, J = 3.6 Hz, 3H), 1.37 (s, 3H), 1.34 (d, J = 6.0 Hz, 3H), 1.34 (d, J = 6.0 Hz, 3H), 1.30 (d, J = 6.0 Hz, 3H) FD-MS: m / Z = 722.2 (M + ) In the following examples, the compound thus obtained was used as the "transition metal compound (a)".

[0167] [Other Transition Metal Compounds] In addition to the transition metal compound (a) obtained in the above synthesis example, as the catalyst (f), a transition metal compound (e) represented by the following formula was used. This transition metal compound (e) is different from the aforementioned transition metal compound (a) in that R 1 is not an adamantyl derivative, and R 2 and R 7 has no ZR 13 and is a transition metal compound.

[0168] [Chemical Formula]

[0169] [Example 1] Under a nitrogen atmosphere, 0.0032 mmol of the metallocene compound (a) as the transition metal compound (A) was placed in a Schlenk tube, dissolved in 6.1 ml of heptane, and then 0.49 ml of a suspension of modified methylaluminoxane (trade name: TMAO341, manufactured by Tosoh Finechem Corporation) (n-hexane solvent, 3.39 M in terms of aluminum atoms, 1.66 mmol) was added, followed by stirring at room temperature for 30 minutes to prepare a catalyst solution with a concentration of the transition metal compound (a) of 0.0005 M. Into a SUS autoclave, 0.1 ml of an n-heptane solution of triisobutylaluminum (0.05 M, 5 μmol) and 3.0 ml of n-heptane as a polymerization solvent were added, and stirring was carried out at 600 revolutions per minute. This solution was heated to 60 °C and then pressurized with propylene until the total pressure reached 0.7 MPa. To the autoclave, 0.1 ml of the catalyst solution (0.05 μmol of the transition metal compound (a)) and 0.7 ml of n-heptane were added to initiate polymerization. After polymerizing at 60 °C for 9 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. To the resulting slurry containing the olefin polymer, 50 ml of methanol and a small amount of aqueous hydrochloric acid solution were added, and stirring was carried out at room temperature for 1 hour. Thereafter, the olefin polymer recovered by filtration was dried under reduced pressure to obtain 0.343 g of an olefin polymer (propylene homopolymer). The polymerization activity was 46 kg-PP / mmol-Zr / hr, the melting point (Tm) of the obtained olefin polymer was 149.3 °C, Mw was 552,000, Mw / Mn was 2.35, the intrinsic viscosity [η] was 3.7 dl / g, and the crystallization temperature (Tc) was 112.3 °C.

[0170] [Example 2] Under a nitrogen atmosphere, 0.0032 mmol of the transition metal compound (a) as the transition metal compound (A) was placed in a Schlenk tube, dissolved in 6.1 ml of heptane, and then 0.49 ml of a suspension of modified methylaluminoxane (trade name: TMAO341, manufactured by Tosoh Finechem Corporation) (n-hexane solvent, 3.39 M in terms of aluminum atoms, 1.66 mmol) was added, followed by stirring at room temperature for 30 minutes to prepare a catalyst solution with a concentration of the transition metal compound (a) of 0.0005 M. Into a SUS autoclave, 0.1 ml (0.05 M, 5 μmol) of an n-heptane solution of triisobutylaluminum and 3.0 ml of n-heptane as a polymerization solvent were added, and stirring was carried out at 600 revolutions per minute. This solution was heated to 70 °C, and then pressurized with propylene until the total pressure reached 0.7 MPa. To the autoclave, 0.1 ml of the catalyst solution (0.05 μmol of transition metal compound (a) and 0.7 ml of n-heptane) was added to initiate polymerization. After polymerization at 70 °C for 9 minutes, a small amount of isobutyl alcohol was added to stop the polymerization. To the resulting slurry containing the olefin polymer, 50 ml of methanol and a small amount of aqueous hydrochloric acid solution were added, and stirring was carried out at room temperature for 1 hour. Thereafter, the olefin polymer recovered by filtration was dried under reduced pressure to obtain 0.321 g of an olefin polymer (propylene homopolymer). The polymerization activity was 43 kg-PP / mmol-Zr / hr, the melting point (Tm) of the obtained olefin polymer was 144.4 °C, Mw was 371,000, Mw / Mn was 2.21, the intrinsic viscosity [η] was 2.9 dl / g, and the crystallization temperature (Tc) was 108.4 °C.

[0171] [Example 3] Under a nitrogen atmosphere, 0.0032 mmol of transition metal compound (a) as transition metal compound (A) was placed in a Schlenk tube and dissolved in 6.1 ml of heptane. Then, 0.49 ml of a suspension of modified methylaluminoxane (trade name: TMAO341, manufactured by Tosoh Finechem Corporation) (n-hexane solvent, 3.39 M in terms of aluminum atom, 1.66 mmol) was added, and stirring was carried out at room temperature for 30 minutes to adjust a catalyst solution with a concentration of transition metal compound (a) of 0.0005 M. Into a SUS autoclave, 0.1 ml (0.05 M, 5 μmol) of an n-heptane solution of triisobutylaluminum and 3.0 ml of n-heptane as a polymerization solvent were added, and stirring was carried out at 600 revolutions per minute. This solution was heated to 80 °C, and then pressurized with propylene until the total pressure reached 0.7 MPa. 0.1 ml of the catalyst solution (0.05 μmol of the transition metal compound (a)) and 0.7 ml of n-heptane were added to the autoclave, and polymerization was initiated. After polymerizing at 80°C for 9 minutes, a small amount of isobutyl alcohol was added to stop the polymerization. 50 ml of methanol and a small amount of aqueous hydrochloric acid solution were added to the resulting slurry containing the olefin polymer, and the mixture was stirred at room temperature for 1 hour. Thereafter, the olefin polymer recovered by filtration was dried under reduced pressure to obtain 0.801 g of an olefin polymer (propylene homopolymer). The polymerization activity was 27 kg-PP / mmol-Zr / hr, the melting point (Tm) of the obtained polymer was 137.9°C, Mw was 187,000, Mw / Mn was 2.11, the intrinsic viscosity [η] was 1.8 dl / g, and the crystallization temperature (Tc) was 103.9°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 changed to the transition metal compound (e) and the polymerization time was changed to 10 minutes. The polymerization activity was 30 kg-PP / mmol-Zr / hr, the melting point (Tm) of the obtained olefin polymer (propylene homopolymer) was 138.7°C, [η] was 1.6 dl / g, and the crystallization temperature (Tc) was 103.4°C.

[0173] [Comparative Example 2] A catalyst solution was prepared and olefin polymerization was carried out in the same manner as in Example 2, except that the transition metal compound (a) used was changed to the transition metal compound (e) and the polymerization time was changed to 10 minutes. The polymerization activity was 39 kg-PP / mmol-Zr / hr, the melting point (Tm) of the obtained olefin polymer (propylene homopolymer) was 138.9°C, [η] was 1.1 dl / g, and the crystallization temperature (Tc) was 102.6°C.

[0174] [Comparative Example 3] The catalyst solution was prepared and olefin polymerization was carried out in the same manner as in Example 3, except that the polymerization time was changed to 10 minutes for the transition metal compound (a) used to the transition metal compound (e). The polymerization activity was 34 kg-PP / mmol-Zr / hr, and the melting point (Tm) of the obtained olefin polymer (propylene homopolymer) was 129.7 °C, [η] was 0.9 dl / g, and the crystallization temperature (Tc) was 95.5 °C.

[0175] For Examples 1 to 3 and Comparative Examples 1 to 3, the physical properties of the obtained propylene homopolymers 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. In Table 4, the unit of polymerization activity is given as "polymerization activity (kg-PP / mmol-M / hr)", which means "polymerization activity (kg-PP / mmol-Zr / hr)" when Zr is used as the transition metal M constituting the catalyst.

[0176] [Table 4]

Claims

1. A transition metal compound (A) represented by the following general formula [I]. 【Chemical 1】 (wherein, R 1 is an adamantyl group derivative, R 2 and R 7 are each independently a substituent represented by ZR 13 (provided that Z is an oxygen atom or a sulfur atom, and R 13 is a 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, and a halogen-containing hydrocarbon group, and is bonded to a fluorenyl ligand via Z).), 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 in the general formula [I], Z is an oxygen atom.

3. In the general formula [I], R 13 is a hydrocarbon group having 1 to 20 carbon atoms, and the transition metal compound (A) according to claim 1.

4. In the general formula [I], R 3 and R 6 are hydrogen atoms, and the transition metal compound (A) according to claim 1.

5. In the general formula [I], R 4 and R 5 are hydrogen atoms, and the transition metal compound (A) according to claim 1.

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

7. In the general formula [I], R 8 ~R 11 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and among R 8 ~R 11 the adjacent substituents may be bonded to each other to form a ring. The transition metal compound (A) according to claim 1.

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

9. In the general formula [I], R 8 and R 9 are hydrocarbon groups having 1 to 20 carbon atoms, and the transition metal compound (A) according to claim 7.

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

11. The transition metal compound (A) according to Claim 1, and an organoaluminum oxy compound (b-1), a compound (b-2) that reacts with the transition metal compound [A] to form an ion pair, and an organoaluminum compound (b-3) and at least one compound (B) selected from to form a catalyst for olefin polymerization.

12. A method for producing an olefin polymer, comprising a step of polymerizing a monomer containing at least one α-olefin having 3 or more carbon atoms under a polymerization temperature condition of 50 to 200°C in the presence of the olefin polymerization catalyst according to Claim 11.

13. The method for producing an olefin polymer according to Claim 12, wherein at least one of the α-olefins having 3 or more carbon atoms is propylene.

14. The method for producing an olefin polymer according to Claim 12, wherein the intrinsic viscosity [η] determined from the following formula (1) of the olefin polymer is 1.0 to 10 dl / g. [η] = K ｍ M ａ ...(1) (In the formula, M represents the molecular weight, and K ｍ is 0.0004, and a is 0.69.)

15. The method for producing an olefin polymer according to Claim 12, wherein the melting point peak (Tm) determined by a differential scanning calorimeter (DSC) of the olefin polymer is 120 to 150°C.

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