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 with high productivity, 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 (particularly, 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, it has become possible to obtain those with a relatively high melting point, which is an index of the stereoregularity of the polymer, and it has also become possible to obtain those with a sufficiently high molecular weight of the polymer. 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 a temperature above room temperature, preferably at a high temperature 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 high polymerization activity even under high temperature conditions advantageous in industrial production methods, and it has been disclosed that the olefin polymer obtained using the olefin polymerization catalyst has characteristics such as high molecular weight and high melting point (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 for obtaining a polymer having a relatively high melting point and a high molecular weight with high productivity 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 with high productivity even under high temperature conditions advantageous in industrial production methods.

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 formula

[0013] [2] In the general formula [I], R 3 and R 6 are hydrogen atoms, and the transition metal compound (A) according to [1]. [3] In the general formula [I], R 4 and R 5 are hydrogen atoms, and the transition metal compound (A) according to [1] or [2]. [4] 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 any one of [1] to [3].

[0014] [5] 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 ~R 8 ~R 11 adjacent substituents may combine with each other to form a ring and the transition metal compound (A) according to any one of [1] to [4]. [6] In the general formula [I], R 10 and R 11 are hydrogen atoms, and the transition metal compound (A) according to [5]. [7] 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 [5] or [6]. [8] In the general formula [I], the transition metal compound (A) according to any one of [1] to [7], wherein n is 1.

[0015] [9] A transition metal compound (A) according to any one of [1] to [8], 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 the group consisting of a catalyst for olefin polymerization.

[0016]

[10] 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 [9].

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

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

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

[10] or

[11] , wherein the intrinsic viscosity [η] of the olefin polymer in decalin at 135 °C is 1.0 to 10 dl / g.

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

[10] to

[12] , wherein the melting point peak (Tm) of the olefin polymer determined by a differential scanning calorimeter (DSC) is 80 to 150 °C.

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

[10] to

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

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

[0018] In this specification, the symbol "~" indicating a numerical range means "not less than M and not more than N" 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 refers to "structural unit corresponding to M", that is, a structural unit having a pair of bonds formed by opening the π bond constituting the double bond of M. Note 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 , R 2 and R 7 〉 In the general formula [I], R 1 , R 2 and R 7 are each independently 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. The 1-adamantyl group, the 3,5-dimethyl-1-adamantyl group, or the 3,5,7-trimethyl-1-adamantyl group is preferable, and the 1-adamantyl group is more preferable. R 1 、R 2 and R 7 may be the same or different from each other, but from the viewpoint of ease of production of the transition metal compound (A), R 2 and R 7 are preferably the same substituent, and R 1 、R 2 and R 7 are more preferably all the same substituent.

[0022] R 1 、R 2 and R 7 are preferably adamantyl group derivatives from the viewpoint of efficiently obtaining the resulting olefin polymer. Due to the steric bulk of R 1 、R 2 and R 7 it is considered that the approach of the anion to the metallocenium cation derived from the general formula [I], which is presumed to be the active species, becomes difficult. For this reason, (1) the coordination space of the metallocenium cation expands, making it easier for the monomer to approach the metallocenium cation, and (2) the Lewis acidity of the metallocenium cation improves, increasing the reactivity with olefins, so it is considered that the catalytic activity improves. In addition, due to the electronic effect of the adamantyl group derivative, the energy difference between monomer insertion and chain transfer reaction in the olefin polymerization reaction increases, and by inhibiting the chain transfer reaction caused by the organoaluminum compound in the polymerization system, it is considered that the intrinsic viscosity of the resulting olefin polymer increases.

[0023] 〈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 、R10 , 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, and R 3 ~R 6 and R 8 ~R 12 Among them, adjacent substituents may be bonded to each other to form a ring.

[0024] 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.

[0025] Examples of the alkyl group 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; 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 the saturated alicyclic group having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; and alicyclic polycyclic groups such as norbornyl group and adamantyl group.

[0027] 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; 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.

[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, neophyl group; 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.

[0029] Examples of silicon-containing groups include alkylsilyl groups such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group; arylsilyl groups such as dimethylphenylsilyl group, diphenylmethylsilyl group, triphenylsilyl group.

[0030] Examples of halogen atoms include fluorine atom, chlorine atom, bromine atom, iodine atom which are atoms of Group 17 elements.

[0031] Examples of the halogen-containing hydrocarbon group include a group 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 trifluoromethyl group; halogen-substituted aryl groups such as fluoroaryl groups like pentafluorophenyl group, chloroaryl groups such as o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, chloronaphthyl group, bromoaryl groups such as o-bromophenyl group, m-bromophenyl group, p-bromophenyl group, bromonaphthyl group, iodoaryl groups such as 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 trifluoromethylphenyl group, bromoalkylaryl groups such as bromomethylphenyl group, dibromomethylphenyl group, iodoalkylaryl groups such as iodomethylphenyl group, diiodomethylphenyl group, etc., which are halogen substituents of the alkylaryl group; halogen-substituted aralkyl groups such as chloroaralkyl groups like o-chlorobenzyl group, m-chlorobenzyl group, p-chlorobenzyl group, chlorophenethyl group, bromoaralkyl groups such as o-bromobenzyl group, m-bromobenzyl group, p-bromobenzyl group, bromophenethyl group, iodoaralkyl groups such as o-iodobenzyl group, m-iodobenzyl group, p-iodobenzyl group, iodophenethyl group, etc., which are halogen substituents of the unsubstituted aralkyl group.

[0032] In the general formula [I], when the 1-position and 8-position of the fluorenyl moiety are hydrogen atoms, an olefin polymer can be efficiently obtained.

[0033] R 3 and R 6 are preferably hydrogen atoms. R 3 and R 6 being hydrogen atoms is preferable from the viewpoints of efficiently obtaining the resulting olefin polymer and the melt fluidity of the resulting olefin polymer.

[0034] R4 and R 5 is preferably, independently of one another, 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. R 4 and R 5 being the above groups is preferable from the viewpoint of efficiently obtaining the resulting olefin polymer.

[0035] 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. R 12 being the above group is preferable from the viewpoint of efficiently obtaining the resulting olefin polymer.

[0036] R 8 , R 9 , R 10 and R 11 are preferably, independently of one another, 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 preferably, independently of one another, a hydrocarbon group having 1 to 20 carbon atoms. Further, R 10 and R 11 are preferably a hydrogen atom.

[0037] Further, adjacent substituents among R 8 to R 11 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 with each other, or R 9 and R 10are preferably groups that are bonded to each other to form a cyclohexane ring with each other, and R 9 and R 10 are more preferably groups that are bonded to each other to form a cyclohexane ring with each other. 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.

[0038] 〈n, M, Q and j〉 n is an integer of 1 to 3, preferably 1 or 2, more preferably 1. When n is the above value, it is preferable from the viewpoint of efficiently obtaining the produced olefin polymer.

[0039] 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, more preferably a zirconium atom.

[0040] 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, the plurality of Qs may be the same or different.

[0041] The halogen atom in Q is a chlorine atom, a fluorine atom, a bromine atom or an iodine atom, and a chlorine atom is preferable.

[0042] As the hydrocarbon group in Q, an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms are preferable. The number of carbon atoms of the hydrocarbon group is more preferably 5 or less.

[0043] 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.

[0044] Examples of cycloalkyl groups having 3 to 10 carbon atoms include cyclohexylmethyl group, cyclohexyl group, and 1-methyl-1-cyclohexyl group.

[0045] Examples of anion ligands 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.

[0046] Examples of neutral ligands capable of coordinating with lone pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ethers such as tetrahydrofuran (THF), diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0047] Q is preferably a halogen atom or an alkyl group having 1 to 10 carbon atoms, 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.

[0048] j is an integer of 1 to 4, preferably 2.

[0049] <Examples of 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.

[0050] For convenience in explanation, MQ of the metallocene compound jThe ligand structure excluding the (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).

[0051]

Chemical formula

[0052] Examples of the structure formed by the combination of two substituents with each other include the following structures: structure (i-1) (R 11 and R 12 combine with each other to form a cyclopentane ring), and structure (i-2) (R 11 and R 12 combine with each other to form a cyclohexane ring).

[0053]

Chemical formula

[0054] For the MQ of the metallocene compound j (excluding the metal part), the ligand structure 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.

[0055]

Table 1

[0056]

Table 2

[0057]

Table 3

[0058] 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 compound represented by the following formula is exemplified.

[0059]

Chemical formula

[0060] 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.

[0061] The above MQ j Compounds in which "zirconium" in the exemplified compounds of MQ is replaced with "hafnium" or "titanium", and metallocene compounds in which "dichloride" is replaced with "dimethyl" or "methylethyl" are also included in the transition metal compound (A) in the same manner.

[0062] ≪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 present 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.

[0063] <Compound (B)> Compound (B) is at least one compound selected from an organoaluminum oxy compound (b-1), a compound (b-2) that reacts with a 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.

[0064] 〈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.

[0065]

Chemical formula

[0066] 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, more preferably 10 or more.

[0067]

Chemical formula

[0068] 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.

[0069] The modified methylaluminoxane having the structure represented by the formula [B3] can be prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. The modified methylaluminoxane having the structure represented by the 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.

[0070] In addition, modified methylaluminoxanes prepared using trimethylaluminum and triisobutylaluminum (i.e., R is an isobutyl group in the formula [B3]), such as those from Tosoh Finechem Corporation, are commercially produced under the names MMAO and TMAO.

[0071] 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 the general formula [B1] or [B2], MMAO is soluble in aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0072] [Chemical formula]

[0073] In the 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.

[0074] Furthermore, benzene-insoluble or poorly soluble organoaluminum oxy compounds as exemplified in JP-A-2-78687, organoaluminum oxy 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, etc. can also be preferably used.

[0075] The "benzene-insoluble or poorly soluble" organoaluminum oxy compound mentioned above refers to an organoaluminum oxy compound that is insoluble or poorly soluble in benzene, and the 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.

[0076] <Compound (b-2) that reacts with transition metal compound (A) to form an ion pair> Examples of the compound (b-2) (hereinafter also referred to as "ionic compound (b-2)") that reacts with the transition metal compound (A) to form an ion pair 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. Further, heteropoly compounds and isopoly compounds are also exemplified. The ionic compound (b-2) may be used alone or in combination of two or more.

[0077] As the ionic compound (b-2), a compound represented by the following general formula [B5] is preferable.

[0078] [Chemical formula]

[0079] In formula [B5], R e+ is, for example, H + , oxonium cation, carbenium cation ion, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal. R f , R g , R h and R iEach independently represents an organic group, preferably an aryl group, or a halogen-substituted aryl group.

[0080] Examples of the carbocation include trisubstituted carbocations such as triphenylcarbocation, tris(methylphenyl)carbocation, and tris(dimethylphenyl)carbocation.

[0081] 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.

[0082] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation, and tris(dimethylphenyl)phosphonium cation.

[0083] R e+ Preferably, R is a carbocation or an ammonium cation, and particularly preferably a triphenylcarbocation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation.

[0084] 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.

[0085] R e+ Examples of the ammonium salt when R is an ammonium cation include trialkylammonium salts, N,N-dialkylanilinium salts, and dialkylammonium salts.

[0086] 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-bis(trifluoromethyl)phenyl)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-bis(trifluoromethyl)phenyl)borate, and dioctadecylmethylammonium.

[0087] 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-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.

[0088] 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.

[0089] (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.

[0090] 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.

[0091] M 2 AlR a 4…[B7] In formula [B7], M 2 is Li, Na or K, and the plurality of Rs a are independently hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

[0092] 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; the 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); dialkylaluminum aryloxides such as diethylaluminum phenoxide and diethylaluminum (2,6-di-tert-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 alkylaluminums such as ethylaluminum dichloride; partially hydrogenated alkylaluminums 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 alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide are exemplified.

[0093] 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 and 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. Examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2.

[0094] As the organoaluminum compound (b-3), trimethylaluminum and triisobutylaluminum are preferred from the viewpoint of easy availability.

[0095] <Support (C)> This olefin polymerization catalyst may further contain a carrier (C) as required. 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.

[0096] (Inorganic compound) Examples of the inorganic compound include porous oxides, inorganic halides, clay minerals, clays (usually composed mainly of the clay minerals), and ion-exchange layered compounds (most clay minerals are ion-exchange layered compounds). Examples of the porous oxides 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 one or both of the components of SiO2 and Al2O3 are preferred.

[0097] 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 as required. Examples of the inorganic halide include MgCl2, MgBr2, MnCl2, and MnBr2. The inorganic halide may be used as it is, or may be used 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.

[0098] As for clay, clay minerals, and ion-exchange layered compounds, not only natural products but also synthetic products can be used. Note that an ion-exchange 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 weak binding forces, and is a compound in which the contained ions are exchangeable.

[0099] Specifically, examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gaylussite clay, allophane, hisingerite, pyrophyllite, synthetic mica, etc. from the ummo group, montmorillonite group, vermiculite, riokite group, palygorskite, kaolinite, nacrite, dickite, hectorite, teniolite, halloysite; examples of ion-exchange layered compounds include ion-crystalline compounds having a layered crystal structure such as hexagonal closest packing type, antimony type, CdCl2 type, CdI2 type. Specifically, examples of ion-exchange 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, γ-Ti(NH4PO4)2·H2O.

[0100] It is also preferable to subject clay and clay minerals 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 clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment.

[0101] In addition, the ion-exchangeable layered compound may be a layered compound with expanded interlayer spaces by utilizing its ion-exchangeability and exchanging the exchangeable ions between the 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.

[0102] Examples of the guest compound to be intercalated 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 (R is a hydrocarbon group, etc.); [Al 13 O4(OH) 24 7+ , [Zr4(OH) 14 2+ , [Fe3O(OCOCH3)6] + and other metal hydroxide ions. These guest compounds may be used alone or in combination of two or more.

[0103] 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 (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.

[0104] (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.

[0105] <Organic compound component (D)> This olefin polymerization catalyst may further contain an organic compound component (D) as required. 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 the olefin polymer. 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.

[0106] <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.

[0107] (1) A method of adding the transition metal compound [A] alone to the polymerization reactor. (2) A method of adding the transition metal compound [A] and compound [B] to the polymerization reactor in an arbitrary order. (3) A method of adding a catalyst component in which the transition metal compound [A] is supported on the carrier [C], and compound [B] to the polymerization reactor in an arbitrary order. (4) A method of adding a catalyst component in which compound [B] is supported on the carrier [C], and the transition metal compound [A] to the polymerization reactor in an arbitrary order. (5) A method of adding a catalyst component in which the transition metal compound [A] and compound [B] are supported on the carrier [C] to the polymerization reactor. (6) A method of adding a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C], and the compound [B] to a polymerization reactor in any order. In this case, the compounds [B] may be the same or different. (7) A method of adding a catalyst component in which a compound [B] is supported on a carrier [C], and a transition metal compound [A] to a polymerization reactor in any order. (8) A method of adding a catalyst component in which a compound [B] is supported on a carrier [C], a transition metal compound [A], and the compound [B] to a polymerization reactor in any order. In this case, the compounds [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 carrier [C], and a component in which a compound [B] is supported on the carrier [C] to a polymerization reactor in any order. (10) A method of adding a component in which a transition metal compound [A] is supported on a carrier [C], a component in which a compound [B] is supported on the carrier [C], and the compound [B] to a polymerization reactor in any order. In this case, the compounds [B] may be the same or different. (11) A method of adding a transition metal compound [A], a compound [B], and an organic compound component [D] to a polymerization reactor in any order. (12) A method of adding a component in which a compound [B] and an organic compound component [D] are brought into contact in advance, and a transition metal compound [A] to a polymerization reactor in any order. (13) A method of adding a component in which a compound [B] and an organic compound component [D] are supported on a carrier [C], and a transition metal compound [A] to a polymerization reactor in any order. (14) A method of adding a catalyst component in which a transition metal compound [A] and a compound [B] are brought into contact in advance, and an organic compound component [D] to a polymerization reactor in any order. (15) A method of adding a catalyst component in which a transition metal compound [A] and a compound [B] are brought into contact in advance, and the compound [B] to a polymerization reactor in any order. In this case, the compounds [B] may be the same or different. (16) A method of adding a catalyst component in which a transition metal compound [A] and a compound [B] are brought into contact in advance, and the compound [B] and an organic compound component [D] to a polymerization reactor in any order. In this case, the compounds [B] may be the same or different. (17) A method of adding to a polymerization reactor, in any order, a catalyst component obtained by pre - contacting a transition metal compound [A] with a compound [B], and a component obtained by pre - contacting the compound [B] with an organic compound component [D]. In this case, the compound [B] may be the same or different. (18) A method of adding to a polymerization reactor, in any order, a component in which a transition metal compound [A] is supported on a carrier [C], the compound [B], and the organic compound component [D]. (19) A method of adding to a polymerization reactor, in any order, a component in which a transition metal compound [A] is supported on a carrier [C], and a component obtained by pre - contacting the compound [B] with the organic compound component [D]. (20) A method of adding to a polymerization reactor a catalyst component obtained by pre - contacting a transition metal compound [A], a compound [B], and an organic compound component [D] in any order. (21) A method of adding to a polymerization reactor, in any order, a catalyst component obtained by pre - contacting a transition metal compound [A], a compound [B], and an organic compound component [D] in any order, and the compound [B]. In this case, the compound [B] may be the same or different. (22) A method of adding to a polymerization reactor a catalyst in which a transition metal compound [A], a compound [B], and an organic compound component [D] are supported on a carrier [C]. (23) A method of adding to a polymerization reactor, in any order, 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 the compound [B]. In this case, the compound [B] may be the same or different.

[0108] The compound [B] may be one kind or two or more kinds. In the solid catalyst component in which the transition metal compound [A] is supported on the carrier [C] and the solid catalyst component in which the transition metal compound [A] and the compound [B] are supported on the carrier [C], olefin may be prepolymerized, and further catalyst components may be supported on the prepolymerized solid catalyst component.

[0109] ≪Method for Producing Olefin Polymer≫ The method for producing an olefin polymer of the present invention (hereinafter also referred to as "this production method") has a monomer step including at least one α-olefin having 3 or more carbon atoms under the polymerization temperature condition of 50 to 200°C in the presence of the olefin polymerization catalyst for this.

[0110] 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 an olefin polymerization catalyst" means adding each component of the olefin polymerization catalyst to a polymerization vessel by an arbitrary method as in each of the methods (1) to (23) above to polymerize a monomer containing at least one α-olefin having 3 or more carbon atoms.

[0111] The monomer is preferably a monomer in which at least one is selected from α-olefins having 3 to 20 carbon atoms, more preferably a monomer in which at least one is selected from α-olefins having 3 to 10 carbon atoms, and still more preferably at least one is propylene.

[0112] Olefin polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods. In the liquid phase polymerization method, it is preferable to use an inert hydrocarbon-based medium. Examples of the inert hydrocarbon-based medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more. Also, a so-called bulk polymerization method using the liquefied olefin itself that can be supplied to the polymerization as a solvent can be used.

[0113] 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.

[0114] (1) Component (A) is usually 10 -9 ~10 -1 mol, preferably 10 -8 ~10 -2 mol and is used in an amount such that the molar ratio [Al / M] of the aluminum atom (Al) in component (b-1) to all transition metal atoms (M) in component (A) is as follows.

[0115] (2) When using component (b-1), the molar ratio [Al / M] of the aluminum atom (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, still more preferably 250 to 750, and particularly preferably 400 to 600, and component (b-1) is used in an amount such that the ratio becomes as described above.

[0116] (3) When using component (b-2), 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, and component (b-2) is used in an amount such that the ratio becomes as described above.

[0117] (4) When using component (b-3), 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, and component (b-3) is used in an amount such that the ratio becomes as described above.

[0118] (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.

[0119] (6) When using component (D), When component (B) is component (b-1), 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, and particularly preferably 0.020 to 0.030, in such an amount that When component (B) is component (b-2), the molar ratio [(D) / (b-2)] is usually 0.01 to 10, preferably 0.1 to 5, in such an amount that When component (B) is component (b-3), component (D) can be used in such an amount that the molar ratio [(D) / (b-3)] is usually 0.01 to 2, preferably 0.005 to 1.

[0120] 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, and 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, and preferably 5 to 20 minutes.

[0121] The polymerization reaction can be carried out by any of the batch, semi-continuous, and continuous methods. Further, the polymerization can also be carried out in two or more stages with different reaction conditions. The molecular weight of the obtained 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.

[0122] In particular, hydrogen can sometimes obtain the effect of improving the polymerization activity of the catalyst and the effect of increasing or decreasing the molecular weight of the polymer, and can be said to be a preferable additive. When hydrogen is added to the system, the amount thereof is suitably about 0.00001 to 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.

[0123] For the olefin polymer obtained by the present 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 performed as necessary.

[0124] According to the present 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.

[0125] 〈Olefin〉 In the present production method, the olefin supplied to the polymerization reaction contains at least one olefin selected from at least α-olefins having 3 or more carbon atoms, preferably α-olefins having 3 to 20 carbon atoms. The α-olefin may be used alone or in combination of two or more.

[0126] 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, at least one selected from propylene and 1-butene is even more preferable, and propylene is particularly preferable.

[0127] When propylene is used as the α-olefin, at least one olefin A selected from ethylene and α-olefins having 4 to 20 carbon atoms can be used in combination as needed. Olefin A is preferably at least one selected from ethylene and α-olefins having 4 to 10 carbon atoms. For example, ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene can be mentioned. Among them, it is more preferably at least one selected from ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene, still more preferably at least one selected from ethylene and 1-butene, and particularly preferably 1-butene.

[0128] 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.

[0129] Also, within the scope not departing from the gist of the present invention, at least one selected from cyclic olefins, olefins having a polar group, terminal hydroxylated vinyl compounds, and aromatic vinyl compounds can coexist in the reaction system to promote polymerization. It is also possible to use polyene in combination. Also, within the scope not departing from the gist of the present invention, other components such as vinylcyclohexane may be copolymerized.

[0130] Examples of the cyclic olefin include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0131] Examples of the olefin having a polar group include 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 of these; 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, isobutyl methacrylate; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate.

[0132] 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-eicosenol; 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.

[0133] Examples of the aromatic vinyl compound 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, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene.

[0134] 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.

[0135] 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; conjugated dienes such as butadiene and isoprene. Among these, α,ω-non-conjugated dienes and dienes having a norbornene skeleton are preferred.

[0136] 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 triazines 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.

[0137] The diene or triene may be used alone or in combination of two or more. Further, the diene and the triene may be used in combination. Among the polyenes, α,ω-non-conjugated dienes and polyenes having a norbornene skeleton are particularly preferred.

[0138] When at least one of the olefins supplied to the polymerization reaction is propylene, the olefin polymerization activity under hydrogen-free conditions in this production method is preferably 50 to 1,000,000 kg / mmol-M / hr, more preferably 70 to 100,000 kg / mmol-M / hr, and even more preferably 70 to 10,000 kg / mmol-M / hr.

[0139] <Olefin Polymer> The olefin polymer obtained by this production method is a propylene homopolymer; a propylene / ethylene copolymer, a propylene / 1-butene copolymer, a propylene / ethylene / 1-butene copolymer, a propylene / 1-octene copolymer, a propylene / 1-hexene copolymer, a propylene / 4-methyl-1-pentene copolymer, a propylene / ethylene / 1-octene copolymer, a propylene / ethylene / 1-hexene copolymer, a propylene / ethylene / 4-methyl-1-pentene copolymer, etc., a propylene / α-olefin (preferably the olefin A) copolymer; an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / propylene / 1-butene copolymer, an ethylene / 1-octene copolymer, an ethylene / 1-hexene copolymer, an ethylene / 4-methyl-1-pentene copolymer, an ethylene / propylene / 1-octene copolymer, an ethylene / propylene / 1-hexene copolymer, an ethylene / propylene / 4-methyl-1-pentene copolymer, etc., an ethylene / α-olefin (preferably propylene) copolymer; a 1-butene homopolymer; preferably a 1-butene / α-olefin (preferably propylene) copolymer such as a 1-butene / propylene copolymer, a 1-butene / ethylene copolymer, a 1-butene / ethylene / propylene copolymer, a 1-butene / propylene / ethylene copolymer, a 1-butene / 1-octene copolymer, a 1-butene / 1-hexene copolymer, a 1-butene / 4-methyl-1-pentene copolymer, a 1-butene / propylene / 1-octene copolymer, a 1-butene / propylene / 1-hexene copolymer, a 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 selected from these polymers may also be used.

[0140] In the present specification, in an olefin polymer (A / B copolymer and B / A copolymer) having constituent components derived from two monomers (monomer A and monomer B), a copolymer in which [content (mol%) of constituent components derived from monomer A] > [content (mol%) of constituent components derived from monomer B] is included in the A / B copolymer. On the other hand, a copolymer in which [content (mol%) of constituent components derived from monomer A] < [content (mol%) of constituent components derived from monomer B] is included in the B / A copolymer. Note that a copolymer in which [content (mol%) of constituent components derived from monomer A] = [content (mol%) of constituent components derived from monomer B] is included in both the A / B copolymer and the B / A copolymer. Also, in an olefin polymer having constituent components derived from three or more monomers, it is distinguished in the same way of thinking.

[0141] The olefin polymer obtained by this production method is most preferably a propylene homopolymer consisting only of constitutional units derived from propylene, a propylene / ethylene copolymer or ethylene / propylene copolymer consisting substantially only of constitutional units derived from propylene and constitutional units derived from ethylene, or a propylene / 1-butene copolymer or 1-butene / propylene copolymer consisting substantially only of constitutional units derived from propylene and constitutional units derived from 1-butene.

[0142] In the case of a propylene / α-olefin copolymer, when the total of the content of constitutional units derived from propylene and the content of constitutional units derived from monomers other than propylene (particularly, constitutional units derived from the olefin A) is 100 mol%, the constitutional units derived from propylene are usually included in the range of 50 to 99.9 mol%, preferably 80 to 99.5 mol%, more preferably 85 to 99 mol%, and still more preferably 90 to 95 mol%, and the constitutional units derived from monomers other than propylene (particularly, constitutional units derived from the olefin A) are usually included in the range of 0.1 to 50 mol% in total, preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%, and still more preferably 5 to 10 mol%. It is preferably a propylene / α-olefin copolymer.

[0143] In the case of an ethylene / α-olefin copolymer, when the total of the content of the structural units derived from ethylene and the content of the structural units derived from monomers other than ethylene is 100 mol%, the structural units derived from ethylene are usually in the range of 50 to 99.9 mol%, preferably 80 to 99.5 mol%, more preferably 85 to 99 mol%, still more preferably 90 to 95 mol%, and the structural units derived from monomers other than ethylene are usually in the range of 0.1 to 50 mol% in total, preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%, still more preferably 5 to 10 mol%. It is preferable that the ethylene / α-olefin copolymer contains the structural units in these ranges.

[0144] In the case of a 1-butene / α-olefin copolymer, when the total of the content of the structural units derived from 1-butene and the content of the structural units derived from monomers other than 1-butene is 100 mol%, the structural units derived from 1-butene are usually in the range of 50 to 99.9 mol%, preferably 80 to 99.5 mol%, more preferably 85 to 99 mol%, still more preferably 90 to 95 mol%, and the structural units derived from monomers other than 1-butene are usually in the range of 0.1 to 50 mol% in total, preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%, still more preferably 5 to 10 mol%. It is preferable that the 1-butene / α-olefin copolymer contains the structural units in these ranges.

[0145] A propylene / α-olefin copolymer in which the structural units derived from monomers other than propylene, particularly the structural units derived from the olefin A, are within the above ranges has excellent moldability. Also, other structural 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, infrared spectroscopy or the like.

[0146] The melting point (Tm) of the olefin polymer obtained by this production method, as determined by DSC, is preferably 80 to 150 °C, more preferably 90 to 150 °C. When the olefin polymer obtained by this production method is a propylene homopolymer or a 1-butene homopolymer, the melting point (Tm) is more preferably 100 to 150 °C, even more preferably 120 to 150 °C, and particularly preferably 130 to 150 °C. When the olefin polymer obtained by this production method is a propylene / α-olefin copolymer, an ethylene / α-olefin copolymer, or a 1-butene / α-olefin copolymer, it is more preferably 90 to 140 °C, and particularly preferably 100 to 120 °C.

[0147] The crystallization temperature (Tc) of the olefin polymer obtained by this production method, as determined by DSC, is preferably 80 to 120 °C, more preferably 90 to 115 °C, and even more preferably 95 to 110 °C. The specific measurement methods for the melting point (Tm) and the crystallization temperature (Tc) will be described in detail in the examples below.

[0148] The intrinsic viscosity [η] of the olefin polymer obtained by this production method in decalin at 135 °C is preferably 1.0 to 50.0 dl / g, more preferably 1.2 to 10.0 dl / g, even more preferably 1.3 to 5.0 dl / g, and particularly preferably 1.3 to 3.0 dl / g. The specific measurement method for the intrinsic viscosity [η] will be described in detail in the examples below.

Examples

[0149] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples in any way.

[0150] 〔Melting point (Tm), Crystallization temperature (Tc)〕 The melting point (Tm) or crystallization temperature (Tc) of the olefin polymer was measured as follows using a DSC 7020 manufactured by Hitachi High-Tech Sciences Corporation. In a nitrogen atmosphere (20 mL / min), the sample (about 5 mg) was heated to 230°C at a rate of (1) and held at 230°C for 3 minutes, then cooled to 30°C at a rate of 10°C / min and held at 30°C for 1 minute, and then (3) heated to 230°C at a rate of 10°C / min. The melting point (Tm) was calculated from the peak apex of the crystal melting peak during the heating process in (3), and the crystallization temperature (Tc) was calculated from the peak apex of the crystallization peak during the cooling process in (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.

[0151] 〔Intrinsic viscosity [η]〕 The intrinsic viscosity [η] of the olefin polymer is the 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 solvent (5 mL) to this decalin solution, 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)

[0152] 〔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 by hot pressing, and then the film obtained by pressure cooling at room temperature was used as the measurement sample, and the propylene structural unit content was measured using a calibration curve. The 1-butene / propylene copolymer samples for preparing the calibration curve are as follows 13 The comonomer content was specified by C-NMR measurement · 1 H-NMR measurement. The calibration curve was obtained by using these samples, selecting the peak intensity ratio of two specific absorption wave numbers that have a linear or nearly linear relationship with the propylene structural unit content ratio data, and graphing these relationships.

[0153] 13 13C-NMR measurement Using o-dichlorobenzene / benzene-d6 (4 / 1 {vol / vol%}) as the measurement solvent, under the measurement conditions of a measurement temperature of 120 °C, a spectral width of 250 ppm, a pulse repetition time of 5.5 seconds, and a pulse width of 4.7 μs (45° pulse) (100 MHz, JEOL ECX400P), or under the measurement conditions of a measurement temperature of 120 °C, a spectral width of 250 ppm, a pulse repetition time of 5.5 seconds, and a pulse width of 5.0 μs (45° pulse) (125 MHz, Bruker BioSpin AVANCEIII cryo-500), 13 13C-NMR spectra were measured, various signals were assigned by conventional methods, and based on the integrated values of the signal intensities, the comonomer content of the 1-butene / propylene copolymer for calibration curve preparation was quantified.

[0154] 1 1H-NMR measurement Using o-dichlorobenzene-d4 as the measurement solvent, under the measurement conditions of a measurement temperature of 120 °C, a spectral width of 250 ppm, a pulse repetition time of 7.0 seconds, and a pulse width of 5.0 μs (45° pulse) (500 MHz, Bruker BioSpin AVANCEIII cryo-500), 1 1H-NMR measurement was performed. The assignment of various signals such as methyl groups was carried out based on conventional methods, and based on the integrated values of the signal intensities, the comonomer content of the 1-butene / propylene copolymer for calibration curve preparation was quantified.

[0155] [Identification of metallocene compounds] 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).

[0156] [Synthesis examples of metallocene compounds] ​​The metallocene compound used in this example can also be synthesized by the methods described in the following patent publications. Specifically, they are 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.

[0157] [Synthesis Example 1] Synthesis of transition metal compound (a) represented by the following formula

[0158]

Chemical formula

[0159] (Synthesis of ligand (a-1)) Under a nitrogen atmosphere, 0.50 g (1.15 mmol) of 2,7-diadamantyl-9H-fluorene and 15 ml of tert-butyl methyl ether were placed in a flask, and 1.10 ml (hexane solution; 1.70 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, and then 0.48 g (1.70 mmol) of 5-adamantyl-1,1-dimethyl-3-methyl-1,2-dihydropentalene was added and stirred at room temperature for 13 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, and 0.59 g (yield 72%) of the target product was obtained as yellow crystals. The formation of the target product was confirmed by FD-MS measurement. FD-MS: m / Z = 714.5 (M + ) 1 By 1H-NMR measurement, it was confirmed that the yellow crystals were a mixture of a plurality of isomers. In the subsequent steps, the compound thus obtained was used as ligand (a-1).

[0160] (Synthesis of transition metal compound (a)) Under a nitrogen atmosphere, 0.59 g (0.83 mmol) of ligand (a-1), 0.22 g (1.86 mmol) of α-methylstyrene, 0.83 g (8.25 mmol) of cyclopentyl methyl ether, and 15 ml of hexane were placed in a Schlenk flask, and 1.10 ml (hexane solution; 1.70 mmol) of n-butyllithium was added while cooling to -78°C. After stirring at 60°C for 4 hours, concentration under reduced pressure was performed and 15 ml of diethyl ether was added. The resulting solution was cooled to -78°C, charged with 0.20 g (0.86 mmol) of zirconium tetrachloride, and stirred for 19 hours while returning to room temperature. The solvent was distilled off, and the soluble component was extracted with toluene. The resulting solution was concentrated, dissolved in hexane, and recrystallized. The precipitated solid was collected by filtration, washed with hexane, and dried under reduced pressure to obtain 30 mg (yield 4%) 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 7.97 (dd, J = 9.2, 2.4 Hz, 2H), 7.76 (s, 1H), 7.60 (dd, J = 8.8, 1.6 Hz, 1H), 7.59 (s, 1H), 7.50 (dd, J = 8.8, 1.2 Hz, 1H), 6.04 (d, J = 2.0 Hz, 1H), 5.35 (d, J = 2.0 Hz, 1H) 4.03 (d, J = 15.2 Hz, 1H), 2.64 (d, J = 14.8 Hz, 1H), 2.31 (s, 3H), 2.15 - 2.11 (m, 9H), 2.00 - 1.60 (m, 36H), 1.39 (s, 3H), 1.37 (s, 3H) FD-MS: m / Z = 874.4 (M + ) In the following examples, the compound thus obtained was used as the "transition metal compound (a)".

[0161] [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. This transition metal compound (e) is different from the aforementioned transition metal compound (a) in that R in the general formula [I] 1 , R 2 and R 7is a transition metal compound that is not an adamantyl derivative.

[0162] [Chemical formula]

[0163] [Example 1] Under a nitrogen atmosphere, 0.0043 mmol of transition metal compound (a) as transition metal compound (A) was placed in a Schlenk tube and dissolved in 8.0 ml of heptane. Then, 0.65 ml of a suspension of modified methylaluminoxane (trade name: TMAO341, manufactured by Tosoh Finechem Corporation) (n-hexane solvent, 3.33 M in terms of aluminum atom, 2.15 mmol) was added, and the mixture was stirred at room temperature for 30 minutes to prepare a catalyst solution with a concentration of 0.0005 M of transition metal compound (a). 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 the mixture was stirred 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 transition metal compound (a)) and 0.7 ml of n-heptane were added to initiate polymerization. After polymerizing at 60°C for 10 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 the mixture was stirred at room temperature for 1 hour. Then, the olefin polymer recovered by filtration was dried under reduced pressure to obtain 0.895 g of an olefin polymer (propylene homopolymer). The polymerization activity was 107 kg-PP / mmol-Zr / hr, the melting point (Tm) of the obtained olefin polymer was 139.6°C, the limiting viscosity [η] was 2.3 dl / g, and the crystallization temperature (Tc) was 103.4°C.

[0164] [Example 2] Under a nitrogen atmosphere, 0.0043 mmol of transition metal compound (a) as transition metal compound (A) was placed in a Schlenk tube, dissolved in 8.0 ml of heptane, and then 0.65 ml of a suspension of modified methylaluminoxane (trade name: TMAO341, manufactured by Tosoh Finechem Corporation) (n-hexane solvent, 3.33 M in terms of aluminum atoms, 2.15 mmol) was added. Stirring was carried out at room temperature for 30 minutes to prepare a catalyst solution with a concentration of 0.0005 M of transition metal compound (a). 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 placed in a SUS autoclave and stirred at 600 revolutions per minute. The temperature of this solution was raised to 70 °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 transition metal compound (a)) and 0.7 ml of n-heptane were added to the autoclave to initiate polymerization. After polymerization at 60 °C for 10 minutes, a small amount of isobutyl alcohol was added to terminate 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 stirring was carried out at room temperature for 1 hour. Thereafter, the olefin polymer recovered by filtration was dried under reduced pressure to obtain 1.089 g of an olefin polymer (propylene homopolymer). The polymerization activity was 145 kg-PP / mmol-Zr / hr, the melting point (Tm) of the obtained olefin polymer was 133.2 °C, the intrinsic viscosity [η] was 1.6 dl / g, and the crystallization temperature (Tc) was 96.6 °C.

[0165] [Example 3] Under a nitrogen atmosphere, 0.0043 mmol of transition metal compound (a) as transition metal compound (A) was placed in a Schlenk tube, dissolved in 8.0 ml of heptane, and then 0.65 ml of a suspension of modified methylaluminoxane (trade name: TMAO341, manufactured by Tosoh Finechem Corporation) (n-hexane solvent, 3.33 M in terms of aluminum atoms, 0.65 mmol) was added. Stirring was carried out at room temperature for 30 minutes to prepare a catalyst solution with a concentration of 0.0005 M of transition metal compound (a). 0.1 ml (0.05 M, 5 μmol) of a solution of triisobutylaluminum in n - heptane and 3.1 ml of n - heptane as a polymerization solvent were placed in a SUS autoclave, and stirring was carried out at 600 revolutions per minute. The temperature of this solution was raised to 80 °C, and then it was pressurized with propylene until the total pressure reached 0.7 MPa. 0.1 ml of the catalyst solution (0.05 μmol of transition metal compound (a)) and 0.7 ml of n - heptane were added to the autoclave to initiate polymerization. After polymerizing at 80 °C for 10 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 stirring was carried out at room temperature for 1 hour. Thereafter, the olefin polymer recovered by filtration was dried under reduced pressure to obtain 0.801 g of an olefin polymer (propylene homopolymer). The polymerization activity was 96 kg - PP / mmol - Zr / hr, the melting point (Tm) of the obtained olefin polymer was 131.1 °C, the intrinsic viscosity [η] was 1.4 dl / g, and the crystallization temperature (Tc) was 96.3 °C.

[0166] [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 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.

[0167] [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 replaced with the transition metal compound (e). 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.

[0168] [Comparative Example 3] A catalyst solution was prepared and olefin polymerization was carried out in the same manner as in Example 3, except that the transition metal compound (a) used was replaced with the transition metal compound (e). The polymerization activity was 34 kg-PP / mmol-Zr / hr, 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.

[0169] 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 the polymerization activity being "polymerization activity (kg-PP / mmol-M / hr)" means "polymerization activity (kg-PP / mmol-Zr / hr)" when Zr is used as the transition metal M constituting the catalyst.

[0170]

Table 4

[0171] [Example 4] Under a nitrogen atmosphere, 0.0024 mmol of the transition metal compound (a) was placed in a Schlenk tube and dissolved in 1.8 ml of heptane. Then, 0.30 ml of a suspension of a modified methylaluminoxane (trade name: TMAO-341, manufactured by Tosoh Finechem Corporation) (n-hexane solvent, 4.00 M in terms of aluminum atoms, 1.2 mmol) was added, and the mixture was stirred at room temperature for 30 minutes to prepare a catalyst solution with a concentration of the transition metal compound (a) of 0.001 M. Into a 1.5 L stainless steel autoclave that had been sufficiently purged with nitrogen, 2.5 ml (0.05 M, 0.125 mmol) of a n-heptane solution of triisobutylaluminum and 300 ml of n-heptane as a polymerization solvent were added, and stirring was carried out at 850 revolutions per minute. After adding 120 g of 1-butene to this solution, 31 ml of hydrogen was charged, the temperature was raised to 60 °C for polymerization, and then propylene was charged at a partial pressure of 0.07 MPa. 0.5 ml (0.5 μmol of transition metal compound (a)) of the catalyst solution was charged into the catalyst pot of the autoclave and pressure-fed to initiate polymerization. After the start of polymerization, n-heptane was charged into the catalyst pot and pressure-fed. Five ml of methanol was added 20 minutes after the start of polymerization to terminate the polymerization. The polymerization solution taken out from the cooled / de-pressurized autoclave was poured into 1.5 L of acetone / methanol (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 12.3 g of an olefin polymer (1-butene / propylene copolymer). The polymerization activity was 74.0 kg-P / mmol-Zr / hr, and the composition of the obtained olefin polymer was 92.0 mol% of 1-butene content, 8.0 mol% of propylene content, the intrinsic viscosity [η] was 1.95 dl / g, and the melting point (Tm) was 101.5 °C.

[0172] [Comparative Example 4] A catalyst solution was prepared and olefin polymerization was carried out in the same manner as in Example 4, except that the transition metal compound (a) used was replaced with the transition metal compound (e). The polymerization activity was 38.9 kg-P / mmol-Zr / hr, and the composition of the olefin polymer (1-butene / propylene copolymer) was 92.3 mol% of 1-butene content, 7.7 mol% of propylene content, the intrinsic viscosity [η] was 1.66 dl / g, and the melting point (Tm) was 103.6 °C.

[0173] For Example 4 and Comparative Example 4, the physical properties of the obtained 1-butene / propylene copolymer are shown in Table 5. Here, the symbols described in the column of "transition metal compound" in Table 5 are based on the symbols of the transition metal compounds used in the preparation of the catalyst. For [η], the values shown in Table 5 are those expressed with three significant figures. In Table 5, the unit of polymerization activity is "polymerization activity (kg-P / mmol-M / hr)", which means "polymerization activity (kg-P / mmol-Zr / hr)" when Zr is used as the transition metal M constituting the catalyst.

[0174]

Table 5

Claims

1. A transition metal compound (A) represented by the following general formula [I]. 【Chemical 1】 (wherein, R 1 , R 2 and R 7 are each independently an adamantyl group derivative, and R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom, a hydrocarbon Selected from the group consisting of a base group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different from each other, R 3 ~R 6 and R 8 ~R 12 Among them, adjacent substituents may be bonded to each other to form a ring. n is an integer from 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 from 1 to 4. )

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

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

4. In the 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.

5. In the general formula [I], R 8 ~R 11 are each independently a hydrogen atom or a carbon number of 1 is a hydrocarbon group having 0 to 20 carbon atoms, and R 8 to R 11 Among them, adjacent substituents are bonded to each other to form a ring The transition metal compound (A) according to Claim 1, which may be...

6. In the general formula [I], R 10 and R 11 are hydrogen atoms, and the transition metal compound (A) according to claim 5.

7. 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 5.

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

9. 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) at least one compound (B) selected from a catalyst for olefin polymerization containing the same.

10. 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 9.

11. The method for producing an olefin polymer according to Claim 10, wherein at least one of the α-olefins having 3 or more carbon atoms is propylene.

12. The method for producing an olefin polymer according to Claim 10, wherein the intrinsic viscosity [η] of the olefin polymer in decalin at 135°C is 1.0 to 10 dl / g.

13. The method for producing an olefin polymer according to Claim 10, wherein the melting point peak (Tm) of the olefin polymer determined by a differential scanning calorimeter (DSC) is 80 to 150°C.

14. The method for producing an olefin polymer according to Claim 10, wherein the melting point peak (Tm) of the olefin polymer determined by a differential scanning calorimeter (DSC) is 120 to 150°C.

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