Method for producing prepolymerization catalyst and method for producing olefin polymer

Abstract

A method for producing a prepolymerized catalyst that has good fluidity and exhibits early-type activity development behavior is provided. [Solution] A method for producing a prepolymerization catalyst (P) includes a step of supplying at least one olefin (O1) selected from olefins having 2 to 5 carbon atoms and at least one olefin (O2) selected from olefins having 6 or more carbon atoms to a solid catalyst component (Sa) containing a transition metal complex (A) and a solid support (S) in the presence of an organoaluminum compound (B-1) and prepolymerizing the components, wherein the heat of fusion of the prepolymer contained in the prepolymerization catalyst (P) measured by differential scanning calorimetry (DSC) is 50 to 130 J / g, or the content of the component derived from the olefin (O2) in the prepolymer contained in the prepolymerization catalyst (P) is more than 6 mass% but less than 33 mass%, when the total of the components derived from the olefin (O1) and the components derived from the olefin (O2) is taken as 100 mass%.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a prepolymerization catalyst and a method for producing an olefin polymer. [Background technology]

[0002] Conventionally, olefin polymerization catalysts comprising a transition metal complex such as zirconocene and a cocatalyst component such as an organoaluminum oxy compound (aluminoxane) have been known as catalysts for producing olefin (co)polymers. Among these, when slurry polymerization or gas phase polymerization is carried out, a solid catalyst in which a transition metal complex or an organoaluminum oxy compound is supported on a solid support such as silica gel is generally used in order to improve the powder properties of the produced polymer (for example, Non-Patent Document 1).

[0003] In addition, methods that have been reported for suppressing fouling, in which polymers adhere to the reactor wall surface during a polymerization reaction, and for suppressing the formation of polymer lumps in the reactor include a method of prepolymerizing an olefin on a solid catalyst (e.g., Patent Document 1) and a method of adding a specific compound to the reaction system (e.g., Patent Documents 2 and 3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 152608 / 1983 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-327707 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-117043 [Non-patent literature]

[0005] [Non-Patent Document 1] Chem.Rev.2005,105,pp.4073-4147 Summary of the Invention [Problem to be solved by the invention]

[0006] However, particularly in gas-phase polymerization processes, productivity declines remain a challenge due to factors such as the produced polymer and solid catalyst components being blown up to the top of the reactor entrained in the vaporized gas (entrainment phenomenon), and the formation of polymer agglomerates due to wall fouling caused by poor fluidity.

[0007] Furthermore, known catalyst activity behaviors for olefin polymers include an initial type, in which polymerization proceeds in a short time after the catalyst is fed into the polymerization vessel, making electrostatic aggregation and adhesion of fine particles unlikely, and a sustained type, in which activity is maintained even in the latter polymerization step in multi-stage polymerization. Various catalyst components with various types of activity behaviors have been desired to meet diverse needs in terms of manufacturing equipment, cost, etc. Furthermore, if the catalyst activity behavior is of the initial type, the polymer particles grow large in a short time, and the weight of the polymer particles is so great that they do not rise to the top of the reactor, thereby suppressing the entrainment phenomenon.

[0008] The present invention has been made in view of the above, and an object of the present invention is to provide a method for producing a prepolymerized catalyst which has good fluidity and exhibits early-type activity development behavior. [Means for solving the problem]

[0009] An example of the present invention is shown below. As a result of extensive research into solving the problems, the present inventors have found that the above problems can be solved by a prepolymerization catalyst obtained by a specific production method.

[0010] That is, the present invention relates to the following [1] to [6]. [1] A solid catalyst component (Sa) containing a transition metal complex (A) and a solid support (S), A method for producing a prepolymerization catalyst (P), comprising a step of supplying at least one olefin (O1) selected from olefins having 2 to 5 carbon atoms and at least one olefin (O2) selected from olefins having 6 or more carbon atoms in the presence of an organoaluminum compound (B-1), and prepolymerizing the olefins, A method for producing a prepolymerized catalyst (P), wherein the heat of fusion of the prepolymer contained in the prepolymerized catalyst (P) is 50 to 130 J / g as measured by a differential scanning calorimeter (DSC).

[0011] [2] A solid catalyst component (Sa) containing a transition metal complex (A) and a solid support (S), A method for producing a prepolymerization catalyst (P), comprising a step of supplying at least one olefin (O1) selected from olefins having 2 to 5 carbon atoms and at least one olefin (O2) selected from olefins having 6 or more carbon atoms in the presence of an organoaluminum compound (B-1), and prepolymerizing the olefins, A method for producing a prepolymerization catalyst (P), wherein the content of the component derived from the olefin (O2) is more than 6 mass% but less than 33 mass%, when the total of the component derived from the olefin (O1) and the component derived from the olefin (O2) in the prepolymer contained in the prepolymerization catalyst (P) is taken as 100 mass%.

[0012] [3] The method for producing a prepolymerization catalyst (P) according to [1] or [2], wherein the transition metal complex (A) contains a transition metal atom of Group 4 of the periodic table, and the solid support (S) is a porous oxide.

[0013] [4] The method for producing the prepolymerization catalyst (P) according to any one of [1] to [3], wherein the prepolymerization catalyst (P) contains an organoaluminum oxy compound (B-2).

[0014] [5] The method for producing the prepolymerization catalyst (P) according to any one of [1] to [4], wherein the transition metal complex (A) is represented by the following general formula [1]:

[0015] [ka] (In the general formula [1], M is a transition metal atom of Group 4 of the periodic table, n is an integer from 1 to 4 that satisfies the valence of M; X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene-based divalent derivative group, and when n is 2 or more, the multiple groups represented by X may be the same or different and may be bonded to each other to form a ring; Cp is a cyclopentadienyl ligand which may have a substituent, and adjacent substituents may be bonded to each other to form a ring which may have a substituent; L is an atom selected from the elements of Groups 15 and 16 of the periodic table, P is a phosphorus atom, The solid lines are covalent or coordinate bonds, and the dotted lines are covalent bonds that exist when L is a Group 15 element atom. z is 3 when L is an atom of a Group 15 element, and is 4 when L is an atom of a Group 16 element; R are independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, and may be the same or different, and adjacent Rs may be bonded to each other to form a ring or a bicyclo ring which may have a substituent.

[0016] [6] A method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin in the presence of the prepolymerization catalyst (P) according to any one of [1] to [5]. [Effects of the Invention]

[0017] According to the present invention, a prepolymerization catalyst can be obtained which exhibits good fluidity of the prepolymer and early-type activity development behavior. The use of the prepolymerization catalyst enables stable and continuous supply of the catalyst to a polymerization vessel in a gas-phase polymerization process, and is expected to suppress a decrease in productivity of olefin polymers (process stabilization) because polymerization proceeds in a short time and electrostatic aggregation and adhesion of fine particles are unlikely to occur. DETAILED DESCRIPTION OF THE INVENTION

[0018] Matters relating to the embodiments will be described in detail below. In this specification, a numerical range indicated using "to" means that the numerical values ​​before and after "to" are included as the lower and upper limits.

[0019] A method for producing a prepolymerized catalyst (P) according to one embodiment of the present invention will be described in detail below. Note that this embodiment shows only one example of the present invention, and the present invention is not limited to this embodiment. Furthermore, various modifications and improvements can be made to this embodiment, and such modifications and improvements can also be included in the present invention.

[0020] <Method for producing prepolymerization catalyst (P)> The method for producing a prepolymerization catalyst (P) according to the present invention is characterized by comprising a step of supplying at least one olefin (O1) (hereinafter also referred to as "component (O1)") selected from olefins having 2 to 5 carbon atoms and at least one olefin (O2) (hereinafter also referred to as "component (O2)") selected from olefins having 6 or more carbon atoms to a solid catalyst component (Sa) containing a transition metal complex (A) (hereinafter also referred to as "component (A)") and a solid support (S) (hereinafter also referred to as "component (S)") in the presence of an organoaluminum compound (B-1) (hereinafter also referred to as "component (B-1)"), thereby prepolymerizing the solid catalyst component (Sa) (hereinafter also referred to as "component (S)") (hereinafter also referred to as "prepolymerization step").

[0021] In the present invention, the term "polymerization" may be used to include not only the homopolymerization of an olefin but also the copolymerization of two or more kinds of olefins, and the term "polymer" may be used to include not only the homopolymer but also the copolymer.

[0022] <Preliminary polymerization step> The prepolymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out under reduced pressure, normal pressure or elevated pressure. In the prepolymerization step, the prepolymerization temperature is preferably 10 to 50° C., more preferably 15 to 45° C., and even more preferably 20 to 40° C. The prepolymerization time is usually 0.5 to 100 hours, preferably 1 to 50 hours, more preferably 2 to 30 hours, and particularly preferably 3 to 10 hours. If the prepolymerization temperature and prepolymerization time are within the above ranges, it is preferable in that fouling in the reactor can be suppressed in the production of the prepolymerized catalyst.

[0023] The prepolymerization step is preferably carried out in an inert hydrocarbon. Specific examples of inert hydrocarbons 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; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof.

[0024] The concentration of the solid catalyst component (Sa) is preferably 1 to 1000 g / L, more preferably 5 to 500 g / L, still more preferably 10 to 200 g / L, and particularly preferably 20 to 100 g / L, per 1 L of the solid catalyst slurry.

[0025] The concentration of component (B-1) is preferably 0.1 to 300 mmol, more preferably 1.0 to 200 mmol, even more preferably 10.0 to 100 mmol, and particularly preferably 30 to 70 mmol, relative to 1.0 mmol of component (A). When component (B-1) is contained in solid catalyst component (Sa), component (B-1) in solid catalyst component (Sa) is not taken into account in the above concentration. When the concentration of component (B-1) is within the above range, a high molecular weight olefin polymer can be easily produced.

[0026] The supply rate of component (O1) is preferably 0.05 to 10.0 g / hr, more preferably 0.10 to 5.0 g / hr, even more preferably 0.30 to 3.0 g / hr, and particularly preferably 0.50 to 1.00 g / hr. The supply rate of component (O2) is preferably 0.001 to 5.0 g / hr, more preferably 0.01 to 1.0 g / hr, even more preferably 0.03 to 0.70 g / hr, and particularly preferably 0.05 to 0.40 g / hr.

[0027] The total amount of the components (O1) and (O2) fed is preferably 1 to 50 g, more preferably 1.5 to 30 g, still more preferably 2.0 to 20 g, and particularly preferably 2.5 to 10 g, per gram of the solid catalyst component (Sa). When the amount of prepolymerization of component (O1) and component (O2) is equal to or greater than the lower limit, liberation of the transition metal component from the solid catalyst component (Sa) in the subsequent polymerization reaction is suppressed, and when the amount of prepolymerization is equal to or less than the upper limit, electrostatic adhesion during prepolymerization is suppressed due to the charging of the prepolymerized components.

[0028] In the method for producing the prepolymerized catalyst (P), a surfactant (G) (hereinafter also referred to as "component (G)") described below may be added (contacted with) before, during, or after the step of producing the prepolymerized catalyst (P) in order to suppress fouling in a polymerization vessel due to electrostatic adhesion of the catalyst or polymer, or to improve the particle properties of the produced polymer. The amount of component (G) used is preferably 0.1 to 20 mass %, more preferably 1 to 10 mass %, further preferably 2 to 7 mass %, particularly preferably 3 to 5 mass %, based on the solid catalyst component (Sa).

[0029] <Prepolymerization catalyst (P)> The prepolymerization catalyst (P) may be used for olefin polymerization as it is in the form of a suspension after the prepolymerization step, or may be separated from the suspension and then suspended again in an inert hydrocarbon for use in olefin polymerization, or may be dried before use in olefin polymerization. The prepolymerization catalyst (P) has a prepolymer component and a catalyst component.

[0030] In one embodiment of the method for producing the prepolymerized catalyst (P), the heat of fusion of the prepolymer contained in the obtained prepolymerized catalyst (P) as measured by a differential scanning calorimeter (DSC) is 50 to 130 J / g, preferably 55 to 125 J / g, more preferably 60 to 120 J / g, even more preferably 65 to 115 J / g, and particularly preferably 70 to 110 J / g. When the heat of fusion of the prepolymer is within the above range, the prepolymerization catalyst (P) has excellent fluidity, and the catalytic activity of the prepolymerization catalyst (P) tends to be of the initial type. The heat of fusion of the prepolymer can be measured by the method described in the Examples below.

[0031] In another embodiment of the method for producing the prepolymerized catalyst (P), when the total of the components derived from component (O1) and the components derived from component (O2) in the prepolymer contained in the obtained prepolymerized catalyst (P) is taken as 100% by mass, the content of the components derived from component (O2) (hereinafter also simply referred to as the "content of component (O2)") is more than 6% by mass and less than 33% by mass, preferably 7 to 32% by mass, more preferably 7 to 30% by mass, even more preferably 8 to 27% by mass, and particularly preferably 10 to 25% by mass. The content of the component (O2) in the prepolymerization catalyst (P) can be measured by the method described in the Examples below.

[0032] When the content of component (O2) in the prepolymer is within the above range, the prepolymerized catalyst (P) has excellent fluidity and tends to exhibit initial catalytic activity. The content of component (O2) in the prepolymer can be measured by the method described in the Examples below. The content of component (O2) in the prepolymerization catalyst (P) can be adjusted by the amounts of component (O1) and component (O2) fed in the prepolymerization step.

[0033] The reason why the catalytic activity development behavior of the prepolymerization catalyst (P) is of the initial type is believed to be that the density of the resulting prepolymer is low due to the inclusion of a constituent component derived from component (O2), which is an olefin having 6 or more carbon atoms, and as a result, the diffusion rate of the monomer (e.g., ethylene) during olefin polymerization increases.

[0034] The melting point of the prepolymer contained in the prepolymerization catalyst (P) is preferably 100 to 130°C, more preferably 110 to 127°C, and even more preferably 120 to 125°C. When the melting point of the prepolymer is within the above range, a prepolymerization catalyst having excellent fluidity can be easily produced. The melting point of the prepolymer can be measured by a differential scanning calorimeter (DSC). Each component constituting the prepolymerization catalyst (P) will be explained below.

[0035] <Solid catalyst component (Sa)> The solid catalyst component (Sa) comprises the component (S) and the component (A), and can be obtained, for example, by contacting the component (S) with the component (A) in an inert hydrocarbon. The component (S) and the component (A) may each be used alone or in combination of two or more types.

[0036] The temperature at which component (S) and component (A) are contacted is usually from -50 to 200°C, preferably from -20 to 150°C, more preferably from 0 to 100°C, and even more preferably from 15 to 30°C. The contact time between component (S) and component (A) is usually 0.01 to 48 hours, preferably 0.1 to 24 hours, more preferably 0.3 to 6 hours, and even more preferably 0.5 to 2 hours.

[0037] The inert hydrocarbon used in the preparation of the solid catalyst component (Sa) may be the same as the specific examples of the inert hydrocarbon that may be used in the prepolymerization step. The inert hydrocarbon used in the preparation of the solid catalyst component (Sa) and the inert hydrocarbon used in the prepolymerization step may be the same or different.

[0038] When two or more types of component (S) and / or component (A) are used, the order of contacting component (S) with component (A) is arbitrary, and two or more types of component (S) and / or component (A) may be contacted in any order or simultaneously.

[0039] Component (A) is used in an amount of usually 1 μmol to 1.0 mmol, preferably 3 μmol to 0.5 mmol, more preferably 5 μmol to 0.3 mmol, and even more preferably 10 μmol to 0.1 mmol, per 1 g of component (S).

[0040] In preparing the solid catalyst component (Sa), a co-catalyst component such as component (B-1), (B-2), or component (B-3) described later can be suitably used in combination, with components (B-1) and (B-2) being preferred, and component (B-1) being more preferred. Although there are no particular limitations on the mode in which a co-catalyst component is used in combination, examples of preferred modes are shown below. The promoter component may be used alone or in combination of two or more kinds.

[0041] (i) A method in which the component (S) and a cocatalyst component are mixed and contacted, and then the component (A) is contacted to prepare the solid catalyst component (Sa). (ii) A method in which the component (A) and a cocatalyst component are mixed and contacted, and then the component (S) is contacted to prepare the solid catalyst component (Sa).

[0042] In the methods (i) and (ii), the contact of the cocatalyst component with the component (S) or the component (A) is preferably carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same inert hydrocarbons as those used in the preparation of the solid catalyst component (Sa).

[0043] In methods (i) and (ii), the contact time between the promoter component and component (S) or component (A) is usually 0.1 to 48 hours, preferably 0.5 to 20 hours, more preferably 1 to 12 hours, and even more preferably 3 to 6 hours, and the contact temperature is usually -50 to 200°C, preferably -20 to 120°C, more preferably -10 to 110°C, and even more preferably -5 to 100°C.

[0044] When the promoter component is used in the preparation of the solid catalyst component (Sa), the promoter component is used in an amount of usually 0.01 to 100 mmol, preferably 0.1 to 50 mmol, more preferably 1.0 to 30 mmol, and even more preferably 5.0 to 20 mmol per 1 g of the component (S).

[0045] In the method for producing the prepolymerized catalyst (P), the transition metal complex (A) and the solid support (S) constituting the solid catalyst component (Sa) are not limited in any way, but suitable examples are shown below.

[0046] <Transition Metal Complex (A) (Component (A))> Component (A) preferably contains a transition metal atom of Group 4 of the periodic table, and more preferably is a transition metal compound represented by the following general formula [1].

[0047] [ka]

[0048] In the general formula [1], M is a transition metal atom of Group 4 of the periodic table. Examples of the transition metal atom of Group 4 of the periodic table include a titanium atom, a zirconium atom, and a hafnium atom, and a titanium atom is preferred.

[0049] n is an integer of 1 to 4 that satisfies the valence of M, preferably 1 or 2, and more preferably 2. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene-based divalent derivative group. X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, or a conjugated diene-based derivative group, and more preferably a halogen atom. When n is 2 or greater, multiple groups represented by X may be the same or different and may be bonded to each other to form a ring.

[0050] The halogen atom includes fluorine, chlorine, bromine, iodine, etc., preferably chlorine or bromine, more preferably chlorine.

[0051] Examples of the hydrocarbon group include: linear or branched alkyl groups such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl (butan-2-yl), tert-butyl (2-methylpropan-2-yl), isobutyl (2-methylpropyl), pentan-2-yl, 2-methylbutyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), cyamyl (1,2-dimethylpropyl), isohexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl (2,3-dimethylbut-2-yl), and 4,4-dimethylpentyl; Vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl group (propa-1,2-dien-1-yl group), but-3-en-1-yl group, crotyl group (but-2-en-1-yl group), but-3-en-2-yl group, methallyl group (2-methylallyl group), buta-1,3-dienyl group, pentaerythritol group, linear or branched alkenyl groups or unsaturated double bond-containing groups such as pent-4-en-1-yl, pent-3-en-1-yl, pent-2-en-1-yl, iso-pentenyl (3-methylbut-3-en-1-yl), 2-methylbut-3-en-1-yl, pent-4-en-2-yl, and prenyl (3-methylbut-2-en-1-yl); linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl, prop-2-yn-1-yl, and propargyl (prop-1-yn-1-yl) groups; Aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups, such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-isopropylbenzyl group), 2,4,6-tri-isopropylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, and benzhydryl group (diphenylmethyl group); cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cycloheptatrienyl, norbornyl, norbornenyl, 1-adamantyl, and 2-adamantyl; Examples of aromatic substituents include a phenyl group, a tolyl group (methylphenyl group), a xylyl group (dimethylphenyl group), a mesityl group (2,4,6-trimethylphenyl group), a cumenyl group (isopropylphenyl group), a duryl group (2,3,5,6-tetramethylphenyl group), a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group. Among the hydrocarbon groups, a methyl group, an isobutyl group, a neopentyl group, a cyamyl group, a benzyl group, a phenyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group are preferred.

[0052] Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, and a hexachloroantimonate anion. Among the halogen-containing groups, a pentafluorophenyl group is preferred.

[0053] Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, and a trimethylsilylmethyl group. Among the silicon-containing groups, a trimethylsilylmethyl group is preferred.

[0054] Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a benzyloxy group, a methoxymethoxy group, a phenoxy group, a 2,6-dimethylphenoxy group, a 2,6-di-isopropylphenoxy group, a 2,6-di-tert-butylphenoxy group, a 2,4,6-trimethylphenoxy group, a 2,4,6-tri-isopropylphenoxy group, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetoxy group, a perchlorate anion, and a periodate anion. Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferred.

[0055] Examples of the sulfur-containing group include a mesyl group (methanesulfonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a triflyl group (trifluoromethanesulfonyl group), a nonaflyl group (nonafluorobutanesulfonyl group), a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a triflate group (trifluoromethanesulfonate group), and a nonaflate group (nonafluorobutanesulfonate group). Among the sulfur-containing groups, a triflate group is preferred.

[0056] Examples of the nitrogen-containing group include an amino group, a cyano group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, a pyrrolyl group, and a bistriflylimide group. Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistriflylimide group are preferred.

[0057] The phosphorus-containing group may, for example, be a hexafluorophosphate anion.

[0058] Examples of the boron-containing group include tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl))borate anion, (benzyl)(tris(pentafluorophenyl))borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, and groups represented by BR4 (each R independently represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

[0059] Examples of the aluminum-containing group include: [ka] or [ka] (M represents M in the general formula [1].) Examples of suitable groups include groups represented by AlR'4 (R' represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like), which can form the following formula:

[0060] Examples of the conjugated diene derivative group include a 1,3-butadienyl group, an isoprenyl group (2-methyl-1,3-butadienyl group), a piperylenyl group (1,3-pentadienyl group), a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group, a cyclopentadienyl group, and a metallocyclopentene group.

[0061] Examples of neutral ligands capable of coordinating with lone electron pairs include ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; amines such as triethylamine and diethylamine; heterocyclic compounds such as pyridine, picoline, lutidine, oxazoline, oxazole, thiazole, imidazole, and thiophene; and organic phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, and tri-tert-butylphosphine.

[0062] Cp is a cyclopentadienyl ligand which may have a substituent. Adjacent substituents among the substituents may be bonded to each other to form a ring which may have a substituent.

[0063] The cyclopentadienyl-type ligand is a substituted ligand having a five-membered carbon ring bonded to a metal by a π-type bond, and includes substituted cyclopentadienyl-type ligands such as substituted cyclopentadienyl ligands, substituted tetrahydroindenyl ligands, substituted octahydrofluorenyl ligands, substituted hydroazulenyl ligands, substituted pentahydroazulenyl ligands, substituted dihydrocyclopentenoannulene ligands, substituted cyclopentenopyrrole ligands, substituted cyclopentenothiophene ligands, and substituted cyclopentenodithiophene ligands; substituted indenyl-type ligands such as substituted indenyl ligands, substituted tetrahydroindenyl ligands, substituted benzoindenyl ligands, substituted dihydroindacenyl ligands, substituted indenopyrrole ligands, substituted indenoindole ligands, and substituted indenothiophenes; and substituted fluorenyl ligands. As the cyclopentadienyl type ligand, a substituted cyclopentadienyl type ligand and a substituted indenyl type ligand are preferred, and a substituted cyclopentadienyl ligand, a substituted dihydrocyclopentenoannulene ligand, a substituted cyclopentenothiophene ligand, a substituted cyclopentenodithiophene ligand, and a substituted indenyl ligand are more preferred.

[0064] L is an atom selected from the group consisting of Group 15 and Group 16 elements of the periodic table. Examples of Group 15 elements include a nitrogen atom, and examples of Group 16 elements include an oxygen atom and a sulfur atom. L is preferably an atom of a Group 15 element of the periodic table, and more preferably a nitrogen atom.

[0065] P is a phosphorus atom. The solid lines are covalent or coordinate bonds, and the dotted lines are covalent bonds that exist when L is an atom of a Group 15 element. z is 3 when L is an atom of a Group 15 element, and z is 4 when L is an atom of a Group 16 element.

[0066] R are independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, preferably a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms. R may be the same or different.

[0067] The hydrocarbon group having 1 to 40 carbon atoms is preferably a hydrocarbon group having 1 to 20 carbon atoms (excluding aromatic hydrocarbon groups) or an aromatic hydrocarbon group having 6 to 40 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 40 carbon atoms also includes a substituent having an aromatic structure such as an arylalkyl group.

[0068] Examples of the hydrocarbon group having 1 to 40 carbon atoms for R include: Methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decanyl, 1-undecanyl, 1-dodecanyl, 1-eicosanyl, isopropyl, sec-butyl, tert-butyl, isobutyl, pentan-2-yl, 2-methylbutyl, isopentyl, neopentyl, tert-pentyl (1,1-dimethylpropyl), cyamyl, pentan-3-yl, 2-methylpentyl, 3-methylpentyl, isohexyl, 1,1-dimethylbutyl, 3-methylpentan-2-yl, 4 linear or branched alkyl groups having 1 to 40 carbon atoms, such as methylpentan-2-yl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl, 3-methylpentan-3-yl, 3,3-dimethylbutan-2-yl, hexane-3-yl, 2-methylpentan-3-yl, heptan-4-yl, 2,4-dimethylpentan-2-yl, 3-ethylpentan-3-yl, 4,4-dimethylpentyl, 4-methylheptan-4-yl, 4-propylheptan-4-yl, 2,3,3-trimethylbutan-2-yl, and 2,4,4-trimethylpentan-2-yl; Vinyl group, allyl group, propenyl group, isopropenyl group, allenyl group, but-3-en-1-yl group, crotyl group, but-3-en-2-yl group, methallyl group, but-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, isopentenyl group, 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1 -yl group, pent-3-en-2-yl group, 2-methyl-but-3-en-2-yl group, pent-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl group (2-methyl-but-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hex-5-en-1-yl group, hex-4-en-1-yl group, hex-3-en- hex-2-en-1-yl group, 4-methyl-pent-4-en-1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-pent-4-en-1-yl group, hex-5-en-2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpent-1-en-1-yl group linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, such as a 2-(cyclopentadienyl)propan-3-yl group, a hexa-3,5-dien-1-yl group, a hexa-2,4-dien-1-yl group, a 4-methylpenta-1,3-dien-1-yl group, a 2,3-dimethyl-buta-1,3-dien-1-yl group, a hexa-1,3,5-trien-1-yl group, a 2-(cyclopentadienyl)propan-2-yl group, or a 2-(cyclopentadienyl)ethyl group; Ethynyl group, prop-2-yn-1-yl group, propargyl group, but-1-yn-1-yl group, but-2-yn-1-yl group, but-3-yn-1-yl group, pent-1-yn-1-yl group, pent-2-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1-yl group, 3-methyl-but-1-yn-1-yl group, pent-3-yn-2-yl group, 2-methyl-but-3-yn-1-yl group linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, such as a pent-4-yn-2-yl group, a hex-1-yn-1-yl group, a 3,3-dimethyl-but-1-yn-1-yl group, a 2-methyl-pent-3-yn-2-yl group, a 2,2-dimethyl-but-3-yn-1-yl group, a hex-4-yn-1-yl group, or a hex-5-yn-1-yl group; Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-isopropylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl group (2-phenylpropan-2-yl group), 2-(4-methylphenyl)propan-2-yl group, 2-(3,5-dimethylphenyl)propan-2-yl group, 2-(4-tert-butylphenyl)propan-2-yl group, 2-(3,5-di-tert-butylphenyl)propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1, 6-dien-4-yl group, 1,2,3-triphenylpropan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3-en-1-yl group, 1,1,2-triphenylethyl group, trityl group (triphenylmethyl group), tri-(4-methylphenyl)methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2-(2-methylphenyl)ethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-isopropylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,(5-di-tert-butylphenyl)ethyl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group (3-phenylallyl group), neophyl group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(tetrahydro-1-indacenyl)propan-2-yl group, (tetrahydro-1-indacenyl ) Aromatic-containing linear or branched alkyl groups or unsaturated double bond-containing groups having 7 to 40 carbon atoms, such as diphenylmethyl group, 2-(tetrahydro-1-indacenyl)ethyl group, 2-(1-benzoindenyl)propan-2-yl group, (1-benzoindenyl)diphenylmethyl group, 2-(1-benzoindenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, 2-(1-azulenyl)propan-2-yl group, (1-azulenyl)diphenylmethyl group, and 2-(1-azulenyl)ethyl group; Cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, dimethylcyclopentadienyl, n-butylcyclopentadienyl, n-butyl-methylcyclopentadienyl, tetramethylcyclopentadienyl, 1-methylcyclopentyl, 1-allylcyclopentyl, 1-benzylcyclopentyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, cyclooctatrienyl group, 1-methylcyclooctyl group, cyclododecyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclo Hexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octan-1-yl group, bicyclo[2.2.2]octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl) cyclic saturated or unsaturated hydrocarbon groups having 3 to 40 carbon atoms, such as 1-(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl), 1-(3,5,7-triphenyladamantyl), pentalenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, and azulenyl group; Examples of aromatic groups having 6 to 40 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a duryl group, a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, an allylphenyl group, a (but-3-en-1-yl)phenyl group, a (but-2-en-1-yl)phenyl group, a methallylphenyl group, a prenylphenyl group, a 4-adamantylphenyl group, a 3,5-di-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group.

[0069] Among the linear or branched alkyl groups having 1 to 40 carbon atoms, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, a 1-octyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a pentan-3-yl group, an isohexyl group, a 1,1-dimethylbutyl group, a 3,3-dimethylbutyl group, a thexyl group, a 3-methylpentan-3-yl group, a heptane-4-yl group, a Preferred are methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, isopropyl, tert-butyl, neopentyl, 2,4-dimethylpentan-2-yl, and 2,4,4-trimethylpentan-2-yl groups, and more preferred are methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, isopropyl, tert-butyl, neopentyl, 2,4-dimethylpentan-2-yl, and 2,4,4-trimethylpentan-2-yl groups.

[0070] Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, a vinyl group, an allyl group, a but-3-en-1-yl group, a crotyl group, a methallyl group, a pent-4-en-1-yl group, a prenyl group, a penta-1,4-dien-3-yl group, a hex-5-en-1-yl group, a 2-methylpent-4-en-2-yl group, a 2-(cyclopentadienyl)propan-2-yl group, a 2-(cyclopentadienyl)ethyl group, and the like are preferred, and a vinyl group, an allyl group, a but-3-en-1-yl group, a pent-4-en-1-yl group, a prenyl group, and a hex-5-en-1-yl group are more preferred.

[0071] Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, an ethynyl group, a prop-2-yn-1-yl group, a propargyl group, a but-2-yn-1-yl group, a but-3-yn-1-yl group, a penta-3-yn-1-yl group, a penta-4-yn-1-yl group, a 3-methyl-but-1-yn-1-yl group, a 3,3-dimethyl-but-1-yn-1-yl group, a hex-4-yn-1-yl group, a hex-5-yn-1-yl group, and the like are preferred, and a prop-2-yn-1-yl group, a propargyl group, a but-2-yn-1-yl group, and a but-3-yn-1-yl group are more preferred.

[0072] Among the above-mentioned aromatic-containing linear or branched alkyl groups having 7 to 40 carbon atoms or unsaturated double bond-containing groups, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-te Preferred are a 2-(3,5-di-tert-butylphenyl)ethyl group, a 2-(3,5-di-tert-butylphenyl)ethyl group, a styryl group, a 2-methyl-1-phenylpropan-2-yl group, a 3-phenylpropyl group, a cinnamyl group, a neophyl group, a cyclopentadienyldiphenylmethyl group, a 2-(1-indenyl)propan-2-yl group, a (1-indenyl)diphenylmethyl group, a 2-(1-indenyl)ethyl group, a 2-(9-fluorenyl)propan-2-yl group, a (9-fluorenyl)diphenylmethyl group, and a 2-(9-fluorenyl)ethyl group, and more preferred are a benzyl group, a benzhydryl group, a cumyl group, a 1,1-diphenylethyl group, a trityl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a cinnamyl group.

[0073] Among the above-mentioned saturated or unsaturated cyclic hydrocarbon groups having 3 to 40 carbon atoms, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a 1-methylcyclopentyl group, a 1-allylcyclopentyl group, a 1-benzylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group, a 1-allylcyclohexyl group, a 1-benzylcyclohexyl group, a cycloheptyl group, a cycloheptenyl group, a cycloheptatrienyl group, a 1-methylcycloheptyl group, a 1-allylcycloheptyl group, a 1-benzylcycloheptyl group, a cyclooct ... Preferred are a cyclohexyl group, a cyclooctenyl group, a cyclooctadienyl group, a cyclododecyl group, a 4-cyclohexyl-tert-butyl group, a norbornyl group, a 2-methylbicyclo[2.2.1]heptan-2-yl group, a bicyclo[2.2.2]octan-1-yl group, a 1-adamantyl group, a 2-adamantyl group, a pentalenyl group, an indenyl group, and a fluorenyl group, and more preferred are a cyclopentyl group, a cyclopentenyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group, a cyclooctyl group, a cyclododecyl group, and a 1-adamantyl group.

[0074] Among the aromatic groups having 6 to 40 carbon atoms, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, an allylphenyl group, a prenylphenyl group, a 4-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, a phenanthryl group, an adenylphenyl group, a phenanthryl ... Preferred are anthracenyl and ferrocenyl groups, and more preferred are phenyl, tolyl, xylyl, mesityl, cumenyl, 2,6-di-isopropylphenyl, 2,4,6-tri-isopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, allylphenyl, 4-adamantylphenyl, naphthyl, biphenyl, binaphthyl, phenanthryl, and anthracenyl groups.

[0075] Examples of the halogen-containing group in R include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, a 3,3,3-trifluoropropyl group, a nonafluorobutyl group, a 4,4,4-trifluorobutyl group, a dodecafluorohexyl group, a 6,6,6-trifluorohexyl group, a chlorophenyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a pentafluorophenylmethyl group, a di-tert-butyl-fluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a bistrifluoromethoxyphenyl group, a trifluoromethylthiophenyl group, a bistrifluoromethylthiophenyl group, a fluorobiphenyl group, a di Examples thereof include a fluorobiphenyl group, a trifluorobiphenyl group, a tetrafluorobiphenyl group, a pentafluorobiphenyl group, a di-tert-butyl-fluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxybiphenyl group, a bistrifluoromethoxybiphenyl group, a trifluoromethyldimethylsilyl group, a trifluoromethoxy group, a pentafluoroethoxy group, a fluorophenoxy group, a difluorophenoxy group, a trifluorophenoxy group, a pentafluorophenoxy group, a di-tert-butyl-fluorophenoxy group, a trifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a trifluoromethoxyphenoxy group, a bistrifluoromethoxyphenoxy group, a difluoromethylenedioxyphenyl group, a bistrifluoromethylphenyliminomethyl group, and a trifluoromethylthio group.

[0076] Among the halogen-containing groups represented by R, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a pentafluorophenylmethyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a pentafluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group, a bistrifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a difluoromethylenedioxyphenyl group, and a trifluoromethylthio group are preferred, and a trifluoromethyl group, a fluorophenyl group, a difluorophenyl group, a pentafluorophenyl group, a pentafluorophenylmethyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, and a pentafluorophenoxy group are more preferred.

[0077] Examples of the silicon-containing group in R include a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a cyclopentadienyldimethylsilyl group, a di-n-butyl(cyclopentadienyl)silyl group, a cyclopentadienyldiphenylsilyl group, an indenyldimethylsilyl group, a di-n-butyl(indenyl)silyl group, a cyclopentadienyldiphenylsilyl group, an indenyldimethylsilyl group, a di-n-butyl(indenyl)silyl group, a cyclopentadienyldiphenylsilyl group, a cyclopentadien ... Examples of such silyl groups include a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-isopropylsilylphenyl group, a 4-tert-butyldiphenylsilylphenyl group, a 4-triphenylsilylphenyl group, a 4-tris(trimethylsilyl)silylphenyl group, and a 3,5-bis(trimethylsilyl)phenyl group.

[0078] Among the silicon-containing groups represented by R, a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, a cyclopentadienyldimethylsilyl group, a cyclopentadienyldiphenylsilyl group, an indenyldimethylsilyl group, an indenyldiphenylsilyl group, a fluorenyldimethylsilyl group, a fluorenyldiphenylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-isopropylsilylphenyl group, a 4-triphenylsilylphenyl group, a 3,5-bis(trimethylsilyl)phenyl group, and the like are preferred, and a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-isopropylsilylphenyl group, and a 3,5-bis(trimethylsilyl)phenyl group are more preferred.

[0079] The oxygen-containing group for R is preferably an oxygen-containing group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a methallyloxy group, a prenyloxy group, a benzyloxy group, a methoxymethoxy group, a methoxyethoxy group, a phenoxy group, a naphthoxy group, a toluyloxy group, an iso-propylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, an iso-propoxyphenoxy group, an allyloxyphenoxy group, a biphenyloxy group, a binaphthyloxy group, a methoxymethyl group, an allyloxymethyl group, a benzyloxymethyl group, a phenoxymethyl group, a methoxyethyl group, an allyloxyethyl group, a benzyloxyethyl group, a phenoxyethyl group, a methoxypropyl group, a methyl ... Examples of groups usable as the methoxyphenyl group include a propyl group, an allyloxypropyl group, a benzyloxypropyl group, a phenoxypropyl group, a methoxyvinyl group, an allyloxyvinyl group, a benzyloxyvinyl group, a phenoxyvinyl group, a methoxyallyl group, an allyloxyallyl group, a benzyloxyallyl group, a phenoxyallyl group, a dimethoxymethyl group, a di-iso-propoxymethyl group, a dioxolanyl group, a tetramethyldioxolanyl group, a dioxanyl group, a dimethyldioxanyl group, a methoxyphenyl group, an iso-propoxyphenyl group, an allyloxyphenyl group, a phenoxyphenyl group, a methylenedioxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a tetrahydrofuryl group, a pyranyl group, a tetrahydropyranyl group, a furofuryl group, a benzofuryl group, and a dibenzofuryl group.

[0080] Among the oxygen-containing groups in R, there are methoxy, ethoxy, isopropoxy, allyloxy, n-butoxy, tert-butoxy, prenyloxy, benzyloxy, phenoxy, naphthoxy, toluyloxy, isopropylphenoxy, allylphenoxy, tert-butylphenoxy, methoxyphenoxy, biphenyloxy, binaphthyloxy, allyloxymethyl, benzyloxymethyl, phenoxymethyl, methoxyethyl, methoxyallyl, benzyloxyallyl, phenoxyallyl, dimethoxymethyl, dioxolanyl, tetramethyldioxolanyl, dioxanyl, dimethyldioxanyl, methoxyphenyl, isopropoxyphenyl, allyl An oxyphenyl group, a phenoxyphenyl group, a methylenedioxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a tetrahydropyranyl group, a furofuryl group, a benzofuryl group, a dibenzofuryl group, and the like are preferred, and a methoxy group, an iso-propoxy group, a tert-butoxy group, an allyloxy group, a phenoxy group, a dimethoxymethyl group, a dioxolanyl group, a methoxyphenyl group, an iso-propoxyphenyl group, an allyloxyphenyl group, a phenoxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a benzofuryl group, and a dibenzofuryl group are more preferred.

[0081] The nitrogen-containing group for R is preferably a nitrogen-containing group having 1 to 20 carbon atoms, and examples thereof include an amino group, a dimethylamino group, a diethylamino group, a di-n-propylamino group, a di-iso-propylamino group, a di-n-butylamino group, a di-iso-butylamino group, a dicyclopentylamino group, a dicyclohexylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, an azepinyl group, an adamantylamino group, a dimethylaminomethyl group, a dibenzylaminomethyl group, a pyrrolidinylmethyl group, a dimethylaminoethyl group, a benzylaminomethyl group, a benzylaminoethyl group, a pyrrolidinylethyl group, a dimethylaminovinyl group, a benzylaminovinyl group, a pyrrolidinylvinyl group, a dimethylaminopropyl group, a benzylaminopropyl group, a pyrrolidinylpropyl group, a dimethylaminoallyl group, a benzylaminoallyl group, a pyrrolidinylallyl group, Aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-isopropyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinylphenyl group, piperidinylphenyl group, morpholylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl Examples of such groups include a di-tert-butylcarbazolylphenyl group, a pyrrolyl group, a methylpyrrolyl group, a phenylpyrrolyl group, a pyridyl group, a quinolyl group, a tetrahydroquinolyl group, an isoquinolyl group, a tetrahydro-isoquinolyl group, an indolyl group, an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzimidazolyl group, an oxazolyl group, an oxazolidinyl group, and a benzoxazolyl group.

[0082] Among the nitrogen-containing groups in R, amino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-isopropylamino group, di-n-butylamino group, di-isobutylamino group, dicyclopentylamino group, dicyclohexylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, adamantylamino group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, ethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinylphenyl group, piperidinylphenyl group, morpholylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di- A tert-butylcarbazolylphenyl group, a pyrrolyl group, a pyridyl group, a quinolyl group, a tetrahydroquinolyl group, an isoquinolyl group, a tetrahydro-isoquinolyl group, an indolyl group, an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzimidazolyl group, an oxazolyl group, an oxazolidinyl group, a benzoxazolyl group, and the like are preferred, and an amino group, a dimethylamino group, a diethylamino group, a di-isopropylamino group, and the like are preferred. More preferred are a cyclohexylamino group, a dicyclopentylamino group, a dicyclohexylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, a dimethylaminophenyl group, a 3,5-dimethyl-4-dimethylaminophenyl group, a 3,5-di-isopropyl-4-dimethylaminophenyl group, a julolidinyl group, a tetramethyljulolidinyl group, a pyrrolidinylphenyl group, a piperidinylphenyl group, a morpholylphenyl group, a pyrrolylphenyl group, a pyrrolyl group, a pyridyl group, a carbazolyl group, and an imidazolyl group.

[0083] Examples of the sulfur-containing group for R include a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group, a phenylthiomethyl group, a naphthylthiomethyl group, a methylthioethyl group, a benzylthioethyl group, a phenylthioethyl group, a naphthylthioethyl group, a methylthiovinyl group, a benzylthiovinyl group, a phenylthiovinyl group, a naphthylthiovinyl group, a methylthiopropyl group, a benzylthiopropyl group, a phenylthiopropyl group, a naphthylthiopropyl group, a methylthioallyl group, a benzylthioallyl group, a phenylthio Examples of such alkyl groups include an alkylthioallyl group, a naphthylthioallyl group, a mercaptophenyl group, a methylthiophenyl group, a thienylphenyl group, a methylthienylphenyl group, a benzothienylphenyl group, a dibenzothienylphenyl group, a benzodithienylphenyl group, a thienyl group, a tetrahydrothienyl group, a methylthienyl group, a thienofuryl group, a thienothienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a dithiolanyl group, a dithianyl group, an oxathiolanyl group, an oxathianyl group, a thiazolyl group, a benzothiazolyl group, and a thiazolidinyl group.

[0084] Among the sulfur-containing groups for R, a thienyl group, a methylthienyl group, a thienofuryl group, a thienothienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a thiazolyl group, and a benzothiazolyl group are preferred.

[0085] Furthermore, among a plurality of R, adjacent Rs may be bonded to each other to form a ring or a bicyclo ring which may have a substituent. In this case, the ring formed is preferably a 4- to 8-membered saturated or unsaturated heterocycle which may have a substituent containing a phosphorus atom. While not particularly limited as long as the effects of the present invention are achieved, a 5- or 7-membered ring is preferred. In this case, examples of the structure combined with the phosphorus atom include a substituted phosphole ring, a substituted phosphorane ring, a substituted dihydrophosphepine ring, a substituted dioxaphosphepine ring, a substituted diazaphosphepine ring, a substituted phospha-adamantane ring, and a substituted trioxaphospha-adamantane ring, and the like. A substituted dihydrophosphepine ring, a substituted dioxaphosphepine ring, a substituted diazaphosphepine ring, or a substituted trioxaphospha-adamantane ring is preferred.

[0086] Examples of the substituent in the cyclopentadienyl ligand include a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, and a sulfur-containing group. Specific examples of these substituents include the same groups as those exemplified as the groups for R.

[0087] Below, we will introduce examples of component (A) when L is an atom of an element in Group 15. Examples of such component (A) include transition metal compounds represented by the following general formula [2].

[0088] [ka]

[0089] In the general formula [2], M, n, X, and Cp have the same meanings as M, n, X, and Cp in the general formula [1], respectively. N is a nitrogen atom and P is a phosphorus atom. R 1 ~R 3 R each independently has the same meaning as R in general formula [1]. 1 ~R 3 may be the same or different.1 ~R 3 may be bonded to each other to form a ring or a bicyclo ring which may have a substituent.

[0090] Specific examples of the component (A), which is a transition metal compound represented by the general formula [2], are shown below. For convenience, the ligand structure of the transition metal compound component (A), excluding the portion represented by MXn (metal portion), is divided into two structures: a cyclopentadienyl-type ligand portion and an imide-type ligand portion. The abbreviation for the cyclopentadienyl-type ligand portion is α, and the abbreviation for the imide-type ligand portion is R. 1 ~R 3 The abbreviation for the substituent is β, the abbreviation for the imide-type ligand partial cyclic structure is γ, and the abbreviations for each substituent are shown in Tables 1 to 3.

[0091] [Table 1]

[0092] [Table 2]

[0093] [Table 3] In addition, R in Table 3 a and R b is a substituent represented by the abbreviation β in Table 2. The wavy line in Table 3 indicates the bonding site with the nitrogen atom.

[0094] Specific examples of the metal moiety MXn include TiF2, TiCl2, TiBr2, TiI2, Ti(Me)2, Ti(Bn)2, Ti(Allyl)2, Ti(CH2-tBu)2, Ti(1,3-butadienyl), Ti(1,3-pentadienyl), Ti(2,4-hexadienyl), Ti(1,4-diphenyl-1,3-pentadienyl), Ti(CH2-S i(Me)3)2, Ti(OMe)2, Ti(OiPr)2, Ti(NMe2)2, Ti(OMs)2, Ti(OTs)2, Ti(OTf)2, ZrF2, ZrCl2, ZrBr2, ZrI2, Zr(Me)2, Zr(Bn)2, Zr(Allyl)2, Zr(CH2-tBu)2, Zr(1,3-butadienyl), Zr(1,3-pentadienyl), Zr(2, 4-hexadienyl), Zr(1,4-diphenyl-1,3-pentadienyl), Zr(CH2-Si(Me)3)2, Zr(OMe)2, Zr(OiPr)2, Zr(NMe2)2, Zr(OMs)2, Zr(OTs)2, Zr(OTf)2, HfF2, HfCl2, HfBr2, HfI2, Hf(Me)2, Hf(Bn)2, Hf(Allyl)2, Hf(C Examples include H2-tBu2, Hf(1,3-butadienyl), Hf(1,3-pentadienyl), Hf(2,4-hexadienyl), Hf(1,4-diphenyl-1,3-pentadienyl), Hf(CH2-Si(Me)3), Hf(OMe)2, Hf(OiPr)2, Hf(NMe2), Hf(OMs)2, Hf(OTs)2, and Hf(OTf)2. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si(Me)3 is a trimethylsilyl group, OMe is a methoxy group, OiPr is an isopropoxy group, NMe2 is a dimethylamino group, OMs is a methanesulfonate group, OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

[0095] Preferred specific examples of the component (A) include compounds represented by the following formulas [3] to [6]. The metal moiety (MXn) in the following formula [6] is Ti(1,3-pentadienyl).

[0096] [ka]

[0097] The compound represented by the general formula [1] can be produced by a conventionally known method, and the production method is not particularly limited. Examples of known production methods include those described in "Organometallics 1999,18,1116.", JP-A-2001-516776, "Organometallics 2001,20,4424.", "Chem. Commun. 2002,608.", "Organometallics 2003,22,1937.", "J. Organomet. Chem. 2004,689,203.", "Organometallics 2004,23,1562.", "Organometallics 2004,23,3309.", International Publication No. 2005 / 090418, U.S. Patent No. 6,239,061, and "Organometallics 2005,24,2548.'', Special Publication No. 2007-529584, ``J.Organomet.Chem. 2011,696,2451.'', ``Dalton Trans. 2011,40,7842.", JP 2012-007171 A, JP 2012-046764 A, JP 2013-155371 A, JP 2013-510214 A, JP 2013-515120 A, U.S. Patent No. 9045504 A, JP 2014-509670 A, U.S. Patent No. 9035081 A, JP 2015-520276 A, JP 2016-532730 A, and JP 2017-509595 A.

[0098] Component (A) may be used singly or in combination of two or more transition metal compounds with different chemical structures. In addition, one optical isomer having the same chemical structure may be used singly, or a mixture of optical isomers (e.g., a meso mixture or a racemic mixture) may be used. Furthermore, when L is a Group 16 element, the same compounds as above except that y=3 and z=4 can be exemplified.

[0099] <Solid Carrier (S) (Component (S))> Component (S) is an inorganic or organic compound, which is a granular or particulate solid. Examples of inorganic compounds include porous oxides, inorganic halides, clay, clay minerals, and ion-exchangeable layered compounds, and examples thereof include porous oxides and inorganic halides such as inorganic chlorides as will be described later. When component (A) contains a transition metal atom of Group 4 of the periodic table, it is preferable that component (S) is a porous oxide, since this improves the morphology of the olefin polymer and enables the olefin polymer to be produced with high productivity.

[0100] Specific examples of porous oxides that can be used include silica (SiO2), Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or composites or mixtures containing these, natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc. Of these, those containing SiO2 as the main component are preferred.

[0101] In addition, the inorganic oxides may contain small amounts of carbonates, sulfates, nitrates, and oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O.

[0102] The properties of porous oxides vary depending on the type and manufacturing method, but the average particle size is usually 0.2 to 300 μm, preferably 1 to 200 μm, more preferably 20 to 100 μm, and even more preferably 40 to 80 μm, and the specific surface area is usually 50 to 1200 m 2 / g, preferably 100 to 1000m 2 / g, more preferably 200 to 600m 2 / g, more preferably 300 to 400m 2 / g, and the pore volume is usually 0.3 to 30 cm 3 / g, preferably 0.5 to 10 cm 3 / g, more preferably 0.8 to 5 cm3 / g, more preferably 1.0 to 2.0 cm 3 / g.

[0103] The average particle size of porous oxides can be measured by dynamic light scattering in the range of 1 nm or more and less than 1 μm, and by laser diffraction / scattering in the range of 1 μm or more and 5 μm or less.

[0104] The specific surface area of ​​the porous oxide can be measured by a method in accordance with JIS K 1150 "Silica Gel Test Method."

[0105] The pore volume of porous oxides can be measured by oven-drying a porous oxide sample at 180°C and titrating it with water. Generally, pore volume is determined from the nitrogen adsorption isotherm, but if the pore diameter of the porous oxide is large, accurate pore volume determination from the nitrogen adsorption isotherm is not possible. Therefore, 5 g of the dried sample is weighed into an approximately 100 ml mayonnaise jar, and water is dropped onto it. The pore volume is measured at the end point, when the powder no longer rises.

[0106] The porous oxide is calcined, if necessary, at, for example, 100 to 1000°C, preferably 150 to 700°C, more preferably 175 to 500°C, and even more preferably 200 to 300°C before use.

[0107] Examples of inorganic halides that can be used include MgCl, MgBr, MnCl, and MnBr. The inorganic halides may be used as they are, or may be used after being pulverized using a ball mill or a vibration mill. Alternatively, the inorganic halides may be dissolved in a solvent such as alcohol and then precipitated into fine particles using a precipitating agent.

[0108] Clay is usually composed mainly of clay minerals. Ion-exchangeable layered compounds are compounds with a crystalline structure in which planes formed by ionic bonds or the like are stacked parallel to one another with weak bonding forces, and the ions they contain are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and synthetic compounds can also be used.

[0109] Examples of clays, clay minerals, or ion-exchangeable layered compounds include clays, clay minerals, and ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl2 type, and CdI2 type.

[0110] Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchange layered compounds include crystalline acid salts of polyvalent metals such as α-Zr(HAsO)·H0, α-Zr(HPO), α-Zr(KPO 3H0, α-Ti(HPO), α-Ti(HAsO)·H0, α-Sn(HPO), H0, γ-Zr(HPO), γ-Ti(HPO,), and γ-Ti(NHPO).

[0111] Such clays, clay minerals, or ion-exchange layered compounds have a pore volume of 0.1 cm2 with a radius of 20 Å or more as measured by mercury intrusion porosimetry. 3 / g or more is preferable, and 0.3 to 5 cm 3 / g is particularly preferred. Here, the pore volume is determined by a mercury intrusion method using a mercury porosimeter, and the pore radius is 20 Å to 3×10 4 Measured in the Å range.

[0112] Pore ​​volume of 0.1 cm with a radius of 20 Å or more 3When a carrier having a molecular weight less than 1 / g is used, it tends to be difficult to obtain high polymerization activity. It is also preferable to subject clay and clay minerals to chemical treatment. Chemical treatments include surface treatments that remove impurities from the surface and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment not only removes surface impurities but also increases the surface area by eluting cations such as Al, Fe, and Mg in the crystalline structure. Alkaline treatment destroys the crystalline structure of the clay, resulting in structural changes. Furthermore, salt treatment and organic treatment form ionic complexes, molecular complexes, organic derivatives, etc., which can change the surface area and interlayer distance.

[0113] The ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with other large, bulky ions. Such bulky ions act as supports supporting the layered structure and are usually called pillars. The introduction of another substance between the layers of a layered compound in this way is called intercalation. Examples of guest compounds 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.), and [Al 13 O4(OH) 24 ] 7+ , [Zr(OH) 14 ] 2+ , [Fe3O(OCOCH3)6] + Examples of the metal hydroxide ions include those mentioned above. These compounds can be used alone or in combination of two or more. When intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, Ge(OR)4, and the like, and colloidal inorganic compounds such as SiO2 can also be present. Examples of the pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them with heat.

[0114] The clay, clay mineral, and ion-exchangeable layered compound may be used as is, or may be used after treatment such as ball milling or sieving. They may also be used after adding and adsorbing new water or after heat dehydration. Furthermore, they may be used alone or in combination of two or more.

[0115] Examples of organic compounds include granular or particulate solids with particle sizes ranging from 1 to 300 μm. Specific examples include (co)polymers containing as the main component an olefin having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, or 4-methyl-1-pentene, or (co)polymers containing as the main component vinylcyclohexane, styrene, or divinylbenzene, and modified products thereof.

[0116] In addition, a solid component obtained by contacting the inorganic or organic compound with component (B-1) described later, and a solid component obtained by insolubilizing component (B-1) described later by the methods described in JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, WO 2010 / 55652, etc., can also be used as component (S).

[0117] <Organoaluminum Compound (B-1) (Component (B-1))> The prepolymerization step is carried out using component (B-1) as a cocatalyst component. That is, the prepolymerization catalyst (P) contains component (B-1). By using component (B-1) as a cocatalyst component, a prepolymerization catalyst that exhibits very high catalytic activity during olefin polymerization can be easily obtained. As described above, the component (B-1) may be used in combination in the preparation of the solid catalyst component (Sa). When the component (B-1) is used in the preparation of the solid catalyst component (Sa), the component (B-1) used in the preparation of the solid catalyst component (Sa) and the component (B-1) used in the prepolymerization step may be the same or different.

[0118] Examples of the component (B-1) include compounds represented by the following general formula (I), (II) or (III). R d m Al(OR e ) n H p X q ···(I) 〔In the general formula (I), R d and R e represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same as or different from each other, X represents a halogen atom, m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3.〕 M a AlR f 4···(II) 〔In the general formula (II), M a represents Li, Na or K, and R f represents a hydrocarbon group having 1 to 15 carbon atoms.〕 化水素基を示す。〕 R g [[ID=ID=37]] r M b R h s X t ···(III) 〔In the general formula (III), R g and R h represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same as or different from each other, M b represents Mg, Zn or Cd, X represents a halogen atom, r is a number where 0 < r ≦ 2, s is a number where 0 ≦ s ≦ 1, t is a number where 0 ≦ t ≦ 1, and r + s + t = 2.〕

[0119] In the general formula (I), R d and R emay be the same or different, and examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, and an aryl group, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a tolyl group, and preferably an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0120] In general formula (II), R f As the hydrocarbon group, R d and R e Examples of hydrocarbon groups include the same as those listed above.

[0121] In the above general formula (III), R g and R h may be the same or different, and the hydrocarbon group may be any of the above R d and R e Examples of hydrocarbon groups include the same as those listed above. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0122] Among the compounds represented by general formula (I), (II) or (III), those represented by general formula (I) are preferred, and specific examples thereof include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum; and alkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride and diisohexylaluminum hydride. These may be used alone or in combination of two or more.

[0123] <Organoaluminum oxy compound (B-2) (ingredient (B-2))> The prepolymerization catalyst (P) preferably contains, in addition to the component (B-1), a further component (B-2) as a cocatalyst component. For example, the component (B-2) may be added in the preparation of the solid catalyst component (Sa), or the component (B-2) may be used in the prepolymerization step. The use of the component (B-2) as a cocatalyst component makes it easy to obtain a prepolymerization catalyst that exhibits extremely high catalytic activity during olefin polymerization.

[0124] Component (B-2) includes organoaluminum oxy compounds, specifically, organoaluminum oxy compounds prepared from trialkylaluminum or tricycloalkylaluminum are preferred, aluminoxanes prepared from trimethylaluminum or triisobutylaluminum are more preferred, and aluminoxanes prepared from trimethylaluminum are even more preferred. Note that aluminoxanes prepared from trimethylaluminum are also called methylaluminoxane or MAO. The component (B-1) may be used alone or in combination of two or more.

[0125] (Other organometallic compounds) Furthermore, other organometallic compounds such as compound (B-3) that react with component (A) to form an ion pair may be used as a promoter, provided that the effects of the present invention are not impaired.

[0126] Specific examples of compound (B-3) that can be used without limitation include Lewis acids, ionic compounds, borane compounds, and carborane compounds, as well as heteropoly compounds and isopoly compounds, described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Patent No. 5,321,106, etc. The other organometallic compounds may be used singly or in combination of two or more.

[0127] <Olefin (O1) having 2 to 5 carbon atoms (Component (O1))> Examples of component (O1) include α-olefins having 2 to 5 carbon atoms, specifically ethylene, propylene, 1-butene, 1-pentene, etc. Of these, ethylene and propylene are preferred, and ethylene is more preferred. Component (O1) may be used alone or in combination of two or more.

[0128] <Olefins (O2) with 6 or more carbon atoms (Component (O2))> Examples of component (O2) include α-olefins having 6 or more carbon atoms, preferably α-olefins having 6 to 20 carbon atoms, and specific examples include 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Of these, 1-hexene and 4-methyl-1-pentene are preferred, and 1-hexene is more preferred. Component (O2) may be used singly or in combination of two or more.

[0129] (Other monomers) Furthermore, within the scope of not impairing the effects of the present invention, polymerization can be carried out in the presence of at least one other monomer selected from cyclic olefins, aromatic vinyl compounds, dienes, etc. These may be used alone or in combination of two or more. The content of the other monomer can be, for example, 20 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of the total of component (O1) and component (O2).

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

[0131] Examples of aromatic vinyl compounds include styrene; mono- or polyalkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene; 3-phenylpropylene, 4-phenylpropylene, and α-methylstyrene.

[0132] Examples of dienes 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, and 1,9-decadiene; non-conjugated dienes such as ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, and 4-ethylidene-8-methyl-1,7-nonadiene; and conjugated dienes such as butadiene and isoprene.

[0133] <Surfactant (G) (Component (G))> As component (G), a compound generally known as a surfactant can be used, and can be used, if necessary, during the production of the prepolymerization catalyst (P). Specific examples of component (G) include at least one compound selected from the group consisting of the following compounds (g-1) to (g-6): (g-1) Polyalkylene oxide block (g-2) Higher aliphatic amide (g-3) Polyalkylene oxide (g-4) Polyalkylene oxide alkyl ether (g-5) Alkyldiethanolamine (g-6) Polyoxyalkylene alkylamine

[0134] Component (G) can be present in the olefin polymerization catalyst to suppress fouling in the polymerization vessel due to electrostatic adhesion of the catalyst or polymer, or to improve the particle properties of the polymer produced. Among components (G), (g-5) is preferred, and specific examples include higher aliphatic diethanolamine.

[0135] <Method for producing olefin polymer> The prepolymerization catalyst (P) can be suitably used for producing olefin polymers such as olefin homopolymers and olefin copolymers, and examples of the olefins include α-olefins having two or more carbon atoms, such as ethylene, propylene, 1-butene, 1-octene, and 4-methyl-1-pentene.

[0136] Examples of the olefin polymer include ethylene polymers, and copolymers of ethylene with an α-olefin having 3 to 10 carbon atoms are preferred. Examples of the α-olefin having 3 to 10 carbon atoms that can be copolymerized with ethylene include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.

[0137] The polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. However, gas phase polymerization, which does not require a solvent and does not require an agitator blade in a polymerization vessel, is preferred from the viewpoint of cost-effectiveness due to simplified equipment, etc. Prepolymerized catalyst (P) enables stable and continuous supply of catalyst into the polymerization vessel in the gas phase polymerization process, and polymerization proceeds in a short time, making it difficult for electrostatic aggregation and adhesion of fine particles to occur.

[0138] The amount of prepolymerization catalyst (P) used is usually 10 -12 ~10 -1 mol, preferably 10 -8 ~10 -2 mol. The polymerization temperature is usually from -50 to 200°C, preferably from 0 to 170°C, and more preferably from 30 to 170°C. The polymerization pressure is usually from atmospheric pressure to 10 MPa gauge pressure, preferably from atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous and continuous systems, and can also be carried out as a multi-stage reaction under two or more different reaction conditions.

[0139] The melt flow rate (MFR; according to ASTM D1238-65T, 190°C, 2.16 kg load) of the resulting ethylene polymer is preferably 1 to 100 g / 10 min, more preferably 3 to 70 g / 10 min, and even more preferably 5 to 50 g / 10 min.

[0140] The molecular weight of the resulting ethylene polymer can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. Hydrogen, in particular, is a preferred additive because it can improve the polymerization activity of the catalyst and increase or decrease the molecular weight of the polymer. When hydrogen is added to the system, the appropriate amount is approximately 0.00001 to 100 nL per mole of olefin. The hydrogen concentration in the system can be adjusted not only by adjusting the amount of hydrogen supplied, but also by performing a reaction that produces or consumes hydrogen within the system, separating hydrogen using a membrane, or releasing a portion of the hydrogen-containing gas outside the system.

[0141] Furthermore, component (G) can be present in the polymerization system to suppress fouling in the polymerization vessel due to electrostatic adhesion of the catalyst or polymer or to improve particle properties. After the polymerization is completed, the obtained olefin polymer may be subjected to known post-treatment steps such as a catalyst deactivation step, a catalyst residue removal step, and a drying step, if necessary.

[0142] In order to suppress variations in physical properties, the olefin polymer particles obtained by the polymerization reaction and other components added as desired are melted by any method, kneaded, granulated, etc. [Example]

[0143] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0144] <Evaluation method> Heat of fusion of prepolymer The heat of fusion of the prepolymers obtained in the examples and comparative examples was measured by a differential scanning calorimeter (DSC). Specifically, the prepolymerized catalyst obtained was heated from room temperature to 200°C at a rate of 500°C / min, held at 200°C for 10 minutes, cooled to 30°C at 10°C / min, held at 30°C for 1 minute, and then heated to 200°C at 10°C / min. The heat of fusion was calculated from the peak area enclosed by the baseline and the DSC curve obtained at each stage.

[0145] 1-Hexene content of prepolymer The 1-hexene content of the prepolymers obtained in the examples and comparative examples was measured by FT-IR. Specifically, the obtained prepolymerization catalyst was formed into a film using a hot press, and the obtained film was used as a measurement sample, and the 1-hexene content (mass%) was measured using a calibration curve. The 1-hexene content in the ethylene / 1-hexene copolymer sample used to create the calibration curve was 13 It was identified by C-NMR measurement.

[0146] Fluidity of prepolymerization catalyst The fluidity of the prepolymerized catalyst was evaluated by observing the state of the sample obtained by vacuum-drying the prepolymerized catalyst obtained in the Examples and Comparative Examples when it was shaken, and by visually observing the amount of the prepolymerized catalyst adhering to the wall of the reactor after removing it from the reactor equipped with a stirrer. The evaluation criteria are as follows: <Sample condition after shaking> A: The cake will unravel. B: The cake won't come apart. <Amount of adhesion on the vessel wall after removal from the reactor> A: No visible adhesion to the container wall / Adhesion is visible, and the amount of adhesion is less than one-third of the entire container wall. B: Adhesion to the container wall can be visually confirmed, and the amount of adhesion is more than one-third but less than two-thirds of the entire container wall. C: Adhesion to the container wall is visible and accounts for more than two-thirds of the entire container wall.

[0147] MFR of ethylene polymer The MFR of the ethylene polymer was measured under conditions of 190°C and a load of 2.16 kg in accordance with ASTM D1238-65T.

[0148] [Synthesis Example 1] Synthesis of transition metal complexes As the transition metal complex (A), a transition metal complex (A-1) represented by the following formula [A-1] was synthesized by the method described in JP-A No. 2006-169521.

[0149] [ka]

[0150] [Example 1] (1) Preparation of prepolymerization catalyst A 1 L reactor equipped with a stirrer was placed under a nitrogen atmosphere with silica (average particle size 70 μm, specific surface area 340 m) manufactured by Fuji Silysia Ltd. as a solid support (S). 2 / g, pore volume 1.3cm 3 43.9 g of methylaluminum hydride (43.9 g / g, calcined at 250°C) was suspended in 300 mL of toluene and then cooled to 0 to 5°C. To this suspension, 23.4 mL of a 1.0 M diisobutylaluminum hydride toluene solution (organoaluminum compound (B-1)) was added dropwise over 30 minutes. The temperature in the system was maintained at 0 to 5°C. After the contact was continued for 30 minutes at 0 to 5°C, 134.1 mL of a toluene solution of methylaluminoxane (3.0 mmol / mL in terms of Al atom) (organoaluminum oxy compound (B-2)) was added dropwise over 30 minutes. The temperature in the system was maintained at 0 to 5°C. After the contact was continued for 30 minutes at 0 to 5°C, the temperature in the system was raised to 95°C over approximately 1.5 hours, and the contact was continued at 95°C for 4 hours. The temperature was then lowered to room temperature, the supernatant liquid was removed by decantation, and the mixture was washed twice with toluene to prepare a toluene slurry with a total volume of 300 mL. A portion of the resulting slurry components was sampled and its concentration was examined, revealing a slurry concentration of 205.0 g / L and an Al concentration of 1.22 mol / L.

[0151] Next, 20.9 mL of toluene and 8.8 mL of the above toluene slurry (solid content = 1.8 g) were charged into a 200 mL reactor equipped with a stirrer and thoroughly purged with nitrogen. Next, 10.4 mL of a 0.008 mol / L toluene solution of transition metal complex (A-1) was added and the mixture was contacted at a system temperature of 20 to 25°C for 1 hour. The supernatant was then removed by decantation, and the mixture was washed twice with hexane to prepare a total of 41.1 mL of solid catalyst slurry.

[0152] The prepared solid catalyst slurry was then cooled to 10°C under a nitrogen atmosphere, and 3.7 mL of a 1.0 M diisobutylaluminum hydride hexane solution (organoaluminum compound (B-1)) was added. After 10 minutes of contact at 10°C, the temperature in the system was raised to 25°C to initiate prepolymerization. The temperature in the system was maintained at 25-35°C, and 3.9 g of ethylene and 1.7 g of 1-hexene were added over 360 minutes. The supernatant was then removed by decantation and washed four times with hexane. Further hexane was added to bring the total volume to 41.1 mL, yielding a prepolymerized catalyst hexane slurry.

[0153] The resulting prepolymerized catalyst hexane slurry was then heated to 40°C under a nitrogen atmosphere, and 3.7 mL of a 20 mg / mL hexane solution of Electrostripper (registered trademark) EA (Kao Corporation) as surfactant (G) was added. The mixture was then allowed to contact for 2 hours at 40°C. The mixture was then transferred to a glass filter that had been thoroughly purged with nitrogen, and the pressure was reduced to -68 kPaG over approximately 1 hour. Once the pressure reached -68 kPaG, the mixture was vacuum-dried for approximately 2 hours to obtain prepolymerized catalyst (P-1). The heat of fusion of the prepolymer was 75 J / g, and the weight fraction of 1-hexene was 22%.

[0154] (2) Production of ethylene polymers A 1-liter stainless steel autoclave was charged with 500 ml of heptane and the system was purged with ethylene. Then, 0.25 mmol of triisobutylaluminum and 60.2 mg of prepolymerization catalyst (P-1) were added, and the system temperature was raised to 80°C. Ethylene was then continuously introduced to maintain a total pressure of 0.8 MPaG and 80°C. The polymerization reaction was carried out for 240 minutes, while recording the ethylene feed rate every minute using a data logger. The moving average ethylene feed rate data for the last 10 minutes after the start of polymerization was calculated. The "moving average ethylene feed rate over the last 10 minutes" refers to a 10-minute moving average of ethylene feed rates, such as the average ethylene feed rate from the start of polymerization to 9 minutes, the average ethylene feed rate from 1 to 10 minutes from the start of polymerization, ..., and the average ethylene feed rate from 231 to 240 minutes from the start of polymerization. These are the ethylene feed rate at the start of polymerization, the ethylene feed rate 1 minute after the start of polymerization, ..., and the ethylene feed rate 231 minutes after the start of polymerization, respectively. Note that for the ethylene feed rates every minute from 232 to 240 minutes after the start of polymerization, raw data at the time of measurement was used. Of the obtained moving average ethylene feed rate data, the maximum ethylene feed rate occurred 8 minutes after the start of polymerization. After polymerization was completed, the polymer was recovered by filtration and dried overnight at 80°C under reduced pressure to yield 103.6 g of ethylene polymer. The polymerization activity (amount of ethylene polymer produced per gram of solid catalyst component) was 6.3 kg-PE / g-solids, and the MFR was 23.1 g / 10 min. The results are shown in Table 1.

[0155] [Example 2] The same procedure as in Example 1 was carried out except that 4.7 g of ethylene and 0.8 g of 1-hexene were fed in the preparation of the prepolymerization catalyst. The results are shown in Table 1.

[0156] [Example 3] The same procedure as in Example 1 was carried out except that 5.0 g of ethylene and 0.6 g of 1-hexene were fed in the preparation of the prepolymerization catalyst. The results are shown in Table 1.

[0157] [Comparative Example 1] The same procedure as in Example 1 was carried out except that 5.2 g of ethylene and 0.3 g of 1-hexene were fed in the preparation of the prepolymerization catalyst. The results are shown in Table 1.

[0158] Comparative Example 2 The procedure was the same as in Example 1, except that 5.5 g of ethylene and no 1-hexene were fed in the preparation of the prepolymerized catalyst. The results are shown in Table 1.

[0159] Comparative Example 3 The same procedure as in Example 1 was carried out except that 2.8 g of ethylene and 2.8 g of 1-hexene were fed in the preparation of the prepolymerization catalyst. The results are shown in Table 1.

[0160] [Table 4]

[0161] As shown in Table 4, the prepolymerization catalysts of Examples 1 to 3 had good fluidity, and the catalyst activity development behavior showed an early-type behavior compared to Comparative Examples 1 and 2 (the time until the ethylene supply rate reached its maximum was shorter compared to Comparative Examples 1 and 2). Furthermore, in Comparative Example 3, the fluidity was significantly deteriorated.

Claims

1. A solid catalyst component (Sa) containing a transition metal complex (A) and a solid support (S) is A method for producing a prepolymerization catalyst (P), comprising a step of supplying at least one olefin (O1) selected from olefins having 2 to 5 carbon atoms and at least one olefin (O2) selected from olefins having 6 or more carbon atoms in the presence of an organoaluminum compound (B-1), and prepolymerizing the resulting mixture, The method for producing a prepolymerized catalyst (P), wherein the prepolymer contained in the prepolymerized catalyst (P) has a heat of fusion of 50 to 130 J / g as measured by a differential scanning calorimeter (DSC).

2. A solid catalyst component (Sa) containing a transition metal complex (A) and a solid support (S) is A method for producing a prepolymerization catalyst (P), comprising a step of supplying at least one olefin (O1) selected from olefins having 2 to 5 carbon atoms and at least one olefin (O2) selected from olefins having 6 or more carbon atoms in the presence of an organoaluminum compound (B-1), and prepolymerizing the resulting mixture, a prepolymerization catalyst (P) containing a prepolymer containing the prepolymerization catalyst (P), the content of the component derived from the olefin (O2) being more than 6 mass% and less than 33 mass%, when the total of the component derived from the olefin (O1) and the component derived from the olefin (O2) in the prepolymer contained in the prepolymerization catalyst (P) is taken as 100 mass%.

3. 3. The method for producing a prepolymerized catalyst (P) according to claim 1 or 2, wherein the transition metal complex (A) contains a transition metal atom of Group 4 of the periodic table, and the solid support (S) is a porous oxide.

4. The method for producing a prepolymerized catalyst (P) according to claim 1 or 2, wherein the prepolymerized catalyst (P) contains an organoaluminum oxy compound (B-2).

5. The method for producing a prepolymerization catalyst (P) according to claim 1 or 2, wherein the transition metal complex (A) is represented by the following general formula [1]: 【Chemistry 1】 (In the general formula [1], M is a transition metal atom of Group 4 of the periodic table, n is an integer from 1 to 4 that satisfies the valence of M; X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene-based divalent derivative group, and when n is 2 or more, the multiple groups represented by X may be the same or different and may be bonded to each other to form a ring; Cp is a cyclopentadienyl ligand which may have a substituent, and adjacent substituents may be bonded to each other to form a ring which may have a substituent; L is an atom selected from the elements of Groups 15 and 16 of the periodic table; P is a phosphorus atom, The solid lines represent covalent or coordinate bonds, and the dotted lines represent covalent bonds that exist when L is an atom of a Group 15 element. z is 3 when L is an atom of a Group 15 element, and is 4 when L is an atom of a Group 16 element; R's are independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, and may be the same or different, and adjacent R's may be bonded to each other to form a ring or a bicyclo ring which may have a substituent.

6. A process for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin in the presence of the prepolymerization catalyst (P) according to claim 1 or 2.

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