Method for producing catalyst slurry for olefin polymerization and method for producing olefin polymer

Abstract

To provide a method for producing a catalyst slurry that suppresses a temporal decrease in antistatic effect.SOLUTION: A method for producing a catalyst slurry for olefin polymerization comprising the following components (A), (B), and (C), includes the following steps (1) to (3): Component (A): a solid catalyst for olefin polymerization (containing no antistatic agent), Component (B): an antistatic agent, Component (C): at least one selected from the group consisting of liquid paraffin, mineral oil, and polybutene, Component (D): a hydrocarbon compound having 4 to 12 carbon atoms, Step (1): preparing a mixture containing the components (A), (B), and (D), Step (2): removing the component (D) from the mixture containing the components (A), (B), and (D), and Step (3): mixing the component (C) into a mixture containing at least the components (A) and (B).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing a catalyst slurry for olefin polymerization, and a method for producing an olefin polymer. [Background technology]

[0002] Patent Document 1 discloses a polymerization catalyst containing a porous metal oxide, a catalyst, and an antistatic agent, in which the antistatic agent is added in an amount of 5,000 to 50,000 ppm by weight relative to the porous metal oxide. Patent Document 2 discloses a method for producing an olefin polymer using a metallocene catalyst containing an antistatic agent, and describes that the method enables highly active production of an olefin polymer while improving fouling and aggregation of polymers. Patent Document 3 discloses a method for preparing a catalyst comprising a solvent, a carrier, a metallocene compound, and a surface modifier (such as an alkoxylated tertiary amine). Patent Document 4 describes a method for producing olefin polymer particles using a solid catalyst for olefin polymerization that contains a compound having a specific structure. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2009-538936 [Patent Document 2] Japanese Patent Application Publication No. 10-60032 [Patent Document 3] Special Publication No. 10-507471 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-159591 Summary of the Invention [Problem to be solved by the invention]

[0004] In the production of olefin polymers, it is necessary to suppress the electrostatic charge of the catalyst slurry. Conventionally, even if charging is suppressed in the initial stage of preparation of the catalyst slurry, there has been a problem that the charging suppression effect decreases over time. The present invention has been made in view of the above circumstances, and has been made to prevent the charge suppressing effect from decreasing over time. As a result of extensive research into achieving the above-mentioned objects, the present inventors have found that an olefin polymerization catalyst slurry produced under specific conditions exhibits favorable properties that can solve the above-mentioned problems, and have completed the present invention based on these findings. The present invention can be realized as the following aspects. [Means for solving the problem]

[0005] [1] A method for producing a catalyst slurry for olefin polymerization, comprising the following components (A), (B) and (C), characterized in that the method comprises the following steps (1) to (3): Component (A): a solid catalyst for olefin polymerization (not including an antistatic agent) The component (B): antistatic agent The component (C): at least one selected from the group consisting of liquid paraffin, mineral oil, and polybutene The component (D): a hydrocarbon compound having 4 to 12 carbon atoms Step (1): preparing a mixture containing the component (A), the component (B), and the component (D). Step (2): A step of removing the component (D) from a mixture containing the component (A), the component (B), and the component (D). Step (3): A step of further mixing the component (C) with a mixture containing at least the component (A) and the component (B).

[0006] [2] [1] The method for producing a catalyst slurry for olefin polymerization according to [1], wherein in the step (1), a mixture is prepared by mixing the component (B) with a premix containing the component (A) and the component (D).

[0007] [3] The method for producing a catalyst slurry for olefin polymerization according to [1] or [2], characterized in that the mass of the component (B) contained in the catalyst slurry for olefin polymerization is 200 ppm by mass to 14,000 ppm by mass relative to the total mass of the component (A), the component (B), and the component (C).

[0008] [4] The method for producing a catalyst slurry for olefin polymerization according to any one of [1] to [3], characterized in that the mass of the component (D) contained in the catalyst slurry for olefin polymerization is 0 mass% or more and 2 mass% or less, when the catalyst slurry for olefin polymerization is taken as 100 mass%.

[0009] [5] The method for producing a catalyst slurry for olefin polymerization according to any one of [1] to [4], wherein the component (B) is at least one selected from the group consisting of polysulfone copolymers, polymeric polyamines, oil-soluble sulfonic acids, tertiary amines, aliphatic amides, fatty acid esters, polyalkylene oxides, and polyalkylene glycols.

[0010] [6] The method for producing a catalyst slurry for olefin polymerization according to any one of [1] to [5], wherein the component (A) comprises the following components (E), (F), and (G): The component (E): at least one selected from metallocene compounds and post-metallocene compounds containing transition metal atoms The component (F): a compound that converts the component (E) into a cationic compound The component (G): an organic compound carrier and / or an inorganic compound carrier

[0011] [7] The method for producing a catalyst slurry for olefin polymerization according to [6], wherein the component (E) is a metallocene compound containing a transition metal atom.

[0012] [8] The method for producing a catalyst slurry for olefin polymerization according to [6], wherein the component (E) is a bridged cyclopentadienyl compound containing a transition metal.

[0013] [9] The method for producing a catalyst slurry for olefin polymerization according to any one of [6] to [8], wherein the component (F) is at least one compound selected from the group consisting of organoaluminum oxy compounds, borane compounds, and borate compounds.

[0014]

[10] The method for producing a catalyst slurry for olefin polymerization according to any one of [6] to [9], wherein the component (G) is the inorganic compound support.

[0015]

[11] The method for producing a catalyst slurry for olefin polymerization according to any one of [1] to

[10] , wherein the mass of the component (B) contained in the catalyst slurry for olefin polymerization is 600 ppm by mass to 10,000 ppm by mass relative to the total mass of the component (A), the component (B), and the component (C).

[0016]

[12] The method for producing a catalyst slurry for olefin polymerization according to any one of [1] to

[11] , wherein the mass of the component (B) contained in the catalyst slurry for olefin polymerization is 1,100 ppm by mass to 10,000 ppm by mass relative to the total mass of the component (A), the component (B), and the component (C).

[0017]

[13] A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst slurry produced by the production method according to any one of [1] to

[12] . [Effects of the Invention]

[0018] According to the production method of the present disclosure, charging of the catalyst slurry for olefin polymerization (also referred to as "catalyst suspension slurry for olefin polymerization" or "oil slurry") is suppressed. Furthermore, the charging suppression effect of the catalyst slurry for olefin polymerization is unlikely to decrease over time. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 is an explanatory diagram for comparing the preparation methods of catalyst slurries A and B in Example 1 and Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0020] The present invention will be described in detail below. Note that when a numerical range is described using "to," it includes both the lower limit and the upper limit unless otherwise specified. For example, the description "10 to 20" includes both the lower limit "10" and the upper limit "20." In other words, "10 to 20" has the same meaning as "10 or more and 20 or less." In addition, in this specification, the upper and lower limits of each numerical range can be combined in any manner.

[0021] 1. Method for producing catalyst slurry for olefin polymerization The method for producing a catalyst slurry for olefin polymerization is a method for producing a catalyst slurry for olefin polymerization containing the following components (A), (B), and (C): The method for producing a catalyst slurry for olefin polymerization is characterized by comprising the following steps (1) to (3): Component (A): Solid catalyst for olefin polymerization (does not contain antistatic agents) Component (B): Antistatic agent Component (C): At least one selected from the group consisting of liquid paraffin, mineral oil, and polybutene Component (D): Hydrocarbon compounds with 4 to 12 carbon atoms Step (1): preparing a mixture containing component (A), component (B), and component (D) Step (2): Removing component (D) from a mixture containing component (A), component (B), and component (D). Step (3): A step of further mixing component (C) with a mixture containing at least component (A) and component (B).

[0022] (1) Component (A) Solid catalyst for olefin polymerization The solid catalyst for olefin polymerization is not particularly limited. Two or more types of solid catalysts for olefin polymerization may be used. The solid catalyst for olefin polymerization does not contain an antistatic agent.

[0023] Various types of solid catalysts for olefin polymerization (hereinafter also referred to as "olefin polymerization catalysts" or "polymerization catalysts") are known today, and there are no particular limitations as long as an olefin polymer can be prepared within the scope of the catalyst component configuration and the polymerization and post-treatment conditions. Specific examples of olefin polymerization catalysts containing transition metals, which are described below, can be cited as examples of technologies suitable for producing olefin polymers and which satisfy economical efficiency on an industrial level.

[0024] (1-1) Metallocene catalyst As a suitable example of the polymerization catalyst, a metallocene catalyst, which is an olefin polymerization catalyst comprising a metallocene compound containing a transition metal atom (hereinafter also referred to as a "metallocene complex") and a cocatalyst component (see, for example, "Next Generation Polymer Industrialization Technology Using Metallocene Catalysts (Vols. 1 and 2); published by Inter Research, Inc., 1994"), is used because it is relatively inexpensive, highly active, and has excellent polymerization process suitability, and furthermore, can produce ethylene polymers with narrow molecular weight distributions and copolymer composition distributions. Among these, catalyst systems for olefin polymerization containing a metallocene complex and an alumoxane, as described in JP-A-60-35007, and catalyst systems using a cocatalyst component other than an alumoxane, as described in JP-A-8-34809, JP-A-8-127613, JP-A-11-193306, and JP-A-2002-515522, are preferred. Metallocene complexes containing central metals from Group 4 of the periodic table, such as Ti, Zr, and Hf, are preferred because they exhibit high activity in ethylene polymerization. Various ligand structures for these central metals are currently known, and their polymerization performance, such as the molecular weight of the resulting polyethylene and olefin copolymerizability, has been investigated. For example, as described in JP-A-11-310612, these can be classified into the following general formulas [1], [2], [3], and [4]:

[0025] [ka]

[0026] [ka]

[0027] [ka]

[0028] [ka]

[0029] [where A 1 ~A 4 is a ligand having a conjugated five-membered ring structure (A 1 ~A 4 may be the same or different), 1 represents a linking group that bridges two conjugated five-membered ring ligands at any position, and Z represents a linking group that bridges two conjugated five-membered ring ligands at any position. 1 , Z 2represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom, a hydrogen atom, a halogen atom, or a hydrocarbon group bonded to M, 2 is an arbitrary position of the conjugated five-membered ring ligand and Z 2 M represents a metal atom selected from Group 4 of the periodic table; and X and Y each represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group bonded to M. The above detailed definitions are to be found in the publication.]

[0030] (1-2) Postmetallocene catalyst As an example of a polymerization catalyst, a postmetallocene catalyst (hereinafter also referred to as a "postmetallocene complex") made of a postmetallocene compound containing a transition metal atom, which is an olefin polymerization catalyst that uses a homogeneous metal complex (non-metallocene complex) other than the above-mentioned metallocene transition metal compound (see, for example, "Polyethylene Technology Reader" published by Kogyo Chosakai Co., Ltd. in 2001, "Living Polymerization with Homogeneous Transition Metal Catalysts" published by IPC Corporation in 1999, "Encyclopedia of Catalyst Usage" published by Kogyo Chosakai Co., Ltd. in 2004), is used because it is relatively inexpensive, has excellent activity, and furthermore, can produce ethylene polymers with narrow molecular weight distributions and copolymer composition distributions. Among these, ligands having at least two N atoms, which are disclosed in JP-T-10-513489, JP-T-2002-521538, JP-T-2000-516295, JP-T-2000-514132, Macromolecules, 1996, p. 5241, JACS, 1997, 119, p. 3830, JACS, 1999, 121, p. 5798, Organometallics, 1998, p. 3155, and the like, bind to transition metals of Groups 3 to 11 of the periodic table through the two N atoms. and bisimide compounds, iminoamide compounds, and bisamide compounds of transition metals having a 4- to 8-membered ring chelate structure containing the transition metal, which is formed by bonding a ligand having at least two O atoms or S atoms to a transition metal of Groups 3 to 11 of the periodic table through the two O atoms or S atoms, as disclosed in JP-A-6-136048 and the like. and iminocarboxylate compounds of transition metals having a 4- to 8-membered ring chelate structure containing a transition metal of Groups 3 to 11 of the periodic table, which are formed by bonding a ligand having at least one N atom, S atom, or P atom and a carboxyl group (COO) to the transition metal through the N atom, S atom, or P atom and the carboxyl group, as disclosed in JP-T-2000-514132, JP-T-2003-535107, JP-A-2007-77395, etc. and β-keto-phosphine compounds, β-keto-imide compounds, and β-keto-amide compounds of transition metals having a 4- to 8-membered ring chelate structure containing a transition metal, which is formed by bonding a ligand having at least one P atom or N atom and a carbonyl group (CO) to a transition metal of Groups 3 to 11 of the periodic table through the P atom or N atom and the carbonyl group, as disclosed in JP-A-64-14217, etc.γ-oxy-phosphine compounds, γ-oxy-imide compounds, and γ-oxy-amide compounds of transition metals having a 4- to 8-membered ring chelate structure containing a transition metal, which is formed by bonding a ligand having at least one P atom or N atom and an O atom to a transition metal of Groups 3 to 11 of the periodic table through the P atom or N atom and an O atom, as disclosed in JP-A-2004-517933, and JP-A-6-184214 and JP-A-10-195090. Preferred examples of compounds that can be used include γ-sulfonatophosphine compounds of transition metals having a 4- to 8-membered ring chelate structure containing a transition metal, which is formed by bonding a ligand having at least one phosphorus atom and a sulfonic acid residue (SO3) to a transition metal of Groups 3 to 11 of the periodic table through the phosphorus atom and the sulfonic acid residue, as disclosed in JP-A Nos. 2002-521534, 2007-46032, and 2007-77395, etc.; and phenoxyimine compounds and phenoxyamine compounds of transition metals having a 4- to 8-membered ring chelate structure containing a transition metal, which is formed by bonding a ligand having at least a nitrogen atom and a phenoxy group to a transition metal of Groups 3 to 11 of the periodic table through the nitrogen atom and the oxygen atom of the phenoxy group, as disclosed in JP-A Nos. 11-315109 and Chemical Communications (2003), (18), 2272-2273, etc. Of these nonmetallocene complexes, those having a central metal in Group 4 of the periodic table, such as Ti, Zr, Hf, V, Cr, Fe, Co, Ni, or Pd, are more preferably used because they exhibit high activity, and those having a central metal in Group 4 of the periodic table, such as Ti, Zr, Hf, Fe, Ni, or Pd, are even more preferably used.

[0031] (1-3) Preferred examples of solid catalysts for olefin polymerization In the present disclosure, the solid catalyst for olefin polymerization as component (A) preferably contains the following components (E), (F) and (G). Component (E): At least one selected from metallocene compounds and post-metallocene compounds containing transition metal atoms Component (F): A compound that converts component (E) into a cationic compound Component (G): Organic Compound Carrier and / or Inorganic Compound Carrier

[0032] (1-3-1) Component (E) Examples of the metallocene compound include the metallocene compounds of the general formulas [1], [2], [3], and [4] described above in the section "(1-1) Metallocene Catalyst." Examples of the post-metallocene compound include the compounds described above in the section "(1-2) Post-metallocene catalyst." Component (E) is preferably a metallocene compound containing a transition metal atom, or a bridged cyclopentadienyl compound containing a transition metal.

[0033] A particularly suitable example of the metallocene compound is a metallocene compound represented by the following general formula (1).

[0034] [ka]

[0035] In the general formula (1), M represents a transition metal selected from the group consisting of Ti, Zr and Hf, preferably Zr or Hf, and more preferably Zr.

[0036] X1 and X2 each independently represent a substituent selected from the group consisting of a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. Examples of the halogen represented by X1 and X2 include a chlorine atom, a bromine atom, and an iodine atom. The hydrocarbon group having 1 to 20 carbon atoms represented by X1 and X2 preferably has 1 to 7 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n- Examples include a butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group, and a benzyl group.

[0037] The oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, represented by X1 and X2, preferably has 1 to 12 carbon atoms, and examples thereof include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, an i-butoxymethyl group, a t-butoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an acetyl group, a 1-oxopropyl group, a 1-oxo-n-butyl group, a 2-methyl-1-oxopropyl group, a 2,2-dimethyl-1-oxopropyl group, a phenylacetyl group, a diphenylacetyl group, a benzoyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-furyl group, and a 2-tetrahydrofuryl group. The nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms preferably has 1 to 10 carbon atoms, and examples thereof include a dimethylaminomethyl group, a diethylaminomethyl group, a di-i-propylaminomethyl group, a bis(dimethylamino)methyl group, a bis(di-i-propylamino)methyl group, a (dimethylamino)(phenyl)methyl group, a methylimino group, an ethylimino group, a 1-(methylimino)ethyl group, a 1-(phenylimino)ethyl group, and a 1-[(phenylmethyl)imino]ethyl group.

[0038] The hydrocarbon-substituted amino group having 1 to 20 carbon atoms, represented by X1 and X2, preferably has 1 to 12 carbon atoms, and examples thereof include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a di-i-propylamino group, a di-n-butylamino group, a di-i-butylamino group, a di-t-butylamino group, and a diphenylamino group. The alkoxy group having 1 to 20 carbon atoms represented by X1 and X2 preferably has 1 to 6 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a t-butoxy group, and a phenoxy group.

[0039] Preferred examples of X1 and X2 include a chlorine atom, a bromine atom, a methyl group, an n-butyl group, an i-butyl group, a methoxy group, an ethoxy group, an i-propoxy group, an n-butoxy group, a phenoxy group, a dimethylamino group, and a di-i-propylamino group. Of these, a chlorine atom, a methyl group, and a dimethylamino group are particularly preferred.

[0040] In general formula (1), Q represents a carbon atom, a silicon atom, or a germanium atom, preferably a carbon atom or a silicon atom, and more preferably a silicon atom. m is 1 or 2, and preferably 1. When m is 2, multiple Qs may be the same or different.

[0041] In general formula (1), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and when m is 2, multiple R1s may be the same or different, and multiple R2s may be the same or different. Furthermore, R1 and R2 may combine to form a ring containing one or more Qs.

[0042] The hydrocarbon group having 1 to 10 carbon atoms represented by R1 and R2 preferably has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and a phenyl group. In addition, when R1 and R2 are bonded together to form a ring including the bonded Q, examples of the ring include a cyclobutylidene group, a cyclopentylidene group, a cyclohexylidene group, a silacyclobutyl group, a silacyclopentyl group, and a silacyclohexyl group.

[0043] Preferred examples of R1 and R2 include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an ethylene group, and a cyclobutylidene group when Q is a carbon atom, and a silicon atom when Q is a silicon atom. In the case of alkyl groups, examples thereof include a methyl group, an ethyl group, a phenyl group, and a silacyclobutyl group.

[0044] R3, R4, R5, R6, R10, R11, R12, and R13 each independently represent a substituent selected from the group consisting of a hydrogen atom, a halogen, a hydrocarbon group having 1 to 50 carbon atoms, a silicon-containing hydrocarbon group having 1 to 6 silicon atoms and 1 to 50 carbon atoms, a halogen-containing hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms and containing an element selected from the group consisting of nitrogen, phosphorus, oxygen, and sulfur, and a hydrocarbon-substituted silyl group having 1 to 50 carbon atoms. Examples of the halogen represented by R3 to R6 and R10 to R13 include a chlorine atom, a bromine atom, and an iodine atom.

[0045] The hydrocarbon group having 1 to 50 carbon atoms, represented by R3 to R6 and R10 to R13, preferably has 1 to 20 carbon atoms, and particularly preferably 1 to 9 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a 4-t-butylphenyl group, and a 3,5-di-t-butylphenyl group. The silicon-containing hydrocarbon group having 1 to 6 silicon atoms and 1 to 50 carbon atoms represented by R3 to R6 and R10 to R13 preferably has 1 to 2 silicon atoms, and more preferably has 1 to 18 carbon atoms, and particularly preferably has 1 to 13 carbon atoms. Examples thereof include a bis(trimethylsilyl)methyl group and a bis(t-butyldimethylsilyl)methyl group.

[0046] The halogen-containing hydrocarbon group having 1 to 50 carbon atoms, represented by R3 to R6 and R10 to R13, preferably has 1 to 20 carbon atoms, and examples thereof include a bromomethyl group, a chloromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 2-bromopropyl group, a 3-bromopropyl group, a 2-bromocyclopentyl group, a 2,3-dibromocyclopentyl group, a 2-bromo-3-iodocyclopentyl group, a 2,3-dibromocyclohexyl group, a 2-chloro-3-iodocyclohexyl group, a 2-chlorophenyl group, a 4-chlorophenyl group, a 2,3,4,5,6-pentafluorophenyl group, and a 4-trifluoromethylphenyl group.

[0047] The nitrogen atom-containing hydrocarbon group having 1 to 50 carbon atoms represented by R3 to R6 and R10 to R13 preferably has 1 to 40 carbon atoms, particularly 1 to 6 carbon atoms, and examples thereof include a pyrrolyl group, a tetrahydropyrrolyl group, and a 2-methylpyrrolyl group. The phosphorus atom-containing hydrocarbon group having 1 to 50 carbon atoms represented by R3 to R6 and R10 to R13 preferably has 1 to 40 carbon atoms, particularly 1 to 6 carbon atoms, and examples thereof include a phosphoryl group, a tetrahydrophosphoryl group, and a 2-methylphosphoryl group. The hydrocarbon group containing an oxygen atom and having 1 to 50 carbon atoms, represented by R3 to R6 and R10 to R13, preferably has 1 to 40 carbon atoms, particularly 1 to 6 carbon atoms, and examples thereof include a furyl group, a tetrahydrofuryl group, and a 2-methylfuryl group. The hydrocarbon group containing a sulfur atom and having 1 to 50 carbon atoms, represented by R3 to R6 and R10 to R13, preferably has 1 to 40 carbon atoms, and particularly preferably 1 to 6 carbon atoms, and examples thereof include a thienyl group, a tetrahydrothienyl group, and a 2-methylthienyl group. The hydrocarbon-substituted silyl group having 1 to 50 carbon atoms, represented by R3 to R6 and R10 to R13, preferably has 1 to 40 carbon atoms, and particularly preferably 1 to 18 carbon atoms. Examples include a trimethylsilyl group, a tri-t-butylsilyl group, a di-t-butylmethylsilyl group, a t-butyldimethylsilyl group, a triphenylsilyl group, a diphenylmethylsilyl group, and a phenyldimethylsilyl group.

[0048] Adjacent substituents among R3 to R6 may be bonded together to form a ring, including a carbon atom of the conjugated five-membered ring to which the substituents are bonded. Adjacent substituents among R10 to R13 may be bonded together to form a ring, including a carbon atom of the conjugated five-membered ring to which the substituents are bonded. Specific examples of methacerone compounds in which R3 to R6 and R10 to R13 do not form a ring are shown in Tables 1-1 to 1-5, but the invention is not limited to these.

[0049] [Table 1-1]

[0050] [Table 1-2]

[0051] [Table 1-3]

[0052] [Table 1-4]

[0053] [Table 1-5]

[0054] It is preferred that only one pair of adjacent substituents among R3, R4, R5, R6, R10, R11, R12, and R13 are bonded to form a ring including the carbon atoms of the conjugated five-membered ring to which these substituents are bonded. Among compounds in which only one pair of adjacent R3, R4, R5, R6, R10, R11, R12, and R13 are bonded to form a ring via a carbon atom of the conjugated 5-membered ring to which these substituents are bonded, a bridged cyclopentadienyl indenyl compound represented by the following general formula (2) is particularly preferred. In addition, in the bridged cyclopentadienyl indenyl compound represented by the following general formula (2), R11 is preferably not a hydrogen atom, and more preferably R11 is not a hydrogen atom and any one of R3 to R6 is not a hydrogen atom.

[0055] [ka]

[0056] In general formula (2), R14 to R17 each independently represent a substituent selected from the group consisting of a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 6 silicon atoms and 1 to 18 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing oxygen or sulfur and having 1 to 40 carbon atoms, and a hydrocarbon-substituted silyl group having 1 to 40 carbon atoms, provided that the total number of carbon atoms contained in R14 to R17 does not exceed 96. Examples of the substituents represented by R14 to R17 are the same as those represented by R3, R4, R5, R6, R10, R11, R12, and R13. Adjacent substituents among R14 to R17 may be bonded to form a ring including the carbon atom of the conjugated six-membered ring to which the substituents are bonded. Furthermore, R14 may be a substituted aryl group represented by the following general formula (3): When R14 is a substituted aryl group represented by the following general formula (3), R14 and R15 do not bond to form a ring including the carbon atom of the conjugated 6-membered ring to which the substituent is bonded.

[0057] [ka]

[0058] In the general formula (3), Y1 represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom. R18, R19, R20, R21, and R22 each independently represent a substituent selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing 1 to 20 carbon atoms and containing oxygen or nitrogen, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 6 silicon atoms and 1 to 18 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. Among R18 to R22, adjacent substituents may be bonded to form a ring including the atom of the ring to which the substituent is bonded. n is 0 or 1, and when n is 0, the substituent R18 does not exist in Y1. p is 0 or 1, and when p is 0, there is no carbon atom to which R21 is bonded, and a conjugated 5-membered ring structure is formed in which the carbon atom to which R20 is bonded and the carbon atom to which R22 is bonded are directly bonded. Examples of the cyclic skeleton of the substituted aryl group represented by general formula (3) include a phenyl ring and a furyl ring.

[0059] Specific examples of bridged cyclopentadienyl indenyl compounds represented by general formula (2), which are methacelone compounds of general formula (1) in which R12 and R13 form a ring, are shown in Tables 2-1 and 2-3, but are not limited to these.

[0060] [Table 2-1]

[0061] [Table 2-2]

[0062] [Table 2-3]

[0063] (1-3-2) Component (F) Examples of the component (F) that can be used include organoaluminum oxy compounds, borane compounds, borate compounds, and mixtures thereof. Furthermore, the component (F) can also be a mixture of two or more borane compounds or borate compounds. Each component will be described in detail below.

[0064] (i) Organoaluminum oxy compounds One example of the component (F) is an organoaluminum oxy compound. The organoaluminum oxy-compound has an Al-O-Al bond in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy-compound is usually a product obtained by reacting an organoaluminum compound with water. The reaction of organoaluminum with water is usually carried out in an inert hydrocarbon (solvent), which may be an aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, or xylene, but is preferably an aliphatic hydrocarbon or aromatic hydrocarbon.

[0065] As the organoaluminum compound used in the preparation of the organoaluminum oxy-compound, any compound represented by the following general formula (4) can be used, and two or more kinds can also be used in combination. R 6 t AlX 3 3-t ...Equation (4) (In general formula (4), R 6 represents a hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, such as an alkyl group, an alkenyl group, an aryl group, or an aralkyl group; X 3 represents a hydrogen atom or a halogen atom, and t represents an integer of 1≦t≦3.

[0066] Among the compounds represented by general formula (4), trialkylaluminum is preferably used. The alkyl group of the trialkylaluminum may be any of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, and dodecyl groups, with methyl being particularly preferred.

[0067] The reaction ratio of water to the organoaluminum compound (water / Al molar ratio) is preferably 0.25 / 1 to 1.2 / 1, particularly 0.5 / 1 to 1 / 1. The reaction temperature is usually -70 to 100°C, preferably -20 to 20°C. The reaction time is usually selected from the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. The water required for the reaction may be not only water but also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate, etc., or a component that can generate water in the reaction system. Among the above-mentioned organoaluminum oxy compounds, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, and methylaluminoxane (including those essentially consisting of methylaluminoxane (MAO)) is particularly suitable as an organoaluminum oxy compound. Of course, two or more of the above-mentioned organoaluminum oxy compounds may be used in combination as the organoaluminum oxy compound, or the organoaluminum oxy compound may be used in the form of a solution or dispersion in the above-mentioned inert hydrocarbon solvent.

[0068] (ii) Borane compounds and borate compounds Other specific examples of component (F) include borane compounds and borate compounds. More specific examples of the borane compounds include triphenylborane, tri(o-tolyl)borane, tri(p-tolyl)borane, tri(m-tolyl)borane, tri(o-fluorophenyl)borane, tris(p-fluorophenyl)borane, tris(m-fluorophenyl)borane, tris(2,5-difluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-trifluoromethylphenyl)borane, tris(3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl), tris(perfluoroanthryl)borane, and tris(perfluorobinaphthyl)borane.

[0069] Specific examples of the borate compound include tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tributylammonium tetra(3,5-ditrifluoromethylphenyl)borate, tributylammonium tetra(2,6-difluorophenyl)borate, tributylammonium tetra(perfluoronaphthyl)borate, dimethylanilinium tetra(pentafluorophenyl)borate, dimethylanilinium tetra(2,6-ditrifluoromethylphenyl)borate, dimethylanilinium tetra(3,5-ditrifluoromethylphenyl)borate, dimethylanilinium tetra(2,6-difluorophenyl)borate, dimethylanilinium tetra(perfluoronaphthyl)borate, triphenyl Nylphosphonium tetra(pentafluorophenyl)borate, triphenylphosphonium tetra(2,6-ditrifluoromethylphenyl)borate, triphenylphosphonium tetra(3,5-ditrifluoromethylphenyl)borate, triphenylphosphonium tetra(2,6-difluorophenyl)borate, triphenylphosphonium tetra(perfluoronaphthyl)borate, trimethylammonium tetra(2,6-ditrifluoromethylphenyl)borate, triethylammonium tetra(pentafluorophenyl)borate, triethylammonium tetra(2,6-ditrifluoromethylphenyl)borate, triethylammonium tetra(perfluoronaphthyl)borate, tripropylammonium tetra(pentafluorophenyl)borate, tripropylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tripropylammonium tetra(perfluoronaphthyl)borate, di(1-propyl)ammonium tetra(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate, trityl tetraphenylborate, trityl tetra(o-tolyl)borate, trityl tetra(p-tolyl)borate, trityl tetra(m-tolyl)borate, trityl tetra(o-fluorophenyl)borate, trityl tetra(p-fluorophenyl)borate, trityl tetra(m-fluorophenyl)borate, trityl tetra(3,5-difluorophenyl)borate, trityl tetra(pentafluorophenyl)borate, trityl tetra(2,6-ditrifluoromethylphenyl)borate, trityl tetra(3,5-ditrifluoromethylphenyl)borate, trityl tetra(perfluoronaphthyl)borate, tropinium tetraphenylborate, tropinium tetra(o-tolyl) Borate, tropinium tetra(p-tolyl)borate, tropinium tetra(m-tolyl)borate, tropinium tetra(o-fluorophenyl)borate, tropinium tetra(p-fluorophenyl)borate, tropinium tetra(m-fluorophenyl)borate, tropinium tetra(3,5-difluorophenyl)borate, tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, tropinium Tropinium tetra(3,5-ditrifluoromethylphenyl)borate, Tropinium tetra(perfluoronaphthyl)borate, NaBPh4, NaB(o-CH3-Ph)4, NaB(p-CH3-Ph)4, NaB(m-CH3-Ph)4, NaB(oF-Ph)4, NaB(pF-Ph)4, NaB(mF-Ph)4, NaB(3,5-F2-Ph)4, NaB(C6F5)4, NaB(2,6-(CF3)2-Ph)4, NaB(3,5-(CF3)2-Ph)4, NaB(C, 10F7)4, HBPh4·2 diethyl ether, HB(3,5-F2-Ph)4·2 diethyl ether, HB(C6F5)4·2 ​​diethyl ether, HB(2,6-(CF3)2-Ph)4·2 diethyl ether, HB(3,5-(CF3)2-Ph)4·2 diethyl ether, HB(C 10 H7) 4·2 diethyl ether can be exemplified.

[0070] (1-3-3) Component (G) The organic compound carrier as component (G) is not particularly limited. Examples of the organic compound carrier include, preferably, α-olefin polymers having 2 to 10 carbon atoms, such as (1) polyethylene, polypropylene, polybutene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexane-1 copolymer, propylene-butene-1 copolymer, propylene-hexene-1 copolymer, and propylene-divinylbenzene copolymer, (2) aromatic unsaturated hydrocarbon polymers, such as polystyrene and styrene-divinylbenzene copolymer, and (3) polar group-containing polymers, such as polyacrylic acid esters, polymethacrylic acid esters, polyacrylonitrile, polyvinyl chloride, polyamide, polyphenylene ether, polyethylene terephthalate, and polycarbonate.

[0071] The inorganic compound support as component (G) is not particularly limited, and examples of the inorganic compound support that can be used include metals, metal oxides, metal chlorides, metal carbonates, carbonaceous materials, and mixtures thereof.

[0072] Suitable metals that can be used in component (G) include, for example, iron, aluminum, nickel, and the like.

[0073] Examples of metal oxides include single oxides or composite oxides of elements in Groups 1 to 14 of the periodic table, such as SiO2, Al2O3, MgO, CaO, B2O3, TiO2, ZrO2, Fe2O3, Al2O3·MgO, Al2O3·CaO, Al2O3·SiO2, Al2O3·MgO·CaO, Al2O3·MgO·SiO2, Al2O3·CuO, Al2O3·Fe2O3, Al2O3·NiO, and SiO2·MgO. In the present application, the above formulas are not molecular formulas but represent only the compositions, and the structure and component ratios of the composite oxides used in the present invention are not particularly limited. Additionally, the metal oxides used in the present disclosure may absorb a small amount of moisture and may contain a small amount of impurities.

[0074] As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferred, and specifically, MgCl2, CaCl2, etc. are particularly suitable. As the metal carbonate, carbonates of alkali metals and alkaline earth metals are preferred, and specifically, magnesium carbonate, calcium carbonate, barium carbonate, etc. are included. As the carbonaceous material, for example, carbon black, activated carbon, etc. are included.

[0075] Any of the above-mentioned inorganic carriers can be suitably used in the present invention, but it is particularly preferable to use metal oxides, and among these, it is preferable to use silica (SiO2), alumina (Al2O3), etc.

[0076] (1-3-4) Content ratio of component (E), component (F), and component (G) The content ratio of component (E), component (F), and component (G) is not particularly limited. In the solid catalyst for olefin polymerization, the content of component (F) per mole of transition metal M in component (E) is preferably in the range of 100 mol to 12,500 mol, more preferably in the range of 200 mol to 10,000 mol, even more preferably in the range of 250 mol to 5,000 mol, still more preferably in the range of 300 mol to 2,000 mol, and particularly preferably in the range of 330 mol to 1,700 mol. In the solid catalyst for olefin polymerization, the content of the component (F) per 1 g of the component (G) is preferably in the range of 3.0 mmol to 12.0 mmol, more preferably in the range of 6.0 mmol to 12.0 mmol, and even more preferably in the range of 7.5 mmol to 10.5 mmol.

[0077] (1-4) Ziegler catalyst Examples of olefin polymerization catalysts suitable for producing olefin polymers such as ethylene polymers include Ziegler-Natta catalysts, which are made up of a combination of a transition metal compound and an alkyl compound of a typical metal, and in particular so-called Mg-Ti Ziegler catalysts, which are made up of a solid catalyst component in which a titanium compound is supported on a magnesium compound, combined with an organoaluminum compound (see, for example, "Encyclopedia of Catalyst Utilization," published by the Industrial Research Institute in 2004, and "Application System Diagram - Transition of Olefin Polymerization Catalysts," published by the Japan Institute of Invention and Innovation in 1995). These catalysts are suitable because they are inexpensive, highly active, and have excellent suitability for polymerization processes.

[0078] Among these, examples include Mg / Ti catalysts supported on an inert carrier material, as described in JP-A-54-142192 and JP-A-54-148093, i.e., catalysts obtained by impregnating porous silica previously treated with triethylaluminum with a homogeneous mixture of a tetrahydrofuran solution of anhydrous MgCl2 and TiCl3 or TiCl4, and then drying the mixture to dryness; and catalysts obtained by subjecting a Mg / Ti catalyst to olefin prepolymerization in the presence of organoaluminum, as described in JP-A-63-117019, such as a prepolymerized catalyst obtained by introducing a mixture of TiCl4 and methylhydrogenpolysiloxane into a solid component obtained by the reaction of MgCl2, Ti(OnBu)4, and methylhydrogenpolysiloxane, and then prepolymerizing the resulting catalyst with ethylene in the presence of triethylaluminum. Further, as described in Japanese Patent Application Laid-Open No. 60-195108, there is an olefin polymerization catalyst which combines a catalyst component containing a low-valent titanium atom obtained by reacting a magnesium-aluminum complex with a tetravalent titanium compound with an organoaluminum compound, and as described in Japanese Patent Application Laid-Open No. 56-61406, there is a catalyst which combines a homogeneous mixture of magnesium ethoxide, tri-n-butoxymonochlortitanium, and n-butanol with ethylaluminum sesquioxide. and solid catalysts for olefin polymerization containing magnesium, halogen, titanium and an electron donor as described in JP-A No. 2001-139635.

[0079] (1-5) Phillips catalyst An example of an olefin polymerization catalyst is a Phillips catalyst. The Phillips catalyst is a chromium catalyst in which a chromium compound is supported on an inorganic oxide support such as silica, silica-alumina, or silica-titania, and activated in a non-reducing atmosphere to convert at least a portion of the supported chromium element to a hexavalent chromium (see, for example, M.P. McDaniel, Advances in Catalysis, Vol. 33, p. 47, 1985, Academic Press Inc.; M.P. McDaniel, Handbook of Heterogeneous Catalysis, p. 2400, 1997, VCH; M.B. Welch et al., Handbook of Polyolefins: Synthesis and Properties, p. 21, 1993, Marcel Dekker et al.). The Phillips catalyst is preferably used because it exhibits high activity in ethylene polymerization.

[0080] (2) Component (C) Component (C) is at least one selected from the group consisting of liquid paraffin, mineral oil, and polybutene. These highly viscous solvents are often used as catalyst slurry media for gas-phase polymerization because they inhibit the settling of solid catalyst components in the catalyst slurry. Purification of component (C) is optional, but if purification is required, examples include bubbling with purified nitrogen and adsorption of impurities using molecular sieves. However, the purification method is not limited to these.

[0081] (3) Component (D) Component (D) is a hydrocarbon compound having 4 to 12 carbon atoms. The hydrocarbon compound having 4 to 12 carbon atoms may be used alone or in combination of two or more. The hydrocarbon compound having 4 to 12 carbon atoms is preferably one or more selected from the group consisting of butane, isobutane, pentane, isopentane, hexane, isohexane, heptane, octane, nonane, decane, undecane, dodecane, toluene, and xylene. More preferably, pentane, isopentane, hexane, isohexane, heptane, octane, nonane, decane, undecane, dodecane, toluene, and xylene, even more preferably, hexane, isohexane, heptane, decane, and toluene, and particularly preferably, hexane, isohexane, and heptane.

[0082] (3) Component (B) Component (B) is an antistatic agent. The antistatic agent is not particularly limited. Examples of antistatic agents include polysulfone copolymers, polymeric polyamines, oil-soluble sulfonic acids, tertiary amines, aliphatic amides, fatty acid esters, polyalkylene oxides, and polyalkylene glycols. Specific examples of mixtures of polysulfone copolymers, polymeric polyamines, and oil-soluble sulfonic acids include STATSAFE (a product of Innospec) and Stadis (a product of Innospec). Among the examples and comparative examples described below, STATSAFE 6000 in Example 1 and Comparative Example 1 correspond to this.

[0083] An example of the antistatic agent is a tertiary amine compound, such as that represented by the following general formula [IX]: [ka] In the above general formula [IX], R d is a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, and R e (CH2) xa hydroxyalkyl group such as an OH group (where x is an integer of 1 to 50, preferably 2 to 25) or (CH2CH2O) x and polyoxyethylene groups such as —H, where x is an integer from 1 to 50, preferably from 2 to 25. Non-limiting examples of such compounds include C 18 H 37 Kemamine AS-990 with N(CH2CH2OH)2 (available from Witco Chemical Corporation, Houston, Texas) or Nimine S-202 (NOF Corporation), C 12 H 25 Examples include Kemamine AS-650 (available from Witco) having N(CHCHOH), Atomer 163 available from ICI Specialties, and polyoxyethylene (10) stearylamine ether available from Wako Pure Chemical Industries. Among the examples and comparative examples described below, Nymeen S-202 in Example 2 and Comparative Example 2 are examples of such an example.

[0084] The antistatic agent may be, for example, an aliphatic amide. The aliphatic amide is not particularly limited. Among the aliphatic amides, higher aliphatic amides are preferably used. Higher aliphatic amides are generally used as nonionic surfactants, and any conventionally known higher aliphatic amides can be used without any limitations. Examples of higher aliphatic amides include those represented by the general formula: (C m H 2m+1 CO)N(CH2CH2OH)2 Preferably, alkyldiethanolamides represented by the general formula (C m H 2m+1), m, which indicates the number of carbon atoms in the alkyl group represented by the formula (I), is desirably in the range of 1 to 30, preferably 6 to 20, and more preferably 8 to 18. Specific examples of higher aliphatic amides include lauryl diethanolamide, cetyl diethanolamide, stearyl diethanolamide, octyl diethanolamide, nonyl diethanolamide, sec-lauryl diethanolamide, and mixtures thereof. Specific examples of mixtures include Staform DF-4 in Example 4 and Comparative Example 4, which will be described later. Among the aliphatic amides, lauryl diethanolamide is preferred.

[0085] An example of an antistatic agent is a fatty acid ester. The fatty acid ester is not particularly limited. The fatty acid ester may be a monoester or poly(2 or more) ester, may be linear or branched, may be saturated or unsaturated, and may be any combination thereof. The fatty acid ester may also be substituted with one or more substituents containing a Group 14, 15, or 16 heteroatom. Non-limiting examples of suitable fatty acid esters include alkyl esters of aliphatic monocarboxylic and dicarboxylic acids, monoglyceryl or polyglyceryl esters of aliphatic monocarboxylic acids, and sorbitan esters of aliphatic monocarboxylic acids. In a further embodiment, the fatty acid ester is a C4-C 30 Monoglyceryl or polyglyceryl esters of fatty acids, C4-C 30 Sorbitan esters of aliphatic monocarboxylic acids are preferred, C4-C 30 Monoglyceryl or polyglyceryl esters of unsaturated fatty acids are more preferred, C4-C 30 Monoglyceryl esters of unsaturated fatty acids are more preferred, and may be glyceryl esters, polyglyceryl esters, or sorbitan esters of lauric acid, stearic acid, or oleic acid, and mixtures thereof. In a further embodiment, the fatty ester is preferably glycerin monooleate. Among the examples and comparative examples described below, the monoolein in Example 3 and Comparative Example 3 corresponds to this.

[0086] An example of an antistatic agent is polyalkylene oxide. The polyalkylene oxide is not particularly limited. A suitable polyalkylene oxide is HO-(CH2CH2O) m Polyethylene oxide represented by -H and HO-{CH2CH(CH3)O} n Examples of suitable polyalkylene oxides include polypropylene oxides represented by the formula H. The value m, which indicates the average degree of polymerization of the polyethylene oxide, is in the range of 2 to 30, preferably 3 to 20, and more preferably 4 to 8, and the value n, which indicates the average degree of polymerization of the polypropylene oxide, is in the range of 2 to 80, preferably 3 to 50, and more preferably 4 to 40. In addition to the polyethylene oxides and polypropylene oxides described above, preferred polyalkylene oxides include, for example, polyalkylene oxides obtained by randomly copolymerizing ethylene oxide and propylene oxide. Suitable polyalkylene oxides include polyoxyalkylene polyols obtained by adding alkylene oxides to polyhydric alcohols such as glycerin and trimethylolpropane. The polyoxyalkylene polyol is preferably one in which 2 mol to 30 mol, preferably 3 mol to 20 mol, more preferably 4 mol to 8 mol of ethylene oxide is added relative to the number of functional groups of the polyhydric alcohol, or one in which 2 mol to 30 mol, preferably 3 mol to 20 mol, more preferably 4 mol to 8 mol of propylene oxide is added relative to the number of functional groups of the polyhydric alcohol.

[0087] An example of the antistatic agent is polyoxyalkylene glycol. The polyoxyalkylene glycol is not particularly limited. As the polyoxyalkylene glycol, a polyethylene oxide-polypropylene oxide-polyethylene oxide block represented by the following general formula (I) is preferred.

[0088] [ka] In the above general formula (I), the sum of m and p (m+p), which indicates the number of repeating oxyethylene units represented by (CH2CH2O), is in the range of 2 to 40, preferably 4 to 20, and more preferably 4 to 15. The ratio of the number of repeating units (m / p) is 0.1 to 10, and preferably 0.5 to 5. On the other hand, n, which indicates the number of repeating oxypropylene units represented by [CH2CH(CH3)O], is in the range of 2-50, preferably 10-50, and more preferably 20-50. In the general formula (I), R1 and R2 are selected from the group consisting of hydrogen and hydrocarbon groups, and may be the same or different. It is preferable that at least one of R1 and R2 is hydrogen, and it is particularly preferable that both R1 and R2 are hydrogen. As the hydrocarbon group, those having 1 to 20 carbon atoms can be used, and among these, preferred are methyl, ethyl, and propyl groups, and particularly preferred are methyl and ethyl groups.

[0089] (4) Content of component (B) The mass of component (B) contained in the olefin polymerization catalyst slurry is not particularly limited. From the viewpoint of preventing deterioration of the antistatic effect over time, the mass of component (B) contained in the olefin polymerization catalyst slurry is preferably 200 ppm by mass to 14,000 ppm by mass, more preferably 600 ppm by mass to 10,000 ppm by mass, and even more preferably 1,100 ppm by mass to 10,000 ppm by mass, relative to the total mass of components (A), (B), and (C).

[0090] (5) Content of component (D) From the viewpoint of preventing a decrease in the anti-static effect over time, the mass of component (D) contained in the olefin polymerization catalyst slurry is preferably from 0 to 2 mass%, more preferably from 0 to 1.5 mass%, and even more preferably from 0 to 0.3 mass%, based on 100 mass% of the olefin polymerization catalyst slurry.

[0091] The effects of the present disclosure will be described. The antistatic effect of catalyst slurries using antistatic agents (catalyst slurries for olefin polymerization) is presumed to be due to the following: (1) the antistatic agent disperses in the solvent of the catalyst slurry, increasing the conductivity of the solvent, and (2) the antistatic agent coats the surfaces of the solid catalyst components in the catalyst slurry, thereby eliminating the electric charge (frictional electrification) generated by friction of the solid catalyst components. Conventionally, a solid catalyst for olefin polymerization is mixed with oil or the like to form an oil slurry, and then a solution of an antistatic agent, a hydrocarbon compound having 4 to 12 carbon atoms, is mixed with the oil slurry to produce a catalyst slurry. The antistatic effect of the catalyst slurry produced in this manner decreases over time. This is presumably due to a change in the state of the antistatic agent in the catalyst slurry over time. The manufacturing method of the present disclosure is characterized by comprising the following steps (1) to (3). As a result of extensive research, the inventors of the present application have found that a catalyst slurry manufactured through these steps does not lose its antistatic effect even after a long time has passed since its manufacture. This is presumably because the catalyst slurry contains a small amount of component (D), which prevents the antistatic agent coating the surface of the solid catalyst component in the catalyst slurry from eluting into component (D) over time. In step (2), component (D) is removed from a mixture containing components (A), (B), and (D). Removing even a portion of component (D) from the mixture constitutes "removal" in this step. In other words, component (D) does not need to be completely removed in step (2). From the viewpoint of preventing deterioration of the charge-suppressing effect over time, it is preferable to remove component (D) from the mixture in step (2) so that the mass of component (D) contained in the olefin polymerization catalyst slurry is 0% by mass or more and 2% by mass or less, assuming that the olefin polymerization catalyst slurry is 100% by mass. Step (1): preparing a mixture containing component (A), component (B), and component (D) Step (2): Removing component (D) from a mixture containing component (A), component (B), and component (D). Step (3): A step of further mixing component (C) with a mixture containing at least component (A) and component (B). Component (A): Solid catalyst for olefin polymerization (does not contain antistatic agents) Component (B): Antistatic agent Component (C): At least one selected from the group consisting of liquid paraffin, mineral oil, and polybutene Component (D): Hydrocarbon compounds with 4 to 12 carbon atoms

[0092] The mass ratio of each component in this production method is not particularly limited, but the preferred ratio is in the following range when component (A) is taken as 100 parts by mass. Component (A): 100 parts by mass Component (B): 1 part by mass to 5 parts by mass Component (C): 300 parts by mass to 700 parts by mass Component (D): 100 parts by mass to 1300 parts by mass

[0093] Furthermore, the catalyst slurry production method disclosed in the present invention can suppress an increase in viscosity of the catalyst slurry. It is believed that the viscosity of the catalyst slurry increases due to aggregation of the solid catalyst components in the slurry. In the method disclosed in the present invention, the addition of a mixture of a hydrocarbon compound having 4 to 12 carbon atoms and an antistatic agent makes it possible to coat the surface of the solid catalyst component with the antistatic agent, which is thought to prevent aggregation due to charging and suppress the increase in viscosity. Furthermore, it is thought that preventing catalyst aggregation also suppresses the generation of polymerization chunks caused by the aggregated catalyst. In the present invention, the reasons why the charging of the catalyst slurry is suppressed, why the charging suppression effect is unlikely to decrease over time, why an increase in the slurry viscosity is suppressed, and why the generation of polymerized chunks is suppressed are not limited to the reasons described above. The reasons described above are merely presumed reasons, and even if the effects of the present invention are achieved for other reasons, the scope of the rights of the present invention should not be interpreted in a restrictive manner by the description of the reasons described above.

[0094] 2. Olefin polymer manufacturing method Olefins are polymerized or copolymerized in the presence of the olefin polymerization catalyst slurry produced by the above-mentioned production method. Olefins include those having 3 to 30 carbon atoms, preferably 3 to 8 carbon atoms, and specific examples include ethylene, propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene. Two or more olefins can also be copolymerized. The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. When ethylene or propylene is copolymerized with another olefin, the amount of the other olefin can be selected arbitrarily within a range of 90 mol % or less of the total monomers, but is generally selected within a range of 40 mol % or less, preferably 30 mol % or less, and more preferably 10 mol % or less. Of course, it is also possible to use a small amount of a comonomer other than an olefin. In this case, examples of the comonomer include compounds having a polymerizable double bond, such as styrenes such as styrene, 4-methylstyrene, and 4-dimethylaminostyrene; dienes such as 1,4-butadiene, 1,5-hexadiene, 1,4-hexadiene, and 1,7-octadiene; cyclic compounds such as norbornene and cyclopentene; and oxygen-containing compounds such as hexenol, hexenoic acid, and methyl octenoate.

[0095] In the present disclosure, the polymerization reaction can be carried out in the presence of the olefin polymerization catalyst slurry of the present disclosure, preferably by slurry polymerization or gas-phase polymerization. Furthermore, the polymerization can be carried out in any of batch, semi-continuous, and continuous modes. In the case of slurry polymerization, olefins and the like are polymerized in a state substantially free of oxygen, water, and the like, in the presence or absence of an inert hydrocarbon solvent selected from aliphatic hydrocarbons such as isobutane, hexane, and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. It goes without saying that liquid monomers such as liquid ethylene and liquid propylene can also be used as solvents. In the case of gas-phase polymerization, olefins and the like are polymerized in a reactor into which gas streams of olefins and comonomers are introduced, circulated, or circulated. In the present disclosure, gas-phase polymerization is more preferred. Polymerization conditions include a temperature of 0 to 250°C, preferably 20 to 110°C, and more preferably 60 to 100°C. The pressure is in the range of normal pressure to 10 MPa, preferably normal pressure to 4 MPa, and more preferably 0.5 to 2 MPa, the polymerization time is 5 minutes to 10 hours, preferably 5 minutes to 5 hours, and in a continuous process, the average residence time can be 1 hour to 50 hours. Furthermore, the residence time may be 1 hour to 20 hours, or 1 hour to 15 hours. Regarding the polymerization mode, the molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system.

[0096] Furthermore, the polymerization can be carried out without any problems even if a component for removing water, a so-called scavenger, is added to the polymerization system. Examples of such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, the organoaluminum oxycompounds, modified organoaluminum compounds containing branched alkyl groups, organozinc compounds such as diethylzinc and dibutylzinc, organomagnesium compounds such as diethylmagnesium, dibutylmagnesium, and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride. Among these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferred, with triethylaluminum being particularly preferred. The method can also be applied without any problems to multi-stage polymerization systems of two or more stages in which the polymerization conditions, such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature, are different from one another.

[0097] [Example]

[0098] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples as long as it does not deviate from the gist of the disclosure. The evaluation methods used in the examples are as follows. The catalyst synthesis step and polymerization step were all carried out under a purified nitrogen atmosphere, and the solvents used were dehydrated and purified using molecular sieves 4A.

[0099] 1. Synthesis of solid catalyst for olefin polymerization (component (A)) (1) Synthesis of Metallocene Compound (C1) (Synthesis of Component (E)) Dimethylsilylene(3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride, shown in the chemical formula below, was synthesized according to the following method. This compound is designated metallocene compound C1 (see the chemical formula below). Metallocene compound C1 is a compound corresponding to component (E).

[0100] [ka]

[0101] (1-1) Synthesis of 1-methyl-7-(2-(5-methyl)-furyl)-indene (1-1-a) Synthesis of 2-bromophenyl-2-chloroethyl ketone 2-Bromobenzoic acid (5.30 g, 26.4 mmol) and 25 mL of thionyl chloride were added to a 100 mL flask and refluxed for 2 hours. After the reaction, excess thionyl chloride was removed by distillation under reduced pressure, and the resulting acid chloride (5.50 g) was used in the next reaction without further purification. A 100 mL flask was charged with the acid chloride (5.00 g, 22.7 mmol) and 50 mL of dichloromethane to form a solution, followed by aluminum chloride (3.02 g, 22.7 mmol). Ethylene was then bubbled through the solution at 20°C for 4 hours. The reaction was quenched with 4 N hydrochloric acid, and the organic and aqueous phases were separated. The aqueous phase was washed three times with 50 mL of methyl t-butyl ether. The organic phase was collected and washed three times with 50 mL of water, 100 mL of saturated aqueous sodium bicarbonate, and then 100 mL of saturated brine. After drying over sodium sulfate, the solvent was evaporated under reduced pressure to give 4.80 g (yield 85%) of 2-bromophenyl-2-chloroethyl ketone, which was used in the next reaction without further purification.

[0102] (1-1-b) Synthesis of 7-bromo-1-indanone Aluminum chloride (7.40 g, 55.6 mmol) and sodium chloride (2.15 g, 37.1 mmol) were added to a 100 mL flask and heated to 130 °C. 2-Bromophenyl-2-chloroethyl ketone (4.60 g, 18.5 mmol) was then slowly added, and the mixture was stirred at 160 °C for 1 hour. After the reaction, the mixture was cooled to 30 °C and quenched with ice water. After adjusting the pH to 5 with concentrated hydrochloric acid, the organic and aqueous phases were separated. The aqueous phase was washed three times with 100 mL of dichloromethane. The combined organic phase was washed with 100 mL of water and 100 mL of saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give the crude product. Further purification was performed using a silica gel column (petroleum ether / ethyl acetate = 30 / 1) to give 1.60 g of 7-bromo-1-indanone (33% yield).

[0103] (1-1-c) Synthesis of 7-(2-(5-methyl)-furyl)-1-indanone A 100 ml flask was charged with 2-methylfuran (0.933 g, 11.4 mmol) and 10 ml of THF to form a solution. Then, at -30 °C, n-butyllithium / hexane solution (2.5 M, 4.70 ml, 11.4 mmol) was added and stirred at room temperature for 2 hours. A separate 100 ml flask was charged with zinc chloride (1.55 g, 11.4 mmol) and 10 ml of THF, followed by the above reaction solution at 0 °C and stirring at room temperature for 1 hour. A separate 100 ml flask was charged with copper(I) iodide (90 mg, 0.473 mmol), Pd(dppf)Cl2 (177 mg, 0.236 mmol), 7-bromo-1-indanone (2.00 g, 9.45 mmol), and 10 ml of DMA. The reaction mixture was added to the suspension and refluxed for 15 hours. After cooling to room temperature, 50 ml of water was added and extraction was performed twice with 50 ml of ethyl acetate. The organic phase was collected, washed twice with 50 ml of water and 50 ml of saturated brine, dried over sodium sulfate, and the solvent was removed under reduced pressure to obtain a crude product. The product was further purified using a silica gel column (petroleum ether / ethyl acetate = 20 / 1) to obtain 0.70 g of 7-(2-(5-methyl)-furyl)-1-indanone (yield 35%).

[0104] (1-1-d) Synthesis of 1-methyl-7-(2-(5-methyl)-furyl)-indene 7-(2-(5-methyl)-furyl)-1-indanone (1.40 g, 6.59 mmol) and 20 mL of THF were added to a 100 mL flask to form a solution, followed by the addition of methyllithium / diethyl ether solution (1.6 M, 7.5 mL, 11.9 mmol) at -78 °C and stirring at room temperature for 10 hours. The reaction was quenched with 20 mL of saturated aqueous ammonium chloride, and the volatile components were removed under reduced pressure. The remaining solution was extracted twice with 50 mL of ethyl acetate. The organic phase was collected, washed with 50 mL of saturated brine, dried over sodium sulfate, and the solvent was removed under reduced pressure to obtain the crude product. This was used in the next reaction without further purification. The crude product and 30 mL of toluene were added to a 100 mL flask to form a solution, followed by the addition of p-toluenesulfonic acid (62.0 mg, 0.330 mmol), and the mixture was stirred at 130 °C for 2 hours. The water generated during stirring was removed using a Dean-Stark trap. After cooling to room temperature, 30 ml of saturated aqueous sodium bicarbonate solution was added, and the organic phase was separated. The aqueous phase was extracted three times with 50 ml of ethyl acetate, and the combined organic phases were washed with 50 ml of saturated brine and dried over sodium sulfate. The solvent was then removed under reduced pressure to obtain a crude product. The product was further purified using a silica gel column (petroleum ether) to obtain 0.850 g (61% yield) of 1-methyl-7-(2-(5-methyl)-furyl)-indene.

[0105] (1-2) Synthesis of (2,3,4,5-tetramethylcyclopentadienyl)dimethylchlorosilane A 200 ml flask was charged with 2.40 g (19.6 mmol) of tetramethylcyclopentadiene and 40 ml of THF to form a solution, which was then cooled to -78 °C and 12.0 ml (30.0 mmol) of n-butyllithium / hexane solution (2.5 M) was added. The mixture was then returned to room temperature and stirred for 3 hours to obtain a reaction solution. A separate 200 ml flask was charged with 5.00 g (38.7 mmol) of dimethyldichlorosilane and 20 ml of THF, cooled to -78 °C, and the reaction solution was added. The mixture was then returned to room temperature and stirred for 12 hours. Volatiles were removed by distillation under reduced pressure to obtain 4.00 g of a yellow liquid. The resulting yellow liquid (main component: (2,3,4,5-tetramethylcyclopentadienyl)dimethylchlorosilane) was used in the next reaction without further purification.

[0106] Synthesis of (1-3)(3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)dimethylsilane A 100 ml flask was charged with 2.60 g (12.4 mmol) of 1-methyl-7-(2-(5-methyl)-furyl)-indene and 40 ml of THF to form a solution, which was then cooled to -78°C and 5.2 ml (13.0 mmol) of n-butyllithium / hexane solution (2.5 M) was added. The mixture was then returned to room temperature and stirred for 3 hours. A separate 200 ml flask was charged with 3.40 g (15.8 mmol) of the crude yellow liquid obtained in (1-2) and 10 ml of THF, cooled to -78°C, and the previous reaction solution was added. The mixture was then returned to room temperature and stirred for 12 hours. The reaction mixture was slowly added to 40 ml of ice water and extracted twice with 200 ml of ethyl acetate. The resulting organic phase was washed with 50 ml of saturated brine and dried over anhydrous sodium sulfate. The sodium sulfate was filtered, and the solution was evaporated under reduced pressure. The residue was purified with a silica gel column (petroleum ether) to obtain 1.40 g (25% yield) of a yellow oil of (3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)dimethylsilane.

[0107] Synthesis of (1-4) dimethylsilylene(3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride A 200 ml flask was charged with 2.20 g (5.70 mmol) of (3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)dimethylsilane and 30 ml of diethyl ether, and the mixture was cooled to -78°C. 4.8 ml (11.9 mmol) of a 2.5 M n-butyllithium / n-hexane solution was added dropwise, and the mixture was allowed to return to room temperature and stirred for 3 hours. The solvent was removed from the reaction solution by distillation under reduced pressure, and 60 ml of dichloromethane was added and the mixture was cooled to -78°C. 1.40 g (6.01 mmol) of zirconium tetrachloride was added, and the mixture was stirred overnight while gradually returning to room temperature. The reaction solution was filtered, and the solvent was removed from the filtrate by distillation under reduced pressure, yielding 3.0 g of a yellow powder. This powder was washed with 25 ml of toluene to obtain 0.75 g (yield 26%) of a yellow powder of dimethylsilylene(3-methyl-4-(2-(5-methyl)-furyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (metallocene compound C1). 1H-NMR value (CDCl3): δ0.94(s,3H), δ1.19(s,3H), δ1.90(s,3H), δ1.95(s,3H), δ1.98(s,3H), δ2.04(s,3H), δ2.28 (s,3H), δ2.38(s,3H), δ5.52(s,1H), δ6.07(d,1H), δ6.38(d,1H), δ7.04(dd,1H), δ7.37(d,1H), δ7.45(d,1H).

[0108] (2) Synthesis of solid catalyst for olefin polymerization (component (A)) Under a nitrogen atmosphere, a 1-L flask was prepared by mixing 32.7 g of silica calcined at 480°C for 6 hours with 213 mL of dehydrated toluene to form a mixed slurry. Under a nitrogen atmosphere, 183 mg of metallocene compound C1 (component (E)) was placed in a separate 200 mL two-neck flask and dissolved in 90 mL of dehydrated toluene. At room temperature, 90 mL of a 20% methylaluminoxane / toluene solution manufactured by Albemarle was added to the toluene solution of metallocene compound C1 and stirred for 30 minutes. The 1-L flask containing the previously prepared toluene slurry of silica (component (G)) was heated and stirred in a 40°C oil bath. The entire toluene solution of the reaction product of metallocene compound C1 and methylaluminoxane (component (F)) was added, and the temperature was maintained at 40°C while stirring for 1 hour. After 1 hour, stirring was stopped, the mixture was left standing at 40°C for 10 minutes, and the supernatant was removed. To this was added 600 ml of dehydrated hexane, and the mixture was stirred for 5 minutes, then allowed to stand for 10 minutes, after which the supernatant was removed. In the same manner, the catalyst was washed again with 700 ml of dehydrated hexane, and the hexane was distilled off under reduced pressure to obtain a solid catalyst a for olefin polymerization (component (A)).

[0109] 2. Comparative experiment on charging characteristics of catalyst slurries for olefin polymerization The following describes the preparation and charging characteristics of catalyst slurries A to I. Note that Fig. 1 is a flow chart illustrating an outline of the method for preparing catalyst slurries A and B. (1) [Example 1] (1-1) Preparation of catalyst slurry A Under a nitrogen atmosphere, 0.32 g of STATSAFE 6000 (component (B): manufactured by Innospec) was added to 2.72 g of hexane (component (D)) in a 50 ml glass screw cap vial and mixed using a vibrator. In a separate 300 ml glass three-neck flask, under a nitrogen atmosphere, 11.04 g of olefin polymerization solid catalyst a (component (A)) was added to 62.73 g of hexane (component (D)) and stirred at 120 rpm at room temperature. The entire STATSAFE 6000 and hexane mixture was then added and stirred at 120 rpm at room temperature for 30 minutes. Thirty minutes after stirring was stopped, 50 g of the supernatant was removed, followed by the addition of 60 g of hexane and stirring at 120 rpm for 10 minutes at room temperature. Thirty minutes after stirring was stopped, 60 g of the supernatant was removed, followed by the addition of 60 g of hexane and stirring at 120 rpm for 10 minutes at room temperature. Thirty minutes after stirring was stopped, 60 g of the supernatant was removed, followed by the addition of 60 g of hexane and stirring at 120 rpm for 10 minutes at room temperature. Thirty minutes after stirring was stopped, 60 g of the supernatant liquid was removed, and the mixture was heated to 40°C in an oil bath and evaporated under reduced pressure to remove hexane (component (D)), thereby obtaining 10.57 g of solid catalyst 1 (antistatic agent-impregnated powder catalyst). In a separately prepared 300 ml glass three-neck flask, 7.18 g of the above solid catalyst 1 (antistatic agent-impregnated powder catalyst) was added under a nitrogen atmosphere, and liquid paraffin (component (C): manufactured by Moresco, trade name: Moresco White P-120, average molecular weight 365, density: 0.853 g / cm) that had been dehydrated by nitrogen bubbling was added. 3 ) was added and stirred at 120 rpm at room temperature to obtain catalyst slurry A.

[0110] (1-2) Measurement of the charge amount of catalyst slurry A The catalyst slurry obtained in (1-1) Preparation of Slurry Catalyst A was added to a 75 ml SUS cylinder equipped with a ball valve at one end and a SUS pipe with an outer diameter of 6 mm, an inner diameter of 4 mm, and a length of 10 cm at the other end under a nitrogen atmosphere, and the internal pressure was adjusted to 0.1 MPa with nitrogen. Under a nitrogen atmosphere, the valve on the side of the cylinder equipped with the pipe was fully opened, and the entire amount of slurry catalyst in the cylinder was placed in a Faraday cage (Kasuga Electric Co., Ltd., Model: KQ-1400) equipped with a coulomb meter (Kasuga Electric Co., Ltd., Model: NK-1001A). The charge amount was measured when the entire amount of catalyst slurry in the cylinder was measured. The charge amount measurements taken 3 hours, 21 hours, and 379 hours after catalyst slurry preparation are summarized in Table 3. The charge suppression rate was calculated using the following formula. If the charge suppression rate does not decrease over time, it means that the charge suppression effect is not likely to decrease over time and that the charge suppression effect is maintained. The charge amount of the catalyst without the addition of an antistatic agent in the formula below means the specific charge amount in Reference Example 1 described below.

[0111]

number

[0112] (2) [Comparative Example 1] (2-1) Preparation of catalyst slurry B Under a nitrogen atmosphere, in a 50 ml glass screw tube bottle, 0.89 g of STATSAFE 6000 (component (B): manufactured by Innospec) was added to 6.52 g of hexane (component (D)) and mixed with a vibrator. In a separately prepared 300 ml glass three-neck flask, under a nitrogen atmosphere, 33.30 g of a solid catalyst a for olefin polymerization (component (A)) was added to liquid paraffin (component (C): manufactured by Moresco, trade name: Moresco White P-120, average molecular weight 365, density: 0.853 g / cm) that had been dehydrated by nitrogen bubbling. 3 The resulting mixture was stirred at 120 rpm at room temperature for 30 minutes.

[0113] (2-2) Measurement of the charge amount of catalyst slurry B (2-1) The catalyst obtained in the preparation of catalyst slurry B was used, and the charge amount of the catalyst slurry was measured in the same manner as in Example 1, except that the charge amount was measured 2 hours, 25 hours, and 73 hours after the preparation of the catalyst slurry. The charge amount measurement results are summarized in Table 3. The charge inhibition rate was calculated by replacing "specific charge amount of Example 1" with "specific charge amount of Comparative Example 1" in the formula used in Example 1 above.

[0114] (3) [Example 2] (3-1) Preparation of catalyst slurry C Under a nitrogen atmosphere, 0.42 g of Nymeen S-202 (component (B) polyoxyethylene stearylamine: NOF Corporation) was added to 11.56 g of hexane (component (D)) in a 50 ml glass screw cap and mixed using a vibrator. In a separate 300 ml glass three-neck flask, under a nitrogen atmosphere, 12.28 g of olefin polymerization solid catalyst a (component (A)) was added to 69.00 g of hexane (component (D)) and stirred at 120 rpm at room temperature. The entire Nymeen S-202 and hexane mixture was then added and stirred at 120 rpm for 30 minutes at room temperature. Thirty minutes after stirring was stopped, 56 g of the supernatant was removed, and then 62 g of hexane was added and stirred at 120 rpm for 10 minutes at room temperature. Thirty minutes after stirring was stopped, 60 g of the supernatant was removed, and then 60 g of hexane was added and stirred for 10 minutes at room temperature at 120 rpm. After 30 minutes after stirring was stopped, 60 g of the supernatant was removed, and the mixture was heated to 40°C in an oil bath and evaporated under reduced pressure to remove hexane (component (D)), yielding 11.22 g of solid catalyst 2 (antistatic agent-impregnated powder catalyst). In a separately prepared 300 ml glass three-neck flask, 11.95 g of the above solid catalyst 2 (antistatic agent-impregnated powder catalyst) was added under a nitrogen atmosphere, and liquid paraffin (component (C): manufactured by Moresco, trade name: Moresco White P-120, average molecular weight 365, density: 0.853 g / cm) that had been dehydrated by nitrogen bubbling was added. 3 ) was added and stirred at 120 rpm at room temperature to obtain catalyst slurry C.

[0115] (3-2) Measurement of the charge amount of catalyst slurry C (3-1) The catalyst obtained in the preparation of catalyst slurry C was used, and the charge amount of the catalyst slurry was measured in the same manner as in Example 1, except that the charge amount was measured 2 hours and 49 hours after the preparation of the catalyst slurry. The charge amount measurement results are summarized in Table 3. The charge inhibition rate was calculated by replacing "specific charge amount of Example 1" with "specific charge amount of Example 2" in the formula used in Example 1 above.

[0116] (4) [Comparative Example 2] (4-1) Preparation of catalyst slurry D Under a nitrogen atmosphere, in a 50 ml glass screw tube bottle, 0.30 g of Nymeen S-202 (component (B) polyoxyethylene stearylamine: manufactured by NOF Corporation) was added to 3.18 g of hexane (component (D)) and mixed with a vibrator. In a separately prepared 300 ml glass three-neck flask, under a nitrogen atmosphere, 12.42 g of solid catalyst a for olefin polymerization (component (A)) was added to liquid paraffin (component (C): manufactured by Moresco, trade name: Moresco White P-120, average molecular weight 365, density: 0.853 g / cm) that had been dehydrated by nitrogen bubbling. 3 The catalyst slurry D was obtained by adding 66.96 g of the above-mentioned mixture of Nymeen S-202 and hexane to the mixture and stirring at 120 rpm at room temperature for 30 minutes.

[0117] (4-2) Measurement of the charge amount of catalyst slurry D (4-1) The catalyst obtained in the preparation of catalyst slurry D was used, and the charge amount of the catalyst slurry was measured in the same manner as in Example 1, except that the charge amount was measured 3 hours, 27 hours, and 51 hours after the preparation of the catalyst slurry. The charge amount measurement results are summarized in Table 3. The charge inhibition rate was calculated by replacing "specific charge amount of Example 1" with "specific charge amount of Comparative Example 2" in the formula used in Example 1 above.

[0118] (5) [Example 3] (5-1) Preparation of catalyst slurry E Under a nitrogen atmosphere, 0.34 g of monoolein (component (B) glycerin monooleate: manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 4.97 g of hexane (component (D)) in a 50 ml glass screw cap vial and mixed using a vibrator. In a separately prepared 300 ml glass three-neck flask, under a nitrogen atmosphere, 11.10 g of solid catalyst a for olefin polymerization (component (A)) was added to 64.49 g of hexane (component (D)) and stirred at 120 rpm at room temperature. The entire monoolein and hexane mixture was then added and stirred at 120 rpm for 30 minutes at room temperature. Thirty minutes after stirring was stopped, 50 g of the supernatant was removed, and 60 g of hexane was added. The mixture was stirred at 120 rpm for 10 minutes at room temperature. Thirty minutes after stirring was stopped, 60 g of the supernatant was removed, and 60 g of hexane was added. The mixture was stirred at 120 rpm for 10 minutes at room temperature. Thirty minutes after stirring was stopped, 60 g of the supernatant was removed, and the mixture was heated to 40°C in an oil bath and evaporated under reduced pressure to remove hexane (component (D)), thereby obtaining 11.43 g of solid catalyst 3 (antistatic agent-impregnated powder catalyst). In a separately prepared 300 ml glass three-neck flask, 11.43 g of the above solid catalyst 3 (antistatic agent-impregnated powder catalyst) was added under a nitrogen atmosphere, and liquid paraffin (component (C): manufactured by Moresco, trade name: Moresco White P-120, average molecular weight 365, density: 0.853 g / cm) that had been dehydrated by nitrogen bubbling was added. 3 ) was added and stirred at 120 rpm at room temperature to obtain catalyst slurry E.

[0119] (5-2) Measurement of the charge amount of catalyst slurry E (5-1) The catalyst obtained in the preparation of catalyst slurry E was used, and the charge amount of the catalyst slurry was measured in the same manner as in Example 1, except that the charge amount was measured 2 hours and 190 hours after the preparation of the catalyst slurry. The charge amount measurement results are summarized in Table 3. The charge inhibition rate was calculated by replacing "specific charge amount of Example 1" with "specific charge amount of Example 3" in the formula used in Example 1 above.

[0120] (6) [Comparative Example 3] (6-1) Preparation of catalyst slurry F In a 50 ml glass screw tube bottle, under a nitrogen atmosphere, 0.47 g of monoolein (component (B) glycerin monooleate: manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 3.50 g of hexane (component (D)) and mixed with a vibrator. In a separately prepared 300 ml glass three-neck flask, under a nitrogen atmosphere, 15.02 g of solid catalyst a for olefin polymerization (component (A)) was added to liquid paraffin (component (C): manufactured by Moresco, trade name: Moresco White P-120, average molecular weight 365, density: 0.853 g / cm) that had been dehydrated by nitrogen bubbling. 3 The mixture was stirred at 120 rpm at room temperature for 30 minutes, and the entire amount of the monoolein and hexane mixture was then added thereto, followed by stirring at 120 rpm at room temperature for 30 minutes, thereby obtaining catalyst slurry F.

[0121] (6-2) Measurement of the charge amount of catalyst slurry F (6-1) The catalyst obtained in the preparation of catalyst slurry F was used, and the charge amount of the catalyst slurry was measured in the same manner as in Example 1, except that the charge amount was measured 1 hour, 48 hours, and 97 hours after the preparation of the catalyst slurry. The charge amount measurement results are summarized in Table 3. The charge inhibition rate was calculated by replacing "specific charge amount of Example 1" with "specific charge amount of Comparative Example 3" in the formula used in Example 1 above.

[0122] (7) [Example 4] (7-1) Preparation of catalyst slurry G Under a nitrogen atmosphere, 0.34 g of Staform DF-4 (component (B) coconut oil fatty acid diethanolamide, manufactured by NOF Corporation) was added to 5.03 g of hexane (component (D)) in a 50 ml glass screw cap and mixed using a vibrator. In a separate 300 ml glass three-neck flask, under a nitrogen atmosphere, 11.13 g of olefin polymerization solid catalyst a (component (A)) was added to 63.76 g of hexane (component (D)) and stirred at 120 rpm at room temperature. The entire mixture of Staform DF-4 and hexane was then added and stirred at 120 rpm at room temperature for 30 minutes. Thirty minutes after stirring was stopped, 50 g of the supernatant was removed, and 60 g of hexane was added. The mixture was stirred at 120 rpm at room temperature for 10 minutes. Thirty minutes after stirring was stopped, 60 g of the supernatant was removed, and 60 g of hexane was added. The mixture was stirred at 120 rpm at room temperature for 10 minutes. Thirty minutes after stirring was stopped, 60 g of the supernatant was removed, and the mixture was heated to 40°C in an oil bath and evaporated under reduced pressure to remove hexane (component (D)), thereby obtaining 11.45 g of solid catalyst 4 (antistatic agent-impregnated powder catalyst). In a separately prepared 300 ml glass three-neck flask, 11.45 g of the above solid catalyst 4 (antistatic agent-impregnated powder catalyst) was added under a nitrogen atmosphere, and liquid paraffin (component (C): manufactured by Moresco, trade name: Moresco White P-120, average molecular weight 365, density: 0.853 g / cm) that had been dehydrated by nitrogen bubbling was added. 3 ) was added, and the mixture was stirred at 120 rpm at room temperature to obtain catalyst slurry G.

[0123] (7-2) Measurement of the charge amount of catalyst slurry G (7-1) The catalyst obtained in the preparation of catalyst slurry G was used, and the charge amount of the catalyst slurry was measured in the same manner as in Example 1, except that the charge amount was measured 2 hours, 21 hours, and 93 hours after the preparation of the catalyst slurry. The charge amount measurement results are summarized in Table 3. The charge inhibition rate was calculated by replacing "specific charge amount of Example 1" with "specific charge amount of Example 4" in the formula used in Example 1 above.

[0124] (8) [Comparative Example 4] (8-1) Preparation of catalyst slurry H Under a nitrogen atmosphere, in a 50 ml glass screw tube bottle, 0.44 g of Staform DF-4 (component (B) coconut oil fatty acid diethanolamide: manufactured by NOF Corporation) was added to 3.22 g of hexane (component (D)) and mixed with a vibrator. In a separately prepared 300 ml glass three-neck flask, under a nitrogen atmosphere, 14.07 g of solid catalyst a for olefin polymerization (component (A)) was added to liquid paraffin (component (C): manufactured by Moresco, trade name: Moresco White P-120, average molecular weight 365, density: 0.853 g / cm) that had been dehydrated by nitrogen bubbling. 3 The resulting mixture was stirred at 120 rpm at room temperature for 30 minutes.

[0125] (8-2) Measurement of the charge amount of catalyst slurry H (8-1) The catalyst obtained in the preparation of catalyst slurry H was used, and the charge amount of the catalyst slurry was measured in the same manner as in Example 1, except that the charge amount was measured 21 hours, 44 hours, and 140 hours after the preparation of the catalyst slurry. The charge amount measurement results are summarized in Table 3. The charge inhibition rate was calculated by replacing "specific charge amount of Example 1" in the formula used in Example 1 above with "specific charge amount of Comparative Example 4."

[0126] (9) [Reference example 1] (9-1) Preparation of catalyst slurry I In a nitrogen atmosphere, 16.07 g of a solid catalyst a for olefin polymerization (component (A)) was added to a 300 ml glass three-neck flask, and liquid paraffin (component (C): manufactured by Moresco, trade name: Moresco White P-120, average molecular weight: 365, density: 0.853 g / cm) that had been dehydrated by nitrogen bubbling was added. 3 ) was added, and the mixture was stirred at 120 rpm at room temperature for 30 minutes to obtain catalyst slurry I.

[0127] (9-2) Measurement of the charge amount of catalyst slurry I (9-1) The catalyst obtained in the preparation of catalyst slurry I was used, and the charge amount of the catalyst slurry was measured in the same manner as in Example 1, except that the charge amount was measured 5 hours and 48 hours after the preparation of the catalyst slurry. The charge amount measurement results are summarized in Table 3. The charge inhibition rate was calculated by replacing "specific charge amount of Example 1" with "specific charge amount of Reference Example 1" in the formula used in Example 1 above.

[0128] [Table 3]

[0129] (10) Results of comparative experiments on the charging characteristics of catalyst slurries for olefin polymerization In Example 1, the charge suppression rate hardly changed between the catalyst slurry 3 hours after preparation and the catalyst slurry 379 hours after preparation, which confirmed that the charge suppression effect in Example 1 was not likely to decrease over time. In Example 2, the charge suppression rate hardly changed between the catalyst slurry 2 hours after preparation and the catalyst slurry 49 hours after preparation, which confirmed that the charge suppression effect in Example 2 was not likely to decrease over time. In Example 3, the charge suppression rate hardly changed between the catalyst slurry 2 hours after preparation and the catalyst slurry 190 hours after preparation, which confirmed that the charge suppression effect in Example 3 was not likely to decrease over time. In Example 4, the charge suppression rate hardly changed between the catalyst slurry 2 hours after preparation and the catalyst slurry 93 hours after preparation, which confirmed that the charge suppression effect in Example 4 was not likely to decrease over time. In Comparative Example 1, since there was no step of removing component (D) in step (2), the charge suppression rate decreased with the passage of time after preparation. Therefore, it was confirmed that in Comparative Example 1, the charge suppression effect decreased over time compared to Example 1. In Comparative Example 2, since there was no step of removing component (D) in step (2), the charge suppression rate decreased with the passage of time after preparation. Therefore, it was confirmed that in Comparative Example 2, the charge suppression effect decreased over time compared to Example 2. In Comparative Example 3, since there was no step of removing component (D) in step (2), the charge suppression rate decreased with the passage of time after preparation. Therefore, it was confirmed that in Comparative Example 3, the charge suppression effect decreased over time compared to Example 3. In Comparative Example 4, since there was no step of removing component (D) in step (2), the charge suppression rate decreased with the passage of time after preparation. Therefore, it was confirmed that the charge suppression effect in Comparative Example 4 decreased over time compared to Example 4.

[0130] 3. Effects of the Example From the above results, it was found that the olefin polymerization catalyst slurries of the examples were less likely to lose their electrification suppression effect over time.

[0131] The present invention is not limited to the above-described embodiments, and various modifications and variations are possible within the scope of the present disclosure.

Claims

1. A method for producing a catalyst slurry for olefin polymerization, comprising the following components (A), (B), and (C), characterized in that the method comprises the following steps (1) to (3): Component (A): a solid catalyst for olefin polymerization (not including an antistatic agent) Component (B): antistatic agent The component (C): at least one selected from the group consisting of liquid paraffin, mineral oil, and polybutene Component (D): a hydrocarbon compound having 4 to 12 carbon atoms Step (1): A step of preparing a mixture containing the component (A), the component (B), and the component (D). Step (2): A step of removing the component (D) from a mixture containing the component (A), the component (B), and the component (D). Step (3): A step of further mixing the component (C) with a mixture containing at least the component (A) and the component (B).

2. 2. The method for producing a catalyst slurry for olefin polymerization according to claim 1, wherein in the step (1), the component (B) is mixed with a premix containing the component (A) and the component (D) to prepare a mixture.

3. 3. The method for producing a catalyst slurry for olefin polymerization according to claim 1, wherein the mass of the component (B) contained in the catalyst slurry for olefin polymerization is 200 ppm by mass to 14,000 ppm by mass relative to the total mass of the component (A), the component (B), and the component (C).

4. 3. The method for producing a catalyst slurry for olefin polymerization according to claim 1, wherein the mass of the component (D) contained in the catalyst slurry for olefin polymerization is 0 mass% or more and 2 mass% or less, when the catalyst slurry for olefin polymerization is taken as 100 mass%.

5. 3. The method for producing a catalyst slurry for olefin polymerization according to claim 1 or 2, wherein the component (B) is at least one selected from the group consisting of polysulfone copolymers, polymeric polyamines, oil-soluble sulfonic acids, tertiary amines, aliphatic amides, fatty acid esters, polyalkylene oxides, and polyalkylene glycols.

6. 3. The method for producing a catalyst slurry for olefin polymerization according to claim 1, wherein the component (A) comprises the following components (E), (F), and (G): The component (E): at least one selected from metallocene compounds and post-metallocene compounds containing transition metal atoms Component (F): a compound that converts component (E) into a cationic compound The component (G): an organic compound carrier and / or an inorganic compound carrier

7. 7. The method for producing a catalyst slurry for olefin polymerization according to claim 6, wherein the component (E) is a metallocene compound containing a transition metal atom.

8. 7. The method for producing a catalyst slurry for olefin polymerization according to claim 6, wherein the component (E) is a bridged cyclopentadienyl compound containing a transition metal.

9. 7. The method for producing a catalyst slurry for olefin polymerization according to claim 6, wherein the component (F) is at least one compound selected from the group consisting of organoaluminum oxy compounds, borane compounds, and borate compounds.

10. 7. The method for producing a catalyst slurry for olefin polymerization according to claim 6, wherein the component (G) is the inorganic compound support.

11. 3. The method for producing a catalyst slurry for olefin polymerization according to claim 1, wherein the mass of the component (B) contained in the catalyst slurry for olefin polymerization is 600 ppm by mass to 10,000 ppm by mass relative to the total mass of the component (A), the component (B), and the component (C).

12. 3. The method for producing a catalyst slurry for olefin polymerization according to claim 1, wherein the mass of the component (B) contained in the catalyst slurry for olefin polymerization is 1,100 ppm by mass to 10,000 ppm by mass relative to the total mass of the component (A), the component (B), and the component (C).

13. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst slurry produced by the method according to claim 1 or 2.

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