Catalyst for olefin polymerization and method for producing olefin polymer

Abstract

To provide a catalyst for olefin polymerization that can produce an olefin polymer having high polymerization activity and containing carbon materials efficiently dispersed therein, and a method for producing an olefin polymer by using the catalyst for olefin polymerization.SOLUTION: A catalyst for olefin polymerization contains a carbon material (A) satisfying the following requirements (A-I) and (A-II), at least one component (B) selected from the group consisting of the following (B-I) and (B-II), and a transition metal compound (C). Requirement (A-I): the oxygen atom / carbon atom molar ratio in X-ray photoelectron spectroscopy (XPS) of 0.018 or more and 0.400 or less. Requirement (A-II): the specific surface area in BET multipoint method of 100 m2 / g or more and 5000 m2 / g or less. Component (B-I): an organic aluminum oxy compound. Component (B-II): a compound to react with the transition metal compound (C), forming an ion pair.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an olefin polymerization catalyst and a process for producing an olefin polymer using the olefin polymerization catalyst. [Background technology]

[0002] By blending carbon materials such as graphite, graphene, and carbon nanotubes (CNTs) with polyolefins, it is possible to impart high thermal conductivity, electrical conductivity, and weather resistance to the polyolefins (see, for example, Patent Document 1). However, there is a problem in that it is difficult to disperse these carbon materials in polyolefins.

[0003] In order to improve the dispersibility of carbon materials in polyolefins, methods have been proposed for producing composites of carbon materials and polyolefins by polymerizing them using a polymerization catalyst in which a metal complex is supported or impregnated on the carbon material (see, for example, Patent Documents 2 to 4). However, there is room for further improvement in terms of olefin polymerization activity and dispersibility of the carbon material. Furthermore, these methods all use expensive organoaluminum oxy compounds such as methylaluminoxane (MAO) as co-catalysts, and there is also a need to reduce production costs. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-071079 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-176601 [Patent Document 3] Japanese Patent Application Laid-Open No. 2007-161741 [Patent Document 4] Special Publication No. 2005-506404 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide an olefin polymerization catalyst that exhibits high polymerization activity and is capable of producing an olefin polymer in which a carbon material is efficiently dispersed, and a method for producing an olefin polymer using the olefin polymerization catalyst.

[0006] Another object of the present invention is to provide an olefin polymerization catalyst that exhibits high polymerization activity even when an expensive organoaluminum oxy-compound is used in an amount smaller than conventional amounts, and that is capable of producing an olefin polymer in which a carbon material is efficiently dispersed; and a method for producing an olefin polymer using the olefin polymerization catalyst. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved by using a specific carbon material, which has led to the completion of the present invention.

[0008] The olefin polymerization catalyst according to the present invention comprises: a carbon material (A) that satisfies the following requirements (AI) and (A-II); At least one component (B) selected from the group consisting of the following (BI) and (B-II): and a transition metal compound (C) represented by the following general formula (CI). (AI) The oxygen atom / carbon atom molar ratio measured by X-ray photoelectron spectroscopy (XPS) is 0.018 or more and 0.400 or less; (A-II) The specific surface area measured by the BET multipoint method is 100 m 2 / g or more 5000m 2 / g or less; (BI) organoaluminum oxy compounds; (B-II) A compound that reacts with a transition metal compound (C) to form an ion pair; L m MX n ···(CI) [In general formula (CI), M is an atom selected from the group consisting of atoms of Groups 3, 4, 5, 6, 7, 8, 9, 10, and 11 of the periodic table, and lanthanide atoms; L is selected from the group consisting of η-bonding cyclic anionic ligands, σ-bonding anionic ligands, and π-bonding neutral ligands, and multiple Ls may be the same or different, and multiple Ls may be connected by a substituent in L; m is an integer equal to or greater than 0, n is an integer of 1 to 6 that satisfies the valence of M, X is selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, and a diene derivative group, and when n is 2 or more, multiple Xs may be the same or different and may be bonded to each other to form a ring. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an olefin polymerization catalyst that exhibits high polymerization activity and is capable of producing an olefin polymer in which a carbon material is efficiently dispersed, and a method for producing an olefin polymer using the olefin polymerization catalyst.

[0010] The present invention also provides an olefin polymerization catalyst that exhibits high polymerization activity even when an expensive organoaluminum oxy-compound is used in an amount smaller than that of conventional catalysts, and that is capable of producing an olefin polymer in which a carbon material is efficiently dispersed; and a method for producing an olefin polymer using the olefin polymerization catalyst. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. [Olefin polymerization catalyst] The olefin polymerization catalyst of the present invention comprises a carbon material (A) that satisfies the following requirements (AI) and (A-II); At least one component (B) selected from the group consisting of the following (BI) and (B-II): The present invention is characterized by including a transition metal compound (C) represented by the following general formula (CI):

[0012] (AI) The oxygen atom / carbon atom molar ratio measured by X-ray photoelectron spectroscopy (XPS) is 0.018 or more and 0.400 or less. (A-II) The specific surface area measured by the BET multipoint method is 100 m 2 / g or more 5000m 2 / g or less.

[0013] (BI) organoaluminum oxy compounds; (B-II) A compound that reacts with a transition metal compound (C) to form an ion pair;

[0014] L m MX n ···(CI) In the general formula (CI), M is an atom selected from the group consisting of atoms of Groups 3, 4, 5, 6, 7, 8, 9, 10, and 11 in the periodic table, and lanthanide atoms; L is selected from the group consisting of η-bonding cyclic anionic ligands, σ-bonding anionic ligands, and π-bonding neutral ligands; multiple Ls may be the same or different from one another, or multiple Ls may be connected by a substituent within L; m is an integer of 0 or greater; n is an integer of 1 to 6 that satisfies the valence of M; X is selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, and a diene derivative group; when n is 2 or greater, multiple Xs may be the same or different from one another, or may be bonded to each other to form a ring.

[0015] Each component constituting the olefin polymerization catalyst of the present invention will be described below. <Carbon material (A)> The carbon material (A) used in the present invention satisfies the following requirements (AI) and (A-II).

[0016] (AI) The oxygen atom / carbon atom molar ratio measured by X-ray photoelectron spectroscopy (XPS) is 0.018 or more and 0.400 or less, preferably 0.020 or more and 0.250 or less, and more preferably 0.022 or more and 0.200 or less.

[0017] The oxygen atom / carbon atom molar ratio is a value obtained by X-ray photoelectron spectroscopy (XPS) measurement, and specifically, the oxygen atom / carbon atom molar ratio is obtained by calculating from the peak areas of oxygen atoms and carbon atoms in the spectrum obtained from the carbon material (A).

[0018] The higher the oxygen atom / carbon atom molar ratio, the more preferable it is because the amount of oxygen atoms that can come into contact with the component (B) described later increases. However, if the oxygen atom / carbon atom molar ratio is too high, the sp 2 The two-dimensional sheet structure due to bonded carbon tends to decrease.

[0019] The oxygen atoms in the carbon material (A) may be those in which some of the carbon atoms in the carbon material are replaced by oxygen atoms, or may be contained in a substituent on the carbon material, or may be contained in a compound coordinated to or adsorbed on the surface or pores of the carbon material, but are preferably present as an oxygen-atom-containing functional group in a substituent on the carbon material. Specific examples of the oxygen-atom-containing functional group include a hydroxyl group, an ether group, an epoxy group, a carbonyl group, and a carboxyl group.

[0020] The amount of oxygen atoms in the carbon material (A) can be controlled by the production conditions of the carbon material, heat treatment (e.g., drying, calcination), water absorption treatment, surface modification or modification treatment (e.g., functional group introduction, oxidation treatment, reduction treatment), etc.

[0021] (A-II) The specific surface area measured by the BET multipoint method is 100 m 2 / g or more 5000m 2 / g or less, preferably 150m 2 / g or more 3000m 2 / g or less, more preferably 200m 2 / g or more 2000m 2 / g or less.

[0022] The specific surface area is a value obtained by the Brunauer-Emmett-Teller (BET) multipoint method using an adsorption isotherm. Specifically, the carbon material (A) is subjected to a vacuum heating degassing treatment at 50°C to 300°C, and the adsorption isotherm is measured using nitrogen gas as the adsorbate. A BET plot is created from the adsorption isotherm, and the monomolecular adsorption amount is determined from the slope and intercept of the plot, from which the specific surface area is calculated.

[0023] When a carbon material (A) having fine pores is used, if the specific surface area is too high, the pore diameter becomes small (in other words, the proportion of micropores increases), and contact with the component (B) and the transition metal compound (C) described below is inhibited.

[0024] In the case of a carbon material (A) having fine pores, the pore volume is preferably 0.1 cm 3 / g or more 5.0cm 3 / g or less, more preferably 0.3 cm 3 / g or more 4.0cm 3 / g or less.

[0025] The specific surface area of ​​the carbon material (A) can be controlled by the raw material, size (nano-sizing), shape, and pores of the carbon material, and methods for forming pores include a method of introducing a template source as exemplified in JP 2020-093977 A and a method using an activation treatment.

[0026] The carbon material (A) used in the present invention is a solid carbon material and is not particularly limited as long as it satisfies the above requirements (A-1) and (A-II), and includes crystalline, low-crystalline, amorphous carbon materials and carbon materials consisting of mixtures thereof.

[0027] Among the carbon materials, examples of crystalline carbon include carbon nanotubes (e.g., single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes (DWCNT), and multi-walled carbon nanotubes (MWCNT)), graphene (e.g., single-layered graphene, multi-layered graphene), fullerenes (e.g., buckminsterfullerene, higher fullerenes), graphite (e.g., natural graphite, artificial graphite), diamond, etc. Examples of low-crystalline and amorphous carbon include carbon black, activated carbon, etc.

[0028] The carbon material (A) may be a carbon material that has been subjected to a surface modification or modification treatment (for example, introduction of a functional group, oxidation treatment, or reduction treatment), may contain a metal or the like, or may be a carbon material in which some of the carbon atoms have been substituted with other atoms.

[0029] The carbon material (A) according to the present invention may be one produced by a conventionally known method, or a commercially available product may be used.

[0030] For example, carbon nanotubes can be produced by methods such as arc discharge, laser deposition, and gas-phase chemical vapor deposition, as exemplified in JP 2009-196873 A, and surface modification treatment can be performed by methods such as those exemplified in JP 2014-501689 A. Commercially available products include "Multi-Walled Carbon Nanotubes NANOCYL NC7000" and "Multi-Walled Carbon Nanotubes NANOCYL NC3101" from Nanocyl Corporation, "Single-Walled Nanotubes OH Functionalized" and "Multi-Walled Nanotubes OH Functionalized" from SkySpring Nanomaterials, and "Multi-Walled Carbon Nanotubes, -OH Functionalized" from IoLiTec.

[0031] Graphene can be produced by methods such as arc discharge, laser deposition, vapor-phase chemical vapor deposition, heat treatment of silicon carbide, mechanical exfoliation, and ultrasonic exfoliation after chemical oxidation, as exemplified in JP 2014-152095 A. Commercially available graphene products include "Graphene Nanoplatelets xGnP" from XG Sciences, and "Reduced Graphene Oxide," "Boron-doped Graphene Powder," "Phosphorus-doped Graphene Powder," "Sulfur-doped Graphene Powder," "Nitrogen-doped Graphene Powder," and "Graphene Film" from Graphitene.

[0032] Fullerenes are produced by methods such as arc discharge, resistance heating, laser evaporation, combustion, and pyrolysis, as exemplified in JP 2013-241379 A, ​​and hydroxyl groups and carboxyl groups can be introduced onto the carbon of fullerenes by chemical treatment. Commercially available fullerenes include "C 60 PCPA" "C 60 (OH) 22-26 " and others.

[0033] Graphite can be broadly divided into natural graphite and artificial graphite, and examples of natural graphite include flake graphite, lump graphite (flake graphite), and amorphous graphite. Artificial graphite can be produced by methods such as precipitation from an Fe, Ni / C melt, decomposition of carbides of Si, Al, etc., cooling of a carbon melt under high temperature and pressure, and high-temperature decomposition and deposition of hydrocarbon gas, as exemplified in Japanese Patent Laid-Open Publication No. 02-083208. Commercially available products include "High Purity Graphite Powder SP-270" and "Artificial Graphite Powder HAG-150" from Nippon Graphite Co., Ltd.

[0034] Carbon black can be produced by pyrolysis or incomplete combustion of hydrocarbons such as oil and natural gas, specifically by methods known as the furnace process, channel process, acetylene process, and pine soot process.

[0035] Activated carbon can be produced by carbonizing and activating wood (e.g., charcoal, sawdust, bark), fruit shells (e.g., coconut shells), grain husks (e.g., rice husks), coal (e.g., peat, tar, coke), petroleum (e.g., tar, pitch), etc. at high temperatures. Commercially available products include "Porous Carbon CNover" from Toyo Tanso Co., Ltd. and "Triporous" from Sony Corporation.

[0036] The carbon material (A) is sp 2 It preferably has a two-dimensional sheet structure of bonded carbon, and also preferably has a cylindrically wound or spherical two-dimensional sheet structure. Specifically, it preferably contains at least one selected from the group consisting of carbon nanotubes, graphene, fullerene, graphite, and activated carbon.

[0037] The shape and size of the carbon material (A) are not particularly limited, and it may be in the form of granules, powder, fibers, sheets, or the like. In the case of a granular or powdery shape, it is preferable that the carbon material (A) has mesopores or macropores, since this promotes contact with the component (B) and the transition metal compound (C), which will be described later.

[0038] The carbon material (A) may be dried or calcined at a temperature of 0° C. or higher and 1000° C. or lower, preferably 50° C. or higher and 800° C. or lower, if necessary, before use.

[0039] <Ingredient (B)> The component (B) used in the present invention is at least one component selected from the group consisting of organoaluminum oxy compounds (BI) and compounds (B-II) (hereinafter also referred to as "ionic compounds (B-II)") that react with the transition metal compound (C) to form an ion pair. Component (B) preferably has a functional group that can form a chemical bond or electronic interaction with the oxygen atom-containing functional group in the carbon material (A).

[0040] <Organoaluminum oxy compounds (BI)> Examples of the organoaluminum oxy compound (BI) include conventionally known aluminoxanes such as compounds represented by the following general formula [b1] and compounds represented by the following general formula [b2], modified methylaluminoxanes having a structure represented by the following general formula [b3], and boron-containing organoaluminum oxy compounds represented by the following general formula [b4].

[0041] [ka]

[0042] In formulas [b1] and [b2], R is a hydrocarbon group having from 1 to 20 carbon atoms, preferably a methyl group, and n is an integer of 2 or more, preferably 3 or more, and more preferably 5 or more. In formulas [b1] and [b2], methylaluminoxane in which R is a methyl group is preferably used.

[0043] [ka]

[0044] In formula [b3], Me is a methyl group, R is a hydrocarbon group having 2 to 20 carbon atoms, and m and n are each independently an integer of 2 or greater. Multiple Rs may be the same or different. Modified methylaluminoxane [b3] can be prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such modified methylaluminoxane [b3] is generally called MMAO (modified methyl aluminoxane). MMAO can be prepared, for example, by the methods described in U.S. Pat. Nos. 4,960,878 and 5,041,584.

[0045] Modified methylaluminoxanes prepared using trimethylaluminum and triisobutylaluminum (i.e., R is an isobutyl group in general formula [b3]) are also commercially produced by Tosoh Finechem Corporation and other companies under the trade names MMAO and TMAO.

[0046] MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, unlike compounds insoluble or poorly soluble in benzene, such as compounds represented by general formula [b1] or [b2], MMAO is soluble in aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0047] [ka]

[0048] In formula [b4], R is a hydrocarbon group having from 1 to 20 carbon atoms. Multiple Rs may be the same or different.

[0049] Examples of the hydrocarbon group in the formulae [b1], [b2], [b3] and [b4] include a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, a 1-octyl group, an isopropyl group, a sec-butyl group (butan-2-yl group), a tert-butyl group (2-methylpropan-2-yl group), an isobutyl group (2-methylpropyl group), a pentan-2-yl group, a 2-methylpropyl ... - linear or branched alkyl groups such as methylbutyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), cyamyl (1,2-dimethylpropyl), isohexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl (2,3-dimethylbut-2-yl), 4,4-dimethylpentyl; Vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl group (propa-1,2-dien-1-yl group), but-3-en-1-yl group, crotyl group (but-2-en-1-yl group), but-3-en-2-yl group, methallyl group (2-methylallyl group), buta-1,3-dienyl group, pentaerythritol group, linear or branched alkenyl groups or unsaturated double bond-containing groups such as pent-4-en-1-yl, pent-3-en-1-yl, pent-2-en-1-yl, iso-pentenyl (3-methylbut-3-en-1-yl), 2-methylbut-3-en-1-yl, pent-4-en-2-yl, and prenyl (3-methylbut-2-en-1-yl); linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl, prop-2-yn-1-yl, and propargyl (prop-1-yn-1-yl); aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups such as benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl (4-isopropylbenzyl), 2,4,6-tri-isopropylbenzyl, 4-tert-butylbenzyl, 3,5-di-tert-butylbenzyl, 1-phenylethyl, benzhydryl (diphenylmethyl), and cumyl; cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cycloheptatrienyl, norbornyl, norbornenyl, 1-adamantyl, and 2-adamantyl; Examples of aromatic substituents (aryl groups) include a phenyl group, a tolyl group (methylphenyl group), a xylyl group (dimethylphenyl group), a mesityl group (2,4,6-trimethylphenyl group), a cumenyl group (isopropylphenyl group), a duryl group (2,3,5,6-tetramethylphenyl group), a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group.

[0050] In the formulas [b1], [b2], [b3] and [b4], compounds in which some of the multiple Rs are replaced with hydrogen atoms, halogen atoms, halogen-containing groups or oxygen-containing groups can also be used as the organoaluminum oxy compound (BI).

[0051] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0052] Examples of the halogen-containing group include those in which some of the hydrogen atoms in the hydrocarbon group have been substituted with the halogen atoms.

[0053] Examples of the oxygen-containing group include alkoxy groups such as a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a benzyloxy group, and a methoxymethoxy group; aryloxy groups such as a phenoxy group, a 2,6-dimethylphenoxy group, a 2,6-di-isopropylphenoxy group, a 2,6-di-tert-butylphenoxy group, a 2,4,6-trimethylphenoxy group, and a 2,4,6-tri-isopropylphenoxy group; a furyl group, a benzofuryl group, a tetrahydrofuryl group, a pyranyl group, a tetrahydropyranyl group, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetoxy group; and groups in which some of the hydrogen atoms in these groups have been substituted with the halogen atoms. Alternatively, the oxygen-containing group may be a hydrocarbon group in which some of the hydrogen atoms have been substituted with the oxygen-containing group.

[0054] The organoaluminum oxy compounds (BI) exemplified above may be used alone or in combination of two or more kinds.

[0055] <Ionic Compound (B-II)> The ionic compound (B-II) can be, without limitation, Lewis acids, ionic compounds, borane compounds, carborane compounds, heteropoly compounds, and isopoly compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, U.S. Patent No. 5,321,106, etc. Among these, the ionic compound (B-II) is preferably a compound represented by the following general formula [b5]:

[0056] [ka]

[0057] In formula [b5], Y +is a hydrogen cation, an oxonium cation, a carbenium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation.

[0058] Examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation, and tris(dimethylphenyl)carbenium cation.

[0059] Examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N,2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.

[0060] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation, and tris(dimethylphenyl)phosphonium cation.

[0061] Y + Among the above examples, carbenium cations and ammonium cations are preferred, and triphenylcarbenium cations, N,N-dimethylanilinium cations and methyldioctadecylammonium cations are particularly preferred.

[0062] M' is an atom of Group 13 of the periodic table, and specific examples include a boron atom and an aluminum atom, with a boron atom being preferred.

[0063] Each Q is independently a hydrogen atom, a hydrocarbon group having from 1 to 40 carbon atoms, a halogen atom, a halogen-containing group, or an oxygen-containing group, and multiple Qs may be the same or different and may be bonded to each other to form a ring.

[0064] Examples of the hydrocarbon group, halogen atom, halogen-containing group, or oxygen-containing group include those exemplified as R in the general formula [b1], [b2], [b3], or [b4] above, and preferably an aryl group having 6 to 40 carbon atoms, represented by the following general formula [b6]:

[0065] [ka]

[0066] In the formula [b6], * represents a bond to M', and R is selected from the group consisting of a hydrogen atom, a hydrocarbon group having from 1 to 40 carbon atoms, a halogen atom, a halogen-containing group, an oxygen-containing group, a silicon-containing group, a sulfur-containing group, a nitrogen-containing group, and a phosphorus-containing group, and multiple Rs may be the same or different and may be bonded to each other to form a ring.

[0067] Examples of the hydrocarbon group, halogen atom, halogen-containing group, and oxygen-containing group include the same groups as those exemplified as R in the formulae [b1], [b2], [b3], and [b4].

[0068] Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a trimethylsilylmethyl group, a chlorodimethylsilyl group, a chlorodiphenylsilyl group, a bromodimethylsilyl group, etc. Among the silicon-containing groups, a trimethylsilylmethyl group, a tri-isopropylsilyl group, a tert-butyldimethylsilyl group, a chlorodimethylsilyl group, and a chlorodiphenylsilyl group are preferred.

[0069] Examples of the sulfur-containing group include a thiol group, a mesyl group (methanesulfonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a triflyl group (trifluoromethanesulfonyl group), a nonaflyl group (nonafluorobutanesulfonyl group), a thiophenyl group, a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a triflate group (trifluoromethanesulfonate group), a nonaflate group (nonafluorobutanesulfonate group), a thiophene group, and a benzothiophene group.

[0070] Examples of the nitrogen-containing group include an amino group, a cyano group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a tert-butylamino group, a di-tert-butylamino group, an allylamino group, a diallylamino group, a benzylamino group, a dibenzylamino group, a nitro group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, a pyrrolyl group, a bistriflylimide group, a pyridinyl group, a pyrimidinyl group, a quinolinyl group, a triazinyl group, an oxazoline group, an imidazole group, an indole group, and a carbazole group.

[0071] The phosphorus-containing group may, for example, be a hexafluorophosphate anion.

[0072] Among the above examples, R is preferably a halogen atom or a halogen-containing group, and particularly preferably a fluorine atom or a fluorine-containing group. In addition, in at least one Q in formula [b5], at least one R in formula [b6] is preferably an oxygen-containing group or a silicon-containing group.

[0073] Specific structures of the formula [b5] include triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(3,5-ditrifluoromethylphenyl)borate, tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate, tris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl)borate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis(o-tolyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(2,4-dimethylphenyl)borate, tri( n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(4-trifluoromethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-ditrifluoromethylphenyl)borate, tri(n-butyl)ammonium tetrakis(o-tolyl)borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis(p-tolyl)borate, dioctadecylmethylammonium tetrakis(o-tolyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(4-trifluoromethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-dimethylanilinium tri(pentafluorophenyl)(p-hydroxyphenyl)borate, N,N-dimethylanilinium tri Examples include (pentafluorophenyl)(p-chlorodimethylsilyltetrafluorophenyl)borate, N,N-dimethylanilinium tri(pentafluorophenyl)(p-chlorodiphenylsilyltetrafluorophenyl)borate, N,N,2,4,6-pentamethylanilinium tetraphenylborate, N,N,2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, diisopropylammonium tetrakis(pentafluorophenyl)borate, and dicyclohexylammonium tetraphenylborate.

[0074] The ionic compound (B-II) may be used alone or in combination of two or more kinds.

[0075] <Organoaluminum Compounds (D)> In the olefin polymerization catalyst of the present invention, an organoaluminum compound (D) represented by the following general formula [b6] may be used together with the component (B).

[0076] R a m Al(OR b ) n H p X q …[b6] In formula [b6], R a and R brepresent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other; X represents a halogen atom; m is an integer of 1 to 3, n is an integer of 0 to 2, p is an integer of 0 to 2, q is an integer of 0 to 2, and m+n+p+q=3.

[0077] The hydrocarbon group having 1 to 15 carbon atoms is, for example, an alkyl group, a cycloalkyl group, or an aryl group, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a tolyl group.

[0078] Specific examples of the organoaluminum compound (D) include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and dimethylaluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum sesquibromide, and the like. Examples of the aluminum hydride include alkyl aluminum dihalides such as aluminum dichloride and ethyl aluminum dibromide; alkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, dihydrophenyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, diisohexyl aluminum hydride, diphenyl aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride and di-sec-nonyl aluminum hydride; and dialkyl aluminum alkoxides such as dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum methoxide and diisobutyl aluminum ethoxide.

[0079] Among the above, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diisobutylaluminum hydride, and diethylaluminum ethoxide are particularly preferred.

[0080] <Transition metal compound (C)> The transition metal compound (C) used in the present invention is not particularly limited, and examples thereof include transition metal compounds used in conventionally known olefin polymerization catalysts, specifically compounds represented by the following general formula (CI):

[0081] L m MX n ···(CI) In the general formula (CI), M is an atom selected from the group consisting of atoms of Groups 3, 4, 5, 6, 7, 8, 9, 10, and 11 of the periodic table, and lanthanide atoms, and is preferably a transition metal atom of Groups 4 and 10 of the periodic table, specifically a titanium atom, zirconium atom, hafnium atom, palladium atom, or nickel atom.

[0082] L is selected from the group consisting of η-bonding cyclic anionic ligands, σ-bonding anionic ligands, and π-bonding neutral ligands, and multiple Ls may be the same or different, and multiple Ls may be connected by a substituent in L.

[0083] Examples of the η-bonding cyclic anionic ligand include a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, an octahydrofluorenyl group, and an octamethyloctahydrofluorenyl group, and these ligands may further have other substituents.

[0084] The σ-bonding anionic ligand is a compound that contains at least one atom selected from the group consisting of oxygen, boron, nitrogen, phosphorus, sulfur, and selenium, and forms a monovalent σ-bond with M in formula (CI).

[0085] The π-bonding neutral ligand is a compound that contains at least one atom selected from the group consisting of oxygen, boron, nitrogen, phosphorus, sulfur, and selenium, and can coordinate to M in the general formula (CI) via a lone electron pair.

[0086] m is an integer of 0 or greater. n is an integer of 1 or more and 6 or less that satisfies the valence of M, and preferably 1 or more and 4 or less.

[0087] X is selected from the group consisting of a hydrogen atom, a hydrocarbon group having from 1 to 40 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, and a diene derivative group. When n is 2 or more, multiple Xs may be the same or different and may bond to each other to form a ring. Preferred are a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, and a conjugated diene derivative group.

[0088] Examples of the hydrocarbon group, halogen atom, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, and phosphorus-containing group include the same groups as those exemplified as R in formula [b6].

[0089] The diene derivative group is a hydrocarbon compound capable of coordinating with M in general formula (CI) via a lone electron pair, and examples thereof include a 1,3-butadienyl group, an isoprenyl group (2-methyl-1,3-butadienyl group), a piperylenyl group (1,3-pentadienyl group), a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group, a cyclopentadienyl group, a metallocyclopentenyl group, and a 1,5-cyclooctadienyl group.

[0090] Examples of such transition metal compounds (C) include those disclosed in JP-A-61-211307, JP-A-5-148317, JP-A-6-239914, WO 2001 / 27124, JP-A-2003-206310, JP-A-2004-2259, JP-A-2004-269825, JP-A-2009-143901, and JP-A-2009-143902. -537656, JP 2011-127121, JP 2012-255165, WO 2014 / 50817, WO 2014 / 123212, JP 2015-500920, JP 2016-527182, JP 2017-535518, JP 2018-58780, JP 2019-59934 Examples of the transition metal compounds include those described in JP-A-5-148317, JP-A-2020-117711, and US Pat. No. 5,272,236, and preferably include at least one compound selected from the group consisting of the compound represented by the general formula [I] in JP-A-5-148317, the compound represented by the general formula (II) in WO 2003 / 091262, the compound represented by the general formula (I) and the compound represented by the general formula (XIVb) in JP-A-2003-206310, the compound represented by the general formula (I) in JP-A-2012-255165, the compound represented by the general formula [2] in JP-A-2020-117711, and the compound represented by the general formula (I) in US Pat. No. 5,272,236.

[0091] Examples of other transition metal compounds (C) include titanium tetrahalides such as TiCl4, TiBr4, ZrCl4, and HfCl4, zirconium tetrahalides, and hafnium tetrahalides; alkoxytitanium trihalides such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(On-C4H9)Cl3, Ti(OC2H5)Br3, and Ti(O-iso-C4H9)Br3; Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, and Ti Examples include dihalogenated dialkoxytitanium compounds such as (O-C4H9)2Cl2 and Ti(OC2H5)2Br2; monohalogenated trialkoxytitanium compounds such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(On-C4H9)3Cl and Ti(OC2H5)3Br; and tetraalkoxytitanium compounds such as Ti(OCH3)4, Ti(OC2H5)4, Ti(On-C4H9)4, Ti(O-iso-C4H9)4 and Ti(O-2-ethylhexyl)4.

[0092] The olefin polymerization catalyst of the present invention, which contains the carbon material (A), the component (B), and the transition metal compound (C), can produce an olefin polymer in which the carbon material is efficiently dispersed, with high polymerization activity.

[0093] The reason why the present invention exhibits its effects is not entirely clear, but the inventors speculate as follows.

[0094] The carbon material (A) that satisfies the requirements (AI) and (A-II) has an oxygen atom-containing functional group and sp that can come into contact with the component (B) and / or the transition metal compound (C). 2The large number of two-dimensional sheet structures formed by bonded carbon allows component (B) and / or transition metal compound (C) to be immobilized at more locations in the carbon material (A) through chemical bonds or electronic interactions. It is therefore presumed that the olefin polymerization catalyst of the present invention can produce an olefin polymer in which the carbon material is efficiently dispersed. Surprisingly, when a carbon material (A) that satisfies the above requirements (AI) and (A-II) is used, a higher polymerization activity can be achieved even with a smaller amount of component (B) and / or transition metal compound (C) immobilized compared to when a conventionally known carrier such as silica gel is used. This phenomenon is due to the sp 2 It is presumed that the two-dimensional sheet structure formed by the bonded carbon results in some kind of electronic effect on component (B) and / or the transition metal compound (C), and this is a technology that even a person skilled in the art would not easily discover.

[0095] <Method for preparing an olefin polymerization catalyst> One preferred embodiment of the olefin polymerization catalyst of the present invention is a solid catalyst component (X) prepared by contacting the carbon material (A), the component (B), and the transition metal compound (C).

[0096] If the component (B) and the transition metal compound (C) are liquid, they are preferably diluted with an inert solvent, or if they are solid, they are dissolved in an inert solvent and then brought into contact with the carbon material (A). Examples of inert solvents that can be used include aromatic hydrocarbons such as benzene, toluene, and xylene, saturated aliphatic hydrocarbons such as hexane, heptane, and decane, alicyclic hydrocarbons such as cyclohexane and methylcyclopentane, halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and mixtures thereof.

[0097] The method for contacting the carbon material (A), the component (B), and the transition metal compound (C) is not particularly limited as long as the effects of the present invention are achieved. Examples of such a method include a method of adding an inert solvent containing the component (B) or the transition metal compound (C) to the carbon material (A) and allowing the pores of the carbon material (A) to be impregnated with the component (B) or the transition metal compound (C), a method of immersing the carbon material (A) in an inert solvent containing the component (B) or the transition metal compound (C) and allowing the carbon material (A) to stand, a method of mixing the carbon material (A) with an inert solvent containing the component (B) or the transition metal compound (C) by stirring, or a method of passing an inert solvent containing the component (B) or the transition metal compound (C) through the carbon material (A). The carbon material (A) may be physically or chemically immobilized on a solid support (including powder, granulated particles, fibers, and films), and may be heated during the contact.

[0098] Among these, a method in which the carbon material (A) and an inert solvent containing the component (B) or the transition metal compound (C) are mixed by stirring or the like is preferred. After the contacting operation, if necessary, the contact liquid may be left to stand and the supernatant liquid may be removed, or the inert solvent may be removed by a method such as filtration, and the mixture may be washed with the inert solvent, if necessary.

[0099] The temperature when the heating operation is carried out varies depending on the solvent used, but is usually from the freezing point of the solvent to 200° C. or less, preferably 150° C. or less. The contact time varies depending on the contact method and temperature, but is usually from 30 seconds to 1,000 hours or less, preferably from 5 minutes to 120 hours.

[0100] In any step of the contact method, the presence of component (G) can further suppress fouling during the polymerization reaction and further improve the particle properties of the resulting polymer. As component (G), a compound having a polar functional group can be used, and nonionic surfactants are preferred, with polyalkylene oxide blocks, higher aliphatic amides, polyalkylene oxides, polyalkylene oxide alkyl ethers, alkyldiethanolamines, polyoxyalkylene alkylamines, glycerin fatty acid esters, and N-acylamino acids being more preferred. These may be used alone or in combination of two or more.

[0101] The order of contacting the carbon material (A), the component (B), and the transition metal compound (C) is not particularly limited as long as the effects of the present invention are exhibited. A step (1-1) of contacting the carbon material (A) with the component (B); a step (1-2) of contacting the contact product obtained in the step (1-1) with the transition metal compound (C) to obtain a solid catalyst component (X); A step (2-1) of contacting the carbon material (A) with the component (B); a step (2-2) of contacting the transition metal compound (C) with the component (B); and a step (2-3) of contacting the contact product obtained in the step (2-1) with the contact product obtained in the step (2-2) to obtain a solid catalyst component (X). In this case, the component (B) used in the step (2-1) and the component (B) used in the step (2-2) may be the same or different.

[0102] In the steps (1-1) and (2-1), when the component (B) is the organoaluminum oxy compound (BI), the component (B) can be used in an amount of preferably 0.1 mmol to 500 mmol, more preferably 0.2 mmol to 200 mmol, and even more preferably 0.5 mmol to 100 mmol, per 1 g of the carbon material (A). When the component (B) is the ionic compound (B-II), the component (B) can be used in an amount of preferably 0.0001 mmol to 200 mmol, more preferably 0.001 mmol to 100 mmol, and even more preferably 0.002 mmol to 50 mmol, per 1 g of the carbon material (A).

[0103] In the step (2-2), when the component (B) is the organoaluminum oxy compound (BI), the component (B) can be used in an amount of preferably 0.1 mmol to 500 mmol, more preferably 0.2 mmol to 200 mmol, and even more preferably 0.5 mmol to 100 mmol, per 1 mmol of the transition metal compound (C). When the component (B) is the ionic compound (B-II), the component (B) can be used in an amount of preferably 0.1 mmol to 500 mmol, more preferably 0.2 mmol to 200 mmol, and even more preferably 0.5 mmol to 100 mmol, per 1 mmol of the transition metal compound (C).

[0104] In the steps (1-2) and (2-3), the transition metal compound (C) can be used in an amount of preferably 0.0001 mmol or more and 1 mmol or less, more preferably 0.0005 mmol or more and 0.5 mmol or less, and even more preferably 0.001 mmol or more and 0.2 mmol or less, per 1 g of the carbon material (A).

[0105] For the production of olefin polymers, the solid catalyst component (X) may be used in a state of being suspended in an inert hydrocarbon or in a dried state, or may be used after prepolymerization with an olefin which may be the same as or different from the olefin used for the production of the olefin polymer.

[0106] [Production method of olefin polymer] The method for producing an olefin polymer of the present invention is characterized by comprising a step of polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst of the present invention. In the present invention, the term "polymerization" may include not only homopolymerization but also copolymerization such as random copolymerization and block copolymerization.

[0107] The olefins to be polymerized in the present invention include ethylene, α-olefins, and cyclic olefins.

[0108] Among these, the α-olefins include linear or branched α-olefins having from 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms. More specific examples include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among these, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1-pentene are preferred, and propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene are more preferred.

[0109] Examples of the cyclic olefin include cyclic olefins having from 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms. More specific examples include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0110] The step of polymerizing an olefin is preferably a step of homopolymerizing ethylene, a step of copolymerizing ethylene and one or more α-olefins having from 3 to 20 carbon atoms, a step of homopolymerizing propylene, a step of copolymerizing propylene and one or more α-olefins having from 4 to 20 carbon atoms, a step of homopolymerizing 4-methyl-1-pentene, or a step of copolymerizing 4-methyl-1-pentene and one or more α-olefins having from 4 to 20 carbon atoms, in the presence of the solid catalyst component (X).

[0111] In the method for producing an olefin polymer of the present invention, polymerization can be carried out either by a liquid phase polymerization method such as suspension polymerization or by a gas phase polymerization method. Examples of inert hydrocarbon media used in liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and mixtures thereof. The olefin itself can also be used as the solvent.

[0112] In the method of the present invention, the lower limit of the temperature for polymerizing olefins is −20° C., preferably 0° C., more preferably 20° C., and particularly preferably 30° C., and the upper limit of the temperature for polymerizing olefins is 200° C., preferably 150° C., more preferably 100° C., and particularly preferably 80° C.

[0113] The polymerization pressure in the method of the present invention is usually from atmospheric pressure to 10 MPa, preferably from atmospheric pressure to 5 MPa, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous systems.

[0114] The method for producing an olefin polymer of the present invention may be a so-called multi-stage polymerization method in which the reaction is carried out in two or more stages under different polymerization reaction conditions.

[0115] The molecular weight of the resulting olefin polymer can be adjusted by making hydrogen present in the polymerization system or by changing the polymerization temperature.

[0116] In the step of polymerizing the olefin, the organoaluminum compound (D) and the component (G) can be present together for the purpose of suppressing adhesion (fouling) to the polymerization reactor or improving particle properties.

[0117] <Olefin polymer> Examples of an embodiment of the olefin polymer obtainable by the method for producing an olefin polymer of the present invention include an ethylene-based polymer containing ethylene-derived structural units in a range of preferably 90 mol% to 100 mol%, more preferably 95 mol% to 100 mol%; a propylene-based polymer containing propylene-derived structural units in a range of preferably 80 mol% to 100 mol%, more preferably 90 mol% to 100 mol%; and a 4-methyl-1-pentene-based polymer containing 4-methyl-1-pentene-derived structural units in a range of preferably 80 mol% to 100 mol%, more preferably 90 mol% to 100 mol%.

[0118] The ethylene polymer preferably contains a total of 0 mol % to 10 mol %, more preferably 0 mol % to 5 mol %, of structural units derived from an α-olefin having from 3 to 20 carbon atoms, where the sum of the content of ethylene-derived structural units and the content of structural units derived from an α-olefin having from 3 to 20 carbon atoms is taken as 100 mol %.

[0119] The propylene-based polymer preferably contains structural units derived from ethylene and an α-olefin having from 4 to 20 carbon atoms in a total amount of from 0 mol % to 20 mol %, more preferably from 0 mol % to 10 mol %, where the total of the content of structural units derived from propylene and the content of structural units derived from ethylene and an α-olefin having from 4 to 20 carbon atoms is taken to be 100 mol %.

[0120] The 4-methyl-1-pentene polymer preferably contains structural units derived from ethylene and α-olefins other than 4-methyl-1-pentene having from 3 to 20 carbon atoms in a total amount of from 0 mol % to 20 mol %, more preferably from 0 mol % to 10 mol %, where the sum of the content of structural units derived from 4-methyl-1-pentene and the content of structural units derived from ethylene and α-olefins other than 4-methyl-1-pentene having from 3 to 20 carbon atoms is taken as 100 mol %.

[0121] Among these polymers, ethylene homopolymer, propylene homopolymer, 4-methyl-1-pentene homopolymer, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / 4-methyl-1-pentene copolymer, propylene / 4-methyl-1-pentene copolymer, 4-methyl-1-pentene / 1-decene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / propylene / 1-octene copolymer, ethylene / propylene / 1-hexene copolymer, and ethylene / propylene / 4-methyl-1-pentene copolymer are preferred. Also suitable are so-called block copolymers (impact copolymers) obtained by mixing or continuously producing two or more polymers selected from these polymers.

[0122] The olefin polymer obtained by the method for producing an olefin polymer contains the carbon material (A) in an amount of preferably 0.005% by weight to 25% by weight, more preferably 0.01% by weight to 10% by weight. The carbon material (A) is efficiently dispersed in the olefin polymer, and is expected to have high thermal conductivity, electrical conductivity, and weather resistance. [Example]

[0123] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples in any way.

[0124] [Carbon materials] The following carbon materials (A-1) to (A-6) and (A'-7) to (A'-8) were used as the carbon materials. Each of the carbon materials was dried under reduced pressure at 100°C for 3 hours before use, and then cooled to room temperature under a nitrogen atmosphere before being used to prepare the solid catalyst component (X).

[0125] Carbon material (A-1): XG Sciences Graphene Nanoplatelets xGnP C750 Carbon material (A-2): Graphitene Reduced Graphene Oxide Carbon material (A-3): Nanocyl Multi-Walled Carbon nanotubes NANOCYL NC3101 Carbon material (A-4): IoLiTec Multi-Walled Carbon Nanotubes -OH functionalized CP-0069-SG Carbon Materials (A-5): Toyo Tanso Co., Ltd. Porous Carbon CNоvel MJ(4)010 Carbon material (A-6): Nippon Graphite Co., Ltd. High-purity graphite powder SP-270 Carbon material (A'-7): Graphitene Graphene Nanocarbon platelets - Powder Carbon material (A'-8): Southwest Nanotechnologies Single Walled Carbon nanotubes Signis SG65i

[0126] <Oxygen content> The oxygen content of the carbon material was determined by X-ray photoelectron spectroscopy (XPS) (AXIS-NOVA, manufactured by KRATOS). The sample was dried under reduced pressure at 100°C for 3 hours, then handled in a nitrogen atmosphere and measured using a monochromated AlKα X-ray source. Charge correction and neutralization were performed during the measurement. The oxygen atom concentration was determined from the peak area of ​​the O1s narrow spectrum, and the carbon atom concentration was determined from the peak area of ​​the C1s narrow spectrum, and the molar ratio of oxygen atoms to carbon atoms was calculated. The results are shown in Table 1.

[0127] ≪Specific surface area≫ The specific surface area of ​​the carbon material was measured by measuring the adsorption / desorption isotherm using nitrogen gas adsorption (Microtrac-Bell "BELSORP-max") at liquid nitrogen temperature. The specific surface area was determined using the BET multipoint method. The analytical results are shown in Table 1.

[0128] [Component (B)] As component (B), the following components (B-1) to (B-4) were used. Ingredient (B-1): Methylaluminoxane (MAO) Component (B-2): Modified methylaluminoxane (MMAO-3A) Component (B-3): a compound represented by the following formula (B-3): Component (B-4): a compound represented by the following formula (B-4):

[0129] [ka]

[0130] [Transition metal compounds] As the transition metal compounds, transition metal compounds (C-1) to (C-10) represented by the following formulas (C-1) to (C-10) were used.

[0131] [ka]

[0132] [Preparation of solid catalyst component (X)] <Preparation Example 1> A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of carbon material (A-1) and 19.5 mL of toluene. Stirring was initiated using a rotor. 0.50 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atoms) was added to this suspension as component (B). Stirring was continued at room temperature for 2 hours, after which stirring was stopped and the mixture was allowed to stand. The supernatant was removed by decantation and analyzed. The Al concentration in the supernatant was found to be below the lower limit of quantitation (less than 0.19 mmol / L). After washing twice with toluene, 2.0 mL of a toluene solution of transition metal compound (C-1) (1.0 mmol / L in terms of Zr atoms) was added. Stirring was continued at room temperature for an additional 30 minutes to prepare a slurry of solid catalyst component (X-1) with a carbon material (A-1) solid concentration of 10.0 g / L.

[0133] <Preparation Example 2> A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of carbon material (A-2) and 19.2 mL of toluene. Stirring was initiated using a rotor. 0.80 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atoms) was added to this suspension as component (B). Stirring was continued at room temperature for 2 hours, after which stirring was stopped and the mixture was allowed to stand. The supernatant was removed by decantation. Analysis of the supernatant revealed that the Al concentration in the supernatant was below the lower limit of quantitation (less than 0.19 mmol / L). After further washing with toluene twice, 2.0 mL of a toluene solution of transition metal compound (C-1) (1.0 mmol / L in terms of Zr atoms) was added. Stirring was continued at room temperature for an additional 30 minutes to prepare a slurry of solid catalyst component (X-2) with a carbon material (A-2) solid concentration of 10.0 g / L.

[0134] <Preparation Examples 3 to 6> Slurries of solid catalyst components (X-3) to (X-6) were prepared in the same manner as in Preparation Example 1, except that carbon materials (A-3) to (A-6) were used instead of carbon material (A-1).

[0135] <Preparation Example 7> A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of carbon material (A'-7) and 19.5 mL of toluene. Stirring was initiated using a rotor. 0.50 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atoms) was added to this suspension as component (B). Stirring was continued at room temperature for 2 hours, after which the stirring was stopped and the mixture was allowed to stand. The supernatant was removed by decantation and analyzed. The Al concentration in the supernatant was found to be 24 mmol / L. After washing twice with toluene, 2.0 mL of a toluene solution of transition metal compound (C-1) (1.0 mmol / L in terms of Zr atoms) was added. Stirring was continued at room temperature for an additional 30 minutes to prepare a slurry of solid catalyst component (X-7) with a solid concentration of carbon material (A'-7) of 10.0 g / L.

[0136] <Preparation Example 8> A slurry of a solid catalyst component (X-8) was prepared in the same manner as in Preparation Example 7, except that the carbon material (A'-8) was used instead of the carbon material (A'-7).

[0137] <Preparation Example 9> In a 30 mL Schlenk tube that had been thoroughly purged with nitrogen, silica gel (particle size: 70 μm, specific surface area: 340 m 2 / g, pore volume: 1.3cm 3 200 mg of (Zr / g) and 19.0 mL of toluene were added, and stirring was initiated using a rotor. To this suspension, 1.0 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atoms) was added as component (B). Stirring was continued at room temperature for 2 hours, after which stirring was stopped and the suspension was allowed to stand. The supernatant was removed by decantation, and analysis of this supernatant revealed that the Al concentration in the supernatant was 2.0 mmol / L. After further washing with toluene twice, 4.0 mL of a toluene solution of transition metal compound (C-1) (1.0 mmol / L in terms of Zr) was added, and stirring was continued for an additional 30 minutes at room temperature to prepare a slurry of solid catalyst component (X-9) with a silica gel solid concentration of 10.0 g / L.

[0138] <Preparation Example 10> A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of carbon material (A-1) and 19.5 mL of toluene. Stirring was initiated using a rotor. 0.50 mL of a hexane solution of component (B-2) (1.0 mol / L in terms of Al atoms) was added to this suspension as component (B). Stirring was continued at room temperature for 2 hours, after which stirring was stopped and the mixture was allowed to stand. The supernatant was removed by decantation. Analysis of this supernatant revealed that the Al concentration in the supernatant was below the lower limit of quantitation (less than 0.19 mmol / L). After further washing with toluene twice, 2.0 mL of a toluene solution of transition metal compound (C-1) (1.0 mmol / L in terms of Zr atoms) was added. Stirring was continued at room temperature for an additional 30 minutes to prepare a slurry of solid catalyst component (X-10) with a carbon material (A-1) solid concentration of 10.0 g / L.

[0139] <Preparation Example 11> A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of carbon material (A-1) and 8.0 mL of toluene. Stirring was initiated using a rotor. To this suspension, 12.0 mL of a toluene solution of component (B-3) (1.0 mmol / L in terms of B atoms) was added as component (B). Stirring was continued at room temperature for 2 hours, after which the stirring was stopped and the mixture was allowed to stand. The supernatant was removed by decantation, and the mixture was washed twice with toluene. 3.0 mL of a toluene solution of transition metal compound (C-1) and triisobutylaluminum (1.0 mmol / L in terms of Zr, 30 mmol / L in terms of Al) was added, and the mixture was stirred at room temperature for an additional 30 minutes to prepare a slurry of solid catalyst component (X-11) with a solid concentration of carbon material (A-1) of 10.0 g / L.

[0140] <Preparation Example 12> A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of carbon material (A-1) and 19.8 mL of toluene. Stirring was initiated using a rotor. 0.20 mL of a toluene solution of triisobutylaluminum (1.0 mol / L in terms of Al) was added to this suspension. Stirring was continued at room temperature for 30 minutes, after which the stirring was stopped and the mixture was allowed to stand. The supernatant was removed by decantation, and the mixture was washed twice with toluene. Next, 12.0 mL of a toluene solution of component (B-4) (1.0 mmol / L in terms of B atoms) was added as component (B), and stirring was continued at room temperature for 1 hour. The stirring was then stopped and the mixture was allowed to stand. The supernatant was removed by decantation, and the mixture was washed twice with toluene. To this was added 3.0 mL of a toluene solution (1.0 mmol / L in terms of Zr, 30 mmol / L in terms of Al) containing a mixture of the transition metal compound (C-1) and triisobutylaluminum, and the mixture was stirred at room temperature for a further 30 minutes to prepare a slurry of the solid catalyst component (X-12) with a solid concentration of the carbon material (A-1) of 10.0 g / L.

[0141] <Preparation Example 13> A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of carbon material (A-1) and 19.8 mL of toluene. Stirring was initiated using a rotor. 0.20 mL of a toluene solution of triisobutylaluminum (1.0 mol / L in terms of Al) was added to the suspension, and stirring was continued at room temperature for 30 minutes. The stirring was then stopped and the suspension was allowed to stand. The supernatant was removed by decantation, and the suspension was washed twice with toluene. 3.0 mL of a toluene solution of transition metal compound (C-1) (1.0 mmol / L in terms of Zr) was added to the suspension, and stirring was continued at room temperature for another 30 minutes to prepare a slurry of solid catalyst component (X-13) with a solid concentration of carbon material (A-1) of 10.0 g / L.

[0142] <Preparation Examples 14-16> Slurries of solid catalyst components (X-14) to (X-16) were prepared in the same manner as in Preparation Example 1, except that transition metal compounds (C-2) to (C-4) were used instead of the transition metal compound (C-1).

[0143] <Preparation Example 17> A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of carbon material (A-1) and 19.8 mL of toluene. Stirring was initiated using a rotor. 0.20 mL of a toluene solution of triethylaluminum (1.0 mol / L in terms of Al) was added to this suspension. Stirring was continued at room temperature for 30 minutes, after which the stirring was stopped and the mixture was allowed to stand. The supernatant was removed by decantation, and the mixture was washed twice with toluene. Next, 12.0 mL of a toluene solution of component (B-4) (1.0 mmol / L in terms of B atoms) was added as component (B), and stirring was continued at room temperature for 1 hour. The stirring was then stopped and the mixture was allowed to stand. The supernatant was removed by decantation, and the mixture was washed twice with toluene. To this was added 3.0 mL of a toluene solution of the transition metal compound (C-5) (1.0 mmol / L in terms of Ti), and the mixture was stirred at room temperature for a further 30 minutes to prepare a slurry of the solid catalyst component (X-17) with a solid concentration of the carbon material (A-1) of 10.0 g / L.

[0144] <Preparation Example 18> A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of carbon material (A-1) and 19.5 mL of toluene. Stirring was initiated using a rotor. 0.50 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atom) was added to this suspension as component (B). Stirring was continued at room temperature for 2 hours, after which the stirring was stopped and the mixture was allowed to stand. The supernatant was removed by decantation, and the mixture was washed twice with toluene. 0.050 mL of a toluene solution of transition metal compound (C-6) (0.10 mol / L in terms of Ti atom) was added. Stirring was continued at room temperature for another 30 minutes to prepare a slurry of solid catalyst component (X-18) with a carbon material (A-1) solid concentration of 10.0 g / L.

[0145] <Preparation Examples 19-21> Slurries of solid catalyst components (X-19) to (X-21) were prepared in the same manner as in Preparation Example 1, except that the transition metal compounds (C-7) to (C-9) were used instead of the transition metal compound (C-1).

[0146] <Preparation Example 22> A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of carbon material (A-4) and 19.5 mL of toluene. Stirring was initiated using a rotor. 0.50 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atom) was added to this suspension as component (B). Stirring was continued at room temperature for 2 hours, after which the stirring was stopped and the mixture was allowed to stand. The supernatant was removed by decantation, and the mixture was washed twice with toluene. 0.10 mL of a toluene solution of transition metal compound (C-9) (0.02 mol / L in terms of Zr) was added, and the mixture was stirred at room temperature for an additional 30 minutes to prepare a slurry of solid catalyst component (X-22) with a solid concentration of carbon material (A-4) of 10.0 g / L.

[0147] <Preparation Example 23> A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of carbon material (A-3) and 19.5 mL of toluene. Stirring was initiated using a rotor. 0.50 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atom) was added to this suspension as component (B). Stirring was continued at room temperature for 2 hours, after which the stirring was stopped and the mixture was allowed to stand. The supernatant was removed by decantation, and the mixture was washed twice with toluene. 0.050 mL of a toluene solution of transition metal compound (C-10) (0.10 mol / L in terms of Zr) was added. Stirring was continued at room temperature for another 30 minutes to prepare a slurry of solid catalyst component (X-23) with a solid concentration of carbon material (A-3) of 10.0 g / L.

[0148] <Metal concentration in the supernatant liquid during preparation of solid catalyst component (X)> The metal (Al) concentration in the supernatant liquid during the preparation of the solid catalyst component (X) was determined by ICP atomic emission spectrometry (ICP-AES) (ICPS-8100, manufactured by Shimadzu Corporation).

[0149] [Production of olefin polymers] Example 1 500 mL of heptane was added to a 1-L stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor with ethylene. Next, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al) and a slurry equivalent to 30 mg of the solid carbon material (A-1) were extracted from the slurry of the solid catalyst component (X-1) obtained in Preparation Example 1 and charged into the reactor. The temperature and pressure were then increased to 80°C and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes at 350 rpm using ethylene. After completion of the reaction, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 94.3 g of an olefin polymer. The weight-average molecular weight (Mw) of the resulting olefin polymer was 2,450,000.

[0150] <Examples 2 to 6> Polymerization reactions were carried out in the same manner as in Example 1, except that slurries of solid catalyst components (X-2) to (X-6) obtained in Preparation Examples 2 to 6 were used instead of solid catalyst component (X-1), and the amounts of the carbon material solids listed in Table 1 were charged into the reactor. After completion of the reaction, the contents in the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding the amounts of olefin polymers listed in Table 1.

[0151] <Comparative Examples 1 to 3> Polymerization reactions were carried out in the same manner as in Example 1, except that slurries of solid catalyst components (X-7) to (X-9) obtained in Preparation Examples 7 to 9 were used instead of solid catalyst component (X-1), and the amounts of carbon material or silica gel solid content shown in Table 1 were charged into the reactor. After completion of the reaction, the contents in the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding the amounts of olefin polymers shown in Table 1.

[0152] [Table 1]

[0153] The carbon material (A) constituting the olefin polymerization catalyst of the example has both a high specific surface area and a high oxygen content, and it is clear that a larger amount of olefin polymer can be obtained compared to a carbon material having a low specific surface area or oxygen content, and a comparative example using silica gel, which is generally used as a support for olefin polymerization catalysts.

[0154] <Examples 7 to 9> Polymerization reactions were carried out in the same manner as in Example 1, except that slurries of the solid catalyst components (X-10) to (X-12) obtained in Preparation Examples 10 to 12 were used instead of the solid catalyst component (X-1), and the amounts of the carbon material (A) solid content listed in Table 2 were charged into the reactor. After completion of the reaction, the contents in the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding the amounts of olefin polymers listed in Table 2.

[0155] <Comparative Example 4> A polymerization reaction was carried out in the same manner as in Example 1, except that the slurry of the solid catalyst component (X-13) obtained in Preparation Example 13 was used instead of the solid catalyst component (X-1), and the amount of the carbon material (A) solid content shown in Table 2 was charged into the reactor. After completion of the reaction, the content in the reactor was filtered and dried under reduced pressure at 80°C for 10 hours, thereby obtaining the amount of olefin polymer shown in Table 2.

[0156] [Table 2]

[0157] It is clear that the Examples using component (B) yielded a larger amount of olefin polymer than the Comparative Examples not using component (B).

[0158] Example 10 500 mL of heptane was added to a 1-L stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor with ethylene. Next, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al) and a slurry equivalent to 20 mg of the solid carbon material (A-1) were extracted from the slurry of the solid catalyst component (X-14) obtained in Preparation Example 14 and charged into the reactor. The temperature and pressure were then increased to 80°C and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes at 350 rpm using ethylene. After completion of the reaction, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 48.8 g of an olefin polymer. The weight-average molecular weight (Mw) of the resulting olefin polymer was 2,110,000.

[0159] Example 11 500 mL of heptane was added to a 1-L stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor with ethylene. Next, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al) and a slurry equivalent to 50 mg of the solid carbon material (A-1) were extracted from the slurry of the solid catalyst component (X-15) obtained in Preparation Example 15 and charged into the reactor. The temperature and pressure were then increased to 50°C and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes at 350 rpm using ethylene. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 12.5 g of an olefin polymer. The weight-average molecular weight (Mw) of the resulting olefin polymer was 3,780,000.

[0160] Example 12 500 mL of heptane was added to a 1-L stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor with ethylene. Next, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al) and a slurry equivalent to 50 mg of the solid carbon material (A-1) were extracted from the slurry of the solid catalyst component (X-16) obtained in Preparation Example 16 and charged into the reactor. The temperature and pressure were then increased to 80°C and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes at 350 rpm using ethylene. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 28.4 g of olefin polymer.

[0161] Example 13 500 mL of heptane was added to a 1-L stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor with ethylene. Next, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al) and a slurry equivalent to 30 mg of the solid carbon material (A-1) were extracted from the slurry of the solid catalyst component (X-17) obtained in Preparation Example 17 and charged into the reactor. The temperature and pressure were then increased to 80°C and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes at 350 rpm using ethylene. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 91.3 g of an olefin polymer. The weight-average molecular weight (Mw) of the resulting olefin polymer was 2,460,000.

[0162] Example 14 500 mL of heptane was added to a 1-L stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor with ethylene. Next, 0.375 mL of a decane solution of triethylaluminum (1.0 mol / L in terms of Al) and a slurry equivalent to 50 mg of the solid carbon material (A-1) were extracted from the slurry of the solid catalyst component (X-18) obtained in Preparation Example 18 and charged into the reactor. The temperature and pressure were then increased to 80°C and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes at 350 rpm using ethylene. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 8.53 g of olefin polymer. The weight-average molecular weight (Mw) of the resulting olefin polymer was 4,230,000.

[0163] Example 15 500 mL of heptane was added to a 1-L stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor with ethylene. Next, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al) and a slurry equivalent to 50 mg of the solid carbon material (A-1) were extracted from the slurry of the solid catalyst component (X-19) obtained in Preparation Example 19 and charged into the reactor. The temperature and pressure were then increased to 60°C and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes at 350 rpm using ethylene. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 12.4 g of an olefin polymer. The weight-average molecular weight (Mw) of the resulting olefin polymer was 138,000 and the melting point was 123°C.

[0164] Example 16 500 mL of heptane was added to a 1-L stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al), and a slurry equivalent to 20 mg of the solid carbon material (A) from the slurry of the solid catalyst component (X-20) obtained in Preparation Example 20 were extracted and charged into the reactor. The temperature and pressure were then increased to 80°C and 0.8 MPaG, and the polymerization reaction was carried out for 60 minutes at 350 rpm using ethylene. After completion of the reaction, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 17.2 g of olefin polymer. The weight-average molecular weight (Mw) of the resulting olefin polymer was 431,000 and the melting point was 124°C.

[0165] Example 17 500 mL of heptane was added to a 1-L stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Propylene was then passed through to saturate the reactor. Next, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al) and a slurry equivalent to 80 mg of carbon material (A) solids were extracted from the slurry of the solid catalyst component (X-21) obtained in Preparation Example 21 and charged into the reactor. 100 mL of hydrogen was then added, and the temperature and pressure were raised to 70°C and 0.5 MPaG with propylene, and the polymerization reaction was carried out for 60 minutes at 350 rpm. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 15.4 g of olefin polymer. The weight-average molecular weight (Mw) of the resulting olefin polymer was 202,000 and the melting point was 161°C.

[0166] Example 18 A 1-liter glass reactor, thoroughly purged with nitrogen, was charged with 400 mL of 4-methyl-1-pentene under a nitrogen atmosphere. The temperature was raised to 40°C. Hydrogen was passed through at 0.50 L / hr. Then, 0.20 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al) was added. A slurry equivalent to 80 mg of the solid carbon material (A) was extracted from the slurry of the solid catalyst component (X-22) obtained in Preparation Example 22 and charged into the reactor. The polymerization reaction was carried out for 60 minutes at 600 rpm. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 5.45 g of olefin polymer. The weight-average molecular weight (Mw) of the resulting olefin polymer was 361,000.

[0167] Example 19 A 1-L stainless steel autoclave reactor, thoroughly purged with nitrogen, was charged with 500 mL of heptane under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor with propylene. Next, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al) and a slurry equivalent to 20 mg of carbon material (A) solids were extracted from the slurry of the solid catalyst component (X-23) obtained in Preparation Example 23 and charged into the reactor. The temperature and pressure were then increased to 80°C and 0.8 MPaG using an ethylene-1-butene mixed gas with a 1-butene concentration of 1.0 vol%, and the polymerization reaction was carried out at 350 rpm for 60 minutes. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 19.4 g of olefin polymer. The resulting olefin polymer had a weight-average molecular weight (Mw) of 754,000 and a melting point of 114°C.

[0168] From the examples using various transition metal compounds (C-1) to (C-10), it is clear that, regardless of the type of transition metal compound, by using a specific carbon material (A), more olefin polymers can be obtained.

[0169] ≪Weight average molecular weight (Mw)≫ The weight average molecular weight (Mw) of the olefin polymer was determined by gel permeation chromatography (GPC) using a Waters Alliance GPC 2000 gel permeation chromatograph (high-temperature size exclusion chromatograph) under the following operating conditions:

[0170] Analysis software: Chromatography data system Empower (Waters) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2 (Inner diameter 7.5mm x length 30cm, Tosoh Corporation) Mobile phase: o-dichlorobenzene Detector: differential refractometer (built-in) Column temperature: 140°C Flow rate; 1.0mL / min Injection volume: 400μL Sampling time interval: 1 second Sample concentration: 0.15% (w / v) Molecular weight calibration: Monodisperse polystyrene (Tosoh Corporation) / molecular weight 495 to 20.6 million

[0171] Melting point (Tm) Using an SII RDC220 differential scanning calorimeter, approximately 5 mg of sample was heated from 30°C to 200°C at a heating rate of 50°C / min under a nitrogen atmosphere and held at that temperature for 10 minutes. The sample was then cooled to 30°C at a heating rate of 10°C / min, held at that temperature for 5 minutes, and then heated to 200°C at a heating rate of 10°C / min. The endothermic peak observed during this second heating was taken as the melting peak, and the temperature at which this melting peak appeared was determined as the melting point (Tm).

Claims

1. A carbon material (A) that satisfies the following requirements (AI) and (A-II); At least one component (B) selected from the group consisting of the following (BI) and (B-II): and a transition metal compound (C) represented by the following general formula (CI): (A-I) The oxygen atom / carbon atom molar ratio measured by X-ray photoelectron spectroscopy (XPS) is 0.018 or more and 0.400 or less; (A-II) Specific surface area by BET multipoint method is 100 m 2 / g or more 5000m 2 / g or less; (B-I) Organoaluminum oxy compounds; (B-II) a compound that reacts with the transition metal compound (C) to form an ion pair; L m MX n ・・・(C-I) [In general formula (C-I), M is an atom selected from the group consisting of atoms of Groups 3, 4, 5, 6, 7, 8, 9, 10, and 11 of the periodic table, and lanthanide atoms; L is selected from the group consisting of η-bonding cyclic anionic ligands, σ-bonding anionic ligands, and π-bonding neutral ligands, and multiple Ls may be the same or different, and multiple Ls may be connected via a substituent in L; m is an integer of 0 or greater, n is an integer of 1 to 6 that satisfies the valence of M; X is selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, and a diene derivative group, and when n is 2 or more, multiple Xs may be the same or different and may be bonded to each other to form a ring.

2. 2. The olefin polymerization catalyst according to claim 1, wherein the oxygen atom / carbon atom molar ratio in the requirement (AI) is 0.020 or more and 0.250 or less.

3. The specific surface area in the above requirement (A-II) is 150 m 2 / g or more 3000m 2 3. The olefin polymerization catalyst according to claim 1, wherein the olefin polymerization catalyst has a molecular weight of 1 / g or less.

4. The olefin polymerization catalyst according to any one of claims 1 to 3, wherein the carbon material (A) comprises at least one selected from the group consisting of carbon nanotubes, graphene, fullerene, graphite, and activated carbon.

5. The olefin polymerization catalyst according to any one of claims 1 to 4, wherein M in the general formula (CI) is a transition metal atom of Group 4 of the periodic table.

6. A method for producing an olefin polymer, comprising a step of polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 5.

7. The method for producing an olefin polymer according to claim 6, wherein the step of polymerizing an olefin is a step of homopolymerizing ethylene or propylene, or a step of copolymerizing ethylene with a linear or branched α-olefin having from 3 to 30 carbon atoms.

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