Catalyst for olefin polymerization and method for producing olefin polymers

Abstract

To provide a catalyst for olefinic polymerization that shows high olefinic polymerization activity even when using a reduced amount of organic aluminum oxy compound, and a method for producing an olefinic polymer using the catalyst.SOLUTION: A catalyst for olefinic polymerization comprises at least one component (A) that is selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride and satisfies the requirement (A-I), at least one component (B) selected from the group consisting of the following (B-I) and (B-II), and a transition metal compound (C). In the requirement (A-I), the molar ratio of oxygen atoms / (boron atoms+aluminum atoms+silicon atoms) by X-ray photoelectron spectroscopy (XPS) is 0.050 or more and less than 2.0. The component (B-I) is an organic aluminum oxy compound and (B-II) is a compound that can react with the transition metal compound (C) to form an ion pair.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] As catalysts used in the production of olefin (co)polymers, catalysts for olefin polymerization consisting of transition metal compounds such as zirconocene and co-catalyst components such as organoaluminum oxy compounds are known. In particular, when performing suspension polymerization or gas-phase polymerization, solid catalysts in which transition metal compounds or organoaluminum oxy compounds are supported on a solid carrier such as silica gel can be used to control the powder properties of the resulting polymer (see, for example, Non-Patent Document 1). However, because organoaluminum oxy compounds are expensive, there is a need to reduce the amount of organoaluminum oxy compounds used and to achieve higher olefin polymerization activity in order to reduce catalyst costs.

[0003] To address these challenges, methods such as using silica gel with specific physical properties or lowering the contact temperature between the transition metal compound and the solid support have been proposed (see, for example, Patent Documents 1 and 2). However, there was still room for further improvement from the viewpoint of olefin polymerization activity. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2012-140606 [Patent Document 2] Japanese Patent Publication No. 2005-298662 [Non-patent literature]

[0005] [Non-Patent Document 1] Chem. Rev. 2005, 105, pp. 4073-4147 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The object of this invention is to provide an olefin polymerization catalyst that exhibits high olefin polymerization activity even when using a smaller amount of organoaluminum oxy compound than conventional catalysts, and a method for producing an olefin polymer using the olefin polymerization catalyst. [Means for solving the problem]

[0007] The inventors of this invention conducted intensive research to solve the above problems. As a result, they discovered that the above problems could be solved by using boron nitride, aluminum nitride, or silicon nitride having specific physical properties, and thus completed the present invention.

[0008] The catalyst for olefin polymerization according to the present invention is A component (A) selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride, and satisfying the following requirement (AI), At least one component (B) selected from the group consisting of (BI) and (B-II) below, A transition metal compound (C) represented by the following general formula (CI) and Includes. (AI) The oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio in X-ray photoelectron spectroscopy (XPS) is between 0.050 and less than 2.0; (BI) Organoaluminum oxy compounds; (B-II) Compounds that react with transition metal compounds (C) to form ion pairs; L m MX n ...(CI) [In the general formula (CI), M is an atom selected from the group consisting of atoms from 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 identical or different from one another, and multiple Ls may be linked together by substituents in L. m is a non-negative integer, n is an integer between 1 and 6 that satisfies the valence of M, X is selected from hydrogen atoms, halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, and diene derivative groups. If n is 2 or more, multiple X groups may be identical or different from each other, and may be bonded together to form a ring. [Effects of the Invention]

[0009] The present invention provides an olefin polymerization catalyst that exhibits high olefin polymerization activity even when using a smaller amount of organoaluminum oxy compound than conventional methods, and a method for producing olefin polymers using the olefin polymerization catalyst. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below. [Catalyst for olefin polymerization] The catalyst for olefin polymerization of the present invention is A component (A) selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride, and satisfying the following requirement (AI), At least one component (B) selected from the group consisting of (BI) and (B-II) below, It is characterized by containing a transition metal compound (C) represented by the following general formula (CI).

[0011] (AI) The oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio in X-ray photoelectron spectroscopy (XPS) is between 0.050 and less than 2.0.

[0012] (BI) Organoaluminum oxy compounds; (B-II) Compounds that react with transition metal compounds (C) to form ion pairs;

[0013] L m MX n ...(CI) In the above general formula (CI), M is an atom selected from the group consisting of atoms from 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 from each other, and multiple Ls may be linked together by substituents in L; m is an integer of 0 or more; n is an integer of 1 to 6 that satisfies the valency of M; X is selected from hydrogen atoms, halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, and diene derivative groups, and if n is 2 or more, multiple Xs may be the same or different from each other, and may be bonded to each other to form a ring.

[0014] The following describes each component constituting the olefin polymerization catalyst of the present invention. <Ingredient (A)> The component (A) used in the present invention is selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride, and satisfies the following requirement (AI).

[0015] (AI) The molar ratio of oxygen atoms to (boron atoms + aluminum atoms + silicon atoms) in X-ray photoelectron spectroscopy (XPS) is 0.050 or more and less than 2.0, preferably 0.050 or more and 1.0 or less, and more preferably 0.060 or more and 0.60 or less.

[0016] The oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio is a value obtained by X-ray photoelectron spectroscopy (XPS) measurement. Specifically, it is obtained by calculating the oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio from the peak areas of oxygen, boron, aluminum, and silicon atoms in the spectrum obtained from component (A).

[0017] A higher oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio is preferable in terms of olefin polymerization activity because it increases the amount of oxygen atoms that can come into contact with component (B), which will be described later. On the other hand, if the oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio becomes too high, the required amount of component (B) increases, which is undesirable in terms of catalyst cost.

[0018] The oxygen atoms in component (A) may be those in which some of the nitrogen atoms in component (A) are replaced by oxygen atoms, may be contained within substituents on component (A), or may be contained in compounds coordinated to or adsorbed on the surface or pores of component (A), but it is preferable that they exist as oxygen atom-containing functional groups within substituents on component (A). Specific examples of oxygen atom-containing functional groups include hydroxyl groups, alkoxy groups, epoxy groups, carbonyl groups, and carboxyl groups.

[0019] The amount of oxygen atoms in component (A) can be controlled by the manufacturing conditions of component (A), heat treatment (e.g., drying, calcination), water absorption treatment, surface modification or modification treatment (e.g., functional group introduction, oxidation treatment, reduction treatment), etc.

[0020] The component (A) is selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride, and as long as it satisfies the above requirement (AI), there are no particular restrictions on its shape, size, or crystal structure. It may be in the form of granules, powder, fibers, or sheets, but particles with a small particle size are preferable because they increase the specific surface area and promote contact with component (B) and the transition metal compound (C).

[0021] The component (A) according to the present invention may be manufactured by conventionally known methods, or a commercially available product may be used.

[0022] For example, boron nitride may be produced by methods such as those exemplified in Japanese Patent Publication No. 2021-91604, or boron nitride nanotubes produced by methods such as those exemplified in Japanese Patent Publication No. 2021-147309 may be used. Examples of commercially available products include Sigma-Aldrich's "Boron Nitride Nanopowder, <150 nm avg. part. size (BET), 99% trace metals basis" and "Boron nitride nanotubes Multiwalled, powder, >90%".

[0023] Aluminum nitride can be manufactured by methods such as those exemplified in International Publication No. 2021 / 157388, and commercially available examples include Sigma-Aldrich's "Aluminum Nitride Nanopowder, <100 nm particle size".

[0024] Silicon nitride can be manufactured by methods such as those exemplified in International Publication No. 2021 / 107021, and commercially available products include Sigma-Aldrich's "Silicon Nitride nanopowder, <50 nm particle size (spherical), ≥98.5% trace metals basis."

[0025] Furthermore, as component (A), aluminum nitride-boron nitride composite particles, as exemplified in Japanese Patent Publication No. 2021-165228, can also be used.

[0026] The aforementioned component (A) may be used after being dried or calcined at a temperature of 0°C to 1000°C, preferably 50°C to 800°C, as needed.

[0027] <Ingredient (B)> 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) that react with transition metal compounds (C) to form ion pairs (hereinafter also referred to as "ionic compound (B-II)"). Component (B) is preferably one having a functional group that can form a chemical bond or electronic interaction with the oxygen atom-containing functional group in component (A).

[0028] ≪Organoaluminum oxy compounds (BI)≫ Examples of organoaluminum oxy compounds (BI) include conventionally known aluminoxanes such as the compounds represented by the following general formula [b1] and the compounds represented by the following general formula [b2], modified methylaluminoxanes having the structure represented by the following general formula [b3], and boron-containing organoaluminum oxy compounds represented by the following general formula [b4].

[0029] [ka]

[0030] In formulas [b1] and [b2], R is a hydrocarbon group having 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. Methylaluminoxane, in which R is a methyl group, is preferably used in formulas [b1] and [b2].

[0031] [ka]

[0032] 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 independent integers of 2 or more. Multiple Rs may be the same or different from one another. Modified methyl aluminoxane [b3] can be prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such modified methyl aluminoxane [b3] is generally called MMAO (modified methyl aluminoxane). Specifically, MMAO can be prepared by the methods described in U.S. Patent No. 4,960,878 and U.S. Patent No. 5,041,584.

[0033] Furthermore, modified methylaluminoxanes prepared using trimethylaluminum and triisobutylaluminum (i.e., R in general formula [b3] is an isobutyl group) are commercially produced by companies such as Tosoh Finechem under trade names MMAO and TMAO.

[0034] MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, unlike compounds that are insoluble or poorly soluble in benzene, such as those represented by general formulas [b1] or [b2], MMAO is soluble in aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0035] [ka]

[0036] In formula [b4], R is a hydrocarbon group having 1 to 20 carbon atoms. Multiple R groups may be identical or different from one another.

[0037] The hydrocarbon groups in formulas [b1], [b2], [b3] and [b4] include, for example, 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 iso-propyl group, a sec-butyl group (butan-2-yl group), a tert-butyl group (2-methylpropane-2-yl group), an iso-butyl group (2-methylpropyl group), a pentane-2-yl group, and 2 Linear or branched alkyl groups such as methylbutyl group, iso-pentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbuta-2-yl group), and 4,4-dimethylpentyl group; Vinyl group, allyl group, propenyl group (propa-1-en-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl group (propa-1,2-dien-1-yl group), buta-3-en-1-yl group, clotyl group (buta-2-en-1-yl group), buta-3-en-2-yl group, metharyl group (2-methylallyl group), buta-1,3-dienyl group, pen Linear or branched alkenyl groups or unsaturated double bond-containing groups such as ta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group (3-methylbuta-3-en-1-yl group), 2-methylbuta-3-en-1-yl group, penta-4-en-2-yl group, and prenyl group (3-methylbuta-2-en-1-yl group); Linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl group, propa-2-in-1-yl group, and propargyl group (propa-1-in-1-yl group); aromatic linear or branched alkyl groups and unsaturated double bond-containing groups such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-iso-propylbenzyl group), 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group (diphenylmethyl group), and cumyl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norborneyl group, 1-adamantyl group, 2-adamantyl group, and other cyclic saturated hydrocarbon groups; Aromatic substituents (aryl groups) such as phenyl group, tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3,5,6-tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, and ferrocenyl group are examples.

[0038] Compounds obtained by replacing some of the multiple Rs in formulas [b1], [b2], [b3], and [b4] with hydrogen atoms, halogen atoms, halogen-containing groups, or oxygen-containing groups can also be used as organoaluminum oxy compounds (BI).

[0039] Examples of the halogen atoms mentioned above include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0040] Examples of the halogen-containing group include those obtained by substituting some of the hydrogen atoms in the hydrocarbon group with halogen atoms.

[0041] Examples of the oxygen-containing groups include alkoxy groups such as hydroxyl group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group, benzyloxy group, and methoxymethoxy group; allyloxy groups such as phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,4,6-trimethylphenoxy group, and 2,4,6-tri-iso-propylphenoxy group; furyl group, benzofuryl group, tetrahydrofuryl group, pyranyl group, tetrahydropyranyl group, acetoxy group, pivaloyloxy group, benzoyloxy group, and trifluoroacetoxy group, as well as those in which some of the hydrogen atoms in these groups are substituted with the halogen atoms. Furthermore, a group in which some of the hydrogen atoms in the hydrocarbon group are replaced with the oxygen-containing group can also be used as the oxygen-containing group.

[0042] The organoaluminum oxy compounds (BI) described above may be used individually or in combination of two or more.

[0043] ≪Ionic Compounds (B-II)≫ As the ionic compound (B-II), Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Publication No. 3-179005, Japanese Patent Publication No. 3-179006, Japanese Patent Publication No. 3-207703, Japanese Patent Publication No. 3-207704, U.S. Patent No. 5321106, etc., as well as heteropoly compounds and isopoly compounds, can be used without limitation. Among these, the compound represented by the following general formula [b5] is preferred as the ionic compound (B-II).

[0044] [ka]

[0045] In equation [b5], Y + These are hydrogen cations, oxonium cations, carbenium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, or ferrocenium cations.

[0046] Examples of the aforementioned carbenium cations include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation, and tris(dimethylphenyl)carbenium cation.

[0047] 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.

[0048] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation, and tris(dimethylphenyl)phosphonium cation.

[0049] Y + Among the examples above, carbenium cations and ammonium cations are preferred, and triphenylcarbenium cations, N,N-dimethylanilinium cations, and methyldioctadecylammonium cations are particularly preferred.

[0050] M' is an atom from Group 13 of the periodic table, specifically, boron or aluminum, with boron being preferred.

[0051] Each Q is independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen atom, a halogen-containing group, or an oxygen-containing group. Multiple Qs may be the same or different from each other, and may be bonded together to form a ring.

[0052] Examples of the hydrocarbon group, halogen atom, halogen-containing group, or oxygen-containing group include those exemplified as R in the general formulas [b1], [b2], [b3], or [b4], and are preferably aryl groups having 6 to 40 carbon atoms represented by the following general formula [b6].

[0053] [ka]

[0054] In the above formula [b6], * indicates a bond with M', and R is selected from the group consisting of a hydrogen atom, a hydrocarbon group having 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. Multiple Rs may be the same or different from each other, and may be bonded to each other to form a ring.

[0055] Examples of the hydrocarbon group, halogen atom, halogen-containing group, and oxygen-containing group include those exemplified as R in formulas [b1], [b2], [b3], and [b4].

[0056] Examples of the silicon-containing groups include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris(trimethylsilyl)silyl group, trimethylsilylmethyl group, chlorodimethylsilyl group, chlorodiphenylsilyl group, and bromodimethylsilyl group. Among the silicon-containing groups, trimethylsilylmethyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, chlorodimethylsilyl group, and chlorodiphenylsilyl group are preferred.

[0057] Examples of the aforementioned sulfur-containing groups include thiol groups, mesyl groups (methanesulfonyl groups), phenylsulfonyl groups, tosyl groups (p-toluenesulfonyl groups), trifuryl groups (trifluoromethanesulfonyl groups), nonafuryl groups (nonafluorobutanesulfonyl groups), thiophenyl groups, mesylate groups (methanesulfonate groups), tosylate groups (p-toluenesulfonate groups), triflate groups (trifluoromethanesulfonate groups), nonaflate groups (nonafluorobutanesulfonate groups), thiophene groups, and benzothiophene groups.

[0058] Examples of the nitrogen-containing groups include amino groups, cyano groups, methylamino groups, dimethylamino groups, ethylamino groups, diethylamino groups, tert-butylamino groups, di-tert-butylamino groups, allylamino groups, diallylamino groups, benzylamino groups, dibenzylamino groups, nitro groups, pyrrolidinyl groups, piperidinyl groups, morpholyl groups, pyrrolyl groups, bistrifrylimide groups, pyridinyl groups, pyrimidinyl groups, quinolinyl groups, triazinyl groups, oxazoline groups, imidazole groups, indole groups, and carbazole groups.

[0059] Examples of the phosphorus-containing group include hexafluorophosphate anions.

[0060] As R, halogen atoms and halogen-containing groups are preferred among the examples above, and fluorine atoms and fluorine-containing groups are particularly preferred. Furthermore, in at least one Q of formula [b5], it is preferable that at least one R of formula [b6] is an oxygen-containing group or a silicon-containing group.

[0061] The specific structures of formula [b5] include triphenylcarbenium tetraphenyl borate, 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 tetraphenyl borate, tripropylammonium tetraphenyl borate, tri(n-butyl)ammonium tetraphenyl borate, 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 tetraphenyl borate, 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 tetraphenyl borate, 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(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, dicyclohexylammonium tetraphenylborate are exemplified.,

[0062] The ionic compound (B-II) may be used alone or in combination of two or more kinds.,

[0063] <Organic aluminum compound (D)> In the olefin polymerization catalyst of the present invention, an organic aluminum compound (D) represented by the following general formula [b6] may be used together with the above component (B).

[0064] R a m Al(OR b ) n H p X q …[b6] In the formula [b6], R a and R b∫ represents a hydrocarbon group 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 between 1 and 3, n is an integer between 0 and 2, p is an integer between 0 and 2, and q is an integer between 0 and 2, and m+n+p+q=3.

[0065] Hydrocarbon groups having 1 to 15 carbon atoms include, for example, alkyl groups, cycloalkyl groups, or aryl groups, specifically methyl groups, ethyl groups, n-propyl groups, isopropyl groups, isobutyl groups, pentyl groups, hexyl groups, octyl groups, cyclopentyl groups, cyclohexyl groups, phenyl groups, tolyl groups, and the like.

[0066] Specific examples of the organoaluminum compound (D) include trialkylaluminum 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, and isopropyl Examples include alkylaluminum dihalides such as aluminum dichloride and ethylaluminum dibromide; alkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride, and di-sec-nonylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, and diisobutylaluminum ethoxide.

[0067] Among the above, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diisobutylaluminum hydride, and diethylaluminum ethoxide are particularly preferred.

[0068] <Transition metal compound (C)> The transition metal compound (C) used in the present invention is not particularly limited, and examples include transition metal compounds used in conventionally known catalysts for olefin polymerization, and specifically, compounds represented by the following general formula (CI).

[0069] L m MX n ...(CI) In the above general formula (CI), M is an atom selected from the group consisting of atoms from Groups 3, 4, 5, 6, 7, 8, 9, 10, and 11 of the periodic table, and lanthanide atoms. Preferably, it is a transition metal atom from Groups 4 and 10 of the periodic table, specifically a titanium atom, a zirconium atom, a hafnium atom, a palladium atom, or a nickel atom.

[0070] 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 each other, and multiple Ls may be linked together by substituents within L.

[0071] Examples of η-bonded cyclic anion ligands include cyclopentadienyl group, indenyl group, tetrahydroindenyl group, fluorenyl group, tetrahydrofluorenyl group, octahydrofluorenyl group, and octamethyloctahydrofluorenyl group, and these ligands may have other substituents.

[0072] A 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).

[0073] 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 is capable of coordinating to M in the general formula (CI) with a lone pair of electrons.

[0074] m is a non-negative integer. n is an integer between 1 and 6 that satisfies the valence of M, preferably between 1 and 4.

[0075] X is selected from the group consisting of a hydrogen atom, a hydrocarbon group having 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 from each other, and may be bonded to each other to form a ring. Preferably, X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, or a conjugated diene derivative group.

[0076] 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 are the same as those exemplified as R in formula [b6].

[0077] The diene derivative group is a hydrocarbon compound that can coordinate to M in the general formula (CI) with a lone pair of electrons, and examples include 1,3-butadienyl group, isoprenyl group (2-methyl-1,3-butadienyl group), piperilenyl group (1,3-pentadienyl group), 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, cyclopentadienyl group, metallocyclopentenyl group, 1,5-cyclooctadienyl group, and others.

[0078] Examples of such transition metal compounds (C) include Japanese Patent Publication No. 61-211307, Japanese Patent Publication No. 5-148317, Japanese Patent Publication No. 6-239914, International Publication No. 2001 / 27124, Japanese Patent Publication No. 2003-206310, Japanese Patent Publication No. 2004-2259, Japanese Patent Publication No. 2004-269825, Japanese Patent Publication No. 2009-143901, Japanese Patent Publication No. 2009-537656, Japanese Patent Publication No. 2011-127121, Japanese Patent Publication No. 2012-255165, International Publication No. 2014 / 50817, International Publication No. 2014 / 123212, and Japanese Patent Publication No. 20 Examples of transition metal compounds include those described in Japanese Patent Publication No. 15-500920, Japanese Patent Publication No. 2016-527182, Japanese Patent Publication No. 2017-535518, Japanese Patent Application Publication No. 2018-58780, Japanese Patent Application Publication No. 2019-59934, Japanese Patent Application Publication No. 2020-117711, and U.S. Patent No. 5,272,236, and preferably at least one compound selected from the group consisting of transition metal compounds represented by the following general formulas (C-II), (C-III), (C-IV), (CV), (C-VI), (C-VII), (C-VIII), and (C-IX).

[0079] [ka]

[0080] In the general formula (C-II) above, M represents a transition metal atom of Group 4 or Group 5 of the periodic table, specifically a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a niobium atom, or a tantalum atom. Preferably, it is a transition metal atom of Group 4 of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom, and particularly preferably a titanium atom or a zirconium atom.

[0081] In general, the dotted line connecting the nitrogen atom (N) and M in the above general formula (C-II) generally indicates that the nitrogen atom (N) is coordinated to M; however, in the present invention, coordination may or may not be required.

[0082] R 1 , R 2 , R 3, R 4 and R 5 These may be identical or different from each other, and represent 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, a boron-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring.

[0083] Specific examples of the halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, and boron-containing group include those similar to those exemplified as X in the general formula (CI), and the germanium-containing group or tin-containing group may be a group in which the silicon of the silicon-containing group is replaced with germanium or tin. In addition, a structure having the halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, and boron-containing group as substituents in the hydrocarbon group is also R 1 , R 2 , R 3 , R 4 , R 5 This can be used as an example.

[0084] The hydrocarbon group is, in particular, a linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, or n-hexyl group; Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl groups, naphthyl groups, biphenyl groups, terphenyl groups, phenanthryl groups, and anthracenyl groups; These aryl groups are preferably substituted with 1 to 5 substituents, such as a halogen atom, an alkyl or alkoxy group having 1 to 30 carbon atoms (preferably 1 to 20 carbon atoms), or an aryl or aryloxy group having 6 to 30 carbon atoms (preferably 6 to 20 carbon atoms).

[0085] R 1From the viewpoint of olefin polymerization catalytic activity and the ability to provide high molecular weight ethylene-based polymers, it is preferable that the group is selected from linear or branched hydrocarbon groups having 1 to 20 carbon atoms, alkyl groups having 3 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms.

[0086] R 6 The group is selected from hydrogen atoms, hydrocarbon groups having 1 to 3 carbon atoms consisting only of primary or secondary carbons, alkyl groups having 4 or more carbon atoms, aryl group-substituted alkyl groups, monocyclic or bicyclic cyclic hydrocarbon groups, aryl groups, and halogen atoms. Of these, from the viewpoint of olefin polymerization catalytic activity and the viewpoint of giving high molecular weight ethylene polymers, it is preferable to select a group from alkyl groups having 4 or more carbon atoms, aryl group-substituted alkyl groups, monocyclic or bicyclic cyclic hydrocarbon groups, and aryl groups, and more preferably a branched alkyl group such as a tert-butyl group; aryl-substituted alkyl groups such as a benzyl group, 1-methyl-1-phenylethyl group (cumyl group), 1-methyl-1,1-diphenylethyl group, and 1,1,1-triphenylmethyl group (trityl group); and cyclic hydrocarbon groups having a ring structure with 6 to 15 carbon atoms such as a cyclohexyl group, adamantyl group, norbornyl group, and tetracyclododecyl group.

[0087] X is a leaving group and is a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, and a neutral ligand that can coordinate with a lone pair of electrons, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group. When n is 2 or more, the multiple Xs may be the same or different from each other, and may bond to each other to form a ring. Preferably, X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, or a conjugated diene derivative group.

[0088] Specific examples of X include those similar to those exemplified as X in the general formula (CI) mentioned above. n is an integer from 1 to 4 that satisfies the valence of M, preferably 1 or 2.

[0089] [ka]

[0090] In the general formulas (C-III), (C-IV), and (CV) above, M represents a transition metal atom of Group 4 of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom, and preferably a titanium atom.

[0091] R 7 These may be the same or different from each other, and represent a hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, boron-containing group, germanium-containing group, or tin-containing group, and adjacent R 7 These may bond to each other to form monocyclic or bicyclic rings which may have substituents. Specific examples of the halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, boron-containing group, germanium-containing group, or tin-containing group include R in the general formula (C-II). 1 , R 2 , R 3 , R 4 , R 5 Examples similar to those given as illustrations can be cited.

[0092] R 7 Preferably, this is a hydrocarbon group having 1 to 25 carbon atoms, an oxygen-containing group having 1 to 25 carbon atoms, or a nitrogen-containing group having 1 to 25 carbon atoms. 7 However, when forming monocyclic or bicyclic rings which may have substituents, it is preferable to form the ring as a saturated or unsaturated heterocycle of 4 to 8 members which may have substituents containing phosphorus or boron atoms.

[0093] Cp is a cyclopentadienyl ligand, which may have substituents. Among the substituents, adjacent substituents may bond to each other to form a ring, which may also have substituents.

[0094] The cyclopentadienyl ligand is a substituted ligand having a five-membered carbocyclic ring bonded to a metal by a π-type bond, and includes substituted cyclopentadienyl ligands, substituted tetrahydroindenyl ligands, substituted octahydrofluorenyl ligands, substituted hydroazlenyl ligands, substituted pentahydroazlenyl ligands, substituted dihydrocyclopentenoannulene ligands, substituted cyclopentenopyrrole ligands, substituted cyclopentenothiophene ligands, and substituted cyclopentenodithiophene ligands, as well as substituted indenyl ligands, substituted tetrahydroindenyl ligands, substituted benzoindenyl ligands, substituted dihydroindacenyl ligands, substituted indenopyrrole ligands, substituted indenindole ligands, and substituted indenothiophene ligands, and substituted fluorenyl ligands, etc. Preferred cyclopentadienyl ligands include substituted cyclopentadienyl ligands and substituted indenyl ligands, and more preferably substituted cyclopentadienyl ligands, substituted dihydrocyclopentenoannulene ligands, substituted cyclopentenothiophene ligands, substituted cyclopentenodithiophene ligands, and substituted indenyl ligands.

[0095] The substituents of the cyclopentadienyl ligand are, independently, a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group.

[0096] Specific examples of hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, and sulfur-containing groups in the substituents of the cyclopentadienyl-type ligand are the R 7 Examples of hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, and sulfur-containing groups are similar to those exemplified in the above.

[0097] Z is an atom from group 15 or 16 of the periodic table, preferably a nitrogen atom or an oxygen atom. N is an atom from Group 15 of the periodic table, and is preferably a nitrogen atom. C is a carbon atom.

[0098] Y 1 This is either a phosphorus atom or a boron atom. Y 2 These atoms are selected from carbon atoms, silicon atoms, germanium atoms, and tin atoms. Solid lines represent covalent or coordinate bonds, while dotted lines represent covalent bonds that exist when Z is a group 15 element.

[0099] y is 2 if Z is an atom of a group 15 element, and 3 if Z is an atom of a group 16 element. z is 3 if Z is an atom of a group 15 element, and 4 if Z is an atom of a group 16 element.

[0100] X is a leaving group and is a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, and a neutral ligand that can coordinate with a lone pair of electrons, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group. When n is 2 or more, the multiple Xs may be the same or different from each other, and may bond to each other to form a ring. Preferably, X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, or a conjugated diene derivative group.

[0101] Specific examples of X include those similar to those exemplified as X in the general formula (CI) above, where n is an integer from 1 to 4 that satisfies the valence of M, preferably 1 or 2.

[0102] [ka]

[0103] In the general formulas (C-VI) and (C-VII) above, M represents an atom selected from the group consisting of atoms from groups 3, 4, 5, and 6 of the periodic table, or lanthanide atoms. Preferably, it is a transition metal atom from group 4 of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom.

[0104] In the general formulas (C-VI) and (C-VII) described above, at least two of the four dotted lines connecting Zα and Zβ to M are covalent bonds, and the other bonds are coordinate bonds. However, in this invention, the bonds showing coordinate bonds may or may not be coordinated.

[0105] If Zα forms a covalent bond with M, Zα may be the same or different from each other and is selected from a nitrogen atom or a phosphorus atom. If Zα does not form a covalent bond with M, Zα may be the same or different from each other and is selected from the group consisting of an oxygen atom, a sulfur atom, -NRα-, and -PRα-.

[0106] If Zβ forms a covalent bond with M, Zβ may be the same or different from each other and is selected from the group consisting of an oxygen atom, a sulfur atom, -NRβ-, and -PRβ-. If Zβ does not form a covalent bond with M, Zβ may be the same or different from each other and is selected from the group consisting of -ORβ, -SRβ, -NRβ2, and -PRβ2.

[0107] The Rα and Rβ mentioned above may be the same or different, and represent 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, or a boron-containing group. A specific example is R in the general formula (C-II). 1 , R 2 , R 3 , R 4 , R 5 Examples similar to those given as illustrations can be cited.

[0108] R 8The bridging group contains 1 to 50 atoms (hydrogen atoms are not included in the count), and preferred structures include linear or branched alkyl groups, alkyl groups containing cyclic saturated hydrocarbons, and alkyl groups containing aromatic hydrocarbons. Among these, linear or branched alkyl groups and alkyl groups containing cyclic saturated hydrocarbons are particularly preferred, specifically including methylene groups, ethylene groups, trimethylene groups, pentane-2,4-diyl groups, and cyclohexane-1,2-dimethylene groups.

[0109] R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 These may be the same or different from each other, and represent 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, or a boron-containing group. A specific example is R in the general formula (C-II) above. 1 , R 2 , R 3 , R 4 , R 5 Examples similar to those exemplified are also given. Two or more of these may be linked together to form a ring. Preferably, R 10 , R 18 At least one of them is not hydrogen, R 10 , R 18 It is particularly preferable that both are selected from the group consisting of an aryl group which may have substituents, or an aryl group which may have substituents and contains one or more heteroatoms in an aryl aromatic ring.

[0110] X is a leaving group and is a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, and a neutral ligand that can coordinate with a lone pair of electrons, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group. When n is 2 or more, the multiple Xs may be the same or different from each other, and may bond to each other to form a ring. Preferably, X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, or a conjugated diene derivative group.

[0111] Specific examples of X include those similar to those exemplified as X in the general formula (CI) above, where n is an integer from 1 to 4 that satisfies the valence of M, preferably 1 or 2.

[0112] [ka]

[0113] In the general formulas (C-VIII) and (C-IX) above, M represents a transition metal atom of Group 4 of the periodic table, specifically a titanium atom, a zirconium atom, and a hafnium atom. Y is selected from carbon atoms, silicon atoms, germanium atoms, and tin atoms.

[0114] R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40may be the same as or different from each other, and represents 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 or a boron-containing group. Specific examples include R in the general formula (C-II). 1 R 2 R 3 R 4 R 5 R

[0115] The substituents R 25 to R 32 on the fluorene ring are preferably symmetric from the viewpoint of synthetic ease, that is, R 25 = R 32 R 26 = R 31 R 27 = R 30 R 28 = R 29 .

[0116] X is a leaving group and is a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand and a neutral ligand capable of coordinating with a lone pair of electrons. The anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene derivative group. When n is 2 or more, the plurality of Xs may be the same as or different from each other, and may be bonded to each other to form a ring. Preferably, it is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group or a conjugated diene derivative group.

[0117] Specific examples of X include the same as those exemplified as X in the general formula (C-I). n is an integer of 1 to 4 that satisfies the valence of M, and is preferably 1 or 2.

[0118] Other examples of transition metal compounds (C) include titanium tetrahalides such as TiCl4, TiBr4, ZrCl4, and HfCl4; zirconium tetrahalides; 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; and Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, Ti Examples include dihalogenated dialkoxytitanium such as (O-C4H9)2Cl2 and Ti(OC2H5)2Br2; monohalogenated trialkoxytitanium such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(On-C4H9)3Cl, and Ti(OC2H5)3Br; and tetraalkoxytitanium such as Ti(OCH3)4, Ti(OC2H5)4, Ti(On-C4H9)4, Ti(O-iso-C4H9)4, and Ti(O-2-ethylhexyl)4.

[0119] The transition metal compound (C) may be used alone or in combination of two or more compounds. Similarly, the structural isomer may be used alone or as a mixture of two or more structural isomers.

[0120] <Method for preparing catalysts for olefin polymerization> In the present invention, one preferred embodiment of the olefin polymerization catalyst is a solid catalyst component (X) prepared by contacting component (A), component (B), and the transition metal compound (C).

[0121] If component (B) and the transition metal compound (C) are in liquid form, it is preferable to dilute them with an inert solvent; if they are in solid form, it is preferable to dissolve them in an inert solvent and bring them into contact with component (A). Examples of inert solvents that can be used include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic saturated hydrocarbons such as hexane, heptane, and decane; alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; or mixtures thereof.

[0122] The method of contacting component (A), component (B), and the transition metal compound (C) is not particularly limited as long as the effects of the present invention are achieved. Examples include adding an inert solvent containing component (B) or the transition metal compound (C) to component (A) and impregnating it into the pores of component (A); immersing component (A) in an inert solvent containing component (B) or the transition metal compound (C) and letting it stand; mixing component (A) and an inert solvent containing component (B) or the transition metal compound (C) by stirring or the like; and circulating an inert solvent containing component (B) or the transition metal compound (C) through component (A). Component (A) may be used in a state where it is physically or chemically immobilized on a solid support (including powder, granulated particles, fibers, and films), and a heating operation may be performed during contact.

[0123] Of these, a preferred method is to mix component (A) with an inert solvent containing component (B) or the transition metal compound (C) by stirring or the like. After the contact operation, the contact solution may be allowed to stand and the supernatant may be removed as needed, or the inert solvent may be removed by filtration or the like, and the mixture may be washed with the inert solvent as needed.

[0124] The temperature during the heating operation depends on the solvent used, but is usually between the freezing point of the solvent and 200°C, preferably 150°C or lower. The contact time depends on the contact method and temperature, but is usually between 30 seconds and 1000 hours, preferably between 5 minutes and 120 hours.

[0125] In any step of the aforementioned 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. Component (G) can be a compound having a polar functional group, 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-acyl amino acids being more preferred. These may be used individually or in combination of two or more.

[0126] The contact order of component (A), component (B), and the transition metal compound (C) is not particularly limited as long as the effects of the present invention are achieved, Step (1-1) of bringing component (A) and component (B) into contact, A method comprising the step (1-2) of contacting the contact obtained in step (1-1) with the transition metal compound (C) to obtain a solid catalyst component (X), Step (2-1) of bringing component (A) into contact with component (B), The step (2-2) involves contacting the transition metal compound (C) with the component (B), One example of such a method is one in which the contact obtained in step (2-1) is brought into contact with the contact obtained in step (2-2) to obtain a solid catalyst component (X), and so on. In this case, the component (B) used in step (2-1) and step (2-2) may be the same or different.

[0127] In steps (1-1) and (2-1) above, if component (B) is the organoaluminum oxy compound (BI), component (B) can be used in a range 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 gram of component (A). If component (B) is the ionic compound (B-II), component (B) can be used in a range 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 gram of component (A).

[0128] In step (2-2) above, if component (B) is the organoaluminum oxy compound (BI), component (B) can be used in a range 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). If component (B) is the ionic compound (B-II), component (B) can be used in a range 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).

[0129] In steps (1-2) and (2-3) described above, the transition metal compound (C) can be used in an amount of preferably 0.0001 mmol to 1 mmol, more preferably 0.0005 mmol to 0.5 mmol, and even more preferably 0.001 mmol to 0.2 mmol per gram of component (A).

[0130] For the production of the olefin polymer, the solid catalyst component (X) may be used suspended in an inert hydrocarbon or in a dried state. Alternatively, the solid catalyst component (X) may be prepolymerized using an olefin that may be the same as or different from the olefin used in the production of the olefin polymer before use.

[0131] [Method for producing olefin polymers] The present invention provides a method for producing an olefin polymer, characterized by comprising the step of polymerizing an olefin in the presence of the olefin polymerization catalyst described above. In the present invention, "polymerization" may include not only homopolymerization but also copolymerization such as random copolymerization and block copolymerization.

[0132] Examples of olefins polymerized in the present invention include ethylene, α-olefins, and cyclic olefins.

[0133] Among these, α-olefins include linear or branched α-olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms. More specifically, 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. Of 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.

[0134] Examples of cyclic olefins include those having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms. More specifically, 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.

[0135] The step of polymerizing the olefin is preferably a step of homopolymerizing ethylene in the presence of the solid catalyst component (X), a step of copolymerizing ethylene with one or more α-olefins having 3 to 20 carbon atoms, a step of homopolymerizing propylene, a step of copolymerizing propylene with one or more α-olefins having 4 to 20 carbon atoms, a step of homopolymerizing 4-methyl-1-pentene, or a step of copolymerizing 4-methyl-1-pentene with one or more α-olefins having 4 to 20 carbon atoms.

[0136] In the method for producing olefin polymers of the present invention, polymerization can be carried out by either a liquid-phase polymerization method such as suspension polymerization or 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, or mixtures thereof. The olefin itself can also be used as the solvent.

[0137] The lower limit of the temperature for polymerizing the olefin in the method of the present invention is -20°C, preferably 0°C, more preferably 20°C, and particularly preferably 30°C, and the upper limit of the temperature for polymerizing the olefin is 200°C, preferably 150°C, more preferably 100°C, and particularly preferably 80°C.

[0138] The polymerization pressure in the method of the present invention is usually above atmospheric pressure and up to 10 MPa, preferably above atmospheric pressure and up to 5 MPa, and the polymerization reaction can be carried out by batch, semi-continuous, or continuous methods.

[0139] Furthermore, the method for producing the olefin polymer of the present invention may be a so-called multi-stage polymerization method, in which the polymerization reaction is carried out in two or more stages by changing the conditions of the polymerization reaction.

[0140] The molecular weight of the resulting olefin polymer can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature.

[0141] In the step of polymerizing the olefin, the organoaluminum compound (D) and component (G) may be present for the purpose of suppressing fouling (adhesion to the polymerization reactor) or improving particle properties.

[0142] <Olefin polymer> One embodiment of the olefin polymer obtained by the method for producing olefin polymers of the present invention is an ethylene-based polymer containing ethylene-derived structural units preferably in the range of 90 mol% to 100 mol%, more preferably in the range of 95 mol% to 100 mol%, a propylene-based polymer containing propylene-derived structural units preferably in the range of 80 mol% to 100 mol%, more preferably in the range of 90 mol% to 100 mol%, and a 4-methyl-1-pentene-based polymer containing 4-methyl-1-pentene-derived structural units preferably in the range of 80 mol% to 100 mol%, more preferably in the range of 90 mol% to 100 mol%,.

[0143] The ethylene-based polymer preferably contains α-olefin-derived structural units having 3 to 20 carbon atoms in a total of 0 mol% to 10 mol%, more preferably 0 mol% to 5 mol%. However, the sum of the content of ethylene-derived structural units and the content of α-olefin-derived structural units having 3 to 20 carbon atoms is 100 mol%.

[0144] The propylene polymer contains ethylene and α-olefin-derived structural units with 4 to 20 carbon atoms in a total of preferably 0 mol% to 20 mol%, more preferably 0 mol% to 10 mol%. However, the sum of the content of propylene-derived structural units and the content of ethylene and α-olefin-derived structural units with 4 to 20 carbon atoms is 100 mol%.

[0145] The 4-methyl-1-pentene polymer contains, preferably, 0 mol% to 20 mol%, more preferably 0 mol% to 10 mol%, of constituent units derived from α-olefins having 3 to 20 carbon atoms other than ethylene and 4-methyl-1-pentene. However, the sum of the content of constituent units derived from 4-methyl-1-pentene and the content of constituent units derived from α-olefins having 3 to 20 carbon atoms other than ethylene and 4-methyl-1-pentene is 100 mol%.

[0146] 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. Alternatively, so-called block copolymers (impact copolymers) obtained by mixing or continuously producing two or more polymers selected from these polymers may also be used.

[0147] In the olefin polymer obtained by the method for producing olefin polymers of the present invention, component (A) is preferably contained in an efficiently dispersed state in a range of 0.005% by weight or more and 50% by weight or less. The use of component (A) in thermoplastic resins such as olefin polymers to enhance the thermal conductivity of the resin has been exemplified in Japanese Patent Publication No. 2019-038912 and Japanese Patent Publication No. 2012-122057, and it is expected that the olefin polymer obtained by the method for producing olefin polymers of the present invention will have superior thermal conductivity compared to conventional materials. [Examples]

[0148] The present invention will be described in more detail below based on examples, but the present invention is not limited in any way to these examples.

[0149] [Components (A) and (A')] Components (A) to (A) below were used as component (A), and component (A'-5) below was used as a nitride-based filler that did not meet requirement (AI) (hereinafter also referred to as "component (A')"). Both component (A) and component (A') were dried under reduced pressure at 100°C for 3 hours before use, and then returned to room temperature under a nitrogen atmosphere before being used to prepare the solid catalyst component (X).

[0150] • Ingredients (A-1): Sigma-Aldrich Boron Nitride nanopowder, <150 nm avg. part size (BET), 99% trace metals basis • Ingredients (A-2): Sigma-Aldrich Boron nitride nanotubes Multiwalled, powder, >90% • Ingredients (A-3): Sigma-Aldrich aluminum nitride nanopowder, <100 nm particle size • Ingredients (A-4): Sigma-Aldrich silicon nitride nanopowder, <50 nm particle size (spherical), ≥98.5% trace metals basis • Ingredient (A'-5): Fujifilm Wako Pure Chemical Industries, Ltd. Boron Nitride

[0151] ≪Oxygen Content≫ The oxygen content of components (A) and (A') was determined by X-ray photoelectron spectroscopy (XPS) (KRATOS "AXIS-NOVA"). The samples were dried under reduced pressure at 100°C for 3 hours, then handled under a nitrogen atmosphere, and measured using monochromatic AlKα as the X-ray source. Charge correction neutralization was performed during measurement. The oxygen atom concentration was determined from the peak area of ​​the O1s narrow spectrum, the boron atom concentration from the peak area of ​​the B1s narrow spectrum, the aluminum atom concentration from the peak area of ​​the Al2p narrow spectrum, and the silicon atom concentration from the peak area of ​​the Si2p narrow spectrum. The molar ratio of oxygen atoms / (boron atoms + aluminum atoms + silicon atoms) was then calculated. The results are shown in Table 1. Note that (boron atoms + aluminum atoms + silicon atoms) represents the sum of the boron atom concentration, aluminum atom concentration, and silicon atom concentration.

[0152] [Component (B)] The following components (B-1) and (B-2) were used as component (B). • Ingredient (B-1): Methylaluminoxane (MAO) • Component (B-2): Compound represented by the following formula (B-2)

[0153] [ka]

[0154] [Transition metal compounds] As transition metal compounds, we used transition metal compounds (C-1) to (C-4) represented by the following formulas (C-1) to (C-4).

[0155] [ka]

[0156] [Preparation of solid catalyst component (X)] <Preparation Example 1> 200 mg of component (A-1) and 19.8 mL of toluene were added to a 30 mL Schlenk tube that had been thoroughly purged with nitrogen, and stirring was started using a rotor. To this suspension, 0.24 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atoms) was added as component (B), and 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 analysis of the supernatant revealed that the Al concentration in the supernatant was 1.5 mmol / L. After further washing with toluene twice, 6.0 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 at room temperature for 30 minutes to prepare a slurry of solid catalyst component (X-1) with a solid content concentration of component (A-1) of 10.0 g / L.

[0157] <Preparation Example 2> 200 mg of component (A-2) and 19.7 mL of toluene were added to a 30 mL Schlenk tube that had been thoroughly purged with nitrogen, and stirring was started using a rotor. To this suspension, 0.30 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atoms) was added as component (B), and 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 analysis of the supernatant showed that the Al concentration in the supernatant was below the limit of quantification (less than 0.19 mmol / L). After further washing with toluene twice, 6.0 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 at room temperature for 30 minutes to prepare a slurry of solid catalyst component (X-2) with a solid content concentration of component (A-2) of 10.0 g / L.

[0158] <Preparation Example 3> 200 mg of component (A-3) and 19.5 mL of toluene were added to a 30 mL Schlenk tube that had been thoroughly purged with nitrogen, and stirring was started using a rotor. To this suspension, 0.45 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atoms) was added as component (B), and 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 analysis of the supernatant showed that the Al concentration in the supernatant was below the limit of quantification (less than 0.19 mmol / L). After further washing with toluene twice, 6.0 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 at room temperature for 30 minutes to prepare a slurry of solid catalyst component (X-3) with a solid content concentration of component (A-3) of 10.0 g / L.

[0159] <Preparation Example 4> 200 mg of component (A-4) and 19.5 mL of toluene were added to a 30 mL Schlenk tube that had been thoroughly purged with nitrogen, and stirring was started using a rotor. To this suspension, 0.50 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atoms) was added as component (B), and 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 analysis of the supernatant showed that the Al concentration in the supernatant was below the limit of quantification (less than 0.19 mmol / L). After further washing with toluene twice, 6.0 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 at room temperature for 30 minutes to prepare a slurry of solid catalyst component (X-4) with a solid content concentration of component (A-4) of 10.0 g / L.

[0160] <Preparation Example 5> 200 mg of component (A'-5) and 19.8 mL of toluene were added to a 30 mL Schlenk tube that had been thoroughly purged with nitrogen, and stirring was started using a rotor. To this suspension, 0.20 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atoms) was added as component (B), and 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 analysis of the supernatant revealed that the Al concentration in the supernatant was 3.9 mmol / L. After further washing with toluene twice, 6.0 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 at room temperature for 30 minutes to prepare a slurry of solid catalyst component (X-5) with a solid content concentration of component (A'-5) of 10.0 g / L.

[0161] <Preparation Example 6> In a 30 mL Schlenk tube that has been thoroughly purged with nitrogen, silica gel (particle size: 70 μm, specific surface area: 340 m²) is placed. 2 / g, pore volume: 1.3cm 3 200 mg of ( / g) and 19.0 mL of toluene were added, and stirring was started 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), and 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 analysis of the supernatant revealed that the Al concentration in the supernatant was 2.0 mmol / L. After further washing with toluene twice, 6.0 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 at room temperature for 30 minutes to prepare a slurry of solid catalyst component (X-6) with a silica gel solid content concentration of 10.0 g / L.

[0162] <Preparation Example 7> In a 30 mL Schlenk tube that had been thoroughly purged with nitrogen, 200 mg of component (A-1) and 19.8 mL of toluene were added, and stirring was started using a rotor. To this suspension, 0.16 mL of a toluene solution of triisobutylaluminum (0.5 mol / L in terms of Al atoms) was added, and 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 the supernatant revealed that the Al concentration in the supernatant was 0.50 mmol / L. After further washing with toluene twice, 6.0 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 at room temperature for 30 minutes to prepare a slurry of solid catalyst component (X-7) with a solid content concentration of component (A-1) of 10.0 g / L.

[0163] <Preparation Example 8> 200 mg of component (A-1) and 19.8 mL of toluene were added to a 30 mL Schlenk tube that had been thoroughly purged with nitrogen, and stirring was started using a rotor. To this suspension, 0.24 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atoms) was added as component (B), and 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 then washed twice with toluene. 3.0 mL of a toluene solution of transition metal compound (C-2) (1.0 mmol / L in terms of Zr) was added, and stirring was continued at room temperature for 30 minutes to prepare a slurry of solid catalyst component (X-8) with a solid content concentration of component (A-1) of 10.0 g / L.

[0164] <Preparation Example 9> 200 mg of component (A-1) and 8.0 mL of toluene were added to a 30 mL Schlenk tube that had been thoroughly purged with nitrogen, and stirring was started using a rotor. To this suspension, 12.0 mL of a toluene solution of component (B-2) (1.0 mmol / L in terms of B atoms) was added as component (B), and 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 then washed twice with toluene. 3.0 mL of a toluene solution of a transition metal compound (C-3) and triisobutylaluminum (1.0 mmol / L in terms of Ti, 10 mmol / L in terms of Al) was added, and stirring was continued at room temperature for 30 minutes to prepare a slurry of solid catalyst component (X-9) with a solid content concentration of component (A-1) of 10.0 g / L.

[0165] <Preparation Example 10> 200 mg of component (A-1) and 19.8 mL of toluene were added to a 30 mL Schlenk tube that had been thoroughly purged with nitrogen, and stirring was started using a rotor. To this suspension, 0.24 mL of a toluene solution of component (B-1) (1.0 mol / L in terms of Al atoms) was added as component (B), and 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 then washed twice with toluene. 2.0 mL of a toluene solution of transition metal compound (C-4) (1.0 mmol / L in terms of Zr) was added, and stirring was continued at room temperature for 30 minutes to prepare a slurry of solid catalyst component (X-10) with a solid content concentration of component (A-1) of 10.0 g / L.

[0166] ≪Metal concentration in the supernatant during preparation of solid catalyst component (X)≫ The concentration of metal (Al) in the supernatant during the preparation of the solid catalyst component (X) was determined by ICP emission spectrometry (ICP-AES) (Shimadzu Corporation ICPS-8100).

[0167] [Manufacturing of olefin polymers] <Example 1> In a 1-liter SUS autoclave reactor, which had been thoroughly purged with nitrogen, 500 ml of heptane was added under a nitrogen atmosphere, and then ethylene was passed through the reactor to saturate it 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 10 mg of the solid component (A-1) obtained in Preparation Example 1 were withdrawn and charged into the reactor. Subsequently, the temperature and pressure were increased to 80°C and 0.8 MPaG with ethylene, and the polymerization reaction was carried out at a rotation speed of 350 rpm for 60 minutes. After the reaction was complete, the contents of the reactor were filtered, and 55.6 g of olefin polymer was obtained by drying under reduced pressure at 80°C for 10 hours. The weight-average molecular weight (Mw) of the obtained olefin polymer was 6,160,000.

[0168] <Examples 2-4> The polymerization reaction was carried out in the same manner as in Example 1, except that a slurry of solid catalyst components (X-2) to (X-4) obtained in Preparation Examples 2 to 4 was used instead of solid catalyst component (X-1), and the amount of solid component (A) shown in Table 1 was charged into the reactor. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain the amount of olefin polymer shown in Table 1.

[0169] <Comparative Examples 1-3> The polymerization reaction was carried out in the same manner as in Example 1, except that a slurry of solid catalyst components (X-5) to (X-7) obtained in Preparation Examples 5 to 7 was used instead of solid catalyst component (X-1), and the amounts of component (A), (A'), or silica gel shown in Table 1 were charged into the reactor. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain the olefin polymer in the amounts shown in Table 1.

[0170] [Table 1]

[0171] It can be seen that component (A) constituting the olefin polymerization catalyst in the example yields more olefin polymer compared to the comparative example using component (A') with a low oxygen content. Furthermore, it can be seen that more olefin polymer can be obtained even with a smaller amount of component (B) added compared to the comparative example using silica gel instead of component (A). Moreover, it can be seen that the example using component (B) yields more olefin polymer compared to the comparative example not using component (B).

[0172] <Example 5> In a 1-liter SUS autoclave reactor, which had been thoroughly purged with nitrogen, 500 ml of heptane was added under a nitrogen atmosphere, and then ethylene was passed through the reactor to saturate it 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 component (A-1) obtained in Preparation Example 8 were withdrawn and charged into the reactor. Subsequently, the temperature and pressure were increased to 80°C and 0.8 MPaG with ethylene, and the polymerization reaction was carried out at a rotation speed of 350 rpm for 60 minutes. After the reaction was complete, the contents of the reactor were filtered, and 30.8 g of olefin polymer was obtained by drying under reduced pressure at 80°C for 10 hours. The weight-average molecular weight (Mw) of the obtained olefin polymer was 2,640,000.

[0173] <Example 6> In a 1-liter SUS autoclave reactor, which had been thoroughly purged with nitrogen, 500 ml of heptane was added under a nitrogen atmosphere, and then ethylene was passed through the reactor to saturate it with ethylene. Next, a slurry equivalent to 20 mg of the solid component (A-1) was withdrawn from the slurry of 3.0 mL of 1-hexene, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al), and the solid catalyst component (X-9) obtained in Preparation Example 9, and charged into the reactor. Subsequently, the temperature and pressure were increased to 80°C and 0.8 MPaG with ethylene, and the polymerization reaction was carried out at a rotation speed of 350 rpm for 60 minutes. After the reaction was complete, the contents of the reactor were filtered, and 38.4 g of olefin polymer was obtained by drying under reduced pressure at 80°C for 10 hours. The weight-average molecular weight (Mw) of the obtained olefin polymer was 1,860,000, and the melting point was 116°C.

[0174] <Example 7> In a 1-liter SUS autoclave reactor, which had been thoroughly purged with nitrogen, 500 ml of heptane was added under a nitrogen atmosphere, and then propylene was 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 80 mg of the solid component (A-1) obtained in Preparation Example 10 were withdrawn and charged into the reactor. Then, 100 mL of hydrogen was added, and the temperature and pressure were increased to 70°C and 0.5 MPaG with propylene, and the polymerization reaction was carried out at a rotation speed of 350 rpm for 60 minutes. After the reaction was complete, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain 13.6 g of olefin polymer. The weight-average molecular weight (Mw) of the obtained olefin polymer was 184,000, and the melting point was 160°C.

[0175] ≪Weight average molecular weight (Mw)≫ The weight-average molecular weight (Mw) of the olefin polymer was determined by gel permeation chromatography (GPC). It was calculated from the molecular weight distribution curve obtained using a Waters Alliance GPC 2000 gel permeation chromatograph (high-temperature size exclusion chromatograph), under the following operating conditions:

[0176] Analysis software; Chromatography data system Empower (Waters Corporation) 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 into the device) 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 for monodisperse polystyrene (Tosoh Corporation) / molecular weight from 495 to 20.6 million

[0177] ≪Melting point (Tm)≫ Using an SII RDC220 differential scanning calorimeter, approximately 5 mg of the sample was heated in a nitrogen atmosphere at a heating rate of 50°C / min from 30 to 200°C, and held at that temperature for 10 minutes. Furthermore, it was cooled to 30°C at a cooling rate of 10°C / min, held at that temperature for 5 minutes, and then heated again at a heating rate of 10°C / min to 200°C. The endothermic peak observed during this second heating was defined as the melting peak, and the temperature at which this melting peak appeared was determined as the melting point (Tm).

Claims

1. A component (A) selected from the group consisting of boron nitride and silicon nitride, and satisfying the following requirements (A-I), At least one component (B) selected from the group consisting of (B-I) and (B-II) below, At least one transition metal compound (C) selected from the group consisting of transition metal compounds represented by the following general formulas (C-II), (C-V), (C-VIII), and (C-IX), and A catalyst for olefin polymerization containing [specific component]. (A-I) The oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio in X-ray photoelectron spectroscopy (XPS) is 0.050 or greater and less than 2.0; (B-I) Organoaluminum oxy compounds; (B-II) Compounds that react with transition metal compounds (C) to form ion pairs; 【Chemistry 1】 [In the general formula (C-II), M represents a transition metal atom of Group 4 or Group 5 of the periodic table.] R1, R2, R3, R4, and R5 may be the same or different from each other, and represent 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, a boron-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring. R 6 is selected from hydrogen atoms, hydrocarbon groups having 1 to 3 carbon atoms consisting only of primary or secondary carbons, alkyl groups having 4 or more carbon atoms, aryl-substituted alkyl groups, monocyclic or bicyclic cyclic hydrocarbon groups, aryl groups, and halogen atoms. n is an integer from 1 to 4 that satisfies the valence of M, X is selected from the group consisting of hydrogen atoms, halogen atoms, hydrocarbon groups, anionic ligands, and neutral ligands that can coordinate with lone pairs of electrons. When n is 2 or more, the multiple Xs may be the same or different from each other, and may bond to each other to form a ring. 【Chemistry 2】 [In the general formula (C-V), M represents a transition metal atom of Group 4 of the periodic table.] R7 may be the same or different from each other, and represent 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, a boron-containing group, a germanium-containing group, or a tin-containing group. Adjacent R7s may be bonded to each other to form a monocyclic or bicyclic ring which may have substituents. Cp is a cyclopentadienyl ligand which may have substituents, N is an atom in Group 15 of the periodic table. Y2 is selected from carbon atoms, silicon atoms, germanium atoms, and tin atoms. The solid lines represent covalent or coordinate bonds. n is an integer from 1 to 4 that satisfies the valence of M, X is selected from the group consisting of hydrogen atoms, halogen atoms, hydrocarbon groups, anionic ligands, and neutral ligands that can coordinate with lone pairs of electrons. When n is 2 or more, the multiple Xs may be the same or different from each other, and may bond to each other to form a ring. 【Transformation 3】 [In the general formulas (C-VII) and (C-IX), M represents a transition metal atom of Group 4 of the periodic table.] Y is selected from carbon atoms, silicon atoms, germanium atoms, and tin atoms. R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, and R40 may be the same or different from each other, and represent 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, or a boron-containing group, and two or more of these may be linked to each other to form a ring. n is an integer from 1 to 4 that satisfies the valence of M, X is selected from the group consisting of hydrogen atoms, halogen atoms, hydrocarbon groups, anionic ligands, and neutral ligands that can coordinate with lone pairs of electrons. When n is 2 or more, the multiple Xs may be the same or different from each other, and may bond to each other to form a ring.

2. The catalyst for olefin polymerization according to claim 1, wherein the oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio in the above requirement (A-I) is 0.050 or more and 1.0 or less.

3. The catalyst for olefin polymerization according to claim 1 or 2, wherein M in the general formula (C-II) is a transition metal atom of group 4 of the periodic table.

4. A method for producing an olefin polymer, comprising the step of polymerizing an olefin in the presence of an olefin polymerization catalyst according to any one of claims 1 to 3.

5. The method for producing an olefin polymer according to claim 4, wherein the step of polymerizing the olefin is a step of homopolymerizing ethylene or propylene, or a step of copolymerizing ethylene with a linear or branched α-olefin having 3 to 30 carbon atoms.

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