Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer

Abstract

To provide a novel transition metal compound that can be used as an olefin polymerization catalyst.SOLUTION: The present disclosure provides a compound having a specific half-metallocene structure, for example, a transition metal compound of a structural formula (A). The transition metal compound shows high activity when used as a catalyst in the polymerization or copolymerization of an ethylene or an olefin having 3 or more carbon atoms, and provides a high-molecular-weight polymer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel transition metal compound, and more particularly to a novel transition metal compound that can be used as an olefin polymerization catalyst, an olefin polymerization catalyst containing said compound, and a method for producing an olefin polymer using said catalyst. [Background technology]

[0002] Catalysts consisting of metallocene compounds and cocatalysts such as organoaluminum oxy compounds are known to be useful for the production of olefin polymers such as ethylene-α-olefin copolymers.

[0003] As such catalysts, various types of transition metal compounds such as metallocene compounds have been actively developed. For example, Patent Document 1 discloses a transition metal compound (A) represented by the following general formula:

[0004] [ka] (In the formula, M represents a transition metal of Group 4 of the periodic table such as Ti, L represents a monovalent anionic ligand in which an element of Group 15 of the periodic table is a coordinating atom, X represents a halogen or the like, m represents an integer of 1 to 3, and R 1 ~R 5 represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, or the like.

[0005] and a method for producing a cyclic olefin copolymer by copolymerizing ethylene and / or an α-olefin having 3 to 20 carbon atoms with at least one cyclic olefin compound in the presence of a polymerization catalyst comprising one or more activators (B) selected from organoaluminum oxy compounds and organoboron compounds. Specific examples of the transition metal compound (A) include CpTi(t-BuC=N)Cl2, and as a comparative example, Cp * Ti(2,6- i (Cp represents a cyclopentadienyl group, Cp * is 5-pentamethylcyclopentadienyl group.

[0006] On the other hand, Patent Document 2 discloses an example of the production of ultra-high molecular weight polyethylene using a complex having a Cp*[t-BuPN]Cl2 skeleton. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-63409 [Patent Document 2] Special Publication No. 2016-534165 Summary of the Invention [Problem to be solved by the invention]

[0008] However, when the transition metal compounds described in Patent Document 1 as metallocene compounds are used as catalysts for the polymerization of ethylene or α-olefins, it has been found that there is room for further improvement in terms of catalytic activity, copolymerizability, and the production of high-molecular-weight polymers.

[0009] Patent Document 2 does not disclose the polymerization reaction of ethylene using a complex other than the above-mentioned structure, nor does it disclose the copolymerization of ethylene with other olefins. From this perspective, it can be considered that there is room for further investigation into the polymerization activity and copolymerization performance.

[0010] In view of the above-mentioned conventional techniques, an object of the present invention is to provide a novel transition metal compound, particularly a novel transition metal compound that can be used as an olefin polymerization catalyst suitable for various olefin polymerizations.

[0011] Another object of the present invention is to provide an olefin polymerization catalyst that is highly active and capable of producing a high-molecular-weight olefin polymer, and a novel transition metal compound that can be used in such an olefin polymerization catalyst. [Means for solving the problem]

[0012] The present inventors have conducted research in light of the above-mentioned problems and objects, and have found that a compound having a specific half-metallocene structure exhibits favorable effects as an olefin polymerization catalyst, thereby completing the present invention. That is, the present invention has the following features. [1] A transition metal compound represented by the following general formula [A-1]:

[0013] [ka] [In formula [A-1], M is a titanium atom, a zirconium atom, or a hafnium atom; n is an integer from 1 to 3, X's each independently 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, an aluminum-containing group, or a diene-based divalent derivative group; R 1 ~R 5 and R 6 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, and R 1 ~R 5 Adjacent groups among these may be bonded to each other to form a ring. Also, R 7 and R 8 is a cyclic hydrocarbon group.

[0014] [2] R 7 and R 8 is a 1-adamantyl group, [1] The transition metal compound according to [1].

[0015] [ka]

[0016] [3] In the general formula [A-2], The transition metal compound according to [2], wherein M is a titanium atom or a zirconium atom. [4] In the general formula [A-2], The transition metal compound according to [2], wherein M is a titanium atom. [5] In the general formula [A-2], R 6 is an adamantyl group, [2]~[4] 1. The transition metal compound according to any one of claims 1 to 9.

[0017] [6] (A) a transition metal compound according to any one of [1] to [5]; (B) (B-1) Organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) A compound that reacts with the transition metal compound to form an ion pair and at least one compound selected from the group consisting of A catalyst for olefin polymerization comprising:

[0018] [7] A method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of the olefin polymerization catalyst according to [6]. [8] The olefin (Z-1) The method for producing an olefin polymer according to [7], wherein the olefin is selected from olefins having 2 to 30 carbon atoms. [Effects of the Invention]

[0019] The transition metal compound of the present invention exhibits high activity when used as a catalyst in the polymerization or copolymerization of ethylene or olefins having 3 or more carbon atoms, and is characterized by giving polymers with high molecular weights. DETAILED DESCRIPTION OF THE INVENTION

[0020] The transition metal compound according to the present invention is specified by the following structure. When the transition metal compound is used in an olefin polymerization reaction, it is preferable to use it in combination with an organometallic compound containing an element of Groups 1, 2, or 13 of the periodic table, such as an organoaluminum compound. Each component will be explained below.

[0021] [Transition metal compounds] The transition metal compound of the present invention (hereinafter also referred to as transition metal compound (A)) is represented by the following general formula [A-1] and is specified by satisfying the following requirements.

[0022] [ka] In the formula [A-1], M is a titanium atom, a zirconium atom, or a hafnium atom.

[0023] The above M is a typical element of the so-called Group 4 elements of the periodic table, which is an element that is considered to have high anionic polymerizability. Among these, titanium and zirconium are preferred, and titanium is more preferred.

[0024] n is an integer of 1 to 3. When n is 2 or more, the groups represented by X may be the same or different and may be bonded to each other to form a ring. X's each independently 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, an aluminum-containing group, or a diene-based divalent derivative group.

[0025] Preferably, each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group. Specific examples of the halogen include fluorine, chlorine, bromine, and iodine, with chlorine or bromine being preferred.

[0026] R 1 ~R 5 and R 6are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, and R 1 ~R 5 Adjacent groups among these may be bonded to each other to form a ring.

[0027] Examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, saturated cyclic hydrocarbon groups having 3 to 20 carbon atoms, linear unsaturated hydrocarbon groups having 2 to 20 carbon atoms, and unsaturated cyclic hydrocarbon groups having 3 to 20 carbon atoms.

[0028] Examples of alkyl groups having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decanyl, and branched saturated hydrocarbon groups such as isopropyl, isobutyl, s-butyl, t-butyl, t-amyl, neopentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-dipropylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl, and cyclopropylmethyl. The number of carbon atoms in the alkyl group is preferably 1 to 6.

[0029] Examples of cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornenyl, 1-adamantyl, and 2-adamantyl groups, as well as groups in which the hydrogen atoms of these cyclic saturated hydrocarbon groups are replaced with hydrocarbon groups having 1 to 17 carbon atoms, such as 3-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-cyclohexylcyclohexyl, and 4-phenylcyclohexyl. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 5 to 11.

[0030] Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), 1-methylethenyl group (isopropenyl group), etc., and alkynyl groups such as ethynyl group, 1-propynyl group, 2-propynyl group (propargyl group), etc. The number of carbon atoms in the chain unsaturated hydrocarbon group is preferably 2 to 4.

[0031] Examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclopentadienyl, norbornyl, phenyl, naphthyl, indenyl, azulenyl, phenanthryl, and anthracenyl groups; groups in which hydrogen atoms of these cyclic unsaturated hydrocarbon groups are replaced with hydrocarbon groups having 1 to 15 carbon atoms, such as 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 4-ethylphenyl, 4-t-butylphenyl, 4-cyclohexylphenyl, biphenylyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, and 2,4,6-trimethylphenyl (mesityl); and groups in which hydrogen atoms of linear or branched saturated hydrocarbon groups are replaced with cyclic saturated or unsaturated hydrocarbon groups having 3 to 19 carbon atoms, such as benzyl and cumyl. The number of carbon atoms in the cyclic unsaturated hydrocarbon group is preferably 6 to 10.

[0032] Examples of alkylene groups having 1 to 20 carbon atoms include methylene, ethylene, dimethylmethylene (isopropylidene), ethylmethylene, 1-methylethylene, 2-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, n-propylene, etc. The alkylene group preferably has 1 to 6 carbon atoms.

[0033] Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 4,4'-biphenylylene group, etc. The arylene group preferably has 6 to 12 carbon atoms.

[0034] Examples of aryl groups partially overlap with the examples of the cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms described above, but include substituents derived from aromatic compounds, such as phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenanthrenyl, tetracenyl, chrysenyl, pyrenyl, indenyl, azulenyl, pyrrolyl, pyridyl, furanyl, and thiophenyl. Preferred aryl groups are phenyl and 2-naphthyl.

[0035] Examples of the aromatic compounds include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene.

[0036] The substituted aryl group partially overlaps with the examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, but examples include groups in which one or more hydrogen atoms of the aryl group are substituted with a substituent selected from a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and specific examples include a 3-methylphenyl group (m-tolyl group), a 4-methylphenyl group (p-tolyl group), a 3-ethylphenyl group, a 4-ethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a biphenylyl group, a 4-(trimethylsilyl)phenyl group, a 4-amino ... Examples of the substituted aryl group include a 4-(dimethylamino)phenyl group, a 4-(diethylamino)phenyl group, a 4-morpholinylphenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-phenoxyphenyl group, a 3,4-dimethoxyphenyl group, a 3,5-dimethoxyphenyl group, a 3-methyl-4-methoxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3-(trifluoromethyl)phenyl group, a 4-(trifluoromethyl)phenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 5-methylnaphthyl group, and a 2-(6-methyl)pyridyl group. Examples of the substituted aryl group include an "electron-donating group-containing substituted aryl group" described below.

[0037] Examples of silicon-containing groups include alkylsilyl groups such as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, and triisopropylsilyl, which are hydrocarbon groups having 1 to 20 carbon atoms and in which a carbon atom has been replaced with a silicon atom; arylsilyl groups such as dimethylphenylsilyl, methyldiphenylsilyl, and t-butyldiphenylsilyl; pentamethyldisilanyl; and trimethylsilylmethyl. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

[0038] Examples of the nitrogen-containing group include an amino group, a nitro group, an N-morpholinyl group, and a group in which the =CH- structural unit in the above-mentioned hydrocarbon group or silicon-containing group having 1 to 20 carbon atoms is replaced with a nitrogen atom, a group in which the -CH2- structural unit is replaced with a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, or a group in which the -CH3 structural unit is replaced with a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded or a nitrile group, such as a dimethylamino group, a diethylamino group, a dimethylaminomethyl group, a cyano group, a pyrrolidinyl group, a piperidinyl group, a pyridinyl group, etc. Preferred nitrogen-containing groups are dimethylamino groups and N-morpholinyl groups.

[0039] Examples of the oxygen-containing group include a hydroxyl group, a group in which the -CH2- structural unit in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group or nitrogen-containing group is replaced with an oxygen atom or a carbonyl group, or a group in which the -CH3 structural unit is replaced with an oxygen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, such as a methoxy group, ethoxy group, t-butoxy group, phenoxy group, trimethylsiloxy group, methoxyethoxy group, hydroxymethyl group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, Examples of the oxygen-containing group include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, an n-2-oxabutylene group, an n-2-oxapentylene group, an n-3-oxapentylene group, an aldehyde group, an acetyl group, a propionyl group, a benzoyl group, a trimethylsilylcarbonyl group, a carbamoyl group, a methylaminocarbonyl group, a carboxy group, a methoxycarbonyl group, a carboxymethyl group, an ethoxymethyl group, a carbamoylmethyl group, a furanyl group, and a pyranyl group. As the oxygen-containing group, a methoxy group is preferred.

[0040] Examples of halogen atoms include group 17 elements such as fluorine, chlorine, bromine, and iodine. Examples of the halogen-containing group include a trifluoromethyl group, a tribromomethyl group, a pentafluoroethyl group, and a pentafluorophenyl group, which are groups in which a hydrogen atom in the above-mentioned hydrocarbon group, silicon-containing group, nitrogen-containing group, or oxygen-containing group having 1 to 20 carbon atoms is substituted with a halogen atom.

[0041] R 6 As the alkyl group, a cyclic saturated hydrocarbon group is preferred, and an adamantyl group is particularly preferred. The aforementioned R 7 , R 8 is a cyclic hydrocarbon group, preferably a cyclic saturated hydrocarbon group. 1 ~R 6 Examples of the cyclic hydrocarbon groups include the same groups as those exemplified above.

[0042] Among the above transition metal compounds, R7 , R 8 A preferred example is a complex having a structure represented by the following formula [A-2], in which is an adamantyl group.

[0043] [ka] The symbols in formula [A-2] are as shown in formula [A-1]. Specific examples of the structure of the phosphinimine moiety in the above formula [A-2] are shown below.

[0044] [ka]

[0045] As will be described later, the transition metal compound of the present invention tends to exhibit higher polymerization activity and copolymerizability than conventional half-metallocene transition metal compounds, making it possible to produce polymers having a wide range of melting points, flexibility, and impact resistance.

[0046] When the olefin is polymerized using the transition metal compound (A), at least one compound selected from the group consisting of (B-1) organometallic compounds, (B-2) organoaluminum oxy-compounds, and (B-3) compounds that react with the transition metal compound (A) to form an ion pair can be used in combination with the transition metal compound (A). Each of these components will be described below.

[0047] ((B-1) Organometallic compound) Specific examples of the organometallic compound (B-1) used in the present invention include compounds containing at least one element of Groups 1, 2, 12, and 13 of the periodic table, represented by the following general formulas (B-1a) to (B-1c): R a p Al(OR b ) q H r Y s (B-1a) (In general formula (B-1a), R aand R b may be the same as or different from each other and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; Y represents a halogen atom; p is a number such that 0 < p ≤ 3, q is a number such that 0 ≤ q < 3, r is a number such that 0 ≤ r < 3, s is a number such that 0 ≤ s < 3, and m + n + p + q = 3. The organoaluminum compound represented by the formula (B-1a); M 3 AlR c 4···(B-1b) (In the general formula (B-1b), M 3 represents Li, Na or K; R c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. The complex alkyl compound of an alkali metal of Group 1 of the periodic table and aluminum represented by the formula (B-1b); R d R e M 4 ···(B-1c) (In the general formula (B-1c), R d and R e may be the same as or different from each other and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; M 4 is Mg, Zn or Cd. The dialkyl compound of an alkaline earth metal of Group 2 or a metal of Group 12 of the periodic table and the metal represented by the formula (B-1c);

[0048] Examples of the organoaluminum compound belonging to the general formula (B-1a) include the following compounds. R a p Al(ОR b ) 3-p ···(B-1a-1) (In the formula (B-1a-1), R a and R b may be the same as or different from each other and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; p is preferably a number such that 1.5 ≤ p ≤ 3. The organoaluminum compound represented by the formula (B-1a-1); R a p AlY 3-p ···(B-1a-2) (In the formula (B-1a-2), R arepresents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably a number where 0 < p < 3.) An organoaluminum compound represented by R a p AlH 3-p ···(B-1a-3) (In the formula (B-1a-3), R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number where 2 ≤ p < 3.) An organoaluminum compound represented by R a p Al(ОR b ) q Y s ···(B-1a-4) (In the formula (B-1a-4), R a and R b may be the same or different from each other, represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, p is a number where 0 < p ≤ 3, q is a number where 0 ≤ q < 3, s is a number where 0 ≤ s < 3, and p + q + s = 3.) An organoaluminum compound represented by

[0049] More specifically, as the organoaluminum compound belonging to the general formula (B-1a), tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tri-branched chain alkylaluminum such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; ​tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; Triarylaluminums such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; (i-C4H9) x Al y (C5H 10 ) z (wherein x, y, and z are positive numbers, and z≧2x), and other trialkenylaluminums such as triisoprenylaluminum; alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminum isopropoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; R a 2.5 Al(OR b ) 0.5 Partially alkoxylated alkylaluminum having an average composition represented by the formula: a and R b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; Dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, etc.; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminums, such as alkylaluminum dihydrides, such as ethylaluminum dihydride and propylaluminum dihydride; Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

[0050] Compounds similar to (B-1a) can also be used in the present invention, such as organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms, such as (C2H5)2AlN(C2H5)Al(C2H5)2.

[0051] The compounds belonging to the general formula (B-1b) include LiAl(C2H5)4, LiAl(C7H 15 )4 can be cited as examples.

[0052] Examples of the compound belonging to the general formula (B-1c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butylethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc, diisobutyl zinc, bis(pentafluorophenyl)zinc, dimethyl cadmium, and diethyl cadmium.

[0053] In addition, as the organometallic compound (B-1), methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, etc. can also be used.

[0054] Furthermore, compounds that form the above-mentioned organoaluminum compounds in the polymerization system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium, can also be used as the organometallic compound (B-1).

[0055] Among the organometallic compounds (B-1), organoaluminum compounds are preferred in terms of catalytic activity. The organometallic compounds (B-1) as described above may be used singly or in combination of two or more.

[0056] ((B-2) Organoaluminum oxy compound) The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound such as those exemplified in JP-A-2-78687.

[0057] Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent. (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or water of crystallization with the organoaluminum compound.

[0058] (2) A method in which water, ice or water vapor is directly reacted with an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

[0059] (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0060] The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the resulting aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0061] Specific examples of organoaluminum compounds used in preparing aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the general formula (B-1a) above.

[0062] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The organoaluminum compounds as described above may be used singly or in combination of two or more.

[0063] Solvents used in the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel; and hydrocarbon solvents such as halides, especially chlorides and bromides, of the above aromatic, aliphatic, and alicyclic hydrocarbons. Ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic or aliphatic hydrocarbons are particularly preferred. These solvents can be used alone or in combination.

[0064] The organoaluminum oxy compound (B-2) according to the present invention may be selected from at least one of aluminoxanes having a structure represented by the following general formula (B-2a) or (B-2b), and aluminoxanes having a structure comprising a repeating unit represented by the following general formula (B-2c) and a repeating unit represented by the following general formula (B-2d).

[0065] [ka] (In the general formula, R c are each independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specific examples thereof include hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a cyclohexyl group, a cyclooctyl group, a phenyl group, a tolyl group, and an ethylphenyl group. Among these examples, a methyl group, an ethyl group, and an isobutyl group are preferred, and a methyl group is particularly preferred. In the general formulae (B-2a), (B-2b), and (B-2c), R cmay be partially substituted with halogen atoms such as chlorine and bromine atoms, and the halogen content may be 40% by weight or less.

[0066] In the general formulae (B-2a) and (B-2b), r represents an integer of 2 to 500, preferably 6 to 300, and particularly preferably 10 to 100. In the general formulae (B-2c) and (B-2d), s and t each represent an integer of 1 or more.

[0067] The aluminoxane having a repeating unit represented by the general formula (B-2c) and a repeating unit represented by the general formula (B-2d) preferably has a molecular weight in the range of 200 to 2000 as measured by cryoscopic method in benzene.

[0068] The benzene-insoluble organoaluminum oxy-compound used in the present invention is preferably one in which the Al component dissolved in benzene at 60°C is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atom, i.e., it is preferably insoluble or poorly soluble in benzene.

[0069] The organoaluminum oxy compound (B-2) used in the present invention may also include boron-containing organoaluminum oxy compounds represented by the following general formula (B-2e).

[0070] [ka] (In general formula (B-2e), R 15 represents a hydrocarbon group having 1 to 10 carbon atoms, and four R 16 may be the same or different, and each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.)

[0071] The boron-containing organoaluminum oxy compound represented by the general formula (B-2e) can be produced by reacting an alkylboronic acid represented by the following general formula (B-2f) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

[0072] R 15 -B(OH)2···(B-2f) (In general formula (B-2f), R 15 represents R in the general formula (B-2e). 15 )

[0073] Specific examples of alkylboronic acids represented by the general formula (B-2f) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These may be used alone or in combination of two or more.

[0074] Specific examples of organoaluminum compounds to be reacted with such alkylboronic acids include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the general formula (B-1a) above.

[0075] The organoaluminum compound is preferably a trialkylaluminum or a tricycloalkylaluminum, and more preferably trimethylaluminum, triethylaluminum, or triisobutylaluminum, which may be used singly or in combination of two or more.

[0076] When an organoaluminum oxy compound (B-2) such as methylaluminoxane is used as a co-catalyst component in addition to the transition metal compound (A), a very high polymerization activity for olefin compounds is exhibited. The organoaluminum oxy compounds (B-2) as described above may be used singly or in combination of two or more.

[0077] ((B-3) A compound that reacts with the transition metal compound (A) to form an ion pair) Examples of the compound (B-3) (hereinafter referred to as "ionizing ionic compound") used in the present invention that reacts with the transition metal compound (A) to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and US Pat. No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds.

[0078] Specifically, the Lewis acid includes a compound represented by BR3 (R is fluorine or a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.

[0079] Examples of the ionic compound include compounds represented by the following general formula (B-3a).

[0080] [ka] (In general formula (B-3a), R 17 is H +, a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal, and R 18 ~R 21 may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups.

[0081] Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0082] Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium 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 di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0083] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0084] R 17 As the cation, a carbonium cation and an ammonium cation are preferred, and a triphenylcarbonium cation, an N,N-dimethylanilinium cation, and an N,N-diethylanilinium cation are particularly preferred.

[0085] Further, examples of the ionic compound include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0086] Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

[0087] Specific examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.

[0088] Specific examples of the dialkylammonium salt include di(1-propyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, and the like.

[0089] Further examples of the ionic compound include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formula (B-3b) or (B-3c).

[0090] [ka] (In formula (B-3b), Et represents an ethyl group.)

[0091] [ka] (In formula (B-3c), Et represents an ethyl group.)

[0092] Specific examples of borane compounds, which are examples of ionizable ionic compounds (compound (B-3)), include decaborane; Salts of anions such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate; Examples include salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydride dodecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydride dodecaborate)nickelate(III).

[0093] Specific examples of carborane compounds, which are examples of ionizable ionic compounds, include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, and undecahydride-7,8-dimethyl-1,3-dicarbanonaborane. methyl-7,8-dicarboxundecaborane, dodecahydride-11-methyl-2,7-dicarboxundecaborane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium Tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 7-carbaundecaborate, tri(n-butyl)ammonium 7,8-dicarbaundecaborate, tri(n-butyl)ammonium 2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate Salts of anions such as undecahydride, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)ferrate salts of metal carborane anions such as salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxundecaborate)chromate(III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxundecaborate)cobaltate(III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)chromate(III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)manganate(IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)cobaltate(III), and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)nickelate(IV).

[0094] Heteropoly compounds, which are examples of ionized ionic compounds, are compounds containing an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten.Specific examples include, but are not limited to, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and salts of these acids. Examples of the salts include salts of the acids with, for example, alkali metals of Group 1 or alkaline earth metals of Group 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0095] Isopoly compounds, which are examples of ionized ionic compounds, are compounds composed of metal ions of one type of atom selected from vanadium, niobium, molybdenum, and tungsten, and can be considered to be molecular ion species of metal oxides. Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Examples of the salts include salts of the acids with metals from Groups 1 and 2 of the periodic table, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium, as well as organic salts such as triphenylethyl salts.

[0096] The above-mentioned ionizing ionic compound (compound (B-3) that reacts with the transition metal compound (A) to form an ion pair) may be used singly or in combination of two or more. The olefin polymerization catalyst according to the present invention may contain the above-mentioned transition metal compound (A) (hereinafter may be abbreviated as "component (A)"), at least one compound (B) (hereinafter may be abbreviated as "component (B)") selected from the group consisting of organometallic compounds (B-1), organoaluminum oxy-compounds (B-2), and ionizing ionic compounds (B-3), and may also contain the following carrier (C), if necessary.

[0097] [(C) Carrier] The carrier (C) used in the present invention is an inorganic or organic compound, and is a granular or fine particle solid. By supporting the transition metal compound (A) and the compound (B) on the carrier (C), a polymer with good morphology can be obtained.

[0098] The inorganic compound is preferably a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral, or an ion-exchangeable layered compound. Specific examples of the porous oxide that can be used include SiO2, Al2O3, MgO, ZrO, TiO2, BO3, CaO, ZnO, BaO, and ThO2, as well as composites or mixtures containing these, and further examples of the porous oxide that can be used include natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-VO5, SiO2-Cr2O3, and SiO2-TiO2-MgO. Of these, porous oxides containing SiO2 and / or Al2O3 as the main component are preferred.

[0099] The porous oxide may contain small amounts of carbonates, sulfates, nitrates, and oxides such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O.

[0100] The properties of such porous oxides vary depending on the type and manufacturing method, but the porous oxides preferably used in the present invention have a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of ​​50 to 1000 m. 2 / g, preferably 100 to 700m 2 / g, and the pore volume is in the range of 0.3 to 3.0 cm 3 / g range. Such porous oxides are calcined at 100 to 1000°C, preferably 150 to 700°C, as required, before use.

[0101] The solid aluminoxane compound may be an aluminoxane selected from at least one of the aluminoxanes shown in (B-2a) to (B-2d). The solid aluminoxane used in the present invention differs from conventionally known olefin polymerization catalyst supports in that it does not contain inorganic solid components such as silica or alumina or organic polymer components such as polyethylene or polystyrene, but rather refers to a solidified product containing an alkylaluminum compound as the main component. The term "solid" as used in the present invention refers to maintaining a substantially solid state under the reaction environment in which the aluminoxane component (B-2) is used. More specifically, it refers to the fact that component (B) is in a solid state under specific temperature and pressure conditions in an inert hydrocarbon solvent such as hexane or toluene used in the reaction, for example, when contacting component (A) with component (B) as described below to prepare a solid catalyst component for olefin polymerization. Furthermore, when suspension polymerization is performed using the solid catalyst component for olefin polymerization prepared using component (B), as described below, it is also necessary that component (B) contained in the catalyst component is in a solid state under specific temperature and pressure conditions in a hydrocarbon solvent such as hexane, heptane, or toluene. The same applies to bulk polymerization in which polymerization is performed in a liquefied monomer instead of a solvent, or gas-phase polymerization in which polymerization is performed in a monomer gas.

[0102] Visual confirmation is the most convenient method for determining whether component (B) is in a solid state under the above-mentioned environment, but visual confirmation is often difficult, for example, during polymerization. In such cases, it is possible to determine this from, for example, the properties of the polymer powder obtained after polymerization or the state of adhesion to the reactor. Conversely, if the properties of the polymer powder are good and adhesion to the reactor is low, even if a portion of component (B) leaches out to a certain extent under the polymerization environment, this does not deviate from the spirit of the present invention. Indicators for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the presence of amorphous polymers, but polymer bulk density is preferred from the viewpoint of quantitative determination. In the present invention, the bulk density is usually 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

[0103] The solid aluminoxane used in the present invention has a solubility in n-hexane maintained at 25°C of usually 0 to 40 mol %, preferably 0 to 20 mol %, and particularly preferably 0 to 10 mol %.

[0104] The solubility of the solid aluminoxane used in the present invention in n-hexane was determined by adding 2 g of the solid aluminoxane carrier to 50 ml of n-hexane kept at 25°C, stirring for 2 hours, separating the solution using a G-4 glass filter, and measuring the aluminum concentration in the filtrate. Therefore, the solubility is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms equivalent to 2 g of the aluminoxane used.

[0105] As the solid aluminoxane according to the present invention, any known solid aluminoxane can be used without limitation. Known production methods are disclosed, for example, in JP-B-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000-38410, JP-A-2000-95810, and WO2010 / 55652.

[0106] The average particle size of the solid aluminoxane according to the present invention is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1,000 μm, and particularly preferably 1 to 200 μm. The average particle size of solid aluminoxane is determined by observing the particles with a scanning electron microscope, measuring the particle sizes of 100 or more particles, and averaging the weights. The particle size of solid aluminoxane was determined by measuring the maximum length of the particle image using the Pythagorean method. That is, the length of the particle image sandwiched between two parallel lines in both the horizontal and vertical directions was measured, and the particle size was calculated using the following formula: Particle size = ((horizontal length) 2 +(vertical length) 2 ) 0.5

[0107] The weight average particle size of the solid aluminoxane can be calculated using the particle size calculated above according to the following formula. Average particle size=Σnd 4 / Σnd 3 (where n is the number of particles, d is the particle size)

[0108] The solid aluminoxane preferably used in the present invention has a specific surface area of ​​50 to 1000 m 2 / g, preferably 100 to 800m 2 / g, and the pore volume is 0.1 to 2.5 cm 3 / g is desirable.

[0109] Examples of inorganic halides that can be used include MgCl, MgBr, MnCl, and MnBr. The inorganic halides may be used as they are or may be pulverized using a ball mill or a vibration mill. Alternatively, the inorganic halides may be dissolved in a solvent such as alcohol and then precipitated into fine particles using a precipitating agent.

[0110] The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compounds are compounds having a crystalline structure in which planes formed by ionic bonds or the like are stacked parallel to one another with weak bonding forces, and the ions they contain are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and synthetic compounds can also be used.

[0111] Examples of clay, clay minerals, or ion-exchange layered compounds include ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl2 type, and CdI2 type.

[0112] Furthermore, examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, halloysite, etc. Ion-exchange layered compounds include α-Zr(HAsO4)2·H2O and α-Zr(HP Examples include crystalline acid salts of polyvalent metals such as α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O.

[0113] Such clays, clay minerals, or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, having a radius of 20 Å or more, as measured by mercury intrusion porosimetry. Here, the pore volume is measured by mercury intrusion porosimetry using a mercury porosimeter for pores with a radius of 20 to 30,000 Å. When a carrier having a pore volume of less than 0.1 cc / g with a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.

[0114] It is also preferable to subject the clay and clay minerals used in the present invention to chemical treatment. Chemical treatments include surface treatments that remove impurities from the surface and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment not only removes surface impurities but also increases the surface area by eluting cations such as Al, Fe, and Mg in the crystalline structure. Alkali treatment destroys the crystalline structure of the clay, resulting in structural changes. Furthermore, salt treatment and organic treatment form ionic complexes, molecular complexes, organic derivatives, etc., which can change the surface area and interlayer distance.

[0115] The ion-exchangeable layered compound used in the present invention may be a layered compound in which the interlayer spacing is expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with other large, bulky ions. Such bulky ions act as supports supporting the layered structure and are usually called pillars. The introduction of another substance between the layers of a layered compound in this manner is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.), and [Al 13 O4(OH) 24 ] 7+ , [Zr4(OH) 14 ] 2+ , [Fe3O(OCOCH3)6] + Examples of suitable pillars include metal hydroxide ions such as those mentioned above. These compounds can be used alone or in combination of two or more. When intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides (where R represents a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, and colloidal inorganic compounds such as SiO2, can also be present. Examples of suitable pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them with heat.

[0116] The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as is, or may be used after treatment such as ball milling or sieving. They may also be used after newly adding and adsorbing water or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

[0117] Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica are particularly preferred. As mentioned above, the carrier (C) is an inorganic or organic compound, and examples of the organic compound include granular or fine particle solids with a particle size in the range of 10 to 300 μm. Specific examples include (co)polymers mainly composed of α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers mainly composed of vinylcyclohexane and styrene, and modified products thereof.

[0118] The olefin polymerization catalyst according to the present invention may further contain the following specific organic compound component (D), in addition to the above-mentioned transition metal compound (A), the above-mentioned compound (B), and, if necessary, the support (C).

[0119] [(D) Organic compound component] In the present invention, the organic compound component (D) is used, if necessary, for the purpose of improving the polymerization performance of the olefin polymerization catalyst of the present invention and the physical properties of the produced polymer (for example, the molecular weight of the produced polymer) (increasing the molecular weight, in the case of molecular weight). Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

[0120] The alcohols and phenolic compounds are generally selected from the group consisting of R 22 -OH is used, where R 22represents a hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols).

[0121] As for alcohols, R 22 The phenolic compound is preferably one in which the α,α'-positions of the hydroxyl group are substituted with a hydrocarbon having 1 to 20 carbon atoms.

[0122] The carboxylic acid is usually R 23 The one expressed as -COOH is used. 23 represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and is particularly preferably a halogenated hydrocarbon group having 1 to 50 carbon atoms.

[0123] As the phosphorus compound, phosphoric acids having a P-O-H bond, phosphates having a P-OR or P=O bond, and phosphine oxide compounds are preferably used. Examples of the sulfonate include those represented by the following general formula (Da).

[0124] [ka] (In the general formula (Da), M 5 is an atom in groups 1 to 14 of the periodic table, and R 24 is hydrogen, carbon atom Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, t is an integer of 1 to 7, u is an integer of 1 to 7, and tu is 1 or greater.

[0125] <Method of producing olefin polymer> The method for producing an olefin polymer according to the present invention includes a step of polymerizing or copolymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst to obtain an olefin polymer. As mentioned above, in this specification, the term "olefin" refers to any compound having a polymerizable double bond.

[0126] In the polymerization, the components constituting the catalyst of the present invention may be used in any manner and added to the polymerization vessel in any order, but the following methods are exemplified. (1) A method in which the transition metal compound (A) is added alone to a polymerization reactor. (2) A method in which the transition metal compound (A) and the compound (B) are added to a polymerization reactor in any order. (3) A method in which a catalyst component in which a transition metal compound (A) is supported on a carrier (C) and a compound (B) are added to a polymerization reactor in any order.

[0127] (4) A method in which the catalyst component in which the compound (B) is supported on the carrier (C) and the transition metal compound (A) are added to a polymerization reactor in any order. (5) A method in which a catalyst component in which a transition metal compound (A) and a compound (B) are supported on a carrier (C) is added to a polymerization reactor.

[0128] (6) A method in which a catalyst component in which a transition metal compound (A) and a compound (B) are supported on a carrier (C), and the compound (B) are added to a polymerization vessel in any order. In this case, the compound (B) supported on the carrier (C) and the compound (B) added alone may be the same or different.

[0129] (7) A method in which the catalyst component in which the compound (B) is supported on the carrier (C) and the transition metal compound (A) are added to a polymerization reactor in any order. (8) A method in which the catalyst component in which compound (B) is supported on carrier (C), transition metal compound (A), and compound (B) are added to a polymerization vessel in any order. In this case, compound (B) supported on carrier (C) and compound (B) added alone may be the same or different.

[0130] (9) A method in which a component in which the transition metal compound (A) is supported on a carrier (C) and a component in which the compound (B) is supported on a carrier (C) are added to a polymerization reactor in any order. (10) A method in which a component in which a transition metal compound (A) is supported on a carrier (C), a component in which a compound (B) is supported on a carrier (C), and compound (B) are added to a polymerization reactor in any order. In this case, compound (B) supported on carrier (C) and compound (B) added alone may be the same or different.

[0131] (11) A method in which the transition metal compound (A), the compound (B), and the organic compound component (D) are added to a polymerization reactor in any order. (12) A method in which the compound (B) and the organic compound component (D) are contacted in advance, and the transition metal compound (A) are added to a polymerization reactor in any order.

[0132] (13) A method in which the compound (B), the organic compound component (D) supported on the carrier (C), and the transition metal compound (A) are added to a polymerization reactor in any order. (14) A method in which a catalyst component in which a transition metal compound (A) and a compound (B) have been previously contacted, and an organic compound component (D) are added to a polymerization reactor in any order.

[0133] (15) A method in which a catalyst component in which a transition metal compound (A) and a compound (B) have been contacted in advance, compound (B), and an organic compound component (D) are added to a polymerization reactor in any order. (16) A method in which a catalyst component in which a transition metal compound (A) and a compound (B) have been contacted in advance, and a component in which a compound (B) and an organic compound component (D) have been contacted in advance, are added to a polymerization vessel in any order. In this case, the compound (B) contacted with the transition metal compound (A) and the compound (B) contacted with the organic compound component (D) may be the same or different.

[0134] (17) A method in which a component in which a transition metal compound (A) is supported on a carrier (C), a compound (B), and an organic compound component (D) are added to a polymerization reactor in any order. (18) A method in which a component in which a transition metal compound (A) is supported on a carrier (C) and a component in which a compound (B) and an organic compound component (D) are previously contacted are added to a polymerization reactor in any order.

[0135] (19) A method in which a catalyst component obtained by previously contacting a transition metal compound (A), a compound (B) and an organic compound component (D) in any order is added to a polymerization reactor. (20) A method in which a catalyst component in which a transition metal compound (A), a compound (B), and an organic compound component (D) have been previously contacted, and the compound (B) are added to a polymerization vessel in any order. In this case, the compound (B) that is contacted with the transition metal compound (A) and the organic compound component (D) and the compound (B) that is added alone may be the same or different.

[0136] (21) A method of adding a catalyst in which a transition metal compound (A), a compound (B), and an organic compound component (D) are supported on a carrier (C) to a polymerization reactor. (22) A method in which a catalyst component comprising a transition metal compound (A), a compound (B), and an organic compound component (D) supported on a carrier (C), and component (B) are added to a polymerization reactor in any order. In this case, the compound (B) supported on the carrier (C) and the compound (B) added alone may be the same or different.

[0137] The solid catalyst component in which the transition metal compound (A) is supported on the support (C) and the solid catalyst component in which the transition metal compound (A) and the compound (B) are supported on the support (C) may be prepolymerized with an olefin, or the prepolymerized solid catalyst component may further have another catalyst component supported on it.

[0138] In the present invention, (co)polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Specific 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. Furthermore, the olefin itself to be subjected to (co)polymerization can also be used as the solvent.

[0139] When olefin polymerization is carried out using the above-mentioned olefin polymerization catalyst, the transition metal compound (A) is usually used in an amount of 10 -12 ~10 -2 moles, preferably 10 -10 ~10 -3 It is used in molar amounts.

[0140] The organometallic compound (B-1) is used in an amount such that the molar ratio of the organometallic compound (B-1) to the total transition metal atoms (M) in the transition metal compound (A) [(B-1) / M] is usually 0.01 to 100,000, preferably 0.05 to 50,000. The organoaluminum oxy compound (B-2) is used in an amount such that the molar ratio of the aluminum atoms in the organoaluminum oxy compound (B-2) to the total transition metal atoms (M) in the transition metal compound (A) [(B-2) / M] is usually 10 to 500,000, preferably 20 to 100,000. The compound (ionizing ionic compound) (B-3) that reacts with the transition metal compound (A) to form an ion pair is used in an amount such that the molar ratio of the ionizing ionic compound (B-3) to the transition metal atoms (M) in the transition metal compound (A) [(B-3) / M] is usually 1 to 10, preferably 1 to 5.

[0141] The organic compound component (D) is used in an amount such that the molar ratio to the organometallic compound (B-1) [(D) / (B-1)] is generally 0.01 to 10, preferably 0.1 to 5. The organic compound component (D) is used in an amount such that the molar ratio to the organoaluminum oxy compound (B-2) [(D) / (B-2)] is generally 0.001 to 2, preferably 0.005 to 1. The organic compound component (D) is used in an amount such that the molar ratio to the ionizing ionic compound (B-3) [(D) / (B-3)] is generally 0.01 to 10, preferably 0.1 to 5.

[0142] The polymerization temperature of olefins using such an olefin polymerization catalyst is usually in the range of −50 to +200° C., preferably 0 to 170° C. The polymerization pressure is usually normal pressure to 100 kg / cm. 2 -G, preferably atmospheric pressure to 50 kg / cm 2 Under the conditions of -G, the polymerization reaction can be carried out in any of batch, semi-continuous, and continuous modes. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0143] The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature, and can also be adjusted by the amount of compound (B) used.

[0144] The olefin that can be polymerized by the olefin polymerization catalyst of the present invention is not particularly limited as long as it has a polymerizable double bond, and examples thereof include linear or branched α-olefins having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, 2-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; Examples of cyclic olefins include those having 3 to 30, preferably 3 to 20, and more preferably 3 to 10 carbon atoms, such as 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.

[0145] The olefin polymerization catalyst of the present invention is more preferably used for the homopolymerization of ethylene or the copolymerization of ethylene with an olefin having 3 to 20 carbon atoms, preferably a linear or branched α-olefin having 3 to 10 carbon atoms. The α-olefins may be used alone or in combination of two or more.

[0146] In the copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, the α-olefin (hereinafter also referred to as olefin A) is not particularly limited as long as the effects of the present invention are achieved, but for example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, and 1-decene are preferred. These α-olefins may be used alone or in combination of two or more. Among these, at least one selected from 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene is more preferred.

[0147] When ethylene is used as the α-olefin and the olefin A is used, the ratio of the amounts of ethylene to the olefin A used is usually 1:10 to 5000:1, preferably 1:5 to 1000:1, in terms of ethylene:olefin A (molar ratio).

[0148] The olefin polymerization catalyst of the present invention may be used to (co)polymerize known chain unsaturated hydrocarbons having polar groups (for example, carbonyl groups, hydroxyl groups, ether-bonded groups, etc.). The olefin polymerization catalyst of the present invention may also be used to (co)polymerize vinylcyclohexane, dienes, polyenes, and the like.

[0149] Examples of the diene or polyene include cyclic or chain compounds having 4 to 30, preferably 4 to 20, carbon atoms and two or more double bonds. Specific examples include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, and dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene; Furthermore, aromatic vinyl compounds, for example, mono- or polyalkylstyrenes such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, etc.; Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, and divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene, and the like.

[0150] As explained above, the transition metal compound (A) of the present invention has a novel structure in which specific substituents are introduced at specific positions of the metallocene skeleton, and the olefin polymerization catalyst of the present invention containing the compound (A) has superior copolymerizability with α-olefins compared to conventional transition metal compounds having a metallocene skeleton (which does not have specific substituents at specific positions), exhibits a good balance between olefin polymerization activity and copolymerizability, and is capable of producing ethylene copolymers having sufficient molecular weight and low density.

[0151] Although the reason for this is currently unknown, the present inventors believe that the effect is due to the following: In other words, the effect is thought to be due to the transition metal compound (A) represented by the general formula [A-1] or [A-2]: (i) the introduction of a heteroatom-containing electron-donating substituent into a specific metallocene site results in a significant improvement in α-olefin copolymerization, and (ii) the introduction of a substituent into the vicinity inhibits the activity reduction phenomenon due to the introduction of a heteroatom.

[0152] More specifically, the effect of the substituent is thought to be related to the bulkiness of the group bonded to the phosphine imide group, which is composed of multiple bulky cyclic hydrocarbon groups. In other words, the transition metal compound (A) exerts a moderate steric effect sufficient to maintain ion separation from the cocatalyst so that the polymerization reaction can continue, while the bulky substituent is located at a position where the steric barrier to the olefin to be coordinated is relatively low. Furthermore, this substituent restricts the direction of olefin coordination in some way with α-olefins having 3 or more carbon atoms, making chain transfer less likely to occur. Therefore, the transition metal compound (A) may be able to polymerize olefins more efficiently, contributing to copolymerization and the ease of obtaining high-molecular-weight polymers. Most preferably, it is speculated that there may be cases where an excellent balance of the performances of activity, copolymerization, and the ease of obtaining high-molecular-weight polymers is achieved. To achieve this effect particularly effectively, an embodiment containing a cyclic hydrocarbon group as the substituent is considered to be preferable.

[0153] [Olefin polymer] According to the present invention, an olefin polymer can be efficiently produced by polymerizing one or more olefins selected from α-olefins having 2 to 30 carbon atoms in the presence of an olefin polymerization catalyst containing the useful and novel transition metal compound (A) having the specific structure described above; preferably, by homopolymerizing ethylene or copolymerizing ethylene with at least one olefin A selected from olefins having 3 to 20 carbon atoms.

[0154] One embodiment of the olefin polymer is an ethylene-based polymer containing ethylene-derived structural units in a range of preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 90 to 100 mol%. The ethylene-based polymer contains the olefin A-derived structural units in a total range of preferably 0 to 50 mol%, more preferably 0 to 30 mol%, and even more preferably 0 to 10 mol%. The total content of the ethylene-derived structural units and the olefin A-derived structural units is 100 mol%. An ethylene-based polymer having the olefin A-derived structural units in the above range exhibits excellent moldability. Furthermore, the polymer may contain other structural units within a range that does not deviate from the spirit of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy, or, when a reference substance is available, infrared spectroscopy, or the like.

[0155] Among these polymers, ethylene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-1-octene polymer, ethylene-1-hexene polymer, ethylene-4-methyl-1-pentene polymer, ethylene-propylene-1-octene polymer, ethylene-propylene-1-hexene polymer, and ethylene-propylene-4-methyl-1-pentene polymer are particularly preferred. The above copolymers are usually random copolymers, but may also be so-called block copolymers (impact copolymers) obtained by mixing or continuously producing two or more selected from these polymers.

[0156] Among the polymers having the structural units described above, the ethylene polymer is preferably an α-olefin polymer consisting essentially of structural units derived from an α-olefin having 2 to 20 carbon atoms. "Substantially" means that the proportion of structural units derived from an α-olefin having 2 to 20 carbon atoms is 95% by weight or more of all structural units.

[0157] The weight average molecular weight of the olefin polymer measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 10,000 to 5,000,000, more preferably 10,000 to 2,000,000, and particularly preferably 20,000 to 1,000,000. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is not particularly limited, but is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 5.

[0158] The density of the olefin polymer is not particularly limited, but is preferably 875 kg / m 3 More than 975kg / m 3 It is preferable that: The intrinsic viscosity [η] of the olefin polymer in decalin at 135° C. is not particularly limited, but is preferably 0.1 to 40 dl / g, more preferably 0.5 to 15 dl / g, and particularly preferably 1 to 10 dl / g.

[0159] The melt mass flow rate (MFR; unit: g / 10 min) of the olefin polymer measured in accordance with ASTM D1238-89 at 190°C under a load of 2.16 kg is not particularly limited, but is preferably 0.001 g / 10 min or more and 300 g / 10 min or less, and more preferably 0.001 g / 10 min or more and 200 g / 10 min or less.

[0160] In addition, the value (I10 / I2) obtained by dividing the MFR value measured under conditions of 190°C and a 10 kg load according to ASTM D1238-89 by the MFR value measured under conditions of 190°C and a 2.16 kg load is preferably 5.0 or more and less than 300. The detailed conditions for measuring the above physical properties are as described in the Examples. [Example]

[0161] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0162] [Measurement method] [Structure of transition metal compounds] The structure of the transition metal compound is 1 The results were determined using H-NMR spectroscopy (270 MHz, JEOL GSH-270) and FD-MS (JEOL JMS-T1000GC).

[0163] [Polymer weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the olefin polymer were 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:

[0164] <Devices and conditions used> Measurement equipment: Gel permeation chromatograph Alliance GPC2000 (Waters) Analysis software: Chromatography Data System Empower (trademark, 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 (ODCB) (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) 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

[0165] [Intrinsic viscosity ([η])] The measurement was carried out at 135°C using decalin as a solvent. Approximately 20 mg of polymer was dissolved in 15 mL of decalin, and the specific viscosity ηsp After diluting this decalin solution by adding 5 mL of decalin solvent, the specific viscosity η sp This dilution procedure was repeated two more times, and the η when the concentration (C) was extrapolated to 0 was measured. sp The value of / C was taken as the intrinsic viscosity. [η]=lim(η sp / C) (C→0)

[0166] [Polymer density] A polymer melted at 190°C was passed through an orifice with an inner diameter of approximately 2.1 mm by melt extrusion to prepare a strand, which was then heat-treated at 120°C for 30 minutes. The strand was left at room temperature for 1 hour, and then cut to an appropriate length as needed to prepare a measurement sample. The density (kg / m) of this sample was measured by the density gradient tube method. 3 ) was measured.

[0167] [Hexene content of polymer] The hexene content of the ethylene-1-hexene copolymer was measured by FT-IR (JASCO FT-IR410 infrared spectrophotometer). FT-IR was performed by heating the polymer obtained in the examples to 135°C, dissolving and stretching it in a hot press, and then cooling it under pressure at room temperature to obtain a film. The measurement sample was a film obtained by heating the polymer obtained in the examples to 135°C, dissolving and stretching it in a hot press, and then cooling it under pressure at room temperature. The measurement sample was a film obtained by heating the polymer to 135°C, dissolving ... -1 ~400cm -1 The hexene content was measured by the C-CH2CH2CH2CH3 skeletal vibration (1378 cm) based on hexene. -1 ) was used as the key band, and the absorbance of the key band (D1378) and the internal standard band (4321 cm -1 The absorbance was calculated from the ratio [D1378 / D4321] of the absorbance (D4321) of the CH stretching vibration and the methylene / methyl bending vibration combination.

[0168] A calibration curve specifying the relationship between the hexene content and the ratio [D1378 / D4321] was used to determine the hexene content. 13Ethylene copolymers of various compositions, the hexene content of which was determined by C NMR, were subjected to FT-IR measurement by the above-mentioned method, and were prepared in advance based on the results of [D1378 / D4321].

[0169] [Ethylene-propylene terpolymer comonomer content] The comonomer content of ethylene-propylene terpolymers was measured by FT-IR (JASCO FT-IR410 infrared spectrophotometer) or 1 1 H NMR measurement.

[0170] (FT-IR measurement method) Films obtained in the same manner as the ethylene-hexene copolymer were used as measurement samples, and the propylene structural unit content and the ethylidene norbornene structural unit content were measured using calibration curves.

[0171] The ethylene-propylene terpolymer sample for creating the calibration curve was prepared under the following conditions: 13 The comonomer content was determined by C NMR measurement. Calibration curves were obtained by using these samples to select peak intensity ratios of two specific absorption wavenumbers that show a linear or nearly linear relationship with the propylene structural unit content and ethylidene norbornene structural unit content data, and then graphing the relationship.

[0172] ( 13 C NMR measurement method) The measurement solvent was o-dichlorobenzene / benzene-d6 (4 / 1 {vol / vol%}) and the measurement conditions were: measurement temperature 120°C, spectral width 250 ppm, pulse repetition time 5.5 seconds, pulse width 4.7 μs (45° pulse) (100 MHz, JEOL ECX400P), or measurement temperature 120°C, spectral width 250 ppm, pulse repetition time 5.5 seconds, pulse width 5.0 μs (45° pulse) (125 MHz, Bruker BioSpin AVANCE IIIcryo-500). 13 The C NMR spectrum was measured, various signals were assigned in a conventional manner, and the comonomer content was quantified based on the integrated value of the signal intensity.

[0173] ( 1 H NMR measurement) The measurement was performed using o-dichlorobenzene-d4 as the measurement solvent, under the following measurement conditions (500 MHz, Bruker Biospin AVANCE III cryo-500): measurement temperature 120 °C, spectral width 250 ppm, pulse repetition time 7.0 seconds, pulse width 5.0 μs (45° pulse). 1 H NMR measurement was performed. Various signals such as methyl groups and ethylidene groups were assigned according to standard methods, and the comonomer content was quantified based on the integrated value of the signal intensity.

[0174] [Production of titanium compounds] [Example A1] Synthesis of transition metal compound A A transition metal compound A represented by the following formula (A) was synthesized by the following method.

[0175] [ka]

[0176] (Synthesis of Ligand) Under a nitrogen atmosphere, 1000 mg (2.29 mmol) of Tris(1-adamantyl)phosphine (Strem), 30 mL of dehydrated toluene, and 396 mg of trimethylsilyl azide were added to a Schlenk flask and heated under reflux for 19 hours. The mixture was then returned to room temperature, the solvent was evaporated under reduced pressure, and the mixture was washed with hexane. 1094 mg of the target product was obtained (yield 90%). 1 The target substance (hereinafter referred to as ligand A1) was identified from the results of H-NMR (CDCl3) measurement. 1 H-NMR(270MHz,CDCl3)δ 0.05(9H,s),2.21-1.71(45H,m)ppm

[0177] (Synthesis of transition metal compounds) Under a nitrogen atmosphere, 100 mg (0.456 mmol) of cyclopentadienyltitanium trichloride, 250 mg (0.477 mmol) of the ligand A1 obtained in the previous reaction, and 50 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 21.5 hours. After the solvent was removed by distillation under reduced pressure, the mixture was dissolved in dichloromethane and hexane was added. Half of the solvent was removed by distillation under reduced pressure, and the precipitated yellow powder was collected by filtration, washed with hexane, and then dried under reduced pressure. 171 mg of a yellow solid (hereafter referred to as transition metal compound A) was obtained in a 59% yield. 1 The target product was identified by H-NMR (CDCl3) and FD-MS measurements. 1 H-NMR(270MHz,CDCl3)δ 2.46-1.73(45H,m),6 0.51(5H,s)ppm FD-MS: m / z = 633.3 (M + )

[0178] [Example A2] Synthesis of transition metal compound B A transition metal compound B represented by the following formula (B) was synthesized by the following method.

[0179] [ka]

[0180] Under a nitrogen atmosphere, 100 mg (0.371 mmol) of indenyltitanium trichloride, 204 mg (0.389 mmol) of Ligand A1 obtained in Example A1, and 40 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 17 hours. The solvent was removed under reduced pressure to 10%, and hexane was then added. The precipitated yellow powder was collected by filtration. A small amount of dichloromethane was added to the obtained yellow solid, and the solution was added to hexane while removing insoluble matter using a membrane filter. The solvent was removed under reduced pressure to 25%, and the precipitated yellow powder was collected by filtration. The mixture was dried under reduced pressure to obtain 201 mg of a yellow powder (hereinafter referred to as transition metal compound B) in a yield of 79%. 1 The target product was identified by H-NMR (CDCl3) and FD-MS measurements. 1 H-NMR(270MHz,CDCl3)δ 2.48-1.73(45H,m),6 .59(2H,d,J=3.3Hz),7.10(1H,t,J=3.3Hz), 7.29 -7.24(2H,m),7.69-7.65(2H,m)ppm FD-MS: m / z = 683.2 (M + )

[0181] [Example A3] Synthesis of transition metal compound C A transition metal compound C represented by the following formula (C) was synthesized by the following method.

[0182] [ka]

[0183] Under a nitrogen atmosphere, 160 mg (0.401 mmol) of pentafluorophenylmethyl cyclopentadienyl titanium trichloride, 210 mg (0.401 mmol) of Ligand A1 obtained in Example A1, and 40 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 18.5 hours. The solvent was removed by distillation under reduced pressure to 20%, and hexane was added. The precipitated yellow powder was collected by filtration. The obtained yellow solid was dissolved in a small amount of dichloromethane and added to hexane. The solvent was removed by distillation under reduced pressure to one-third of the original volume, and the precipitated yellow powder was collected by filtration. After drying under reduced pressure, 261 mg of a yellow powder (hereinafter referred to as transition metal compound C) was obtained in an 80% yield. 1 The target product was identified by H-NMR (CDCl3) and FD-MS measurements. 1 H-NMR(270MHz,CDCl3)δ 2.47-1.73(45H,m),4 .05(2H, s)6.28(2H,t,J=2.6Hz),6.46(2H,t,J=2.6Hz)ppm FD-MS: m / z = 813.2 (M + )

[0184] [Example A4] Synthesis of transition metal compound D A transition metal compound D represented by the following formula (D) was synthesized by the following method.

[0185] [ka]

[0186] Under a nitrogen atmosphere, 168 mg (0.475 mmol) of adamantyl-cyclopentadienyl titanium trichloride, 250 mg (0.477 mmol) of Ligand A1 obtained in Example A1, and 50 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 17 hours. The solvent was removed by distillation under reduced pressure to 10%, and hexane was added. The precipitated yellow powder was collected by filtration. The obtained yellow powder was dissolved in a small amount of dichloromethane and added to hexane. The solvent was removed by distillation under reduced pressure to 2 / 3 of the original volume, and the precipitated yellow powder was collected by filtration. After drying under reduced pressure, 206 mg of a yellow powder (hereinafter referred to as transition metal compound D) was obtained in a 56% yield. 1 The target product was identified by H-NMR (CDCl3) and FD-MS measurements. 1 H-NMR(270MHz,CDCl3)δ 2.47-1.79(60H,m), 6.48-6.41(4H,m)ppm FD-MS: m / z = 767.4 (M + )

[0187] [Example A5] Synthesis of transition metal compound E A transition metal compound E represented by the following formula (E) was synthesized by the following method.

[0188] [ka]

[0189] (Synthesis of Ligand E1) Under a nitrogen atmosphere, 502 mg (1.39 mmol) of Di(1-adamantyl)-n-butylphosphine (cataCXium®, manufactured by Aldrich), 30 mL of dehydrated toluene, and 176 mg (1.53 mmol) of trimethylsilyl azide were added to a Schlenk flask and refluxed at 80°C for 5 hours. The mixture was returned to room temperature, the solvent was evaporated under reduced pressure, and the mixture was washed with hexane. 536 mg of the target product was obtained (yield 86%). 1From the results of H-NMR (CDCl3) measurement, the target substance represented by the following formula (E1) (hereinafter referred to as ligand E1) was identified. 1 H-NMR(270MHz,CDCl3)δ 0.00(9H,s),0.93(3H,t),1.32-1.96(36H,m)ppm

[0190] [ka]

[0191] (Synthesis of transition metal compounds) Under a nitrogen atmosphere, 144 mg (0.657 mmol) of cyclopentadienyltitanium trichloride, 307 mg (0.689 mmol) of the ligand E1 obtained in the previous reaction, and 50 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 16 hours. After the solvent was removed by distillation under reduced pressure, the mixture was dissolved in dichloromethane and hexane was added. Half of the solvent was removed by distillation under reduced pressure, and the precipitated yellow powder was collected by filtration, washed with hexane, and then dried under reduced pressure. 294 mg of a yellow solid (hereafter referred to as transition metal compound E) was obtained in an 82% yield. 1 The target product was identified by H-NMR (CDCl3) and FD-MS measurements. 1 H-NMR(270MHz,CDCl3)δ 1.02(3H,t),1.42-1.53(2H,m),1.68-2.35(34H,m),6.47(5H,s)ppm FD-MS: m / z = 555.2 (M + )

[0192] [Example A6] Synthesis of transition metal compound F A transition metal compound F represented by the following formula (F) was synthesized by the following method.

[0193] [ka]

[0194] Under a nitrogen atmosphere, 246 mg (0.616 mmol) of pentafluorophenylmethyl cyclopentadienyl titanium trichloride, 287 mg (0.664 mmol) of the ligand E1 obtained in the previous reaction, and 50 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 16 hours. After the solvent was removed by distillation under reduced pressure, the mixture was dissolved in dichloromethane and hexane was added. Half of the solvent was removed by distillation under reduced pressure, and the precipitated yellow powder was collected by filtration, washed with hexane, and then dried under reduced pressure. 287 mg of yellow powder (hereafter referred to as transition metal compound (F)) was obtained in a 59% yield. 1 The target product was identified by H-NMR (CDCl3) and FD-MS measurements. 1 H-NMR(270MHz,CDCl3)δ 0.95(3H, t),1.38-1.46(2H,m),1.68-2.09(34H,m),3.97(2H,s),6.20(2H,d),6.33(2H,t)ppm FD-MS: m / z = 735.1 (M + )

[0195] [Example A7] Synthesis of transition metal compound G A transition metal compound G represented by the following formula (G) was synthesized by the following method.

[0196] [ka]

[0197] Under a nitrogen atmosphere, 150 mg (0.559 mmol) of indenyltitanium trichloride, 261 mg (0.587 mmol) of the ligand E1 obtained in the previous reaction, and 50 mL of dehydrated toluene were added to a Schlenk flask and stirred at 100°C for 16 hours. After the solvent was removed by distillation under reduced pressure, the mixture was dissolved in dichloromethane and hexane was added. Half of the solvent was removed by distillation under reduced pressure, and the precipitated yellow powder was recovered by filtration, washed with hexane, and then dried under reduced pressure. 226 mg of yellow powder (hereafter referred to as transition metal compound G) was obtained in a yield of 67%. 1 The target product was identified by H-NMR (CDCl3) and FD-MS measurements. 1 H-NMR(270MHz,CDCl3)δ 0.96(3H,t),1.36-1.50(2H,m)1.36-2.83(34H,m),6.50(2H,d),6.91(1H,t),7.14-7.22(2H,m),7.57-7.62(2H,m)ppm FD-MS: m / z = 605.2 (M + )

[0198] [Comparative Synthesis Example a1] Synthesis of transition metal compound a Transition metal compound a represented by the following formula (a) was synthesized as described in Organometallics 1999, 18, 1116-1118. It was synthesized by the method described in

[0199] [ka]

[0200] [Comparative Synthesis Example a2] Synthesis of transition metal compound b A transition metal compound b represented by the following formula (b) was synthesized by the method described in J. Organomet. Chem. 2004, 689, 203.

[0201] [ka]

[0202] [Comparative Synthesis Example a3] Synthesis of transition metal compound c A transition metal compound c represented by the following formula (c) was synthesized by the method described in JP-A-2006-169521.

[0203] [ka]

[0204] [Comparative Synthesis Example a4] Synthesis of transition metal compound d A transition metal compound d represented by the following formula (d) was synthesized by the following method: In formula (d), "Adm" represents an adamantyl group.

[0205] [ka]

[0206] In a nitrogen atmosphere, 354 mg (1 .00mmol), 1,1,1-tri-tert-butyl-N-(trimethylsilyl)-phosphanimine 326 mg (1.12 mmol) and 50 mL of dehydrated toluene were added, and the mixture was stirred at 100°C for 19 hours. After the solvent was distilled off under reduced pressure, a small amount of dichloromethane was dissolved and the solution was added to hexane. The precipitated yellow powder was collected by filtration. The obtained yellow powder was dissolved in a small amount of dichloromethane, and hexane was added to the solution to recrystallize at -10°C. The precipitated crystals were collected by filtration and recrystallized with hexane. After washing and drying under reduced pressure, 326 mg of a yellow solid was obtained in a yield of 61%. 1 H-NMR (CD The target substance was identified by the results of Cl3) and FD-MS measurements. 1 H-NMR(270MHz,CDCl3)δ 2.03-1.52(42H,m), 6.45-6.39(4H,m)ppm FD-MS: m / z = 533.2 (M + )

[0207] [Production of ethylene polymers and ethylene-1-hexene copolymers] [Example p1] Under a nitrogen atmosphere, a reactor with an internal volume of 270 L and a stirrer was used. Silica gel (Fuji Silysia Chemical Ltd., cumulative 50% particle size of volume distribution by laser light diffraction scattering method: 70 μm, specific surface area: 340 m) was 2 / g, pore volume: 1.3cm 3 10 kg of methylaluminoxane (3.5 mol / L in terms of Al atoms, dried at 250°C for 10 hours) was suspended in 77 L of toluene and then cooled to 0-5°C. 19.4 L of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) was added dropwise to this suspension over 30 minutes. The system temperature was maintained at 0-5°C. After contacting the suspension for 30 minutes at 0-5°C, the system temperature was raised to 95°C over 1.5 hours and continued contacting the suspension for 4 hours at 95°C. The system was then cooled to room temperature, the supernatant liquid was removed by decantation, and the suspension was washed twice with toluene to prepare a total of 115 L of support slurry. A portion of the resulting support slurry was sampled and analyzed, revealing a solids concentration of 122.6 g / L and an Al concentration of 0.612 mol / L.

[0208] Under a nitrogen atmosphere, 30 mL of toluene and 1.63 mL of the support slurry (solid weight 0.2 g) were added to a 200 mL reactor equipped with a stirrer. Next, a 5.0 μmol toluene solution of transition metal compound A obtained in Synthesis Example A1 was added, and the mixture was contacted at a system temperature of 20 to 25°C for 1 hour. The supernatant was then removed by decantation, and the mixture was washed twice with hexane. This resulted in a catalyst slurry with a total volume of 40 mL.

[0209] 500 mL of heptane was added to a 1 L stainless steel autoclave that had been thoroughly purged with nitrogen. Ethylene was then passed through to saturate the reactor with ethylene. Next, 1-hexene was added in the amount shown in Table 1, followed by 0.375 mmol of triisobutylaluminum and 2.5 mg of Adeka Pluronic L-71 (ADEKA Corporation) as a decane solution. The catalyst slurry was added in an amount equivalent to 20.0 mg of solids. The temperature and pressure were then increased to 80°C and 0.8 MPaG with ethylene, and the polymerization reaction was carried out for 90 minutes. The resulting polymer was filtered and dried under reduced pressure at 80°C for 10 hours to yield 41.5 g of ethylene polymer. The polymer production per gram of catalyst slurry solids (activity in Table 1) was calculated to be 2070 g / g-cat. The analytical values ​​of the resulting polymer are shown in Table 1.

[0210] [Examples p2 to p8] Preparation of catalyst slurry and production of ethylene polymer and ethylene-1-hexene copolymer were carried out in the same manner as in Example p1, except that the amounts of transition metal compound and 1-hexene added in Example p1 were changed to those shown in Table 1. The activity (g / g-cat) calculated from the amount of the obtained polymer and the analytical values ​​of the polymer are shown in Table 1.

[0211] [Comparative examples p1~p8] Preparation of catalyst slurry and production of ethylene polymer and ethylene-1-hexene copolymer were carried out in the same manner as in Example p1, except that the amounts of transition metal compound and 1-hexene added in Example p1 were changed to those shown in Table 1. The activity (g / g-cat) calculated from the amount of the obtained polymer and the analytical values ​​of the polymer are shown in Table 1.

[0212] [Table 1]

[0213] The following can be seen from the figures in Table 1 above. In ethylene homopolymerization, the present invention tends to have high activity. -The content of olefins with 3 or more carbon atoms tends to be high. Generally, as the content of olefins with 3 or more carbon atoms increases, the polymerization activity tends to decrease. However, in the embodiment of the present invention, even if the olefin content is high, the polymerization activity is at approximately the same level or higher than that of the comparative example. Generally, as the olefin content increases, the molecular weight tends to decrease, but in the embodiment of the present invention, even if the olefin content is high, the molecular weight is at the same level or higher.

[0214] [Example p9] A solid aluminoxane was synthesized according to the method described in International Publication WO 2010 / 055652 (Preliminary Experiment 1 and Example 5) and used as a support. However, in consideration of safety concerns such as the risk of fire from trimethylaluminum, the experiment was carried out at a concentration approximately 1 / 6 of the conditions disclosed in the document.

[0215] Specifically, 100 mL of a 0.5 mol / L solution of trimethylaluminum in toluene was placed in a glass reactor equipped with a stirrer. The solution was cooled to 15°C, and 2.18 g of benzoic acid was slowly added at a rate that maintained the solution temperature below 25°C. The mixture was then heated and aged at 50°C for 1 hour. At this time, the molar ratio of trimethylaluminum to oxygen atoms in benzoic acid was 1.40. The reaction solution was heated at 70°C for 4 hours, then at 60°C for 6 hours, and then cooled to room temperature. It was then heated at 100°C for 8 hours to precipitate a solid component. After cooling the solution to below 30°C, 100 mL of hexane was added with stirring for washing. After standing for 30 minutes, 150 mL of the supernatant was removed, and another 150 mL of hexane was added with stirring. After standing for 15 minutes, 150 mL of the supernatant was removed, and another 150 mL of hexane was added with stirring. Finally, after leaving the mixture to stand for 15 minutes, 180 mL of the supernatant was removed, and hexane was added to a total volume of 14.6 mL to obtain a carrier slurry. A portion of the obtained carrier slurry was sampled and analyzed, and the solid concentration was 41.0 g / L and the Al concentration was 0.583 mol / L. Furthermore, particle observation of the obtained carrier with a scanning electron microscope revealed an average particle diameter of 6.8 μm and a specific surface area of ​​18.1 m.2 / mmol-Al.

[0216] Under a nitrogen atmosphere, 30 mL of toluene and 2.44 mL of the support slurry (solid weight 0.1 g) were added to a 200 mL reactor equipped with a stirrer. Next, a 5.0 μmol toluene solution of transition metal compound A was added, and the mixture was allowed to contact for 1 hour at a system temperature of 20 to 25°C. The supernatant was then removed by decantation, and the mixture was washed twice with hexane. This resulted in a catalyst slurry with a total volume of 40 mL.

[0217] 500 mL of heptane was added to a 1 L stainless steel autoclave that had been thoroughly purged with nitrogen. Ethylene was then passed through to saturate the reactor with ethylene. Next, 1-hexene was added in the amount shown in Table 1, followed by 0.25 mmol of triisobutylaluminum and 2.5 mg of Adeka Pluronic L-71 (ADEKA Corporation) as a decane solution. The catalyst slurry was then added in an amount equivalent to 5.0 mg of solids. The temperature and pressure were raised to 75°C and 0.65 MPaG using an ethylene / hydrogen gas mixture with a hydrogen concentration of 0.10 vol%. Polymerization was carried out for 90 minutes. The resulting polymer was filtered and dried under reduced pressure at 80°C for 10 hours to yield 48.6 g of ethylene polymer. The polymer production per gram of catalyst slurry solids (activity in Table 2) was calculated to be 9710 g / g-cat. The analytical values ​​of the resulting polymer are shown in Table 2.

[0218] [Examples p10 to p16] Preparation of catalyst slurry and production of ethylene polymer and ethylene-1-hexene copolymer were carried out in the same manner as in Example p9, except that the amounts of transition metal compound and 1-hexene added in Example p9 were changed to those shown in Table 2. The activity (g / g-cat) calculated from the amount of the obtained polymer and the analytical values ​​of the polymer are shown in Table 2.

[0219] [Comparative Examples p9-p16] Preparation of catalyst slurry and production of ethylene polymer and ethylene-1-hexene copolymer were carried out in the same manner as in Example p9, except that the amounts of transition metal compound and 1-hexene added in Example p9 were changed to those shown in Table 2. The activity (g / g-cat) calculated from the amount of the obtained polymer and the analytical values ​​of the polymer are shown in Table 2.

[0220] [Table 2]

[0221] The results in the above table also show that the embodiment of the present invention has higher polymerization activity than the comparative example, and the molecular weight is almost the same.

[0222] [Examples p17 to p20] Preparation of catalyst slurry and production of ethylene polymer and ethylene-1-hexene copolymer were carried out in the same manner as in Example p9, except that the amounts of transition metal compound and 1-hexene used in Example p9 were changed to those shown in Table 3. The results of Examples p17 to p20 are shown in Table 3, along with the results of Comparative Examples 9 and 11 to 13.

[0223] [Table 3]

[0224] The results in Table 3 show that in the embodiments using transition metal compounds E to G, polymers having higher molecular weights than conventional polymers tend to be obtained more easily.

[0225] [Example p21] <Production of ethylene-propylene-ENB copolymer> A 2 L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 1030 mL of hexane and ethylidene norbornene (ENB). The system temperature was raised to 95°C, and then propylene was added at the specified partial pressure. Ethylene was then introduced to adjust the total pressure to 1.6 MPa-G. Next, 0.3 mmol of triisobutylaluminum, 0.05 μmol of the transition metal compound E obtained above as the main catalyst, and triphenylcarbenium tetrakis(pentafluorophenyl)borate as a cocatalyst in an amount 4 times the molar amount of the transition metal compound were introduced under nitrogen pressure. Polymerization was initiated by increasing the stirring speed to 250 rpm. Subsequently, ethylene alone was continuously introduced to maintain the total pressure at 1.6 MPa-G, and polymerization was carried out for 15 minutes at 95°C. The polymerization was terminated by adding a small amount of ethanol to the system, and unreacted ethylene was purged. The resulting polymer solution was poured into a large excess of a methanol / acetone mixed solution to precipitate the polymer. The polymer was collected by filtration and dried overnight under reduced pressure at 120°C to produce ethylene-propylene-ENB copolymer. The analytical results of the obtained polymer are shown in Table 4.

[0226] [Examples pp. 22-24, Comparative Examples pp. 17-20] An ethylene-propylene-ENB copolymer was produced in the same manner as in Example p21, except that the amounts of transition metal compound and ENB used in Example p21 were changed to the conditions shown in Table 4. The results are shown in Table 4.

[0227] [Table 4]

[0228] The results in Table 4 show that in the embodiments using transition metal compounds E to G, it is easier to obtain polymers with a higher content of structural units derived from α-olefins such as propylene and ethylidene norbornene or diene compounds than conventional polymers.

Claims

1. A transition metal compound represented by the following general formula [A-2]: 【Chemistry 1】 [In formula [A-2], M is a titanium atom, a zirconium atom, or a hafnium atom; n is an integer from 1 to 3, X's each independently 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, an aluminum-containing group, or a diene-based divalent derivative group; R 1 ~R 5 and R 6 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group; R 1 ~R 5 Adjacent groups among these may be bonded to each other to form a ring.]

2. In the general formula [A-2], 2. The transition metal compound according to claim 1, wherein M is a titanium atom or a zirconium atom.

3. In the general formula [A-2], 2. The transition metal compound of claim 1, wherein M is a titanium atom.

4. In the general formula [A-2], R 6 The transition metal compound according to any one of claims 1 to 3, wherein is an adamantyl group.

5. (A) the transition metal compound according to any one of claims 1 to 4; (B) (B-1) organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) A compound that reacts with the transition metal compound to form an ion pair and at least one compound selected from the group consisting of 1. A catalyst for olefin polymerization comprising:

6. A method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 5.

7. The olefin is 7. The method for producing an olefin polymer according to claim 6, wherein (Z-1) is an olefin selected from olefins having 2 to 30 carbon atoms.

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