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 a catalyst for olefin polymerization.SOLUTION: The transition metal compound is represented by the general formula [A-1] in the figure. (In the formula [A-1]: M is Ti, Zr, or Hf; n is an integer from 1 to 3; X is a halogen atom or the like; and R1 and R2 are each a hydrocarbon group having 1 to 20 carbon atoms or the like.)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 are known as catalysts for producing olefin polymers such as ethylene-α-olefin copolymers, ethylene polymers, and propylene polymers.

[0003] As such catalysts, transition metal compounds such as various types of metallocene compounds have been actively developed. For example, Patent Document 1 describes 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-Bu2C=N)Cl2 and Cp * Ti(2,6- i Pr2PhO)Cl2 (Cp represents a cyclopentadienyl group, Cp * is η 5-pentamethylcyclopentadienyl group.

[0006] On the other hand, Patent Document 2 describes Cp * An example of the production of ultra-high molecular weight polyethylene using a complex having a [t-BuPN]Cl2 skeleton is disclosed.

[0007] Patent Document 3 describes, as a comparative example, the production of an ethylene-propylene-ethylidenenorbornene (ENB) copolymer using a transition metal compound represented by the following formula:

[0008] [ka]

[0009] Furthermore, Non-Patent Document 1 describes the production of polyethylene using a transition metal compound represented by the following formula:

[0010] [ka]

[0011] Furthermore, Non-Patent Document 2 describes the production of polyethylene using a transition metal compound represented by the following formula:

[0012] [ka] [Prior art documents] [Patent documents]

[0013] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-63409 [Patent Document 2] Special Publication No. 2016-534165 [Patent Document 3] Patent Publication No. 2021-116302 [Non-patent literature]

[0014] [Non-Patent Document 1] Organometallics 1993, 18, 1116 [Non-patent document 2] Organometallics 2003, 22, 1937 Summary of the Invention [Problem to be solved by the invention]

[0015] However, it has been found that when the transition metal compounds described in Patent Document 1 as metallocene compounds are used as catalysts for polymerizing ethylene or α-olefins, there is room for further improvement in terms of increasing the molecular weight of the polymer.

[0016] 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 these viewpoints, it is considered that there is room for further investigation into the polymerization activity and copolymerization performance. Non-Patent Documents 1 and 2 also do not disclose copolymerization of ethylene with other olefins. On the other hand, in the production of the ethylene-propylene-ENB copolymer described above in Patent Document 3, there was room for further study in terms of increasing the content of olefins other than ethylene and producing a copolymer with a high molecular weight.

[0017] In view of the above-described 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, and an olefin polymerization catalyst containing the transition metal compound.

[0018] Another aspect of the present invention aims to provide a transition metal compound that, when used as a catalyst in the copolymerization of ethylene with other olefins, can produce an ethylene copolymer having a high content of olefins other than ethylene and a high molecular weight, and an olefin polymerization catalyst containing the transition metal compound. [Means for solving the problem]

[0019] As a result of extensive research aimed at solving the above problems, the present inventors have found that the above problems can be solved by the following embodiments, and have completed the present invention.

[0020] [1] A transition metal compound represented by the following general formula [A-1]: [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 represents a hydrogen atom, a hydrocarbon group, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a divalent diene derivative group, and when n is 2 or more, the multiple Xs may be the same or different from one another; R 1 and R 2 are each independently 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 sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group. [2] The transition metal compound according to item [1], wherein M is a titanium atom. [3] R 1 and R 2 and each independently represent a hydrocarbon group having 1 to 3 carbon atoms. [4] (A) A transition metal compound according to any one of [1] to [3], (B) (B-1) Organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) A compound that reacts with the transition metal compound (A) to form an ion pair At least one compound (B) selected from the group consisting of A catalyst for olefin polymerization comprising: [5] A method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of the olefin polymerization catalyst according to item [4]. [6] The method for producing an olefin polymer according to item [5], wherein the olefin is selected from olefins having 2 to 30 carbon atoms. [Effects of the Invention]

[0021] The transition metal compounds of the present invention are novel and can be used, inter alia, as catalysts for olefin polymerization. Furthermore, when the transition metal compound of the present invention is used as a catalyst in the copolymerization of ethylene with other olefins, an ethylene copolymer having a high content of olefins other than ethylene and a high molecular weight can be produced. DETAILED DESCRIPTION OF THE INVENTION

[0022] The present invention will be described in detail below.

[0023] [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].

[0024] [ka]

[0025] 《M》 In formula [A-1], M is a titanium atom, a zirconium atom, or a hafnium atom, and is preferably a titanium atom.

[0026] "n, X" In formula [A-1], n is an integer of 1 to 3, and preferably 2. When n is 2 or greater, the multiple groups represented by X may be the same or different and may be bonded to each other to form a ring.

[0027] In formula [A-1], X represents a hydrogen atom, a hydrocarbon group, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a divalent diene derivative group.

[0028] Examples of hydrocarbon groups include linear hydrocarbon groups, branched hydrocarbon groups, cyclic saturated hydrocarbon groups, cyclic unsaturated hydrocarbon groups, and groups in which one or more hydrogen atoms of a saturated hydrocarbon group are substituted with a cyclic unsaturated hydrocarbon group. The hydrocarbon group usually has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.

[0029] Examples of halogen atoms include fluorine, chlorine, bromine, iodine, etc., which are elements of Group 17. Chlorine is preferred as the halogen atom. 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 hydrocarbon group, silicon-containing group, nitrogen-containing group, or oxygen-containing group is substituted with a halogen atom.

[0030] Examples of the silicon-containing group include alkylsilyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, and triisopropylsilyl group, which are groups in which a carbon atom in a hydrocarbon group having 1 to 20 carbon atoms is replaced with a silicon atom; arylsilyl groups such as dimethylphenylsilyl group, methyldiphenylsilyl group, and t-butyldiphenylsilyl group; pentamethyldisilanyl group; and trimethylsilylmethyl group.

[0031] Examples of the oxygen-containing group include a hydroxyl group, a group in which the -CH2- structural unit in the hydrocarbon group, 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, 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, 1-methoxyethyl ... Examples of the alkyl group include an ethyl 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.

[0032] Examples of sulfur-containing groups include mesyl (methanesulfonyl) group, phenylsulfonyl group, tosyl (p-toluenesulfonyl) group, triflyl (trifluoromethanesulfonyl) group, nonaflyl (nonafluorobutanesulfonyl) group, mesylate (methanesulfonate) group, tosylate (p-toluenesulfonate) group, triflate (trifluoromethanesulfonate) group, and nonaflate (nonafluorobutanesulfonate) group.

[0033] 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 hydrocarbon group or the silicon-containing group is replaced with a nitrogen atom, a group in which the -CH2- structural unit is replaced with a nitrogen atom bonded to a hydrocarbon group, or a group in which the -CH3 structural unit is replaced with a nitrogen atom bonded to a hydrocarbon group or a nitrile group, such as a dimethylamino group, a diethylamino group, a dimethylaminomethyl group, a cyano group, a pyrrolidinyl group, a piperidinyl group, or a pyridinyl group.

[0034] An example of the phosphorus-containing group is a hexafluorophosphate anion.

[0035] Examples of the boron-containing group include tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl))borate anion, (benzyl)(tris(pentafluorophenyl))borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, and groups represented by BR4 (each R independently represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

[0036] Examples of the aluminum-containing group include:

[0037] [ka] (M represents M in the general formula (1) above.) Examples of suitable groups include groups represented by AlR4 (wherein R represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like) which can form the following formula:

[0038] Examples of the diene-based divalent derivative group include a 1,3-butadienyl group, an isoprenyl (2-methyl-1,3-butadienyl) group, a piperylenyl (1,3-pentadienyl) group, a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group, a cyclopentadienyl group, and a metallocyclopentene group.

[0039] 《R 1 and R 2 》 In formula [A-1], R 1 and R 2 are each independently 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 sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group.

[0040] Examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, linear unsaturated hydrocarbon groups having 2 to 20 carbon atoms, and cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms.

[0041] Examples of the alkyl group having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl, ethyl, n-propyl, 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.

[0042] 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.

[0043] Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as ethenyl (vinyl), 1-propenyl, 2-propenyl, and 1-methylethenyl (isopropenyl), and alkynyl groups such as ethynyl, 1-propynyl, and 2-propynyl (propargyl).

[0044] 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 a linear hydrocarbon group or a branched saturated hydrocarbon group are replaced with a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group having 3 to 19 carbon atoms, such as benzyl and cumyl.

[0045] R 1 and R 2 is preferably a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms. Specifically, it is preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a t-butyl group, more preferably a methyl group, an ethyl group, or an n-propyl group, and even more preferably a methyl group.

[0046] [Method for producing transition metal compounds] The transition metal compound of the present invention can be produced by combining known methods, and an example of a typical synthesis route is shown below, but the production method is not particularly limited. For example, the production method includes reacting a precursor of the ligand represented by the formula -N=P(i-Pr)3 in the transition metal compound of the present invention with a transition metal atom-containing compound to produce compound (a-1) containing the transition metal atom M, and then reacting the compound with a cyclopentadiene compound.

[0047] The compound (a-1) (e.g., X n+1A compound having a structure represented by M=P(i-Pr)3 (wherein X, n, and M have the same meanings as those in formula [A-1]) can be synthesized by a known method (Organometallics 2000, 19, 2994-3000).

[0048] Various cyclopentadiene compounds can be produced by known methods, and the production method is not particularly limited. For example, Japanese Patent Application Laid-Open No. 2000-136195, Japanese Patent Application Laid-Open No. 2009-24019, Japanese Patent No. 3674509, International Publication No. 1998 / 015510, International Publication No. 2000 / 049029, "J.Organomet.Chem. 1999,577,211," "J.Organomet.Chem. 2003,677,133," "Organometallics 1988,7,1828," "Organometallics 1996,15,4857," "Organometallics 1997,16,2503," "Organometallics 2004,23,4693," and "J.Am.Chem.Soc. 2004,126,2089.," Macromol.Chem.Phys. 2004,205,2275.," Örg.Lett. 2008,10,2545.," Chem.Rev. 1992,92,965.," Science 2012,338,504.," Organometallics 2006,25,3824. and the like can be cited as examples of production methods.

[0049] The transition metal compound of the present invention can be produced by a known method using a cyclopentadiene compound and compound (a-1). However, in this case, a specific combination of compound (a-1) and cyclopentadiene compound is selected so as to correspond to the structure of the desired transition metal compound. Known production methods can be used to react the two compounds. Examples of such production methods include the method for producing compound (a-1) and the production method described in "Organometallics 2008, 27, 6343."

[0050] [Olefin polymerization catalyst] The olefin polymerization catalyst of the present invention is (A) the transition metal compound according to the present invention described above, and (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with the transition metal compound (A) to form an ion pair [[ID={12}]]and at least one compound (B) selected from the group consisting of and is characterized by containing The olefin polymerization catalyst of the present invention may further contain (C) a carrier and (D) an organic compound, if necessary.

[0051] [[ID=1{9}]] [Compound (B)] [(B-1) Organometallic compound] Examples of the organometallic compound (B-1) (hereinafter also referred to as "component (B-1)") include organoaluminum compounds (B-1a) represented by the general formula (B-1a), complex alkylates of Group 1 metals and aluminum (B-1b) represented by the general formula (B-1b), and dialkyl compounds (B-1c) of Group 2 or Group 12 metals represented by the general formula (B-1c). Organometallic compounds of Groups 1, 2, 12, and 13 are exemplified.

[0052] (B-1a): Ra m Al(ORb) n H p X q In the formula (B-1a), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, X is a halogen atom, m satisfies 0 < m ≤ 3, n satisfies 0 ≤ n < 3, p satisfies 0 ≤ p < 3, q satisfies 0 ≤ q < 3, and m + n + p + q = 3. Examples of the organoaluminum compound (B-1a) include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, and tricycloalkylaluminum.

[0053] (B-1b):M2AlRa4 In formula (B-1b), M2 is Li, Na, or K, and Ra is a hydrocarbon group having 1 to 15 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms. Examples of the alkylated complex (B-1b) include LiAl(C2H5)4, LiAl(C7H 15 )4 can be mentioned.

[0054] (B-1c):RaRbM3 In formula (B-1c), Ra and Rb each independently represent a hydrocarbon group having 1 to 15 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, and M3 represents Mg, Zn, or Cd. Examples of compound (B-1c) include dimethyl magnesium, diethyl magnesium, di-n-butyl magnesium, ethyl-n-butyl magnesium, diphenyl magnesium, dimethyl zinc, diethyl zinc, di-n-butyl zinc, and diphenyl zinc. Among the organometallic compounds (B-1), organoaluminum compounds (B-1a) are preferred. The organometallic compound (B-1) may be used alone or in combination of two or more kinds.

[0055] [Organoaluminum oxy compound (B-2)] As the organoaluminum oxy compound (B-2) (hereinafter also referred to as "component (B-2)"), a conventionally known aluminoxane can be used as it is. Specifically, aluminoxanes represented by the following general formula [B2-1] can be used.

[0056] [ka] and / or the following general formula [B2-2]

[0057] [ka] (In formulas [B2-1] and [B2-2], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or greater.) benzene-insoluble organoaluminum oxy compounds described in JP-A Nos. 2-78687 and 2-167305, and aluminoxanes having two or more types of alkyl groups described in JP-A No. 3-103407.

[0058] Further, examples of the organoaluminum oxy compound (B-2) include modified methylaluminoxanes represented by the following general formula [B2-3].

[0059] [ka] (In formula [B2-3], R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represent an integer of 2 or greater.)

[0060] This modified methylaluminoxane is prepared using trimethylaluminum and alkylaluminums other than trimethylaluminum. Such compounds are commonly referred to as MMAO. Such MMAOs can be prepared by the methods described in U.S. Patent Nos. 4,960,878 and 5,041,584.

[0061] Further examples of the organoaluminum oxy compound (B-2) include boron-containing organoaluminum oxy compounds represented by the following general formula [B2-4].

[0062] [ka] (In formula [B2-4], R c R represents a hydrocarbon group having 1 to 10 carbon atoms. d may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.)

[0063] As the organoaluminum oxy-compound (B-2), methylaluminoxane, which is commercially available and therefore easily available, and MMAO prepared from trimethylaluminum and triisobutylaluminum are preferred. Among these, MMAO, which has improved solubility in various solvents and storage stability, is particularly preferred.

[0064] [Compound (B-3) that reacts with transition metal compound (A) to form an ion pair] Examples of the compound (B-3) (hereinafter also referred to as "ionic compound (B-3)" or "component (B-3)") 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 Nos. 1-501950, 1-502036, 3-179005, 3-179006, 3-207703, 3-207704, and U.S. Pat. No. 5,321,106. Heteropoly compounds and isopoly compounds are also included. However, these do not include the organoaluminum oxy compounds (B-2).

[0065] The ionic compound (B-3) is preferably a boron compound represented by the following general formula [B3-1].

[0066] [ka] In formula [B3-1], R e+ As for H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, etc. f From R i may be the same or different and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and are preferably substituted aryl groups.

[0067] Examples of the boron compound represented by the general formula [B3-1] include those described in paragraphs

[0133] to

[0144] of WO 2015 / 122414, such as triphenylcarbenium tetrakis(pentafluorophenyl)borate. The ionic compound (B-3) may be used alone or in combination of two or more.

[0068] [Carrier (C)] The support (C) is an inorganic or organic compound, and is a granular or fine particle solid. Supports conventionally used in olefin polymerization using a transition metal complex and a support as catalyst components, such as those described in

[0110] to

[0122] of JP 2011-122146 A, can be used.

[0069] [Organic compound component (D)] An organic compound component (D) may be used as a constituent of the olefin polymerization catalyst, if necessary. The organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the resulting polymer. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0070] [Method for producing olefin polymer] The process for producing an olefin polymer of the present invention is characterized by polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst of the present invention.

[0071] In the method for producing an olefin polymer of the present invention, an olefin homopolymer may be produced by polymerizing one type of olefin, or an olefin copolymer may be produced by copolymerizing two or more types of olefins. In this specification, polymerization and copolymerization are not particularly distinguished from each other and are also referred to as "polymerization," and olefin homopolymers and olefin copolymers are not particularly distinguished from each other and are also referred to as "olefin polymers."

[0072] The method of using each component constituting the olefin polymerization catalyst of the present invention and the order of adding them to a polymerization vessel can be selected arbitrarily, but the following method is exemplified: Hereinafter, the transition metal compound (A), compound (B), support (C), and organic compound component (D) will also be referred to as "components (A) to (D)," respectively. (1) Component (A) is added alone to a polymerization reactor. (2) A method in which component (A) and component (B) are added to a polymerization reactor in any order. (3) A method in which a catalyst component in which component (A) is supported on component (C) and component (B) are added to a polymerization vessel in any order. (4) A method in which a catalyst component in which component (B) is supported on component (C) and component (A) are added to a polymerization reactor in any order. (5) A method in which a catalyst component in which component (A) and component (B) are supported on component (C) is added to a polymerization reactor.

[0073] In each of the above methods, component (D) may be added at any stage. In each of the above methods, at least two of the catalyst components may be contacted in advance. In the above methods (4) and (5) in which component (B) is supported, unsupported component (B) may be added in any order, if necessary. In this case, the components (B) may be the same or different. Furthermore, the solid catalyst component in which component (A) is supported on component (C) and the solid catalyst component in which components (A) and (B) are supported on component (C) may be prepolymerized with an olefin, or the prepolymerized solid catalyst component may have further catalyst components supported thereon.

[0074] Olefin 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. 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; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more.

[0075] 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 1×10 per liter of reaction volume. -12 ~1×10 -2 mol, preferably 1 x 10 -10 ~1×10 -3 It is used in molar amounts.

[0076] 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 generally 0.01 to 50,000, preferably 0.05 to 10,000.

[0077] The organoaluminum oxy compound (B-2) is used in an amount such that the molar ratio [(B-2) / M] of the aluminum atoms in the organoaluminum oxy compound (B-2) to the total transition metals (M) in the transition metal compound (A) is generally 10 to 5,000, preferably 20 to 2,000.

[0078] The ionic compound (B-3) is used in an amount such that the molar ratio of the ionic compound (B-3) to the transition metal atom (M) in the transition metal compound (A) [(B-3) / M] is generally 1 to 10,000, preferably 1 to 5,000.

[0079] When the carrier (C) is used, it is used in an amount such that the weight ratio of the transition metal compound (A) to the carrier (C) [(A) / (C)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5, and even more preferably 0.001 to 0.1.

[0080] In the production method of the present invention, the polymerization temperature in the polymerization step is usually -50 to +200°C, preferably 0 to 180°C; the polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous, and continuous systems. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0081] The molecular weight of the resulting olefin polymer can be adjusted by adding hydrogen to the polymerization system, by changing the polymerization temperature, or by the amount of compound (B) used. When hydrogen is added, the amount is suitably about 0.001 to 5,000 nL per kg of the resulting olefin polymer.

[0082] Examples of the olefins to be subjected to the polymerization reaction in the method for producing an olefin polymer of the present invention include linear or branched α-olefins and cyclic olefins, specifically linear α-olefins such as 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, ethylidenenorbornene, vinylnorbornene, and dicyclopentadiene; Branched α-olefins such as 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene; Examples of cyclic olefins include cyclopentene, cyclohexene, norbornene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, and norbornadiene. The olefin to be polymerized preferably has 2 to 30 carbon atoms, and more preferably 2 to 20 carbon atoms.

[0083] In the method for producing an olefin polymer of the present invention, an aromatic vinyl compound or the like may be optionally added to the polymerization reaction together with the olefin, provided that the effects of the present invention are not impaired. Specific examples of such an aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, 3-phenylpropylene, and α-methylstyrene.

[0084] According to the process for producing an olefin polymer of the present invention, when ethylene and another olefin are copolymerized, an ethylene copolymer having a high content of olefins other than ethylene and a high molecular weight can be produced. The reason for this is presumed to be as follows. In the transition metal compound represented by formula [A-1], the steric hindrance of the isopropyl group on the phosphorus atom is relatively small, which presumably allows olefins other than ethylene to easily approach the central metal M, resulting in an ethylene copolymer with a high content of olefins other than ethylene and a high molecular weight. 1 , R 2 In the substituent of (1), the adoption of a bulky substituent is presumed to prevent contact with alkyl aluminum, which may be a factor in reducing activity. [Example]

[0085] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples in any way.

[0086] <Measurement method> [Structure of transition metal compounds] The structure of transition metal compounds is 400MHz 1H-NMR (JEOL ECZ400S), 270MHz 1 The determination was performed using H-NMR (JEOL GSH-270) and FD-MS (JEOL SX-102A).

[0087] [Polymer weight average molecular weight (Mw), number average molecular weight (Mn) 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:

[0088] <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

[0089] [Ethylene-propylene terpolymer comonomer content] The comonomer content of ethylene-propylene terpolymers was measured by FT-IR (JASCO FT-IR410 infrared spectrophotometer) or 1Measured by H-NMR measurement.

[0090] (FT-IR measurement method) In FT-IR, the polymer obtained in the examples was heated to 135°C, melt-stretched in a hot press, and then cooled under pressure at room temperature to obtain a film, which was used as a measurement sample. The propylene structural unit content and the ethylidene norbornene structural unit content were measured using a calibration curve.

[0091] 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 plot the relationship between the peak intensity ratios of two specific absorption wavenumbers that showed a linear or nearly linear relationship with the propylene structural unit content and ethylidene norbornene structural unit content data.

[0092] ( 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.

[0093] ( 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). 1H-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.

[0094] [Synthesis example of transition metal compound] [Example A] A transition metal compound (a) represented by the following formula (a) was synthesized by the following method.

[0095] [ka]

[0096] <Synthesis of Ligand (a)> Under a nitrogen atmosphere, 1.00 g (6.24 mmol) of triisopropylphosphine and 15 ml of toluene were placed in a flask, and 1.08 g (9.40 mmol) of trimethylsilyl azide was added at room temperature. The mixture was stirred at 80°C for 14 hours, the solvent was distilled off, and the soluble matter was extracted with hexane. The resulting solution was concentrated, and crystals were precipitated, yielding 1.46 g of the target product (hereinafter also referred to as "ligand (a)") represented by the formula: Me3Si-N=P(i-Pr)3 (where Me is a methyl group and i-Pr is an isopropyl group). The resulting ligand (a) was used in the next step without purification.

[0097] <Synthesis of transition metal compound (a)> Under a nitrogen atmosphere, 1.46 g of ligand (a) and 80 mL of toluene were placed in a flask, and 5.90 mL of titanium tetrachloride was added at -78°C. After stirring at 110°C for 16 hours, the solvent was distilled off. The soluble matter was extracted with hexane and filtered through Celite to remove the insoluble matter. The resulting solution was concentrated to precipitate crystals, yielding 1.49 g of the target product. The resulting solid was used in the next step without purification. Under a nitrogen atmosphere, 1.49 g of the solid obtained above and 50 mL of toluene were placed in a flask, and 0.417 g (4.15 mmol) of 1,3-dimethylcyclopentadienyllithium dissolved in 18 mL of tetrahydrofuran was added at -78°C. After the addition, the mixture was stirred at room temperature for 10 hours, and the solvent was distilled off. The soluble matter was extracted with hexane and filtered through Celite to remove the insoluble matter. The resulting solution was concentrated, and the crystals were precipitated with hexane and washed with hexane to obtain 0.417 g (47% yield, 3 steps) of the target product as yellow crystals. 1 The production of the target compound (hereinafter also referred to as "transition metal compound (a)") was confirmed by H-NMR (CDCl3) and FD-MS measurements. 1 H-NMR (400MHz, CDCl3): δ6.12(d,J=2.0Hz,2H),6.06(t,J=2.0Hz,1H),2.42-2.28(m,3H),2.26(s,6H),1.35(dd,J=15.6,7.2Hz,18H) FD-MS: m / z = 385.1 (M + )

[0098] [Comparative example A] A transition metal compound (b) represented by the following formula (b) was synthesized by the method described in Organometallics 2003, 22, 1937.

[0099] [ka]

[0100] [Comparative example B] A transition metal compound (c) represented by the following formula (c) was synthesized by the method described in Organometallics 2003, 22, 1937.

[0101] [ka]

[0102] [Example 1] <Polymerization of ethylene, propylene, and ENB> A 2-L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 1030 mL of hexane and 12 mL of 5-ethylidene-2-norbornene (ENB). The system was then heated to 95°C, followed by the addition of 0.90 MPa of propylene at a partial pressure. Ethylene was then added to the system to adjust the total pressure to 1.6 MPa-G. Next, 0.3 mmol of triisobutylaluminum, 0.0005 mmol of the transition metal compound (a), and 0.002 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added under nitrogen pressure, and polymerization was initiated by increasing the stirring speed to 250 rpm. Ethylene alone was then continuously added, maintaining 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, after which unreacted ethylene was purged. The resulting polymer solution was poured into a large excess of a methanol / acetone mixed solution and air-dried overnight. The resulting polymer was recovered by filtration and dried overnight under reduced pressure at 120°C to obtain 1.69 g of ethylene-propylene-ENB copolymer. The catalytic activity was 13.5 kg / mmol-Ti / hr, the composition was ethylene content 60.3 mass %, propylene content 21.1 mass %, ENB content 18.6 mass %, and the molecular weight (Mw) was 1,120,000.

[0103] [Comparative Example 1] <Polymerization of ethylene, propylene, and ENB> The same procedure as in Example 1 was carried out except that 0.0005 mmol of the transition metal compound (a) was changed to 0.0001 mmol of the transition metal compound (b), thereby obtaining 13.0 g of ethylene-propylene-ENB copolymer. The catalytic activity was 520.0 kg / mmol-Ti / hr, the composition was ethylene content 70.1 mass %, propylene content 14.7 mass %, ENB content 15.2 mass %, and the molecular weight (Mw) was 800,000.

[0104] Comparative Example 2 <Polymerization of ethylene, propylene, and ENB> The same procedure as in Example 1 was carried out except that 0.0005 mmol of the transition metal compound (a) was changed to 0.0001 mmol of the transition metal compound (c), thereby obtaining 27.3 g of ethylene-propylene-ENB copolymer. The catalytic activity was 1090.4 kg / mmol-Ti / hr, the composition was ethylene content 73.2 mass %, propylene content 20.8 mass %, ENB content 6.0 mass %, and the molecular weight (Mw) was 611,000.

[0105] [Table 1]

Claims

1. A transition metal compound represented by the following general formula [A-1]: 【Chemical 1】 (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 represents a hydrogen atom, a hydrocarbon group, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a divalent diene derivative group, and when n is 2 or more, the multiple Xs may be the same or different from one another; R 1 and R 2 are each independently 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 sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group.

2. 2. The transition metal compound according to claim 1, wherein M is a titanium atom.

3. The R 1 and R 2 and each independently represent a hydrocarbon group having 1 to 3 carbon atoms.

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

5. A method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 4.

6. 6. The method for producing an olefin polymer according to claim 5, wherein the olefin is selected from olefins having 2 to 30 carbon atoms.

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