Method for producing olefin copolymer and transition metal compound

Abstract

To provide a method for producing an olefin copolymer, by which the molecular weight of a copolymer formed from ethylene, an alicyclic cyclic olefin, and a cyclic olefin including an aromatic structure can be made higher.SOLUTION: A method for producing an olefin copolymer, in which ethylene, an alicyclic cyclic olefin, and a cyclic olefin including an aromatic structure are copolymerized in the presence of an olefin polymerization catalyst comprising (A) a transition metal compound having a specific nitrogen-containing aromatic ligand and a cyclopentadienyl group, and (B) at least one compound selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound capable of forming an ion pair by reacting with the transition metal compound (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing an olefin copolymer, and also to a novel transition metal compound. [Background technology]

[0002] Conventionally, catalysts consisting of metallocene compounds and cocatalysts such as organoaluminum oxy compounds have been known as catalysts for producing olefin copolymers such as ethylene-α-olefin copolymers.

[0003] 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 atom or the like, m represents an integer of 1 to 3, and R 1 ~R 5 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or the like. 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.

[0005] Furthermore, Non-Patent Document 1 describes that copolymerization of ethylene with norbornene or the like was carried out in the presence of a transition metal compound represented by the following formula and methylaluminoxane (MAO).

[0006] [ka]

[0007] It has also been reported that copolymers of ethylene, alicyclic olefins, and cyclic olefins containing aromatic structures are suitable for use as resins for lenses, medical containers such as syringes and drug solution storage containers, etc. (e.g., Patent Document 2). [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-63409 [Patent Document 2] International Publication No. 2019 / 107363 [Non-patent literature]

[0009] [Non-Patent Document 1] Macromolecules 2011,44,1986-1998 Summary of the Invention [Problem to be solved by the invention]

[0010] Olefin polymerization catalysts using the transition metal compounds described in Non-Patent Document 1 as metallocene compounds were thought to be suitable for copolymers of ethylene, alicyclic cyclic olefins, and cyclic olefins containing an aromatic structure, but the olefin copolymers produced using the transition metal compounds described in Non-Patent Document 1 do not necessarily meet the recently increasing demand for mechanical strength in resins, and there has been a demand for olefin copolymers with superior mechanical strength and transition metal compounds that can produce such copolymers. Normally, improving the mechanical strength of a resin tends to be achieved by using a resin with a higher molecular weight.

[0011] Therefore, an object of the present invention is to provide a production method capable of increasing the molecular weight of an olefin copolymer, which is a copolymer of ethylene, an alicyclic cyclic olefin, and a cyclic olefin containing an aromatic structure, and to provide a transition metal compound suitable for the production method. [Means for solving the problem]

[0012] The present invention relates to, for example, the following [1] to

[12] . [1] (A) a transition metal compound represented by the following general formula [A], (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 in the presence of an olefin polymerization catalyst comprising A method for producing an olefin copolymer, comprising copolymerizing ethylene, an alicyclic olefin, and a cyclic olefin containing an aromatic structure.

[0013] [ka] [In formula [A], M is a titanium atom, a zirconium atom, or a hafnium atom; n is an integer from 1 to 4, X is independently 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 8‘ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding tertiary cyclic hydrocarbon groups), a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, or a tertiary cyclic hydrocarbon group, R 1‘ ~R 5‘ at least one of the groups is a tertiary cyclic hydrocarbon group, and adjacent groups may be bonded to each other to form a ring; R 6‘ ~R 8‘ At least one of the groups is a secondary hydrocarbon group.

[0014] [2] The method for producing an olefin copolymer according to [1], wherein M in the general formula [A] is a titanium atom.

[0015] [3] In the general formula [A], R 1‘ ~R 5‘ The method for producing an olefin copolymer according to [1] or [2], wherein at least one of the groups is a tertiary cyclic hydrocarbon group and the others are hydrogen atoms.

[0016] [4] In the general formula [A], R 1‘ ~R 5‘ The method for producing an olefin copolymer according to any one of [1] to [3], wherein one of the groups is a tertiary cyclic hydrocarbon group and the other four are hydrogen atoms.

[0017] [5] In the general formula [A], R 5‘The method for producing an olefin copolymer according to any one of [1] to [4], wherein is a 1-adamantyl group.

[0018] [6] In the general formula [A], R 6‘ ~R 8‘ The method for producing an olefin copolymer according to any one of [1] to [5], wherein at least two of the above are isopropyl groups.

[0019] [7] A transition metal compound represented by the following general formula [A]:

[0020] [ka] [In formula [A], M is a titanium atom, a zirconium atom, or a hafnium atom; n is an integer from 1 to 4, X is independently 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 8‘ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding tertiary cyclic hydrocarbon groups), a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, or a tertiary cyclic hydrocarbon group, R 1‘ ~R 5‘ at least one of the groups is a tertiary cyclic hydrocarbon group, and adjacent groups may be bonded to each other to form a ring; R 6‘ ~R 8‘ At least one of the groups is a secondary hydrocarbon group.

[0021] [8] [7] The transition metal compound according to [7], wherein M is a titanium atom in the general formula [A].

[0022] [9] In the general formula [A], R 1‘ ~R 5‘ The transition metal compound according to [7] or [8], wherein at least one of the groups is a tertiary cyclic hydrocarbon group and the others are hydrogen atoms.

[0023]

[10] In the general formula [A], R 1‘ ~R 5‘ The transition metal compound according to any one of [7] to [9], wherein one of the groups is a tertiary cyclic hydrocarbon group and the other four are hydrogen atoms.

[0024]

[11] In the general formula [A], R 5‘ The transition metal compound according to any one of [7] to

[10] , wherein is a 1-adamantyl group.

[0025]

[12] In the general formula [A], R 6‘ ~R 8‘ The transition metal compound according to any one of [7] to

[11] , wherein at least two of the above are isopropyl groups. [Effects of the Invention]

[0026] By using the method for producing an olefin copolymer of the present invention, an olefin copolymer having a high molecular weight can be produced. Furthermore, when the transition metal compound of the present invention is used as, for example, a polymerization catalyst, an olefin copolymer having a high molecular weight can be produced. Furthermore, the various polymerizable compounds in the present invention may be derived from fossil raw materials, may be derived from living organisms such as biomass, or may be a mixture thereof. DETAILED DESCRIPTION OF THE INVENTION

[0027] The process for producing the olefin copolymer according to the present invention, the transition metal compound, etc. will be described in more detail below.

[0028] [Transition metal compounds] The transition metal compound (A) used in the method for producing the olefin copolymer of the present invention is represented by the following general formula [A].

[0029] [ka]

[0030] [Transition metal compound (A)] First, the transition metal compound (A) will be explained.

[0031] "M" In formula [A], M is a titanium atom, a zirconium atom, or a hafnium atom, preferably a titanium atom or a zirconium atom, and more preferably a titanium atom.

[0032] 《R 1‘ ~R 8‘ 》 In formula [A], R 1‘ ~R 8‘ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding tertiary cyclic hydrocarbon groups), a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, or a tertiary cyclic hydrocarbon group, and R 1‘ ~R 5‘ At least one of R is a tertiary cyclic hydrocarbon group. 1‘ ~R 5‘ Adjacent groups among these may be bonded to each other to form a ring.

[0033] Examples of the hydrocarbon group having 1 to 20 carbon atoms include linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, and an n-hexyl group; a linear or branched alkenyl group having 2 to 20, preferably 2 to 10, carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group; linear or branched alkynyl groups having 2 to 20, preferably 2 to 10, carbon atoms, such as an ethynyl group or a propargyl group; a cyclic saturated hydrocarbon group having 3 to 20, preferably 3 to 10, carbon atoms, excluding tertiary cyclic hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; cyclic unsaturated hydrocarbon groups having 5 to 20 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl groups; Aryl groups having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; and Alkyl-substituted aryl groups such as tolyl, isopropylphenyl, tert-butylphenyl, dimethylphenyl, and di-tert-butylphenyl groups Examples include:

[0034] Further examples include those in which the hydrogen atoms of the above-mentioned hydrocarbon groups are substituted with hydrocarbon groups, such as aryl-substituted alkyl groups such as benzyl and cumyl groups. R 1‘ ~R 5‘ Examples of the cyclopentadienyl moiety having a ring formed by bonding adjacent groups to each other include the following ring structures, which may further have a substituent.

[0035] [ka]

[0036] The rings formed by bonding together may be either an alicyclic structure or a ring structure containing an aromatic structure. An alicyclic structure is preferred, and a structure having a substituent such as a hydrocarbon group is preferred. In particular, a structure containing a bulky substituent (e.g., a tertiary cyclic hydrocarbon group) as described below is preferred.

[0037] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0038] Examples of the halogen-containing group include halogenated hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group.

[0039] Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Specific examples of the hydrocarbon-substituted silyl group include a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group, a dimethyl-tert-butylsilyl group, and a dimethyl(pentafluorophenyl)silyl group. Among these, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, and a triphenylsilyl group are preferred, and a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and a dimethylphenylsilyl group are more preferred. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

[0040] Examples of the oxygen-containing group include an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic anhydride group, and a furyl group.

[0041] Preferred examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group. Preferred examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group. Preferred examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group. Preferred examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.

[0042] Examples of the sulfur-containing group include a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group.

[0043] Preferred examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group. Preferred examples of the alkylthio group include a methylthio group and an ethylthio group. Preferred examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group. Preferred examples of the sulfonate group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group. Preferred examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

[0044] Examples of the nitrogen-containing group include an amino group, an imino group, an amido group, an imido group, a pyrrolidino group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, and an amino group in the form of an ammonium salt.

[0045] Preferred examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group. Preferred examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group. Preferred examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group. Preferred examples of the imido group include an acetimido group and a benzimido group.

[0046] Examples of the phosphorus-containing groups include phosphido groups, phosphoryl groups, thiophosphoryl groups, and phosphato groups.

[0047] Examples of the tertiary cyclic hydrocarbon group include a 1-norbornyl group, a 2-norbornen-1-yl group, a 2,5-norbornadiene-1-yl group, a 2-methylnorbornan-1-yl group, a 3-methylnorbornan-1-yl group, a 4-methylnorbornan-1-yl group, a 7-methylnorbornan-1-yl group, a 7,7-dimethylnorbornan-1-yl group, a bicyclo[2.2.2]octan-1-yl group, a tribenzobicyclo[2.2.2]octatrien-1-yl group, a 1-adamantyl group, a 1- Examples include a (2-methyl)adamantyl group, a 1-(3-methyl)adamantyl group, a 1-(4-methyl)adamantyl group, a 1-(2-phenyl)adamantyl group, a 1-(3-phenyl)adamantyl group, a 1-(4-phenyl)adamantyl group, a 1-(3,5-dimethyl)adamantyl group, a 1-(3,5,7-trimethyl)adamantyl group, and a 1-(3,5,7-triphenyl)adamantyl group, and preferably a tertiary cyclic hydrocarbon group having 3 to 20 carbon atoms such as a 1-adamantyl group. The cyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

[0048] (R 1‘ ~R 5‘ ) In formula [A], R 1‘ ~R 5‘It is preferred that at least one of R is a tertiary cyclic hydrocarbon group and the others are hydrogen atoms. 1‘ ~R 5‘ It is more preferable that one of the tertiary cyclic hydrocarbon groups is the tertiary cyclic hydrocarbon group and the other four are hydrogen atoms, and the tertiary cyclic hydrocarbon group is further preferably a 1-adamantyl group, and R 5‘ is a 1-adamantyl group, and R 1‘ ~R 4‘ is particularly preferably a hydrogen atom. In the present invention, the hydrogen atom refers to a hydrogen atom as a substituent represented by H-.

[0049] (R 6‘ ~R 8‘ ) In formula [A], R 6‘ ~R 8‘ At least one of the groups is a secondary hydrocarbon group. Examples of the secondary hydrocarbon group include an isopropyl group, a 2-butyl group, a 2-pentyl group, a 3-pentyl group, a 4-heptyl group, a 3-methylbutan-2-yl group, a 3,3-dimethylbutan-2-yl group, a 2,4-dimethylpentan-3-yl group, a 2,2,4,4-tetramethylpentan-3-yl group, a dicyclopropylmethyl group, a dicyclobutylmethyl group, a dicyclopentylmethyl group, a dicyclohexylmethyl group, a dicycloheptylmethyl group, a dicyclooctylmethyl group, a diphenyl ... Examples of secondary hydrocarbon groups include di-1-naphthylmethyl, di-2-naphthylmethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-adamantyl, 2-norbornyl, 2-norbornen-5-yl, 7,7-dimethylnorbornan-2-yl, 9-fluorenyl, and 9,10-dihydroanthracen-9-yl, and are preferably secondary hydrocarbon groups having 3 to 20 carbon atoms such as an isopropyl group. The secondary hydrocarbon group may be a saturated or unsaturated hydrocarbon group.

[0050] In formula [A], R 6‘ ~R 8‘ It is preferable that at least two of R are the secondary hydrocarbon groups. 6‘and R 7‘ are both secondary hydrocarbon groups, and R 8‘ is more preferably a hydrogen atom, and R 6‘ and R 7‘ are both isopropyl groups, and R 8‘ It is more preferred that is a hydrogen atom.

[0051] n In the formula [A], n is an integer of 1 to 4, and is selected depending on the valence of M and the type of X so that the transition metal compound (A) as a whole is electrically neutral.

[0052] X In formula [A], X's are independently 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 divalent diene derivative group.

[0053] Specific embodiments of the halogen atom, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, and phosphorus-containing group in X are the same as those described above for R 1‘ ~R 8‘ The specific embodiments of the halogen atom, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, and phosphorus-containing group in the above are the same as those of the specific embodiments of the halogen atom, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, and phosphorus-containing group in the above. Examples of the hydrocarbon group in X include the above-mentioned R 1‘ ~R 8‘ Examples of the hydrocarbon groups include hydrocarbon groups having 1 to 20 carbon atoms and tertiary cyclic hydrocarbon groups.

[0054] Examples of the boron-containing group include a boranediyl group, a boranetriyl group, a diboranyl group, as well as groups such as alkyl-substituted boron, aryl-substituted boron, boron halide, and alkyl-substituted boron halide.

[0055] Examples of the alkyl group-substituted boron include groups represented by (Et)2B-, (iPr)2B-, (iBu)2B-, (Et)3B, (iPr)3B, or (iBu)3B. Examples of the aryl group-substituted boron include groups represented by (C6H5)2B-, (C6H5)3B, (C6F5)3B, or (3,5-(CF3)2C6H3)3B. Examples of the boron halide include groups represented by BCl2- or BCl3. Examples of the alkyl-substituted boron halide include groups represented by (Et)BCl-, (iBu)BCl-, and (C6H5)2BCl. Trisubstituted boron atoms may be coordinated. Here, Et stands for ethyl, iPr for isopropyl, and iBu for isobutyl.

[0056] Examples of the aluminum-containing group include alkyl group-substituted aluminum, aryl group-substituted aluminum, aluminum halide, and alkyl group-substituted aluminum halide.

[0057] Examples of the alkyl group-substituted aluminum include groups represented by (Et)2Al-, (iPr)2Al-, (iBu)2Al-, (Et)3Al, (iPr)3Al, or (iBu)3Al. An example of the aryl group-substituted aluminum is a group represented by (C6H5)2Al-. Examples of the aluminum halide include groups represented by AlCl2- or AlCl3. Examples of the alkyl group-substituted aluminum halide include groups represented by (Et)AlCl- and (iBu)AlCl-. Trisubstituted aluminum may be in a coordinate bond state. Here, Et stands for ethyl, iPr for isopropyl, and iBu for isobutyl.

[0058] 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.

[0059] Furthermore, X may have a structure in which the groups exemplified as specific examples of X are bonded to each other, and may form a ring together with M. For example, X may be an alkylene group in which two alkyl groups are bonded, and this alkylene group may form a ring together with M.

[0060] When ethylene, a cyclic olefin having an alicyclic structure, and a cyclic olefin having an aromatic structure are copolymerized in the presence of a transition metal compound (A), a high molecular weight olefin copolymer can be produced. 1‘ ~R 5‘ At least one of the groups is a tertiary cyclic hydrocarbon group (especially, R 5‘ is a tertiary cyclic hydrocarbon group), and R 6‘ ~R 8‘ If at least one of the groups is a secondary cyclic hydrocarbon group, it is thought that the steric bulkiness around the metal, which is the center of the catalytic reaction, can be made appropriate, and it is expected that the chain transfer reaction to compound (B), etc., which can act as a chain transfer agent present in the polymerization reaction system, can be suppressed while maintaining copolymerizability to sterically bulky cyclic olefins to a certain extent, and as a result, the polymer elongation reaction is promoted and the molecular weight of the obtained polymer is thought to be increased.

[0061] [Method for producing transition metal compounds] The transition metal compound (A) used in 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. A step (1-1) of reacting a pyrazole compound (a-1) represented by the following general formula [a-1] with an alkyl lithium (a-2) to produce an anion (a-3) of a pyrazole compound represented by the following general formula [a-3]: a step (1-2) of reacting the anion (a-3) with a compound (a-4) represented by the following general formula [a-4] to produce a transition metal compound (A) represented by the formula [A]: The manufacturing method includes the steps of:

[0062] [ka] [In formula [a-1], formula [a-3] and formula [a-4], R 1‘ ~R 8‘ , M, X and n are R in the formula [A]. 1‘ ~R 8‘ , M, X and n are synonymous with each other.

[0063] The cyclopentadiene compound in the formula [a-4] can be produced by known methods, and the production method is not particularly limited. Known production methods are described, for example, in JP 2000-136195 A, JP 2009-24019 A, Japanese Patent No. 3674509, WO 1998 / 015510, WO 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.," and "Organometallics 2006,25,3824."

[0064] The method for deriving compound (a-4) from the cyclopentadiene compound produced by the above method may be a known method, and the production method is not particularly limited. Examples of known production methods include those described in "Organometallics 2006, 25, 631," "Macromolecules 2000, 33, 2796," "J. Organomet. Chem. 1995, 489, 195," "J. Am. Chem. Soc. 1996, 118, 1906," and "Organometallics 2006, 25, 3824."

[0065] The pyrazole compound (a-1) can be produced by a known method, and the production method is not particularly limited. Examples of known production methods include those described in "J. Org. Chem. 1985, 50, 4736.", "Inorg. Chem. 2012, 51, 150.", and JP-A-2012-121875.

[0066] The anion of the pyrazole compound (a-3) can be produced by a known method, and the production method is not particularly limited. Examples of known production methods include those described as the production method for the pyrazole compound (a-1) above, as well as production methods described in "Adv. Synth. Catal. 2005, 347, 463.", "Organometallics, 1997, 16, 2709.", "Organometallics, 2000, 19, 2707.", and "Inorg. Chem. 2009, 48, 5011."

[0067] The transition metal compound (A) used in the present invention can be produced by a known method using the anion (a-3) of the pyrazole compound and the compound (a-4). However, in this case, the anion (a-3) of the pyrazole compound and the compound (a-4) are selected in a specific combination so as to correspond to the structure of the desired transition metal compound (A). Known production methods can be used to react the two compounds. Examples of such production methods include the method for producing the anion (a-3) of the pyrazole compound, as well as the production method described in "Macromolecules, 2011, 44, 1986."

[0068] [Olefin polymerization catalyst] The olefin polymerization catalyst used in the present invention is (A) the transition metal compound according to the present invention described above; (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 selected from the group consisting of and is characterized by including

[0069] The olefin polymerization catalyst used in the present invention may further contain a carrier (C) and may further contain an organic compound (D) as necessary.

[0070] 〈Compound (B)〉 《Organometallic compound (B-1》 Examples of the organometallic compound (B-1) (hereinafter also referred to as "component (B-1)") include organoaluminum compounds (B-1a) represented by the following general formula (B-1a), complex alkylated products of Group 1 metals and aluminum (B-1b) represented by the following general formula (B-1b), dialkyl compounds (B-1c) of Group 2 or Group 12 metals represented by the following general formula (B-1c), etc., and organometallic compounds of Groups 1, 2 and Groups 12, 13. s

[0071] (B-1a): R a m Al(OR b ) n H p X q In formula (B-1a), R a and R b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 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.

[0072] Examples of the organoaluminum compound (B-1a) include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, and tricycloalkylaluminum.

[0073] (B-1b): M 2 AlR a 4 In formula (B-1b), M2 is Li, Na, or K, and R a are independently hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the alkylated complex (B-1b) include LiAl(C2H5)4, LiAl(C7H 15 )4 can be mentioned.

[0074] (B-1c):R a R b M 3 In formula (B-1c), R a and R b are each independently a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; M 3 is Mg, Zn or Cd. Examples of the dialkyl 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.

[0075] 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.

[0076] 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 is. Specific examples include compounds represented by the following general formula [B2-1]; compounds represented by the following general formula [B2-2]; benzene-insoluble organoaluminum oxy compounds described in JP-A Nos. 2-78687 and 2-167305; and aluminoxanes having two or more alkyl groups described in JP-A No. 3-103407.

[0077] [ka] (In the formula, R is independently a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or greater.)

[0078] Further, examples of the organoaluminum oxy compound (B-2) include modified methylaluminoxanes represented by the following general formula [B2-3].

[0079] [ka] (In the formula, R independently represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n independently represent an integer of 2 or greater.)

[0080] 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.

[0081] Further examples of the organoaluminum oxy compound (B-2) include boron-containing organoaluminum oxy compounds represented by the following general formula [B2-4].

[0082] [ka] (In the formula, R c represents a hydrocarbon group having 1 to 10 carbon atoms, and R d are independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0083] 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. The organoaluminum oxy compound (B-2) may be used alone or in combination of two or more.

[0084] <<Compound (B-3) that reacts with transition metal complex (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 complex (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 U.S. Pat. No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds. However, this does not include the organoaluminum oxy compound (B-2).

[0085] The ionic compound (B-3) is preferably a boron compound represented by the following general formula [B3-1].

[0086] [ka]

[0087] In the formula, R e+ As for H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation with a transition metal. f ~R i are each independently a substituent selected from a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and are preferably a substituted aryl group.

[0088] Examples of the boron compound represented by the general formula [B3-1] include those described in paragraphs

[0133] to

[0144] of WO 2015 / 122414. The ionic compound (B-3) may be used alone or in combination of two or more.

[0089] <Carrier (C)> The olefin polymerization catalyst used in the present invention may further contain a support (C) as required. The support (C) is an inorganic or organic compound, and is a granular or fine particle solid. Supports that have conventionally been used in olefin polymerization using a transition metal complex and a support as catalyst components, such as those described in paragraphs

[0110] to

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

[0090] <Organic compound component (D)> The olefin polymerization catalyst used in the present invention may further contain an organic compound component (D) as needed. The organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0091] [Method for producing olefin copolymer] The method for producing an olefin copolymer of the present invention is characterized by copolymerizing ethylene, an alicyclic cyclic olefin, and a cyclic olefin containing an aromatic structure in the presence of the above-mentioned olefin polymerization catalyst.

[0092] The method of using each component constituting the olefin polymerization catalyst and the order of adding them to the polymerization vessel can be selected arbitrarily, but examples include the following: Hereinafter, the transition metal complex (A), compound (B), and optional components, carrier (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.

[0093] In the method (2), the component (A) and / or the component (B) may be supported on the component (C) as required. 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 components may be contacted in advance.

[0094] When component (B) is supported on component (C), component (B) that is not supported on component (C) may be added in any order, as needed. In this case, the components (B) may be the same or different. In addition, 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 further support a catalyst component.

[0095] 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.

[0096] In the production method of the present invention, when olefin polymerization is carried out, the transition metal compound (A) is used in an amount of preferably 1×10 per liter of reaction volume. -12 ~1×10 -2 moles, more preferably 1 x 10 -10 ~1×10 -3Use in a molar amount.

[0097] When an organometallic compound (B-1) is used as component (B), 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 preferably 0.01 to 50,000, more preferably 0.05 to 10,000.

[0098] When an organoaluminum oxy compound (B-2) is used as component (B), it is used in an amount such that the molar ratio of aluminum atoms in the organoaluminum oxy compound (B-2) to the total transition metals (M) in the transition metal compound (A) [(B-2) / M] is preferably 10 to 5,000, more preferably 20 to 2,000.

[0099] When an ionizing ionic compound (B-3) is used as component (B), the ionizing ionic compound (B-3) is used in an amount such that the molar ratio [(B-3) / M] of the ionizing ionic compound (B-3) to the transition metal atom (M) in the transition metal compound (A) is preferably 1 to 10,000, more preferably 1 to 5,000.

[0100] In the production method of the present invention, when the support (C) is used, it is used in an amount such that the weight ratio of the transition metal compound (A) to the support (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.

[0101] In the production method of the present invention, when the organic compound component (D) is used, it is used in an amount such that the molar ratio of the transition metal compound (A) to the organic compound component (D) [(D) / (A)] is preferably 1 to 10,000, more preferably 10 to 5,000, and even more preferably 100 to 1,000.

[0102] In the production method of the present invention, the olefin polymerization temperature 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 olefin polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0103] The molecular weight of the olefin copolymer obtained by the production method of the present invention can be adjusted by adding hydrogen to the polymerization system, changing the polymerization temperature, or by adjusting 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 olefin copolymer produced.

[0104] In the production method of the present invention, the olefins to be subjected to the polymerization reaction are (Z-1) ethylene, (Z-2) an alicyclic olefin, and (Z-3) a cyclic olefin containing an aromatic structure.

[0105] (Z-2) Alicyclic Cyclic Olefins In the production method of the present invention, the alicyclic cyclic olefin (Z-2) is subjected to a polymerization reaction. The alicyclic olefin (Z-2) is preferably a compound represented by the following general formula [Z-2]: By using such a compound, it tends to be easier to obtain a polymer having a high refractive index. The alicyclic olefin (Z-2) may be used alone or in combination of two or more kinds.

[0106] [ka] (In formula [Z-2], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 ~R 18 and R a and R b are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with a halogen atom, and R 15 ~R18 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and R 15 and R 16 and, or R 17 and R 18 and may form an alkylidene group, provided that the monocyclic and polycyclic rings do not include aromatic rings.

[0107] The olefin copolymer obtained by the production method of the present invention contains structural units derived from bicyclo[2.2.1]-2-heptene, tetracyclo[4.4.0.1]-2-heptene, and the like. 2,5 .1 7,10 ]-3-dodecene-derived building blocks, and hexacyclo[6.6.1.1 3,6 .1 10,13 .0 2,7 .0 9,14 ]-4-heptadecene-derived structural units, and bicyclo[2.2.1]-2-heptene-derived structural units and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene-derived structural units, and more preferably, tetracyclo[4.4.0.1 2,5 .1 7,10 It is more preferable that the copolymer contains a structural unit derived from ]-3-dodecene.

[0108] That is, the alicyclic olefin (Z-2) may be bicyclo[2.2.1]-2-heptene, tetracyclo[4.4.0.1]-2-heptene, or the like. 2,5 .1 7,10 ]-3-dodecene, and hexacyclo[6,6,1,1 3,6 ,1 10,13 ,0 2,7 ,0 9,14 ]-4-heptadecene is preferred, and at least one selected from bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene is more preferred, and tetracyclo[4.4.0.1 2,5 .17,10 ]-3-dodecene (hereinafter also simply referred to as "tetracyclododecene").

[0109] (Z-3) Cyclic olefins containing aromatic structures In the production method of the present invention, a cyclic olefin (Z-3) containing an aromatic structure is subjected to a polymerization reaction. Examples of the cyclic olefin (Z-3) containing an aromatic structure include a compound represented by the following general formula [Z-3a], a compound represented by the following formula [Z-3b], and a compound represented by the following formula [Z-3c]. The aromatic structure-containing cyclic olefin (Z-3) may be used alone or in combination of two or more.

[0110] [ka]

[0111] In the above formula [Z-3a], n and q are each independently 0, 1, or 2. n is preferably 0 or 1, and more preferably 0. q is preferably 0 or 1, and more preferably 0.

[0112] R 1 ~R 17 are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and R 10 ~R 17 One of them is a bond, and R 15 is preferably a bond.

[0113] R 1 ~R 17 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom. Also, when q=0, R 10 and R 11 , R 11 and R12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 10 may each independently bond to each other to form a monocyclic or polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10 may each independently bond to each other to form a monocycle or a polycycle, and the monocycle or the polycycle may have a double bond, or the monocycle or the polycycle may be an aromatic ring.

[0114] [ka]

[0115] In the above formula [Z-3b], n and m are each independently 0, 1, or 2, and q is 1, 2, or 3. m is preferably 0 or 1, and more preferably 1. n is preferably 0 or 1, and more preferably 0. q is preferably 1 or 2, and more preferably 1.

[0116] R 18 ~R 31 are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom.

[0117] R 18 ~R 31 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom. Also, when q=1, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 may each independently bond to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , R 31 and R 31 may each independently bond to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, or the monocycle or the polycycle may be an aromatic ring.

[0118] [ka]

[0119] In the above formula [Z-3c], q is 1, 2 or 3, preferably 1 or 2, and more preferably 1.

[0120] R 32 ~R 39 are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom.

[0121] R 32 ~R 39 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom. Also, when q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 may each independently bond to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39 and R 39 may each independently bond to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, or the monocycle or the polycycle may be an aromatic ring.

[0122] Examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups having 4 to 20 carbon atoms. More specifically, alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups, cycloalkyl groups include cyclohexyl groups, and aromatic hydrocarbon groups include aryl groups or aralkyl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

[0123] Among these, the cyclic olefin (Z-3) containing an aromatic structure is preferably one having one aromatic ring, and for example, at least one selected from benzonorbornadiene, indenenorbornene, and methylphenylnorbornene is preferred, and it is more preferred that it contains benzonorbornadiene.

[0124] Further, examples of the cyclic olefin (Z-3) containing an aromatic structure include a compound represented by the following general formula [Z-3a1], a compound represented by the following general formula [Z-3b1], and a compound represented by the following general formula [Z-3c1].

[0125] [ka]

[0126] In the above formulas [Z-3a1], [Z-3b1] and [Z-3c1], m and n are 0, 1 or 2, and R 1 ~R 36 are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 25 and R 26 , R 26 and R 27 , R 27 and R 28 , R 33 and R 34 , R 34 and R 35 , R 35 and R 36 may each independently be bonded to each other to form a monocyclic ring, and the monocyclic ring may have a double bond.

[0127] In the above formulas [Z-3a1], [Z-3b1] and [Z-3c1], m is preferably 0 or 1, more preferably 1. n is preferably 0 or 1, more preferably 0. R 1 ~R 36 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom.

[0128] Examples of the hydrocarbon group having 1 to 20 carbon atoms include the same groups as the hydrocarbon groups having 1 to 20 carbon atoms in the formulae [Z-3a] to [Z-3c].

[0129] The cyclic olefin (Z-3) containing an aromatic structure can adjust the Abbe number of the resulting olefin copolymer, and is therefore suitable for controlling the physical properties when obtaining an olefin copolymer with physical properties suitable for use as a lens material, for example.

[0130] <Other polymerizable compounds> In the production method of the present invention, polymerizable compounds other than the above (Z-1) to (Z-3) (hereinafter also referred to as "other polymerizable compounds") may be used within a range that does not impair the effects of the present invention. Other polymerizable compounds include linear or branched α-olefins having 3 or more carbon atoms, conjugated / non-conjugated polyenes, vinylcyclohexane, compounds having a polar group and a polymerizable unsaturated bond, aromatic vinyl compounds, and functional group-containing styrene derivatives.

[0131] The linear or branched α-olefin having 3 or more carbon atoms preferably has 3 to 30 carbon atoms, and more preferably 2 to 30 carbon atoms. Specific examples of the α-olefin include 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.

[0132] The conjugated / non-conjugated polyene may be a cyclic or chain hydrocarbon having two or more double bonds, and preferably has 4 to 30, and more preferably 4 to 20, carbon atoms. Specific examples of the conjugated / non-conjugated polyene 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, and ethylidene norbornene. Examples of the compounds include those exemplified in paragraph

[0211] of JP 2011-122146 A, such as vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatrienebutadiene, isoprene, ethylidenenorbornene, vinylnorbornene, and dicyclopentadiene.

[0133] Specific examples of compounds having a polar group and a polymerizable unsaturated bond include compounds exemplified as unsaturated hydrocarbons having a polar group in paragraphs

[0208] to

[0210] of JP-A No. 2011-122146.

[0134] Specific examples of aromatic vinyl compounds and functional group-containing styrene derivatives include the compounds exemplified in

[0211] of JP-A No. 2011-122146.

[0135] In the polymerization reaction of ethylene (Z-1), cyclic olefin (Z-2), and cyclic olefin (Z-3), the pressure of ethylene (Z-1) and the concentrations of cyclic olefins (Z-2) and (Z-3) can be set arbitrarily within a range that does not impair the effects of the present invention, and are not particularly limited. However, it is preferable that the pressure of ethylene (Z-1) is the above-mentioned polymerization pressure.

[0136] For example, in the case of liquid phase polymerization using the inert solvent, the cyclic olefin (Z-2) is used at a concentration of preferably 0.0001 to 100 mol / liter, more preferably 0.001 to 10 mol / liter, and even more preferably 0.01 to 1 mol / liter.

[0137] In the case of liquid phase polymerization using the inert solvent, the cyclic olefin (Z-3) is used at a concentration of preferably 0.0001 to 1000 mol / liter, more preferably 0.001 to 100 mol / liter, and even more preferably 0.01 to 10 mol / liter.

[0138] The molar ratio of the cyclic olefins (Z-2) to (Z-3) [(Z-2) / (Z-3)] can be set arbitrarily within a range that does not impair the effects of the present invention, but is preferably 0.01 to 10. The lower limit is more preferably 0.05, even more preferably 0.1, and particularly preferably 0.5. On the other hand, the upper limit is more preferably 5, even more preferably 3, and particularly preferably 2.

[0139] The olefin copolymer obtained by the production method of the present invention has a sufficiently high molecular weight, making it suitable as a resin required to have excellent mechanical strength. Furthermore, various physical properties such as refractive index and Abbe number can be adjusted by selecting the type of copolymerized monomer, and therefore it can be used as a material for various lenses and medical containers such as syringes and drug solution storage containers. [Example]

[0140] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0141] [Measurement method] [Structure of transition metal compounds] The structure of the transition metal compound is 1 The molecular weight was determined by H-NMR spectroscopy (400 MHz, JEOL Ltd., ECZ400S).

[0142] [Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of olefin copolymer] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the olefin copolymer were calculated from the molecular weight distribution curve obtained by gel permeation chromatography (GPC), and the operating conditions were as follows:

[0143] <Devices and conditions used> Measurement equipment: Gel permeation chromatograph (high-temperature size exclusion chromatograph) Alliance GPC 2000 (Waters) Analysis software: Chromatography Data System Empower (trademark, manufactured by Waters) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2 (inner diameter 7.5 mm x length 30 cm, manufactured by 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 4.95 to 20.6 million

[0144] [Cyclic olefin content of olefin copolymer] According to the description in paragraphs

[0216] to

[0219] of JP 2011-122146 A and paragraph

[0132] of WO 2019 / 107363 A, 13 The cyclic olefin ((Z-2) alicyclic cyclic olefin and (Z-3) cyclic olefin containing aromatic structure) content of the polymer was determined by C-NMR spectrum.

[0145] [Olefin copolymer glass transition temperature (Tg)] DSC measurements were carried out under the following conditions to determine the glass transition temperature (Tg) of the olefin copolymer. Equipment: SII Nanotechnology DSC6220 Measurement conditions: The sample was held at 300°C for 5 minutes, then rapidly cooled to 0°C, and the Tg was measured during the process of increasing the temperature to 250°C at a rate of 20°C / min.

[0146] [Intrinsic viscosity of olefin copolymer [η]] Using a moving viscometer (Rigo Co., Ltd., Model VNR053U), 0.25 to 0.30 g of olefin copolymer was dissolved in 25 mL of decalin to prepare a sample. The specific viscosity of the polymer was measured at 135°C in accordance with ASTM J1601, and the ratio of this to the concentration was extrapolated to a concentration of 0 to determine the intrinsic viscosity [η] of the olefin copolymer.

[0147] [Example A1] [Production of Transition Metal Compounds] A thoroughly dried flask was charged with 0.152 g (1.0 mmol) of 3,5-diisopropyl-1H-pyrazole and 50 mL of dehydrated diethyl ether under a nitrogen atmosphere. 0.70 mL of n-butyllithium (1.52 M n-hexane solution, 1.1 mmol) was added dropwise under ice cooling to prepare solution (1). After stirring at room temperature for 2 hours, a separate dried flask was charged with 0.354 g (1.0 mmol) of (1-adamantyl)cyclopentadienyltrichlorotitanium dissolved in 50 mL of dehydrated diethyl ether under a nitrogen atmosphere to prepare solution (2). Solution (1) was added dropwise to solution (2) using a cannula while cooling to -78°C, and the mixture was stirred overnight while naturally warming to room temperature. The solvent from the resulting reaction solution was evaporated under reduced pressure, and 15 mL of dehydrated dichloromethane was added, followed by filtration through Celite. The resulting yellow filtrate was concentrated under reduced pressure, 5 mL of dehydrated pentane was added, and the mixture was cooled to -30°C and allowed to stand overnight. The precipitated yellow crystals were washed with dehydrated hexane and dried under reduced pressure to obtain 0.175 g (0.37 mmol, 37%, yellow crystals) of a transition metal compound represented by the following formula [1]. 1 H-NMR(399MHz,CDCl3)δ / ppm 6.69(2H,t,J=2.8Hz),6.55(1H,s),6.45(2H,t,J=2.8Hz),3.03(2H,sept,J=6.8Hz),2.04(4H,br s),1.87(6H,d,J=2.8Hz),1.76-1.68(5H,m),1.32(12H,d,J=6.8Hz).

[0148] [ka] [During the ceremony, i Pr is an isopropyl group.

[0149] [Production of Olefin Copolymer] [Example B1] A dry, 2.0 L pressure-resistant autoclave was thoroughly purged with nitrogen, and 710 mL of a dehydrated and purified cyclohexane / hexane (mixing ratio = 3 / 1) mixed solution, 50 mmol of tetracyclododecene (TD), 240 mmol of benzonorbornadiene (BNBD), and 1.0 mmol of MMAO (manufactured by Tosoh Finechem Co., Ltd.) (in terms of aluminum atom) were sequentially charged under a nitrogen stream. The temperature was then raised to 50°C, and ethylene was supplied to maintain an ethylene partial pressure of 0.1 MPaG, and this state was maintained. Subsequently, 0.002 mmol of the transition metal compound represented by formula [1] obtained in Example A1 was added, followed by 0.008 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate to initiate polymerization. While maintaining the internal temperature at 50°C, ethylene was supplied to maintain an ethylene partial pressure of 0.1 MPaG, and polymerization was carried out for 5 minutes. After the predetermined time had elapsed, the ethylene supply was stopped, and a small amount of methanol was added to terminate the polymerization. The reaction mixture was added to 3 liters of a mixed solvent of acetone and methanol (3:1 ratio) containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the polymer was dried under reduced pressure at 130°C for 10 hours to obtain 764 mg of ethylene-tetracyclododecene-benzonorbornadiene copolymer. The polymerization activity and physical properties of the ethylene-tetracyclododecene-benzonorbornadiene copolymer are as follows: Polymerization activity: 382g-polymer / mmol-Ti Glass transition temperature: 159°C Intrinsic viscosity [η]: 3.32dl / g Mw:1,420,000 Mn:624,000 Mw / Mn: 2.27 Structural unit molar ratio (ethylene:TD:BNBD)=59.1:23.0:17.9

[0150] [Comparative Example B1] A dry, 2.0 L pressure-resistant autoclave was thoroughly purged with nitrogen and charged with 710 mL of a dehydrated, purified cyclohexane / hexane (3 / 1) mixture, 50 mmol of tetracyclododecene (TD), 240 mmol of benzonorbornadiene (BNBD), and 1.0 mmol of triethylaluminum (calculated as aluminum atom) under a nitrogen stream. The temperature was then raised to 50 °C, and ethylene was supplied to maintain an ethylene partial pressure of 0.1 MPaG. This condition was maintained. Subsequently, 0.005 mmol of a transition metal compound represented by formula [2] (synthesized according to the method described in "Macromolcules 2011, 44, 1986-1998") was added, followed by the addition of 0.02 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate to initiate polymerization. While maintaining the internal temperature at 50 °C, ethylene was supplied to maintain an ethylene partial pressure of 0.1 MPaG, and polymerization was carried out for 5 minutes. After the specified time had elapsed, the ethylene supply was stopped and the polymerization was terminated by adding a small amount of methanol. The reactants were then added to 3 liters of a mixed solvent of acetone and methanol (3:1) containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the polymer was dried under reduced pressure at 130°C for 10 hours, yielding 1.91 g of ethylene-tetracyclododecene-benzonorbornadiene copolymer. The polymerization activity and physical properties of the ethylene-tetracyclododecene-benzonorbornadiene copolymer are as follows: Polymerization activity: 382g-polymer / mmol-Ti Glass transition temperature: 163℃ Intrinsic viscosity [η]: 2.44dl / g Mw:946,000 Mn: 461,000 Mw / Mn: 2.05 Structural unit molar ratio (ethylene:TD:BNBD)=61.7:20.9:17.3

[0151] [ka] [During the ceremony, t Bu is a tert-butyl group; i Pr is an isopropyl group.

[0152] The method for producing an olefin copolymer of the present invention (Example B1) was able to produce an olefin copolymer with a higher molecular weight in both Mw and Mn than the conventional production method using a transition metal compound (Comparative Example B1). The present invention leads to the production of resins that require higher mechanical strength, and is therefore industrially preferable.

Claims

1. (A) a transition metal compound represented by the following general formula [A], (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 In the presence of an olefin polymerization catalyst comprising A method for producing an olefin copolymer, comprising copolymerizing ethylene, an alicyclic olefin, and a cyclic olefin containing an aromatic structure. 【Chemical 1】 [In formula [A], M is a titanium atom, a zirconium atom, or a hafnium atom; n is an integer from 1 to 4, X is independently 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 ８‘ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding tertiary cyclic hydrocarbon groups), a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, or a tertiary cyclic hydrocarbon group, R １‘ ~R ５‘ at least one of the groups is a tertiary cyclic hydrocarbon group, and adjacent groups may be bonded to each other to form a ring; R ６‘ ~R ８‘ At least one of the groups is a secondary hydrocarbon group.

2. 2. The method for producing an olefin copolymer according to claim 1, wherein in the general formula [A], M is a titanium atom.

3. In the general formula [A], R １‘ ~R ５‘ The method for producing an olefin copolymer according to claim 1, wherein at least one of the groups is a tertiary cyclic hydrocarbon group and the others are hydrogen atoms.

4. In the general formula [A], R １‘ ~R ５‘ The method for producing an olefin copolymer according to claim 1, wherein one of the groups is a tertiary cyclic hydrocarbon group and the other four are hydrogen atoms.

5. In the general formula [A], R ５‘ The method for producing an olefin copolymer according to claim 4, wherein is a 1-adamantyl group.

6. In the general formula [A], R ６‘ ~R ８‘ The method for producing an olefin copolymer according to claim 1, wherein at least two of the above are isopropyl groups.

7. A transition metal compound represented by the following general formula [A]: 【Chemistry 2】 [In formula [A], M is a titanium atom, a zirconium atom, or a hafnium atom; n is an integer from 1 to 4, X is independently 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 ８‘ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding tertiary cyclic hydrocarbon groups), a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, or a tertiary cyclic hydrocarbon group, R １‘ ~R ５‘ at least one of the groups is a tertiary cyclic hydrocarbon group, and adjacent groups may be bonded to each other to form a ring; R ６‘ ~R ８‘ At least one of the groups is a secondary hydrocarbon group.

8. 8. The transition metal compound according to claim 7, wherein M in the general formula [A] is a titanium atom.

9. In the general formula [A], R １‘ ~R ５‘ The transition metal compound according to claim 7, wherein at least one of the groups is a tertiary cyclic hydrocarbon group and the others are hydrogen atoms.

10. In the general formula [A], R １‘ ~R ５‘ The transition metal compound according to claim 7, wherein one of the groups is a tertiary cyclic hydrocarbon group and the other four are hydrogen atoms.

11. In the general formula [A], R ５‘ The transition metal compound according to claim 10, wherein is a 1-adamantyl group.

12. In the general formula [A], R ６‘ ~R ８‘ 8. The transition metal compound according to claim 7, wherein at least two of are isopropyl groups.

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