Method for producing olefin copolymers and transition metal compounds

Abstract

To provide a method that can efficiently produce a cyclic olefin copolymer containing an aromatic structure, and a novel transition metal compound suitable as a component of a catalyst for olefin polymerization in the production method.SOLUTION: A method includes copolymerizing an ethylene, an aliphatic cyclic olefin, and a cyclic olefin containing an aromatic structure in the presence of a catalyst for olefin polymerization containing a transition metal compound represented by, for example, formula (1) and at least one compound selected from the group consisting of an organic metal compound, an organic aluminum oxy compound, and a compound reactable with the transition metal compound to form an ion pair.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a method for producing olefin copolymers. Furthermore, this invention relates to novel transition metal compounds. [Background technology]

[0002] Conventionally, catalysts consisting of a metallocene compound and a co-catalyst such as an organoaluminum oxy compound have been known as catalysts for producing olefin polymers such as ethylene-α-olefin copolymers.

[0003] Various types of transition metal compounds, such as metallocene compounds, are being actively developed. For example, Patent Document 1 describes a transition metal compound (A) represented by the following general formula:

[0004] [ka]

[0005] (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 acts as the coordinating atom, X represents halogens, etc., m represents an integer from 1 to 3, R 1 ~R 5 (This represents hydrogen, halogens, or alkyl groups with 1 to 20 carbon atoms, etc.) Furthermore, a method for producing a cyclic olefin copolymer is described, in which copolymerization is carried out between ethylene and / or an α-olefin having 3 to 20 carbon atoms and 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, and specific examples of transition metal compounds (A) include CpTi(t-Bu2C=N)Cl2 and Cp * Ti(2,6- i Pr2PhO)Cl2 is mentioned. (Cp is a cyclopentadienyl group, Cp * is η 5 - Represents a pentamethylcyclopentadienyl group.

[0006] Furthermore, Non-Patent Document 1 describes a copolymerization of ethylene and norbornene, etc., in the presence of a transition metal compound represented by the following formula and methyl aluminoxane (MAO).

[0007] [ka]

[0008] Furthermore, copolymers of ethylene, alicyclic olefins, and cyclic olefins containing aromatic structures have been reported to be suitable for lens resins and the like. (For example, Patent Document 2) [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2007-63409 [Patent Document 2] International Publication No. 2019 / 107363 [Non-patent literature]

[0010] [Non-Patent Document 1] Macromolecules 2011, 44, 1986-1998 [Overview of the project] [Problems that the invention aims to solve]

[0011] The transition metal compound described in Non-Patent Document 1 as a metallocene compound was considered suitable as a catalyst for olefin polymerization for copolymers of ethylene, alicyclic olefins, and cyclic olefins containing aromatic structures. However, the inventors' studies yielded results where the polymerization activity and the molecular weight of the resulting polymer were not sufficient. This is thought to be because the use of a cyclic olefin containing aromatic structures may have caused the active sites derived from the transition metal compound to be affected electronically by the aromatic structure, reducing the polymerization rate and relatively increasing the chain transfer rate.

[0012] Therefore, an object of the present invention is to provide a suitable method for producing a copolymer of ethylene, an alicyclic cyclic olefin, and a cyclic olefin containing an aromatic structure. Further preferably, an object is to provide a transition metal compound suitable for the above production method.

Means for Solving the Problems

[0013] The present invention relates to, for example, the following [1] to [8]. [1] (A) A transition metal compound represented by the following general formula [A] 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 to form an ion pair and at least one compound selected from the group consisting of in the presence of an olefin polymerization catalyst containing a method for producing an olefin copolymer by copolymerizing ethylene, an alicyclic cyclic olefin, and a cyclic olefin containing an aromatic structure.

[0014]

Chemical Formula

[0015] [2] A method for producing the olefin copolymer of [1], wherein M is a titanium atom in the general formula [A].

[0016] [3] In the above general formula [A], R 1` R is a hydrocarbon group having 1 to 20 carbon atoms. 2` ~R 5` A method for producing the olefin copolymer of [1], wherein is a hydrogen atom.

[0017] [4] In the above general formula [A], the R 6` ~R 8` A method for producing the olefin copolymer of [1], wherein at least one of the substituents is selected from aryl groups or substituted aryl groups having 6 to 20 carbon atoms.

[0018] [5] A transition metal compound represented by the following general formula [A-1].

[0019] [ka] [In formula [A-1], M is a titanium atom, a zirconium atom, or a hafnium atom. n is an integer from 1 to 4. Each of 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 of these is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. R 1` ~R 5` Among these, adjacent groups may be bonded to each other to form a ring structure. R 1` ~R 5` In cases where adjacent groups bond to each other to form a ring structure, the ring structure is an alicyclic structure. R 6` ~R 8` At least one of them is a tertiary hydrocarbon group.

[0020] [6] The transition metal compound of [5] in the general formula [A-1], wherein M is a titanium atom.

[0021] [7] In the above general formula [A-1], R 1` R is a hydrocarbon group having 1 to 20 carbon atoms. 2` ~R 5` The transition metal compound [5] is a hydrogen atom.

[0022] [8] In the above general formula [A-1], the R 6` ~R 8` The transition metal compound [5] wherein at least one of the substituents is selected from aryl groups or substituted aryl groups having 6 to 20 carbon atoms. [Effects of the Invention]

[0023] By using the olefin copolymer production method of the present invention, polymers with high molecular weight can be produced with relatively high activity. Furthermore, the transition metal compounds used in the method for producing olefin copolymers of the present invention include novel compounds. [Modes for carrying out the invention]

[0024] The method for producing olefin copolymers according to the present invention, as well as transition metal compounds, will be described in more detail below. [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].

[0025] [ka]

[0026] Furthermore, transition metal compound (A-1) with a specific structure among transition metal compounds (A) is a novel compound. [Transition metal compound (A)] First, let's discuss transition metal compounds (A).

[0027] 《M》 In formula [A], M represents a titanium atom, a zirconium atom, or a hafnium atom, preferably a titanium atom or a zirconium atom, and more preferably a titanium atom.

[0028] 《R 1` ~R 8` 》 In equation [A], R 1` ~R 8` Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, and R 1` ~R 5` Adjacent groups may be bonded to each other to form a ring.

[0029] Examples of the aforementioned halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of the hydrocarbon groups include linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl; Linear or branched alkenyl groups having 2 to 20, preferably 2 to 10, carbon atoms, such as vinyl, allyl, and isopropenyl; Linear or branched alkynyl groups having 2 to 20, preferably 2 to 10, carbon atoms, such as ethynyl and propargyl; Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and other cyclic saturated hydrocarbon groups having 3 to 20, preferably 3 to 10, carbon atoms; Cyclopentadienyl, indenyl, fluorenyl, and other cyclic unsaturated hydrocarbon groups with 5 to 20 carbon atoms; Aryl groups having 6 to 20 carbon atoms, preferably 6 to 10, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; and Alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl. These are some examples.

[0030] Furthermore, examples include hydrocarbon groups in which the hydrogen atoms of the aforementioned hydrocarbon groups are substituted with hydrocarbon groups, such as aryl-substituted alkyl groups like benzyl and cumyl. R 1` ~R 5` Examples of cyclopentadienyl moieties having a ring formed by the bonding of adjacent groups to each other include the following ring structure, which may further have substituents.

[0031] [ka]

[0032] Among the structures having rings formed by the bonding of these rings, the structure having an alicyclic structure is a structure possessed by a novel compound, which is one embodiment of the compound represented by formula [A-1] of the present invention, as described later.

[0033] In the present invention, the above-described structure results in relatively high polymerization activity, and the molecular weight of the resulting polymer tends to increase easily. Examples of the halogen-containing groups include halogenated hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10, such as trifluoromethyl, pentafluorophenyl, and chlorophenyl.

[0034] Examples of the silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups. Specific examples of hydrocarbon-substituted silyl groups include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl(pentafluorophenyl)silyl. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, and triphenylsilyl are preferred. Trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are particularly preferred. Specific examples of hydrocarbon-substituted siloxy groups include trimethylsiloxy.

[0035] Examples of the oxygen-containing groups include alkoxy groups, allyloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxyl groups, peroxy groups, carboxylic acid anhydride groups, and furyl groups.

[0036] Among oxygen-containing groups, preferred examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy. Preferred examples of allyloxy groups include phenoxy, 2,6-dimethylphenoxy, and 2,4,6-trimethylphenoxy. Preferred examples of ester groups include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, and p-chlorophenoxycarbonyl. Preferred examples of acyl groups include formyl, acetyl, benzoyl, p-chlorobenzoyl, and p-methoxybenzoyl groups.

[0037] Examples of the sulfur-containing groups include mercapto groups, thioester groups, dithioester groups, alkylthio groups, arylthio groups, thioacyl groups, thioether groups, thiocyanate ester groups, isothiocyanate ester groups, sulfone ester groups, sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, and sulfenyl groups.

[0038] Among sulfur-containing groups, preferred examples of thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl. Preferred examples of alkylthio groups include methylthio and ethylthio. Preferred examples of arylthio groups include phenylthio, methylphenylthio, and naphthylthio. Preferred examples of sulfonate ester groups include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Preferred examples of sulfonamide groups include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

[0039] Examples of the nitrogen-containing groups include amino groups, imino groups, amide groups, imide groups, pyrrolidino groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and ammonium salts of amino groups.

[0040] Among nitrogen-containing groups, preferred examples of amino groups include dimethylamino, ethylmethylamino, and diphenylamino. Preferred examples of imino groups include methylimino, ethylimino, propylimino, butylimino, and phenylimino. Preferred examples of amide groups include acetamide, N-methylacetamide, and N-methylbenzamide. Preferred examples of imide groups include acetimide and benzimide. Examples of the phosphorus-containing groups include phosphine groups, phosphoryl groups, thiophosphoryl groups, and phosphat groups.

[0041] (R 1` ~R 5` ) R 1` ~R 5` One or more of these are linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl; Aryl groups having 6 to 20 carbon atoms, preferably 6 to 10, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; These aryl groups are substituted aryl groups in which one or more hydrogen atoms of the aryl group are replaced by halogen atoms, alkyl groups, alkoxy groups, aryl groups, or aryloxy groups. Preferably, it is a hydrocarbon group having 1 to 20 carbon atoms.

[0042] Also, R 1` ~R 5` It is also preferable that one or more of them are hydrogen atoms. In this invention, a hydrogen atom refers to hydrogen as a substituent represented by H-. Among the above embodiments, R 1` R is a hydrocarbon group with 1 to 20 carbon atoms.2` ~R 5` It is preferable that R is a hydrogen atom. 1` It is preferable that the group be selected from a secondary hydrocarbon group and a tertiary hydrocarbon group, with a tertiary hydrocarbon group being particularly preferred.

[0043] (R 6` ~R 8` ) In equation [A], R 6` ~R 8` One or more of these are tertiary hydrocarbon groups. Such hydrocarbon groups are tertiary hydrocarbon groups having 4 to 20 carbon atoms, and specifically include t-butyl group, t-pentyl group, t-hexyl group, adamantyl group, 1,1-dimethylbenzyl group, etc. Of course, the tertiary hydrocarbon group may also have a structure containing halogen, silicon, oxygen, nitrogen, sulfur, or phosphorus. Preferably, it is a tertiary hydrocarbon group that does not contain the so-called heteroatoms described above.

[0044] Among the above, R 6` and / or R 7` It is preferable that R is a tertiary hydrocarbon group. It is also preferable that two or more are tertiary hydrocarbons. In particular, R 6` and R 7` It is preferable that both are tertiary hydrocarbon groups.

[0045] In formula [A], in addition to the above requirements, R 6` ~R 8`Preferably, one or more of the substituents are selected from aryl groups or substituted aryl groups having 6 to 20 carbon atoms. Specifically, examples include aryl groups having 6 to 20 carbon atoms, preferably 6 to 10, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl, as well as the aforementioned aryl groups having substituents such as hydrocarbon groups or oxygen-containing groups. Specific examples of the substituents are the same as those for the hydrocarbon groups and oxygen-containing groups mentioned above. Among these, preferred hydrocarbon groups are tertiary hydrocarbon groups such as t-butyl, t-pentyl, t-hexyl, and dimethylbenzyl groups, and preferred oxygen-containing groups are alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy groups. Among the above aryl groups, substituted aryl groups are preferred, and aryl groups having tertiary hydrocarbon groups are particularly preferred.

[0046] The aforementioned R 6` ~R 8` However, when such aryl groups or substituted aryl groups are present, copolymers with a high content of structural units derived from cyclic olefins can be easily obtained through copolymerization reactions between olefins and cyclic olefins, as described later, and these polymers tend to have relatively high molecular weights. For this reason, the above configuration is preferred when providing materials with high glass transition temperatures and excellent strength.

[0047] 《n》 In formula [A], n is an integer from 1 to 4, selected depending on the valence of M and the type of X, such that the transition metal compound (A) as a whole is electrically neutral.

[0048] 《X》 In formula [A], 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.

[0049] Specific embodiments of these halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, and phosphorus-containing groups are as described above in R 1` ~R 5` and R 8` The specific embodiments are the same as those of halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, and phosphorus-containing groups.

[0050] Examples of the boron-containing groups include boranediyl groups, borantriyl groups, diboranyl groups, and groups such as alkyl-substituted boron, aryl-substituted boron, boron halides, and alkyl-substituted boron halides.

[0051] Examples of alkyl group-substituted boron include groups represented as (Et)2B-, (iPr)2B-, (iBu)2B-, (Et)3B, (iPr)3B, or (iBu)3B. Examples of aryl group-substituted boron include groups represented as (C6H5)2B-, (C6H5)3B, (C6F5)3B, or (3,5-(CF3)2C6H3)3B. Examples of boron halides include the group represented by BCl2- or BCl3. Examples of alkyl-substituted boron halides include the groups represented by (Et)BCl-, (iBu)BCl-, and (C6H5)2BCl. Of these, the trisubstituted borons may exist in a coordinate bond state. Here, Et represents the ethyl group, iPr represents the isopropyl group, and iBu represents the isobutyl group.

[0052] Examples of the aforementioned aluminum-containing groups include alkyl-substituted aluminum, aryl-substituted aluminum, aluminum halides, and alkyl-substituted aluminum halides.

[0053] Examples of alkyl-substituted aluminum include groups represented as (Et)2Al-, (iPr)2Al-, (iBu)2Al-, (Et)3Al, (iPr)3Al, or (iBu)3Al. An example of aryl-substituted aluminum is the group represented by (C6H5)2Al-. Examples of aluminum halides include groups represented by AlCl2- or AlCl3. Examples of alkyl-substituted aluminum halides include the groups represented by (Et)AlCl- and (iBu)AlCl-. Of these, the trisubstituted aluminum may be in a coordinate bond state. Here, Et represents the ethyl group, iPr represents the isopropyl group, and iBu represents the isobutyl group.

[0054] Examples of the aforementioned diene-based divalent derivative groups include metallocyclopentene groups such as 1,3-butadienyl group, isoprenyl(2-methyl-1,3-butadienyl) group, piperelenyl(1,3-pentadienyl) group, 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, and cyclopentadienyl group.

[0055] Furthermore, X may be a structure in which the groups listed 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 with a structure in which two alkyl groups are bonded, and this alkylene group may form a ring together with M. Specific examples of transition metal compounds (A) include the compounds represented by the following formula.

[0056] [ka]

[0057] [ka]

[0058] When ethylene is copolymerized with an alicyclic olefin and a cyclic olefin containing an aromatic structure in the presence of a transition metal compound (A), a copolymer with a high molecular weight can be produced with relatively high activity. This is because R 6` ~R 8`At least one of the, especially R 6` and R 7` The inventors speculate that the presence of a tertiary hydrocarbon group may suppress the approach of the aromatic portion of the cyclic olefin to the catalytic active site, and also suppress electronic influences. Furthermore, it is possible that the electron-donating property of the tertiary hydrocarbon group supplies electrons to the metal, which is thought to be the active site of the transition metal compound, thereby increasing the reaction activity.

[0059] Furthermore, R 6` ~R 8` If the compound also contains aryl groups or substituted aryl groups, these aryl groups have a cyclic structure, and preferably a structure that is easily rotated. This may have the effect of making it easier for bulky cyclic olefins, such as ethylene, to approach the active site compared to olefins. Furthermore, the aromatic structural portion of the aryl group may exhibit affinity for the aromatic structural portion of the cyclic olefin having the aromatic structure, thereby increasing the local concentration and potentially making it a catalyst with high polymerization activity. The transition metal compound (A-1) of the present invention is represented by the following general formula [A-1].

[0060] [ka]

[0061] The above R 1` ~R 8` , M, X, and n are all R in the general formula [A] representing a transition metal compound (A). 1` ~R 8` , is synonymous with M, X, and n. However, as mentioned above, R 1` ~R 5` When molecules combine with each other to form a ring structure, that ring structure is limited to an alicyclic structure.

[0062] The compounds described above are novel compounds, and when used as catalysts for olefin polymerization, they tend to yield polymers with high activity and high molecular weight, as mentioned above.

[0063] [Method for producing transition metal compounds] The transition metal compound (A) 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, in terms of manufacturing methods, (1-1) A step to produce an anionic form (a-3) of a pyrazole compound represented by the following general formula [a-3] by reacting a pyrazole compound (a-1) represented by the following general formula [a-1] with an alkyllithium (a-2), and (1-2) A step to produce a transition metal compound (A) represented by the general formula [A] by reacting the anionic material (a-3) with a compound (a-4) represented by the general formula [a-4] below. Examples of manufacturing methods include those that include the following.

[0064] [ka]

[0065] [In equations [a-1], [a-3], and [a-4], R 1` ~R 8` M, X, and n are R in equation [A], respectively. 1` ~R 8` This is synonymous with M, X, and n. First, various cyclopentadiene compounds can be produced by known methods, and the production method is not particularly limited. For example, Japanese Patent Publication No. 2000-136195, Japanese Patent Publication 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.", "J. Am. Chem. Soc." Examples of manufacturing methods include those described in "2004, 126, 2089.", "Macromol. Chem. Phys. 2004, 205, 2275.", "Org. Lett. 2008, 10, 2545.", "Chem. Rev. 1992, 92, 965.", "Science 2012, 338, 504.", and "Organometallics 2006, 25, 3824.".

[0066] Methods for derivating compound (a-4) from various cyclopentadiene compounds are well known, and the manufacturing method is not particularly limited. Known manufacturing 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."

[0067] Pyrazole compound (a-1) can be produced by known methods, and the production method is not particularly limited. Known production methods include, for example, those described in "J.Org.Chem.1985,50,4736.", "Inorg.Chem.2012,51,150.", and Japanese Patent Publication No. 2012-121875.

[0068] Anionic forms of pyrazole compounds (a-3) can be produced by known methods, and the production method is not particularly limited. Known production methods include, for example, those listed above as methods for producing pyrazole compounds, as well as those described in "Adv.Synth.Catal.2005,347,463.", "Organometallics,1997,16,2709.", "Organometallics,2000,19,2707.", and "Inorg.Chem.2009,48,5011.".

[0069] The transition metal compound (A) of the present invention can be produced by known methods using a compound (a-4) represented by general formula [a-4] and an anionic form of a pyrazole compound (a-3). However, in this case, the anionic form of the pyrazole compound (a-3) and compound (a-4) are selected in a specific combination to correspond to the desired structure of the transition metal compound (A). Known production methods can be used to react the two, and such production methods include the method for producing the anionic form of the pyrazole compound, as well as the production method described in, for example, "Macromolecules, 2011, 44, 1986."

[0070] [Catalyst for olefin polymerization] The catalyst for olefin polymerization of the present invention is (A) The transition metal compound according to the present invention described above, (B) (B-1) Organometallic compound, (B-2) Organic aluminum oxy compounds, and (B-3) Compounds that react with transition metal compounds (A) to form ion pairs At least one compound selected from the group consisting of and It is characterized by containing [something].

[0071] The olefin polymerization catalyst of the present invention may optionally further contain (C) a support and (D) an organic compound.

[0072] <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 general formula (B-1a), complex alkylated products (B-1b) of Group 1 metals and aluminum represented by the general formula (B-1b), dialkyl compounds (B-1c) of Group 2 or Group 12 metals represented by the general formula (B-1c), etc., and organometallic compounds of Groups 1, 2, 12, and 13.

[0073] (B-1a):R a m Al(OR b ) n H p X q In the 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. Examples of the organoaluminum compound (B-1a) include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, and tricycloalkylaluminum.

[0074] (B-1b):M 2 AlR a 4 In the formula (B-1b), M 2 is Li, Na, or K, and R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the complex alkylated product (B-1b) include LiAl(C2H5)4 and LiAl(C7H 15 )4.

[0075] (B-1c):R a R b M3 In formula (B-1c), R a and R b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 3 is Mg, Zn or Cd. Examples of the compound (B-1c) include dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, ethyl n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, di-n-butylzinc, and diphenylzinc.

[0076] 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.

[0077] Organoaluminum oxy compounds (B-2) As the organoaluminum oxy compound (B-2) (hereinafter also referred to as "component (B-2)"), conventionally known aluminoxanes can be used as they are. Specifically, the following general formula [B2-1]

[0078]

Chemical formula

[0079]

Chemical formula

[0080] In addition, as the organoaluminum oxy compound (B-2), modified methylaluminoxane represented by the following general formula [B2-3] and the like are also included.

[0081] [ka] (In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represent an integer greater than or equal to 2.)

[0082] These modified methylaluminoxanes are prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such compounds are commonly referred to as MMAOs. Such MMAOs can be prepared by the methods described in U.S. Patent No. 4,960,878 and U.S. Patent No. 5,041,584.

[0083] Furthermore, as organoaluminum oxy compounds (B-2), organoaluminum oxy compounds containing boron, represented by the following general formula [B2-4], can also be mentioned.

[0084] [ka] (In the formula, R c R represents a hydrocarbon group having 1 to 10 carbon atoms. d These may be identical or different from each other, and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0085] As the organoaluminum oxy compound (B-2), methylaluminoxane, which is readily available as a commercially available product, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred. Of these, MMAO with improved solubility in various solvents and storage stability is particularly preferred.

[0086] Compounds (B-3) that react with transition metal complexes (A) to form ion pairs. Compounds (B-3) that react with transition metal complexes (A) to form ion pairs (hereinafter also referred to as "ionic compounds (B-3)" or "component (B-3)") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Publication No. 3-179005, Japanese Patent Publication No. 3-179006, Japanese Patent Publication No. 3-207703, Japanese Patent Publication No. 3-207704, USP No. 5321106, etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. However, the aforementioned (B-2) organoaluminum oxy compounds are not included.

[0087] The ionic compound (B-3) is preferably a boron compound represented by the following general formula [B3-1].

[0088] [ka]

[0089] In the formula, R e+ H + Examples include carbenium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, and ferrocenium cations containing transition metals. f From R i These substituents may be the same or different from each other, and are 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.

[0090] Examples of boron compounds represented by the general formula [B3-1] include those described in International Publication No. 2015 / 122414, sections

[0133] to

[0144] . The ionic compound (B-3) may be used alone or as a mixture of two or more types.

[0091] (Carrier (C)) The carrier (C) is an inorganic or organic compound, in the form of a granular or particulate solid, and can be one that has been conventionally used in olefin polymerization using a transition metal complex and a carrier as a catalyst component, for example, one described in paragraphs

[0110] to

[0122] of Japanese Patent Application Publication No. 2011-122146.

[0092] (Organic compound component (D)) An organic compound component (D) may be used as a component of the olefin polymerization catalyst as needed. The organic compound component (D) is used to improve polymerization performance and the physical properties of the resulting polymer. Examples of organic compound components (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0093] [Method for producing olefin copolymers] The present invention provides a method for producing olefin copolymers, characterized by copolymerizing ethylene with an alicyclic olefin and a cyclic olefin containing an aromatic structure (these are also collectively referred to simply as "olefins") in the presence of the olefin polymerization catalyst of the present invention described above.

[0094] In polymerization, the method of using each component constituting the olefin polymerization catalyst of the present invention and the order of addition to the polymerizer can be arbitrarily selected, but the following methods are examples. Hereinafter, the transition metal complex (A), compound (B), support (C), and organic compound component (D) will also be referred to as "components (A) to (D)," respectively. (1) A method of adding component (A) alone to the polymerizer. (2) A method of adding component (A) and component (B) to a polymerizer in any order. (3) A method of adding a catalyst component in which component (A) is supported on component (C) and component (B) to a polymerizer in any order. (4) A method of adding a catalyst component in which component (B) is supported on component (C) and component (A) to a polymerizer in any order. (5) A method of adding a catalyst component, in which components (A) and (B) are supported on component (C), to a polymerizer.

[0095] 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 in contact with each other beforehand.

[0096] In the methods described in (4) and (5) above, in which component (B) is supported, unsupported component (B) may be added in any order as needed. In this case, component (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 component (A) and component (B) are supported on component (C), may have the olefin prepolymerized, and further catalyst components may be supported on the prepolymerized solid catalyst component.

[0097] The polymerization of olefins can be carried out by either liquid-phase polymerization methods such as solution polymerization or suspension polymerization, or by gas-phase polymerization methods. 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 media may be used alone or in mixtures of two or more.

[0098] When polymerizing olefins using the above-described catalyst for olefin polymerization, the transition metal compound (A) is typically present in a concentration of 10 per liter of reaction volume. -12 ~10 -2 moles, preferably 10 -10 ~10 -3 It is used in quantities that equal moles.

[0099] The organometallic compound (B-1) is used in an amount such that the molar ratio [(B-1) / M] of the organometallic compound (B-1) to the total transition metal atoms (M) in the transition metal compound (A) is typically 0.01 to 50,000, preferably 0.05 to 10,000.

[0100] The organoaluminum oxy compound (B-2) is used in an amount such that the molar ratio [(B-2) / M] of aluminum atoms in the organoaluminum oxy compound (B-2) to the total transition metal (M) in the transition metal compound (A) is usually 10 to 5,000, preferably 20 to 2,000.

[0101] The ionized ionic compound (B-3) is used in an amount such that the molar ratio [(B-3) / M] of the ionized ionic compound (B-3) to the transition metal atoms (M) in the transition metal compound (A) is usually between 1 and 10,000, preferably between 1 and 5,000.

[0102] When a 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.

[0103] In the manufacturing 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 batch, semi-continuous, or continuous manner. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions.

[0104] The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system, by changing the polymerization temperature, or by the amount of compound (B) used. When hydrogen is added, the appropriate amount is approximately 0.001 to 5,000 NL per 1 kg of the resulting olefin polymer.

[0105] In the method for producing olefin polymers of the present invention, the olefin used in the polymerization reaction is ethylene, and linear or branched α-olefins having 3 or more carbon atoms can also be used in combination. In addition, the following cyclic olefins are also essential components: namely, alicyclic olefins (Z-2) and cyclic olefins containing aromatic structures (Z-3).

[0106] (Z-1) Ethylene and any linear or branched α-olefins with 3 or more carbon atoms. In the method for producing olefin polymers of the present invention, ethylene is subjected to a polymerization reaction. Furthermore, linear or branched α-olefins having 3 or more carbon atoms may be optionally subjected to the polymerization reaction. The number of carbon atoms in these α-olefins is preferably 3 to 30, more preferably 2 to 30.

[0107] Specific examples of α-olefins 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.

[0108] Hereinafter, ethylene and any linear or branched α-olefins with 3 or more carbon atoms will be collectively referred to as "α-olefin (Z-1)".

[0109] (Z-2) Alicyclic olefin As the alicyclic olefin (Z-2) (hereinafter also simply referred to as "cyclic olefin (Z-2)"), compounds represented by the following general formula [Z-2] are preferred. Using such compounds tends to make it easier to obtain polymers with a high refractive index.

[0110] [ka] (In the above equation [Z-2], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R 1 ~R 18 Furthermore, Ra and R b Each is independently a hydrogen atom, a halogen atom, or a hydrocarbon group which may be substituted with a halogen atom, and R 15 ~R 18 They may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R 15 and R 16 And, or R 17 and R 18 They may form alkylidene groups. However, the monocyclic and polycyclic rings do not contain aromatic rings.

[0111] Among these, the olefin copolymer produced by the production method of the present invention includes a constituent unit derived from bicyclo[2.2.1]-2-heptene, and tetracyclo[6.2.1.1 3,6 .0 2,7 ] Dodeca-4-ene (tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene) derived constituent units and hexacyclo[6,6,1,1 3,6 ,1 10,13 ,0 2,7 ,0 9,14 Preferably, it contains at least one constituent unit selected from constituent units derived from heptadeca-4-ene, and constituent units derived from bicyclo[2.2.1]-2-heptene and tetracyclo[6.2.1.1 3,6 .0 2,7 It is more preferable to include at least one constituent unit selected from constituent units derived from dodeca-4-ene, and tetracyclo[6.2.1.1 3,6 .0 2,7 It is particularly preferable that the constituent units include those derived from dodeca-4-ene.

[0112] (Z-3) Cyclic olefin containing an aromatic structure Examples of cyclic olefins (Z-3) containing aromatic structures (hereinafter also simply referred to as "cyclic olefins (Z-3)") include the compounds represented by the following formula (Z-31), the compounds represented by the following formula (Z-32), and the compounds represented by the following formula (Z-33). These cyclic olefins having aromatic structures may be used individually or in combination of two or more.

[0113] [ka]

[0114] In the above formula (Z-31), 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.

[0115] R 1 ~R 17 Each of these is 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 bonding hand, R 15 It is preferable that the coupling is a joint.

[0116] R 1 ~R 17 Each of these is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q=0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 10 Each of these elements may be independently linked to each other to form a monoring or polyring, and when q=1 or 2, R 10and 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 Each of these elements may be independently bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0117] Among the compounds represented by the above formula (Z-31), the compound represented by the formula (Z-31') described later is preferred.

[0118] [ka]

[0119] In the above formula (Z-32), 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.

[0120] R 18 ~R 31 Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a halogen atom other than a fluorine atom.

[0121] R 18 ~R 31 Each of these is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q=1, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 Each of these elements may be independent of the others, or they may be bonded to each other to form a monoring or polyring, 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 Each of these elements may be independently bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0122] [ka]

[0123] In the above formula (Z-33), q is 1, 2, or 3, preferably 1 or 2, and more preferably 1. R 32 ~R 39 Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a halogen atom other than a fluorine atom.

[0124] R 32 ~R 39 Each of these is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 Each of these elements may be independent of the others, or they may be bonded to each other to form a monoring or polyring, and when q=2 or 3, R 36 and R36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39 and R 39 Each of these elements may be independently bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0125] Furthermore, examples of hydrocarbon groups having 1 to 20 carbon atoms include, independently, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. 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 or aralkyl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

[0126] Among these, the cyclic olefin (Z-3) having an aromatic structure is preferably one having one aromatic ring, for example, at least one selected from benzonorbornane, indenenorbornene, and methylphenylnorbornene is preferred.

[0127] Furthermore, examples of aromatic cyclic olefins (Z-3) include the compound represented by formula (Z-31'), the compound represented by formula (Z-32'), and the compound represented by formula (Z-33'). These aromatic cyclic olefins (Z-3) may be used individually or in combination of two or more.

[0128] [ka]

[0129] [ka]

[0130] [ka]

[0131] In the above equations (Z-31'), (Z-32'), and (Z-33'), m and n are 0, 1, or 2, and R 1 ~R 36 Each of these is 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 Each of these elements may be independently bonded to each other to form a monoring, and this monoring may have a double bond.

[0132] Furthermore, in the above formulas (Z-31'), (Z-32'), and (Z-33'), m is preferably 0 or 1, and more preferably 1. n is preferably 0 or 1, and more preferably 0. 1 ~R 36 It is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

[0133] In addition, examples of the hydrocarbon group having 1 to 20 carbon atoms include, independently of each other, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aromatic hydrocarbon group include an aryl group or an aralkyl group such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group. These hydrocarbon groups may be substituted with a halogen atom excluding a fluorine atom.

[0134] Among these, as the cyclic olefin (Z-3) having an aromatic structure, those having one aromatic ring are preferable, and for example, at least one selected from benzonorbornadiene, indenonorbornene, and methylphenylnorbornene is preferable.

[0135] Since the cyclic olefin (Z-3) having such an aromatic structure can adjust the Abbe number of the olefin copolymer obtained by the method of the present invention, it is suitable for controlling the physical properties when obtaining an olefin copolymer having physical properties suitable for a lens material by the method of the present invention.

[0136] Examples of the olefin used in the polymerization reaction in the method for producing an olefin polymer of the present invention further include a conjugated / non-conjugated polyene and vinylcyclohexane. Examples of the conjugated / non-conjugated polyene include cyclic or chain hydrocarbons having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and having two or more double bonds. Specific examples thereof include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene, and compounds exemplified in

[0211] of JP-A No. 2011-122146 such as butadiene, isoprene, ethylidene norbornene, vinyl norbornene, and dicyclopentadiene.

[0137] In the method for producing an olefin polymer of the present invention, a polymerizable compound other than an olefin may be polymerized together with the above-described olefin. Examples of such a polymerizable compound include a compound having a polar group and a polymerizable unsaturated bond, an aromatic vinyl compound, and a functional group-containing styrene derivative.

[0138] Specific examples of the compound having a polar group and a polymerizable unsaturated bond include compounds exemplified as unsaturated hydrocarbons having a polar group in

[0208] to

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

[0139] Specific examples of the aromatic vinyl compound and the functional group-containing styrene derivative include compounds exemplified in

[0211] of JP-A No. 2011-122146. A preferred embodiment of the production method of the present invention is ethylene and tetracyclo[6.2.1.1 3,6 .0 2,7One embodiment involves copolymerizing dodeca-4-ene with benzonorbornene, indenenorbornene, and methylphenylnorbornene (preferably benzonorbornene) as the cyclic olefin (Z-3).

[0140] In the manufacturing method of the present invention, the pressure of α-olefin (Z-1) and the concentrations of cyclic olefins (Z-2) and (Z-3) can be set arbitrarily and are not particularly limited. The pressure of α-olefin (Z-1) is preferably the polymerization pressure.

[0141] The cyclic olefin (Z-2) is preferably used at a concentration of 0.0001 to 100 moles / liter, more preferably 0.001 to 10 moles / liter, and even more preferably 0.01 to 1 mole / liter, in the case of liquid-phase polymerization using the inert solvent. The concentration of the cyclic olefin (Z-3) is preferably 0.0001 to 1000 moles / liter, more preferably 0.001 to 100 moles / liter, and even more preferably 0.01 to 10 moles / liter.

[0142] The (Z-2) / (Z-3) molar ratio used can be set arbitrarily, but is preferably between 0.01 and 10. A more preferable lower limit is 0.02, even more preferably 0.05, and particularly preferably 0.1. On the other hand, a more preferable upper limit is 5, even more preferably 2, and particularly preferably 1.

[0143] As described above, the olefin polymer obtained by the method for producing olefin polymers of the present invention can be used to produce resins with adjusted refractive index, Abbe number, etc., and can therefore be used, for example, as a material for lenses. [Examples]

[0144] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0145] [Measurement method] [Structure of transition metal compounds] The structure of transition metal compounds is, 1 The determination was made by 1H-NMR spectroscopy (270 MHz, JEOL GSH-270).

[0146] [Weight-average molecular weight (Mw), molecular weight distribution (Mw / Mn) of polymers] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). The calculations were performed using molecular weight distribution curves obtained from a Waters Alliance GPC 2000 gel permeation chromatograph (high-temperature size exclusion chromatograph), under the following operating conditions:

[0147] <Equipment and conditions used> Measurement device: Gel permeation chromatograph allianceGPC2000 model (Waters Corporation) Analysis software; Chromatography data system Empower (trademark, Waters Inc.) Column; TSKgel GMH6-HT×2 + TSKgel GMH6-HT×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 into the device) Column temperature: 140°C Flow rate; 1.0mL / min Injection volume; 400μL Sampling time interval: 1 second Sample concentration: 0.15% (w / v) Molecular weight calibration for monodisperse polystyrene (Tosoh Corporation) / molecular weight from 495 to 20.6 million

[0148] [Comonomer (cyclic olefin) content of polymers] In accordance with the descriptions in sections

[0216] to

[0219] of Japanese Patent Publication No. 2011-122146, 13 The comonomer (cyclic olefin) content of the polymer was determined by 13C-NMR spectroscopy.

[0149] [Tg of the polymer DSC measurement was carried out under the following conditions to determine the glass transition temperature (Tg) of the polymer. Apparatus; DSC6220 manufactured by SII NanoTechnology Inc. Measurement conditions; A sample held at 300 °C for 5 minutes was rapidly cooled to 0 °C, and then Tg was determined in the process of heating up to 250 °C at a heating rate of 20 °C / min.

[0150] [Production of titanium compound [Synthesis Example 1] 1.84 g (10.0 mmol) of dipivaloylmethane and 10 mL of methanol were charged into a 50 mL reactor, and 0.75 g (15 mmol) of hydrazine monohydrate and 0.1 mL of hydrochloric acid were added while stirring, followed by heating under reflux for 2 hours. Water was added, and the soluble component was extracted with n-hexane. The obtained fraction was washed with water and saturated brine and dried over anhydrous magnesium sulfate. After filtering off magnesium sulfate, the filtrate was concentrated to obtain 1.73 g (yield 96%) of 3,5-di-tert-butyl-1H-pyrazole as a colorless solid. 1 H-NMR (270 MHz, CDCl3) δ 9.91 (1H, br s, NH), 5.90 (1H, s, CH), 1.32 (18H, s, C(CH3)3) ppm

[0151] [Example A1] 186 mg (1.03 mmol) of 3,5-di-tert-butyl-1H-pyrazole obtained in Synthesis Example 1 and 10 mL of n-hexane were charged into a 30 mL reactor that had been sufficiently dried and purged with nitrogen, and the mixture was stirred. To this solution, 0.67 mL (n-hexane solution, 1.64 M, 1.1 mmol) of n-butyllithium solution was added at 0 °C, followed by stirring at room temperature for 3 hours, and the reaction solution was concentrated to dryness.

[0152] 288 mg (1.05 mmol) of tert-butylcyclopentadienyltrichlorotitanium and 5 mL of diethyl ether were charged into a separate, thoroughly dried, nitrogen-purged 30 mL reactor and stirred. To this solution, the previously obtained dry material and the solution prepared with 5 mL of diethyl ether were added at -78°C, and stirring was continued at room temperature for 24 hours. After removing the solvent from the reaction mixture by distillation, dichloromethane was added to the resulting orange-yellow solid to prepare a suspension, and insoluble matter was removed by Celite filtration. After concentrating the obtained solution under reduced pressure, n-hexane was added, and the mixture was allowed to stand at -30°C to obtain orange crystals. These crystals were collected, washed, and dried under reduced pressure to obtain 270 mg (yield 63%) of titanium compound (1) represented by the following formula (1). 1 H-NMR(270MHz,CDCl3)δ 6.77(2H,t,J=2.6Hz,CpH),6.58(1H,s,CH),6.06(2H,t,J=2.6Hz,CpH),1.46(9H,s,C(CH3)3),1.35(18H,s,C(CH3)3)ppm

[0153] [ka] [In the formula, tBu is a tert-butyl group.]

[0154] [Example A2] In a thoroughly dried, nitrogen-purged 30 mL reactor, 189 mg (1.05 mmol) of 3,5-di-tert-butyl-1H-pyrazole obtained in Synthesis Example 1 and 10 mL of n-hexane were charged and stirred. To this solution, 0.69 mL of n-butyllithium solution (n-hexane solution, 1.59 M, 1.1 mmol) was added at 0°C, and the mixture was stirred at room temperature for 3 hours to concentrate the reaction mixture to dryness.

[0155] In a separate, thoroughly dried, nitrogen-purged 30 mL reactor, 276 mg (1.02 mmol) of (indenyl)titanium trichloride and 5 mL of diethyl ether were charged and stirred. To this solution, the previously obtained dry material and the solution prepared with 5 mL of diethyl ether were added at -78°C, and stirring was continued at room temperature for 24 hours. After the solvent of the reaction mixture was removed by distillation, dichloromethane was added to the obtained purplish-brown solid to prepare a suspension, and insoluble matter was removed by Celite filtration. The obtained solution was concentrated under reduced pressure, then n-hexane was added, and the mixture was allowed to stand at -30°C to remove the resulting solid. The filtrate was concentrated, and the obtained dark purple crystals were collected, washed, and dried under reduced pressure to obtain 91 mg (yield 22%) of titanium compound (2) represented by the following formula (2). 1 H-NMR(270MHz,CDCl3)δ 7.58-7.61(2H,m,IndH),7.29-7.31(2H,m,IndH),7.02(2H,d,J=3.3Hz,IndH),6.73(1H,t,J=3.3Hz,IndH),6.56(1H,s,CH),1.31(18H,s,C(CH3)3)ppm

[0156] [ka]

[0157] [Production of olefin polymers] [Example B1] A dry, 2.0 L pressure-resistant autoclave was thoroughly purged with nitrogen, and 710 mL of dehydrated and purified cyclohexane / hexane(9 / 1) mixed solution and tetracyclo[6.2.1.1 3,6 .0 2,750 mmol of dodeca-4-ene (hereinafter referred to as "tetracyclododecene" or "TD"), 240 mmol of benzonorbornadiene (hereinafter referred to as "BNBD"), and 1.0 mmol of triethylaluminum (calculated as aluminum atoms) were sequentially added under a nitrogen atmosphere. 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 titanium compound (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 supply of ethylene was stopped, and polymerization was halted by adding a small amount of methanol. The reactants were added to 3 liters of acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid, and the polymer was precipitated. After washing with the same solvent, the copolymer was dried under reduced pressure at 130°C for 10 hours to obtain 7.86 g of ethylene-tetracyclododecene-benzonorbornadiene copolymer. The polymerization activity and physical properties of the ethylene-tetracyclododecene-benzonorbornadiene copolymer are as follows. Polymerization activity: 3.93 kg-polymer / millimole-Ti Glass transition temperature: 124℃ Intrinsic viscosity [η]:6.5dl / g Molar ratio of structural units (ethylene:TD:BNBD) = 65.5:16.0:18.4

[0158] [Example B2] The same procedure as in Example B1 was followed, except that titanium compound (1) was replaced with titanium compound (2) obtained in Example A2, to obtain 0.91 g of ethylene-tetracyclododecene-benzonorbornadiene copolymer. The polymerization activity and physical properties of the ethylene-tetracyclododecene-benzonorbornadiene copolymer are as follows. Polymerization activity: 0.45 kg-polymer / millimole-Ti Glass transition temperature: 96℃ Intrinsic viscosity [η]: 4.45dl / g Molar ratio of structural units (ethylene:TD:BNBD) = 72.3:14.6:13.1

[0159] [Comparative Example B1] Except for synthesizing titanium compound (1) using the method described in Macromolcules 2011, 44, 1986-1998 to obtain titanium compound (3) represented by the following formula (3), 0.005 mmol of titanium compound (3) was used, triethylaluminum was changed to 0.5 mmol in terms of aluminum atoms, and triphenylcarbenium tetrakis(pentafluorophenyl) borate was changed to 0.02 mmol, the same procedure as in Example B1 was carried out to obtain 1.91 g of ethylene-tetracyclododecene-benzonorbornadiene copolymer. The physical properties of the ethylene-tetracyclododecene-benzonorbornadiene copolymer are shown below.

[0160] [ka] [In the formula, tBu is a tert-butyl group and iPr is an isopropyl group.]

[0161] Polymerization activity: 0.38 kg-polymer / millimole-Ti Glass transition temperature: 163°C Intrinsic viscosity [η]: 2.44dl / g Molar ratio of structural units (ethylene:TD:BNBD) = 61.7:20.9:17.3

[0162] [Manufacturing of titanium compounds] [Synthesis Example 2] In a 100 mL Schlenk flask that had been thoroughly heated and dried, 12.8 g (114 mmol) of potassium tert-butoxide and 20 mL of anhydrous DMF were added. Under cooling at 0°C, 10.0 g (100 mmol) of pinacolin and 19.2 g (100 mmol) of methyl 4-tert-butylbenzoate were added, and the mixture was stirred overnight while slowly raising the temperature to room temperature. Under cooling at 0°C, dilute hydrochloric acid and water were added, and the mixture was extracted with ethyl acetate. The obtained fraction was washed with water and saturated saline solution and dried over anhydrous magnesium sulfate. After filtration and concentration under reduced pressure, 30 mL of methanol, 5.5 mL (113 mmol) of hydrazine monohydrate, and 0.1 mL of hydrochloric acid were added to the resulting pale brown liquid at room temperature, and the mixture was heated under reflux for 1 hour. After cooling to room temperature, water was added, and the mixture was extracted with ethyl acetate. The obtained fraction was washed with water and saturated saline solution, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. By adding hexane to the resulting oily substance and filtering and recovering the precipitated components, 14.4 g (56% yield) of 3-(tert-butyl)-5-(4-(tert-butyl)phenyl)-1H-pyrazole was obtained as a colorless solid. 1 H-NMR(270MHz,CDCl3)δ 10.46(1H,br s,NH),7.67(2H,br s,ArH),7.42(2H,d,J=8.6Hz,ArH),6.36(1H,s,CH),1.38(9H,s,C(CH3)3),1.34(9H,s,C(CH3)3)ppm

[0163] [Example A3] In a thoroughly dried, nitrogen-purged 50 mL reactor, 257 mg (1.0 mmol) of 3-(tert-butyl)-5-(4-(tert-butyl)phenyl)-1H-pyrazole and 20 mL of diethyl ether were charged and stirred. To this solution, 0.70 mL of n-butyllithium solution (n-hexane solution, 1.58 M, 1.1 mmol) was added at 0°C, and the mixture was stirred at room temperature for 2 hours. In a thoroughly dried, nitrogen-purged 100 mL reactor, 275 mg (1.0 mmol) of tert-butylcyclopentadienyltrichlorotitanium and 20 mL of diethyl ether were charged and stirred. Under cooling to -78°C, the previously obtained pyrazole solution was added, and the mixture was stirred at room temperature for 15 hours. After removing the solvent from the reaction mixture, dichloromethane was added to the resulting solid to prepare a suspension, and insoluble matter was removed by Celite filtration. The obtained solution was concentrated under reduced pressure, then n-hexane was added, and the mixture was allowed to stand at -30°C. The resulting orange crystals were collected, washed, and dried under reduced pressure to obtain 312 mg (63% yield) of the titanium compound shown in formula (4) below. 1 H-NMR(495MHz,CDCl3)δ 7.76 (2H,d,J=8.4Hz,ArH),7.43(2H,d,J=8.4Hz,ArH), 7.03(1H,s,CH),6.75(2H,t,J=2.5Hz,CpH),6.33(2H,t,J=2.5Hz,CpH),1.41(9H,s,(CH3)3),1.35(9H,s,(CH3)3),1.27(9H,s,(CH3)3)ppm.

[0164] [ka] [In the formula, tBu is a tert-butyl group.]

[0165] [Synthesis Example 3] To a 100 mL Schlenk flask that had been thoroughly heated and dried, 12.7 g (113 mmol) of potassium tert-butoxide and 20 mL of anhydrous DMF were added. Under cooling at 0°C, 15.1 g (100 mmol) of p-methoxyacetophenone and 11.6 g (100 mmol) of methyl pivalate were added, and the mixture was stirred overnight while slowly raising the temperature to room temperature. Under cooling at 0°C, dilute hydrochloric acid and water were added, and the mixture was extracted with ethyl acetate. The resulting fraction was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration and concentration under reduced pressure, 30 mL of methanol, 4.5 mL (92 mmol) of hydrazine monohydrate, and 0.1 mL of hydrochloric acid were added to the resulting brown solid at room temperature, and the mixture was heated under reflux for 1 hour. After cooling to room temperature, water was added, and the mixture was extracted with ethyl acetate. The resulting fraction was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. By adding hexane to the resulting oily substance, the precipitated components were filtered and recovered to obtain 7.23 g (31% yield) of 3-(tert-butyl)-5-(4-methoxyphenyl)-1H-pyrazole as a pale yellow solid. 1 H-NMR(270MHz,CDCl3)δ 9.95(1H,br s,NH),7.66(2H,br s,ArH),6.96-6.92(2H,m,ArH),6.32(1H,s,CH),3.84(3H,s,CH3)1.37(9H,s,C(CH3)3)ppm

[0166] [Example A4] In a thoroughly dried, nitrogen-purged 50 mL reactor, 200 mg (0.87 mmol) of 3-(tert-butyl)-5-(4-methoxyphenyl)-1H-pyrazole and 20 mL of diethyl ether were charged and stirred. To this solution, 0.60 mL of n-butyllithium solution (n-hexane solution, 1.58 M, 0.96 mmol) was added at 0°C, and the mixture was stirred at room temperature for 2 hours. In a thoroughly dried, nitrogen-purged 100 mL reactor, 240 mg (0.87 mmol) of tert-butylcyclopentadienyltrichlorotitanium and 20 mL of diethyl ether were charged and stirred. Under cooling to -78°C, the previously obtained pyrazole solution was added, and the mixture was stirred at room temperature for 15 hours. After removing the solvent from the reaction mixture, dichloromethane was added to the resulting solid to prepare a suspension, and insoluble matter was removed by Celite filtration. The obtained solution was concentrated under reduced pressure, then n-hexane was added, and the mixture was allowed to stand at -30°C. The resulting reddish-orange crystals were collected, washed, and dried under reduced pressure to obtain 387 mg (95% yield) of the titanium compound shown in formula (5) below. 1 H-NMR(495MHz,CDCl3)δ 7.78(2H,d,J=8.9Hz,ArH),6.97(1H,s,CH),6.94(2H,d,J=8.9 Hz,ArH),6.72(2H,t,J=2.5Hz,CpH),6.40(2H,t,J=2.5Hz,CpH),3.85(3H,s,CH3),1.41(9H,s,(CH3)3),1.22(9H,s,(CH3)3)ppm.

[0167] [ka] [In the formula, tBu is a tert-butyl group.]

[0168] [Production of olefin polymers] [Example B3] The same procedure as in Example B1 was followed, except that titanium compound (1) was replaced with titanium compound (4) obtained in Example A3, to obtain 3.54 g of ethylene-tetracyclododecene-benzonorbornadiene copolymer. The polymerization activity and physical properties of the ethylene-tetracyclododecene-benzonorbornadiene copolymer are as follows. Polymerization activity: 1.77 kg-polymer / millimole-Ti Glass transition temperature: 152℃ Intrinsic viscosity [η]: 4.34dl / g Molar ratio of structural units (ethylene:TD:BNBD) = 60.3:21.3:18.4

[0169] [Example B4] The same procedure as in Example B1 was followed, except that titanium compound (1) was replaced with titanium compound (5) obtained in Example A4, to obtain 2.12 g of ethylene-tetracyclododecene-benzonorbornadiene copolymer. The polymerization activity and physical properties of the ethylene-tetracyclododecene-benzonorbornadiene copolymer are as follows. Polymerization activity: 1.06 kg-polymer / millimole-Ti Glass transition temperature: 145℃ Intrinsic viscosity [η]: 4.16dl / g Molar ratio of structural units (ethylene:TD:BNBD) = 62.4:19.8:17.8

[0170] From the above examples and comparative examples, it can be seen that the olefin polymerization method of the present invention can efficiently produce cyclic olefin copolymers containing highly active aromatic structures with high molecular weight.

Claims

1. (A) Transition metal compounds represented by the following general formula [A] and (B) (B-1) organometallic compound, (B-2) Organoaluminum oxy compounds, and (B-3) Compounds that react with the transition metal compound to form an ion pair At least one compound selected from the group consisting of and In the presence of an olefin polymerization catalyst containing A method for producing an olefin copolymer by copolymerizing ethylene, an alicyclic olefin, and a cyclic olefin containing an aromatic structure. 【Chemistry 1】 [In formula [A], M is a titanium atom, a zirconium atom, or a hafnium atom. n is an integer from 1 to 4, Each of 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 of these is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. R 1` ~R 5` Adjacent groups may be bonded to each other to form a ring. R 6` ~R 8` At least one of them is a tertiary hydrocarbon group.

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

3. In the general formula [A], R 1` is a hydrocarbon group having 1 to 20 carbon atoms, and R 2` to R 5` are hydrogen atoms. The method for producing an olefin copolymer according to claim 1.

4. In the above general formula [A], the R 6` ~R 8` A method for producing an olefin copolymer according to claim 1, wherein at least one of the substituents is selected from aryl groups or substituted aryl groups having 6 to 20 carbon atoms.

5. A transition metal compound represented by the following general formula [A-1]. 【Chemistry 2】 [In formula [A-1], M is a titanium atom, a zirconium atom, or a hafnium atom. n is an integer from 1 to 4, Each of 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 of these is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. R 1` ~R 5` Among these, adjacent groups may be bonded to each other to form a ring structure. R 1` ~R 5` In cases where adjacent groups bond to each other to form a ring structure, the ring structure is an alicyclic structure. R 6` ~R 8` At least one of them is a tertiary hydrocarbon group.

6. The transition metal compound according to claim 5, wherein in the general formula [A-1] above, M is a titanium atom.

7. In the above general formula [A-1], R 1` R is a hydrocarbon group having 1 to 20 carbon atoms. 2` ~R 5` The transition metal compound according to claim 5, wherein is a hydrogen atom.

8. In the above general formula [A-1], the R 6` ~R 8` The transition metal compound according to claim 5, wherein at least one of the substituents is selected from aryl groups or substituted aryl groups having 6 to 20 carbon atoms.

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