Method for producing olefin copolymers and transition metal compounds

Abstract

To provide a method that can efficiently produce a cyclic olefin copolymer including an aromatic structure, preferably its high-molecular-weight body, and to provide a novel transition metal compound suitable as a component of a catalyst for olefinic polymerization in the production method.SOLUTION: According to a method herein, in the presence of a catalyst for olefinic polymerization, illustrated by a compound of the following structure with a hafnium atom, an ethylene, an aliphatic cyclic olefin and a cyclic olefin including an aromatic structure are copolymerized.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 metallocene compounds and co-catalysts such as organoaluminum oxy compounds have been known as catalysts for producing olefin polymers such as ethylene-α-olefin copolymers. Specifically, representative examples include transition metal compounds containing multiple cyclopentadienyl ligands, transition metal compounds containing multiple indenyl ligands, and transition metal compounds containing cyclopentadienyl ligands and fluorenyl ligands.

[0003] Furthermore, transition metal compounds containing cyclopentadienyl ligands and indenyl ligands have also been reported. (Non-patent documents 1, 2) Copolymers of ethylene and cyclic olefins (hereinafter sometimes referred to as COCs) are known to be suitable for optical materials because they are amorphous, highly transparent, and have a high glass transition temperature. Recently, their use has been increasing in DVD pickup lenses and imaging lenses for mobile phones and smartphones.

[0004] While catalysts for olefin polymerization containing the aforementioned metallocene complex are known to exhibit excellent copolymerizability as one of their properties, it is known that in copolymerization reactions involving the aforementioned cyclic olefins, cyclic olefins may tend to be less reactive or their molecular weight may not increase easily. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry 1994, 5, 657. [Non-Patent Document 2] Macromolecules 2001, 34, 3830. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] 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.

[0007] Therefore, the present invention aims to provide a suitable method for producing copolymers of ethylene, alicyclic olefins, and cyclic olefins containing aromatic structures. Furthermore, it is also desirable to provide transition metal compounds suitable for the above-mentioned production method. [Means for solving the problem]

[0008] The present invention relates, for example, to the following [1] to [4]. [1] (A) Transition metal compounds represented by the following general formula [A] and (B) (B-1) Organometallic compound, (B-2) Organic aluminum 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.

[0009] [Chemical formula]

[0010] [In formula [A], M is a hafnium atom, n is an integer from 1 to 4, Y is carbon or silicon Each Q 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’, R 1` ~R 10` are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, Two or more of the plurality of R 5' ~R 10' also include a structure that forms a cyclic structure or a multiple bond structure in which two or more of them are linked R 6` and R 7` are bonded to each other. ] [2] In the general formula [A], R 1` is a hydrocarbon group having 1 to 20 carbon atoms, and R 2` ~R 4` is a hydrogen atom. A method for producing the olefin copolymer of [1].

[0011] [3] A transition metal compound represented by the following general formula [A].

[0012] [Chemical formula]

[0013] [In formula [A], M is a hafnium atom, n is an integer from 1 to 4, Y is carbon or silicon. Q 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', R 1` ~R 10` 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. Multiple R 5' ~R 10' This includes structures that form ring-shaped structures or multiple bond structures in which two or more of these are linked. R 6` and R 7` This is a structure in which elements are interconnected.

[0014] [4] In the above general formula [A], R 1` R is a hydrocarbon group having 1 to 20 carbon atoms. 2` ~R 4` The transition metal compound [3] is a hydrogen atom. [Effects of the Invention]

[0015] 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]

[0016] 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].

[0017] [ka]

[0018] Furthermore, a specific transition metal compound (A) with a particular structure is a novel compound.

[0019] [Transition metal compound (A)] First, let's discuss transition metal compounds (A). 《M》 In formula [A], M represents a hafnium atom.

[0020] 《R ` 、R 1` ~R 10` 》 In equation [A], R ` , R 1` ~R 10` 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.

[0021] R 1` ~R 10` This includes structures that bond to each other to form a ring structure. A more specific example of this ring structure is R 1` ~R 10` Among these, we can cite ring structures and multiple bonds (double bonds, triple bonds) in which adjacent groups (substituents bonded to adjacent carbon atoms) are bonded to each other. Also, there are multiple R 5' ~R 8' A cyclic structure in which groups bonded to the same carbon atom are bonded to each other (for example, two R 5' One example is a ring structure formed by the bonding of two Rs. 5' Impossible structures, such as those where atoms directly bond to form multiple bonds, are excluded from this rule.

[0022] 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 having 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, anthracenyl; and Alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl. These are some examples.

[0023] 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 4` Ya R 5` ~R 10` Among the above, an example of a structure having a ring formed by the bonding of adjacent groups to each other is the following ring structure, and this ring structure may further have substituents. 1` ~R 4` It is preferable that the structure does not bond to itself.

[0024] [ka]

[0025] Among the structures described above, R bonded to adjacent carbon atoms 5' ~R 8' It is sometimes preferable for these elements to directly bond to each other, forming multiple bonds and creating an aromatic ring structure. Such a structure can be specifically represented as follows.

[0026] [ka]

[0027] 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.

[0028] 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.

[0029] 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.

[0030] Among oxygen-containing groups, preferred examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy, while 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] (R ` 、R 1` ~R 4` ) R ` , R 1` ~R 4` 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.

[0036] Also, R 1` ~R 4` 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 4` 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 more preferable.

[0037] (R 6` ~R 7` ) In equation [A], R 6` and R 7` This is characterized by a structure that forms a ring-shaped structure by being bonded together. Preferably, this ring-shaped structure is R 6` and R 7` It is preferable to have a structure that forms a so-called 3- to 10-membered ring, which includes the above. More preferably, it forms a 4- to 8-membered ring, and even more preferably a 5- to 7-membered ring. Such a structure is represented by the following equation [A '' A structure like the one shown can be used as an example.

[0038] [ka]

[0039] Formula [A '' In ], R 6` and R 7` The bonding between carbon atoms that form the skeleton of the cyclic structure formed by the bonding with may be a single bond or a multiple bond. 11` The number of elements is 0, 1, or 2, depending on the combination format. 11` This is the aforementioned R 1` ~R10` The substituent has the same definition as above, and m is preferably an integer from 1 to 8.

[0040] The above cyclic structures also include structures containing substituents such as hydrogen atoms, halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, boron-containing groups, aluminum-containing groups, or diene-based divalent derivative groups. Specific examples of such substituent structures include the aforementioned R ` , R 1` ~R 10` A similar structure to the example above can be given.

[0041] 《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.

[0042] 《Q》 In formula [A], Q 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.

[0043] Among these, halogen atoms and hydrocarbon groups are preferred, and hydrocarbon groups are more preferred. Among hydrocarbon groups, alkyl groups are preferred. Preferred examples of alkyl groups are methyl groups, ethyl groups, propyl groups, and butyl groups, with methyl groups and ethyl groups being more preferred, and methyl groups being particularly preferred.

[0044] 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 10` 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.

[0045] 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.

[0046] 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-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.

[0047] Examples of the aforementioned aluminum-containing groups include alkyl-substituted aluminum, aryl-substituted aluminum, aluminum halides, and alkyl-substituted aluminum halides.

[0048] 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.

[0049] 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.

[0050] Furthermore, Q may be a structure in which the groups listed as specific examples of Q are bonded to each other, and may form a ring together with M. For example, Q 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.

[0051] 《Y》 In formula (A), Y is carbon or silicon, and is preferably carbon. Specific examples of transition metal compounds (A) include the compounds represented by the following formula.

[0052] [ka]

[0053] These transition metal compounds can be used in combination of two or more types. In the presence of a transition metal compound (A), copolymerization of ethylene with an alicyclic olefin and a cyclic olefin containing an aromatic structure can produce high molecular weight copolymers with relatively high activity. This is a surprising characteristic, as, as shown in the examples and comparative examples described later, zirconium complexes having a complex structure similar to that of the present invention do not produce the same effects, and hafnium complexes and zirconium complexes having ligands outside the scope of the present invention yield polymers of the same molecular weight level. The reason for this effect is not yet clear, but the inventors speculate as follows.

[0054] The transition metal complex of the present invention is R 6` and R 7` This is a special structure in which the two elements bond to each other to form a cyclic structure. This cyclic structure tends to increase electron-donating ability, which is likely why the activity as a transition metal complex is enhanced. Also, R 6` and R 7` The introduction of substituents such as those described above may potentially hinder the approach of cyclic olefins to metal M. However, since rotation is suppressed in cyclic structures compared to single substituents, it is presumed that the effect of the aforementioned hindering can be made relatively small. Because M is hafnium, which is a larger atom than zirconium, it is possible that the controlled cyclic olefins can easily approach hafnium, which is the polymerization reaction active site, and that the effect of chain transfer agents such as hydrogen is relatively reduced.

[0055] The inventors speculate that one or more of the above-mentioned effects contribute to the unique performance of the transition metal complex of the present invention in copolymerization reactions involving cyclic olefins. Such effects are due to the R bonded to adjacent carbon atoms as described above. 5' ~R 8'It can also be argued that a structure in which the elements directly bond to each other to form a multiple bond, such as the aromatic ring structure shown in formula (A'), is more preferable. If such an aromatic structure is included, in addition to the steric effects mentioned above, it is thought that there is a possibility of increased interaction with the cyclic olefin containing the aromatic structure through electronic effects, and an effect of activating the hafnium, which is the active site.

[0056] The transition metal compound (A) of the present invention is represented by the following general formula [A].

[0057] [ka]

[0058] The above R', R 1` ~R 10` , M, Q, Y, and n are all R', R in the general formula [A] representing a transition metal compound (A). 1` ~R 10` It is synonymous with M, Q, Y, and n. 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.

[0059] [Method for producing transition metal compounds] The transition metal compound (A) of the present invention can be produced by combining known methods. Specifically, a well-known method involves reacting an anion obtained by reacting a corresponding ligand compound precursor with an organoalkali metal compound such as alkyllithium with the corresponding hafnium halide compound.

[0060] [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 is characterized by containing

[0061] The olefin polymerization catalyst of the present invention may further contain a (C) carrier and / or a (D) organic compound, if necessary.

[0062] <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 alkylates (B-1b) of Group 1 metals and aluminum represented by the general formula (B-1b), and dialkyl compounds (B-1c) of Group 2 or Group 12 metals represented by the general formula (B-1c). Organometallic compounds of Groups 1, 2, 12, and 13 are exemplified.

[0063] (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.

[0064] (B-1b):M 2 AlR a 4 In the formula (B-1b), M 2 is Li, Na, or K, and Ra 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, LiAl(C7H 15 )4 and the like.

[0065] (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 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, diphenylzinc.

[0066] Among the organometallic compounds (B-1), the organoaluminum compound (B-1a) is preferred. The organometallic compound (B-1) may be used alone or in combination of two or more.

[0067] Organoaluminum oxy compounds (B-2) As the organoaluminum oxy compound (B-2) (hereinafter also referred to as "component (B-2)"), a conventionally known aluminoxane can be used as it is. Specifically, the following general formula [B2-1]:

[0068]

Chemical formula

[0069]

Chemical formula

[0070] (In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.) Examples include compounds represented by , benzene-insoluble organoaluminum oxy compounds described in Japanese Patent Publication No. 2-78687 and Japanese Patent Publication No. 2-167305, and aluminoxanes having two or more alkyl groups described in Japanese Patent Publication No. 3-103407.

[0071] Furthermore, examples of organoaluminum oxy compounds (B-2) include modified methylaluminoxanes represented by the following general formula [B2-3].

[0072] [ka]

[0073] (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.)

[0074] 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.

[0075] Furthermore, as organoaluminum oxy compounds (B-2), organoaluminum oxy compounds containing boron, represented by the following general formula [B2-4], can also be mentioned.

[0076] [ka]

[0077] (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.

[0078] 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.

[0079] 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, and U.S. Patent No. 5321106, etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. However, the organoaluminum oxy compounds mentioned above (B-2) are not included.

[0080] The ionic compound (B-3) is preferably a boron compound represented by the following general formula [B3-1].

[0081] [ka]

[0082] 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.

[0083] 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.

[0084] (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.

[0085] (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.

[0086] [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.

[0087] 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.

[0088] 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. 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.

[0089] 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 as a mixture of two or more. When producing cyclic olefin copolymers, it is preferable that the inert hydrocarbon media include alicyclic hydrocarbons. Specific preferred examples include cyclohexane and methylcyclopentane.

[0090] When polymerizing olefins using the olefin polymerization catalyst described above, the amount of transition metal compound (A) is typically 1 × 10⁻¹⁶ per liter of reaction volume. -12 ~1 × 10 -2 Moles, preferably 1 × 10⁻⁶ -10 ~1 × 10 -3 It is used in quantities that equal moles.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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 with 3 or more carbon atoms can also be used in combination. In addition, the following cyclic olefins are also essential components: alicyclic olefins (Z-2) and cyclic olefins containing aromatic structures (Z-3).

[0098] (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.

[0099] 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.

[0100] 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)".

[0101] (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.

[0102] [ka]

[0103] (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, R a 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.

[0104] 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 ] Constituent units derived from dodeca-4-ene 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 2,7It 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.

[0105] (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.

[0106] [ka]

[0107] 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.

[0108] 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.

[0109] R 1 ~R 17 Each of these is preferably an independent 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 R12 , 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 independent of the others, or they may be bonded to each other to form a monoring or polyring, 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 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.

[0110] Among the compounds represented by the above formula (Z-31), the compound represented by the formula (Z-31') described later is preferred.

[0111] [ka]

[0112] 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.

[0113] R 18 ~R 31Each 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.

[0114] R 18 ~R 31 Each of these is preferably an independent 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.

[0115] [ka]

[0116] 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.

[0117] R 32 ~R 39Each of these is preferably an independent 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 R 36 , 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] 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 one another to form a monoring, and this monoring may have a double bond.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] The cyclic olefin (Z-3) having the aromatic structure described above can adjust the Abbe number of the olefin copolymer obtained by the method of the present invention, and is therefore suitable for controlling the physical properties when obtaining an olefin copolymer with physical properties suitable for lens materials using the method of the present invention.

[0129] Examples of olefins used in the polymerization reaction in the method for producing olefin polymers of the present invention include conjugated / unconjugated polyenes and vinylcyclohexane.

[0130] Examples of the conjugated / unconjugated polyenes include cyclic or chain-like hydrocarbons having 4 to 30 carbon atoms, preferably 4 to 20, and possessing two or more double bonds. Specific examples include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylone Examples of compounds exemplified in section

[0211] of Japanese Patent Publication No. 2011-122146 include rubornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethlylidene-8-methyl-1,7-nonadienene, 5,9-dimethyl-1,4,8-decatrienebutadiene, isoprene, ethlylidenenorbornene, vinylnorbornene, and dicyclopentadiene.

[0131] In the method for producing olefin polymers of the present invention, polymerizable compounds other than olefins may be polymerized together with the olefins described above. Examples of such polymerizable compounds include compounds having polar groups and polymerizable unsaturated bonds, aromatic vinyl compounds, and functional group-containing styrene derivatives.

[0132] Specific examples of compounds having polar groups and polymerizable unsaturated bonds include the compounds exemplified as unsaturated hydrocarbons having polar groups in sections

[0208] to

[0211] of Japanese Patent Publication No. 2011-122146.

[0133] Specific examples of aromatic vinyl compounds and functional group-containing styrene derivatives include the compounds exemplified in

[0211] of Japanese Patent Publication No. 2011-122146. A preferred embodiment of the manufacturing method of the present invention is ethylene and tetracyclo[6.2.1.1] as the cyclic olefin (Z-2). 3,6 .0 2,7Examples of copolymerization include copolymerizing dodeca-4-ene with benzonorbornadiene, indenonorbornene, or methylphenylnorbornene (preferably benzonorbornadiene) as the cyclic olefin (Z-3).

[0134] In the production method of the present invention, the pressure of the α-olefin (Z-1) and the concentrations of the cyclic olefins (Z-2) and (Z-3) can be arbitrarily set and are not particularly limited. The pressure of the α-olefin (Z-1) is preferably the polymerization pressure.

[0135] For example, in the case of liquid-phase polymerization using the inert solvent, the cyclic olefin (Z-2) is preferably used under the conditions of 0.0001 to 100 mol / liter, more preferably 0.001 to 10 mol / liter, and even more preferably 0.01 to 1 mol / liter. Also, the concentration of the cyclic olefin (Z-3) is preferably used under the conditions of 0.0001 to 1000 mol / liter, more preferably 0.001 to 100 mol / liter, and even more preferably 0.01 to 10 mol / liter.

[0136] The (Z-2) / (Z-3) molar ratio used can also be arbitrarily set, but is preferably 0.01 to 10. A more preferable lower limit value is 0.02, even more preferably 0.05, and particularly preferably 0.1. On the other hand, a more preferable upper limit value is 5, even more preferably 2, and particularly preferably 1.

[0137] As described above, the olefin polymer obtained by the production method of the olefin polymer of the present invention can be a resin with adjusted refractive index, Abbe number, etc., and thus can be used, for example, as a material for lenses.

Examples

[0138] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited thereto. [Measurement method] [Structure of transition metal compound] The structure of the transition metal compound is1 It was determined by 1H-NMR spectrum (270 MHz, JEOL GSH-270).

[0139] 〔Weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer〕 The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). They were calculated from the molecular weight distribution curve obtained by a gel permeation chromatograph (high-temperature size exclusion chromatograph) “Alliance GPC 2000” manufactured by Waters, and the operating conditions were as follows:

[0140] 〔Apparatus and conditions used〕 Measuring apparatus: Gel permeation chromatograph Alliance GPC2000 type (Waters) Analysis software: Chromatography data system Empower (trademark, Waters) Column: TSKgel GMH6-HT×2 + TSKgel GMH6-HT×2 (Inner diameter 7.5 mm × length 30 cm, Tosoh Corporation) Mobile phase: o-dichlorobenzene 〔=ODCB〕(Special grade reagent, FUJIFILM Wako Pure Chemical Corporation) Detector: Differential refractometer (built-in to the apparatus) Column temperature: 140 °C Flow rate: 1.0 mL / min Injection volume: 400 μL Sampling time interval: 1 second Sample concentration: 0.15% (w / v) Molecular weight calibration: Monodisperse polystyrene (Tosoh Corporation) / Molecular weight from 495 to 20.6 million

[0141] 〔Content of comonomer (cyclic olefin) in the polymer〕 According to the descriptions in

[0216] to

[0219] of JP-A-2011-122146, 13 The content of the comonomer (cyclic olefin) in the polymer was determined by 13C-NMR spectrum.

[0142] 〔Tg of the polymer〕 The glass transition temperature (Tg) of the polymer was determined by DSC measurements under the following conditions. Device; SII Nanotechnology Co., Ltd. DSC6220 Measurement conditions: The sample was held at 300°C for 5 minutes, rapidly cooled to 0°C, and then heated to 250°C at a rate of 20°C / min. The Tg was determined during this process.

[0143] [Production of ligands, hafnium, and zirconium compounds] [Synthesis Example 1] In a thoroughly dried, nitrogen-purged 200 mL reactor, 1.99 g (12.7 mmol) of 1,2,3,5-tetrahydro-s-indacene and 100 mL of tert-butyl methyl ether were added. At 0°C, 9.0 mL of n-butyllithium solution (n-hexane solution, 1.58 M, 14.3 mmol) was added, and the mixture was allowed to return to room temperature and stirred for 20 hours. Separately, in a thoroughly dried, nitrogen-purged 500 mL reactor, 3.23 g (14.0 mmol) of 6,6-diphenylflubene and 100 mL of tert-butyl methyl ether were added, and the reaction mixture prepared above was added. The mixture was refluxed at 55°C for 21 hours. After returning to room temperature, aqueous ammonium chloride solution was added, water was added, and the mixture was extracted with diethyl ether. The resulting solution was washed with aqueous sodium bicarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained powder was washed with hexane and dried to yield 3.16 g (64%) of 5-(1,3-cyclopentadienyldiphenylmethyl)-1,2,3,5-tetrahydro-s-indacene as a pale yellow powder. 1 H-NMR(270MHz,CDCl3)δ 7.40-7.15(9H,m,ArH),6.96(1H,s,ArH),6.62-6.17(5H,m,CpH+IndH),4.84 / 4.79(1H,s,IndH), 3.06 / 2.90(2H,s,CpH),2.84-2.79(2H,m,CH2),2.74-2.68(2H,m,CH2),2.05-1.97(2H,m,CH2)ppm

[0144] [ka]

[0145] [Example A1] After thorough heating and drying, the 100 mL flask was placed under a nitrogen atmosphere with nitrogen purging. 600.2 mg (1.55 mmol) of 5-(1,3-cyclopentadienyldiphenylmethyl)-1,2,3,5-tetrahydro-s-indacene synthesized in Synthesis Example 1, 229.5 mg (3.18 mmol) of tetrahydrofuran, and 2.1 mL (1.58 M, 3.26 mmol) of n-butyllithium were added to 50 mL of toluene at 0°C, and the mixture was refluxed at 45°C for 5 hours. After returning to room temperature and removing the solvent under reduced pressure, the dilithio compound was washed with hexane to obtain 614.1 mg (1.13 mmol) of the dilithio compound as a yellow powder. Under a nitrogen atmosphere, 525.7 mg (1.13 mmol) of tetrachlorobis(tetrahydrofuran)hafnium and 50 mL of anhydrous diethyl ether were added to a 100 mL flask. 2.1 mL of methyllithium solution (diethyl ether solution, 1.08 M, 2.26 mmol) was added at 0°C and the mixture was stirred for 30 minutes. The isolated dilithio compound was added to this reaction mixture at -78°C and the mixture was stirred for 17 hours. After returning to room temperature and removing the solvent under reduced pressure, the mixture was extracted with toluene, followed by solvent distillation and washing with hexane to obtain 605.4 mg (yield 65%) of hafnium compound (1) as a reddish-orange powder. 1 H-NMR(270MHz,C6D6)δ 7.82(2H,d,J=7.3Hz,ArH),7.75(1H,d,J=7.8Hz,ArH),7.59(1H,d,J=7.8Hz,ArH),7.31(1H,s, IndH),7.12-6.92(6H,m,ArH),6.60(1H,d,J=3.2Hz,IndH),6.28-6.24(1H,m,CpH),6.20(2H,br s,ArH+CpH),5.76(1H,d,J=3.2Hz,IndH),5.51-5.48(1H,m,CpH),5.25-5.22(1H,m,CpH),2.88-2.67 (2H,m,CH2),2.45-2.36(2H,m,CH2),1.77-1.66(2H,m,CH2),-0.13(3H,s,CH3),-1.12(3H,s,CH3)ppm FD-MS:m / Z=594(M+)

[0146] [ka]

[0147] [Experimental Example A2] In a thoroughly heated and dried 100 mL flask under a nitrogen atmosphere, 350.0 mg (1.01 mmol) of 1-(cyclopentadienyldiphenylmethyl)-1H-indene synthesized in Synthesis Example 1 and 0.17 mL (2.09 mmol) of anhydrous tetrahydrofuran were dissolved in 50 mL of anhydrous toluene. Under an ice bath, 1.3 mL (1.59 M, 2.07 mmol) of n-butyllithium was added, and the mixture was heated in a 45 °C oil bath for 5 hours. After cooling, the concentrated residue of the reaction mixture was washed with hexane to obtain 439.0 mg (0.83 mmol) of the dilithio compound as a yellow powder. Subsequently, in a 100 mL flask under a nitrogen atmosphere, 381 mg (1.01 mmol) of tetrachlorobis(tetrahydrofuran)hafnium was dissolved in 50 mL of anhydrous diethyl ether. Under an ice bath, 1.53 mL (1.09 M, 2.02 mmol) of methyllithium was added, and the mixture was stirred for 15 minutes. The reaction mixture was cooled to -78°C in an acetone-dry ice bath, and then the anhydrous tetrahydrofuran solution of the dilithio compound described above was added dropwise. The mixture was stirred for 17 hours while gradually increasing the temperature to room temperature. The concentrated residue was extracted with toluene and filtered through Celite. The residue after filtrate concentration was washed with hexane to obtain 210 mg (38% yield) of hafnium compound (2) as a pale orange powder. 1H-NMR(270MHz, CDCl3) δ 7.76(2H, d, J = 7.6Hz, ArH), 7.70(1H, d, J = 7.8Hz, ArH), 7.46 - 7.43(3H, m, ArH), 7.09 - 6.86(6H, m, ArH), 6.59(1H, d, J = 3.6Hz, ArH), 6.45(1H, dd, J = 8.5, 6.8Hz, ArH), 6.29(1H, d, J = 8.5Hz, ArH) 6.22 - 6.19(1H, m, CpH), 6.15 - 6.12(1H, m, CpH), 5.76(1H, d, J = 3.6Hz, ArH), 5.38 - 5.35(1H, m, CpH), 5.22 - 5.19(1H, m, CpH), -0.18(3H, s, HfMe), -1.22(3H, s, HfMe) ppm FD-MS: m / Z = 554(M+)

[0148] [Chemical formula]

[0149] [Synthesis Example A3] After sufficient heating and drying, under a nitrogen atmosphere with the 100 mL flask purged with nitrogen, 300.1 mg (0.78 mmol) of 5-(1,3-cyclopentadienyldiphenylmethyl)-1,2,3,5-tetrahydro-s-indacene synthesized in Synthesis Example 1, 229.5 mg (1.63 mmol) of tetrahydrofuran, and 25 mL of toluene were placed in the flask. At 0 °C, 1.0 mL (1.59 M, 1.63 mmol) of n-butyllithium was added, and the mixture was refluxed at 45 °C for 5 hours. After returning to room temperature, the solvent was distilled off under reduced pressure, and the dilithio compound washed with hexane was obtained as a yellow powder, 291.6 mg (0.54 mmol). Under a nitrogen atmosphere, 120.0 mg (0.54 mmol) of zirconium tetrachloride and 50 mL of dehydrated diethyl ether were added to a 100 mL flask. At 0 °C, 1.0 mL (diethyl ether solution, 1.09 M, 1.07 mmol) of methyl lithium solution was added and stirred for 30 minutes. The isolated dilithio compound was added to this reaction solution at -78 °C and stirred for 15 hours. After returning to room temperature, the solvent was distilled off under reduced pressure, extracted with toluene, and then washed with hexane after solvent evaporation to obtain 257.9 mg (yield 65%) of the zirconium compound (3) as a red-orange powder. 1 H-NMR(270MHz,CDCl3)δ 7.82(2H,d,J=7.2Hz,ArH),7.75(1H,d,J=7.2Hz,ArH),7.59(1H,J=7.2Hz,ArH),7.30(1H,s,ArH),7. 11―6.92(6H,m,ArH)6.60(1H,d,J=2.2Hz,IndH),6.27―6.24(1H,m,CpH),6.21―6.19(1H,m,CpH),6.20 (1H,s,ArH),5.76(1H,d,J=2.2Hz,IndH),5.51-5.48(1H,m,CpH),5.25-5.22(1H,m,CpH),2.88-2.67 (2H,m,CH2),2.50-2.30(2H,m,CH2),1.80-1.63(2H,m,CH2),-0.13(3H,s,CH3),-1.12(3H,s,CH3)ppm

[0150] [ka]

[0151] [Synthesis example A4] Based on the literature (J. Chem. Soc., Dalton Trans.: Inorg. Chem. 1994, 5, 657.), zirconium compound (4) was prepared.

[0152] [ka]

[0153] [Production of olefin polymers] [Example B1] A dry, 1.5 L pressure-resistant autoclave was thoroughly purged with nitrogen, and 703 mL of dehydrated and purified cyclohexane / hexane (3 / 1) mixed solution, 120 mmol of tetracyclododecene (TD), 209 mmol of benzonorbornadiene (BNBD), and 10.0 mmol of triisobutylaluminum were sequentially added 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, 0.005 mmol of the hafnium compound (1) obtained in Example A1 was added, followed by 0.02 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate, and polymerization was started. 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 a 3-liter acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours to obtain 0.45 g of ethylene-tetracyclododecene-benzonorbornadiene copolymer. The polymerization activity and physical properties of the ethylene-tetracyclododecene-benzonorbornadiene copolymer are as follows. Polymerization activity: 90g-polymer / millimole-Hf Glass transition temperature: 146℃ Intrinsic viscosity [η]: 0.69dl / g Weight average molecular weight (Mw): 150,000g / mol Mw / Mn: 1.70 Molar ratio of structural units (ethylene:TD:BNBD) = 61.2:21.7:17.2

[0154] [Comparative Example B1] The procedure was the same as in Example B1, except that hafnium compound (1) was replaced with hafnium compound (2) obtained in Synthesis Example A2, to obtain 0.28 g of ethylene-tetracyclododecene copolymer. The polymerization activity and physical properties of the ethylene-tetracyclododecene-benzonorbornadiene copolymer are as follows. Polymerization activity: 60g-polymer / millimole-Hf Glass transition temperature: 145℃ Intrinsic viscosity [η]: 0.48dl / g Weight average molecular weight (Mw): 86,700g / mol Mw / Mn: 1.51 Molar ratio of structural units (ethylene:TD:BNBD) = 59.3:24.0:16.6

[0155] [Comparative example B2] The procedure was the same as in Example B1, except that the hafnium compound (1) was replaced with the zirconium compound (3) obtained in Synthesis Example A3, to obtain 3.19 g of ethylene-tetracyclododecene copolymer. The polymerization activity and physical properties of the ethylene-tetracyclododecene-benzonorbornadiene copolymer are as follows. Polymerization activity: 640g-polymer / millimole-Zr Glass transition temperature: 156℃ Intrinsic viscosity [η]: 0.39dl / g Weight average molecular weight (Mw): 76,800g / mol Mw / Mn: 1.80 Molar ratio of structural units (ethylene:TD:BNBD) = 58.7:21.0:20.4

[0156] [Comparative Example B3] Except for replacing the hafnium compound (1) with the zirconium compound (4) obtained in Synthesis Example A4 and changing the polymerization time to 10 minutes, the same procedure as in Example B1 was performed to obtain 4.24 g of ethylene-tetracyclododecene copolymer. The polymerization activity and physical properties of the ethylene-tetracyclododecene-benzonorbornadiene copolymer are as follows. Polymerization activity: 850g-polymer / millimole-Zr Glass transition temperature: 156℃ Intrinsic viscosity [η]: 0.43dl / g Weight average molecular weight (Mw): 83,800g / mol Mw / Mn: 1.80 Molar ratio of structural units (ethylene:TD:BNBD) = 56.6:23.5:19.9

[0157] [Table 1]

[0158] From the above examples and comparative examples, it can be seen that the olefin polymerization method of the present invention makes it easier to produce cyclic olefin copolymers containing aromatic structures with high molecular weights compared to the method using the corresponding zirconium compound.

[0159] For compounds having ligand structures outside the range of the transition metal compounds of the present invention, there is no significant difference in the molecular weight of the copolymers obtained between hafnium compounds and zirconium compounds. Therefore, the performance of transition metal compounds like those in this application can be said to be an unexpectedly desirable effect.

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 Ethylene, alicyclic olefins, and cyclic olefins containing aromatic structures are copolymerized. A method for producing olefin copolymers. 【Chemistry 1】 In formula [A''], M is a hafnium atom, n is an integer from 1 to 4, Y is carbon or silicon. Q 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', R １` R8' and R11' are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. m is an integer from 1 to 8. R9' and R10' are hydrogen atoms, Multiple R ５` ~R １０` This also includes structures that form cyclic or multiple bond structures when two or more of these elements are linked together.

2. The method for producing an olefin copolymer according to Claim 1, wherein in the general formula [A''], R 11' is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group.

3. A transition metal compound represented by the following general formula [A'']. 【Chemistry 2】 In formula [A''], M is a hafnium atom, n is an integer from 1 to 4, Y is carbon or silicon. Q 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', R １` R8' and R11' are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. m is an integer from 1 to 8. R9' and R10' are hydrogen atoms, Multiple R ５` ~R １０` This also includes structures that form cyclic or multiple bond structures when two or more of these elements are linked together.

4. The transition metal compound according to claim 3, wherein in the general formula [A''], R 11' is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group.

Images