Catalyst for olefin polymerization

Abstract

To provide a method for efficiently producing cyclic olefin copolymers containing aromatic structures. Also, to provide novel transition metal compounds suitable as components of the catalyst for olefin polymerization in the aforementioned production method. [Solution] A method for copolymerizing ethylene, an aliphatic cyclic olefin, and a cyclic olefin containing an aromatic structure in the presence of an olefin polymerization catalyst comprising a transition metal compound represented by a specific structure and at least one compound selected from the group consisting of organometallic compounds, organoaluminum oxy compounds, and compounds that react with the transition metal compound to form an ion pair.

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] (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 The present invention describes a method for producing a cyclic olefin copolymer in which ethylene and / or an α-olefin having 3 to 20 carbon atoms copolymerizes with at least one cyclic olefin compound in the presence of a polymerization catalyst comprising (A) (where (A) represents hydrogen, halogen, or alkyl group having 1 to 20 carbon atoms, etc.) and 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.

[0005] 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).

[0006] [ka]

[0007] 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]

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

[0009] [Non-Patent Document 1] Macromolecules 2011, 44, 1986-1998 [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] 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 showed that it was difficult to obtain polymers with a high content of cyclic olefins containing aromatic structures. This suggests that the use of cyclic olefins 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.

[0011] 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. Another object is preferably to provide a transition metal compound suitable for the above production method.

Means for Solving the Problems

[0012] The present invention relates to, for example, the following [1] to [6]. [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 at least one compound selected from the group consisting of and a method for producing an olefin copolymer in which ethylene, an alicyclic cyclic olefin, and a cyclic olefin containing an aromatic structure are copolymerized in the presence of an olefin polymerization catalyst.

Chemical Formula

[0013] [2] A method for producing the olefin copolymer of [1], wherein M is a titanium atom in the general formula [A].

[0014] [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.

[0015] [4] A transition metal compound represented by the following general formula [A-1].

[0016] [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` One of these is 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` ~R5` Adjacent groups may be bonded to each other to form a ring structure. R 6` ~R 8` At least one of them is a substituent having an aromatic structure.

[0017] [5] The transition metal compound of [4] in the general formula [A-1], wherein M is a titanium atom.

[0018] [6] 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 [4] is a hydrogen atom. [Effects of the Invention]

[0019] By using the olefin copolymer production method of the present invention, it is possible to produce polymers with a high content of cyclic olefins containing aromatic structures and a high glass transition temperature. Furthermore, the transition metal compound used in the method for producing the olefin copolymer of the present invention is a novel compound. [Modes for carrying out the invention]

[0020] The method for producing olefin copolymers according to the present invention, as well as transition metal compounds, will be described in more detail below.

[0021] [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].

[0022] [ka] Furthermore, transition metal compound (A-1) with a specific structure among transition metal compounds (A) is a novel compound.

[0023] [Transition metal compound (A)] First, let's discuss transition metal compounds (A).

[0024] 《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.

[0025] 《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.

[0026] 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.

[0027] 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.

[0028] [ka] The rings formed by the bonding of the above components may be alicyclic structures or ring structures including aromatic structures. Preferably, they are alicyclic structures, and it is preferable that they have substituents such as hydrated carbides. In particular, it is preferable that they include bulky substituents as described later.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] Examples of the phosphorus-containing groups include phosphine groups, phosphoryl groups, thiophosphoryl groups, and phosphat groups.

[0038] (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. It is preferable that the substituent is a hydrocarbon group having 1 to 20 carbon atoms. In the present invention, a transition metal compound containing one or more such substituents is a novel compound and is, for example, a preferred embodiment as a component of an olefin polymerization catalyst described later.

[0039] 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 is a hydrogen atom. The above R1' is preferably selected from a secondary hydrocarbon group and a tertiary hydrocarbon group, with a tertiary hydrocarbon group being particularly preferred.

[0040] (R 6` ~R8` ) In equation [A], R 6` ~R 8` One or more of these substituents are aromatic substituents. Such hydrocarbon groups are aromatic hydrocarbon groups having 4 to 20 carbon atoms, and specifically include phenyl groups, tolyl groups, ethylphenyl groups, naphthyl groups, etc. Of course, the aromatic structure may also be a structure containing so-called heteroatoms such as halogens, silicon, oxygen, nitrogen, sulfur, and phosphorus. For example, this could be a pyridyl group or a substituted pyridyl group, which contains a heteroatom in the aromatic ring structure, or a phenyl group or naphthyl group having a substituent with a heteroatom, such as an alkoxyphenyl group. Preferably, the substituent is an aromatic substituent containing a substituent with a heteroatom as described above. Preferred substituents include phenyl groups, tolyl groups, naphthyl groups, methoxyphenyl groups, ethoxyphenyl groups, butoxyphenyl groups, etc.

[0041] Among the above, R 6` and / or R 7` It is preferable that the substituent has an aromatic structure. It is also preferable that two or more substituents have an aromatic structure. In particular, R 6` and R 7` It is preferable that both substituents have an aromatic structure.

[0042] 《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.

[0043] 《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.

[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 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.

[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, 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.

[0051] [ka]

[0052] 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 following, especially R 6` and R 7`If the substituent has an aromatic structure, it is presumed to have a high affinity for the aromatic portion of the cyclic olefin having an aromatic structure, as described later. Therefore, it is possible that it may have the effect of mitigating the influence on the polymerization reaction active site of the cyclic olefin (which is thought to be the metal atom M of the transition metal compound (A)). Furthermore, due to the aforementioned affinity, it is thought that it may have the effect of increasing the local concentration of the cyclic olefin having an aromatic structure around the polymerization reaction active site, thus potentially increasing the reactivity of the cyclic olefin.

[0053] [ka] 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` One of these is 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.

[0054] The compounds described above are novel compounds, and when used as catalysts for olefin polymerization, they tend to yield polymers with high glass transition temperatures.

[0055] [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, the production method is as follows: (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.

[0056] [ka] [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.

[0057] 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.".

[0058] 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."

[0059] 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.

[0060] 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.".

[0061] 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."

[0062] [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].

[0063] The olefin polymerization catalyst of the present invention may optionally further contain (C) a support and (D) an organic compound.

[0064] <Compound (B)> 《Organometallic compound (B-1》) Examples of organometallic compounds (B-1) (hereinafter also referred to as "component (B-1)") include organoaluminum compounds represented by general formula (B-1a) (B-1a), complex alkylates of group 1 metals and aluminum represented by general formula (B-1b) (B-1b), and dialkyl compounds of group 2 or group 12 metals represented by general formula (B-1c) (B-1c), which are organometallic compounds of groups 1, 2 and 12 and 13.

[0065] (B-1a):Ra m Al(OR b ) n H p X q In formula (B-1a), R a and R[[ID=1)] 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 trialkylaluminum such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydride such as diisobutylaluminum hydride, and tricycloalkylaluminum.

[0066] (B-1b): M 2 AlR a 4 In 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 alkyl compound (B-1b) include LiAl(C2H5)4 and LiAl(C7H 15 )4.

[0067] (B-1c): R a R b M 3 In formula (B-1c), R<0000 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.

[0068] Among 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.

[0069] 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 is. Specifically, the following general formula [B2-1]

[0070] [ka] and / or the following general formula [B2-2]

[0071] [ka] (In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer greater than or equal to 2.) 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.

[0072] Furthermore, examples of organoaluminum oxy compounds (B-2) include modified methylaluminoxanes represented by the following general formula [B2-3].

[0073] [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.)

[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] (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.

[0077] 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.

[0078] 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.

[0079] As the ionic compound (B-3), preferably, a boron compound represented by the following general formula [B3-1] can be mentioned.

[0080] [Chemical formula] In the formula, R e+ includes H + , a carbocation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, a ferrocenium cation having a transition metal, and the like. R f to R i may be the same as or different from each other, and is a substituent selected from a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and is preferably a substituted aryl group.

[0081] Examples of the boron compound represented by the general formula [B3-1] include those described in

[0133] to

[0144] of International Publication No. 2015 / 122414. The ionic compound (B-3) may be used alone or in combination of two or more.

[0082] (Carrier (C)) The carrier (C) is an inorganic or organic compound, and is a granular or particulate solid, and those conventionally used in olefin polymerization using a transition metal complex and a carrier as catalyst components, for example, those described in

[0110] to

[0122] of JP-A No. 2011-122146 can be used.

[0083] (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.

[0084] [Method for producing olefin polymers] The method for producing olefin polymers according to the present invention is characterized by polymerizing olefins in the presence of the olefin polymerization catalyst described above.

[0085] In the method for producing olefin polymers of the present invention, one type of olefin may be polymerized to produce an olefin homopolymer, or two or more types of olefins may be copolymerized to produce an olefin copolymer. In this specification, polymerization and copolymerization are not particularly distinguished and are also referred to as "polymerization," and olefin homopolymers and olefin copolymers are also referred to as "olefin polymers."

[0086] 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.

[0087] 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 pre-contacted.

[0088] In each of the above methods (4) and (5) in which component (B) is supported, the unsupported component (B) may be added in any order as necessary. In this case, component (B) may be the same or different. Further, 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 be prepolymerized with an olefin, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

[0089] The polymerization of olefins can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more. [[ID=ll]]

[0090] [[ID=ls]] When carrying out the polymerization of olefins using the olefin polymerization catalyst as described above, the transition metal compound (A) is usually 10 -12 ~10 -2 mol, preferably 10 -10 ~10 -3 mol per liter of the reaction volume.

[0091] The organometallic compound (B-1) is used in such an amount that the molar ratio [(B-1) / M] of the organometallic compound (B-1) to all transition metal atoms (M) in the transition metal compound (A) is usually 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 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).

[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] (Z-2) Alicyclic olefin As the alicyclic 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.

[0101] [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, 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.

[0102] Among these, the constituent units derived from bicyclo[2.2.1]-2-heptene, and 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 heptadecene-4, and constituent units derived from bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 2,5 .1 7,10 It is more preferable to include at least one constituent unit selected from constituent units derived from ]-3-dodecene, and tetracyclo[4.4.0.1 2,5 .1 7,10 It is particularly preferable that the constituent units include those derived from ]-3-dodecene.

[0103] (Z-3) Cyclic olefin containing an aromatic structure Examples of cyclic olefins containing aromatic structures (Z-3) include the compounds shown in formula (Z-31), formula (Z-32), and formula (Z-33). These cyclic olefins having aromatic structures may be used individually or in combination of two or more.

[0104] [ka]

[0105] 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.

[0106] R 1 ~R 17Each 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.

[0107] 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 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.

[0108] Among the compounds represented by the above formula (Z-31), the compound represented by the following formula (Z-31') is preferred.

[0109] [ka]

[0110] 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.

[0111] 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.

[0112] 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.

[0113] [ka]

[0114] In the above formula (Z-33), q is 1, 2, or 3, preferably 1 or 2, and more preferably 1.

[0115] 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.

[0116] 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 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] 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.

[0124] 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.

[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] 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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 a copolymerization of the α-olefin (Z-1) and the cyclic olefin (Z-2). In this embodiment, ethylene is preferred as the α-olefin (Z-1), and tetracyclo[4.4.0.1 2,5 .1 7,10]-3-dodecene is preferred.

[0133] When copolymerizing the α-olefin (Z-1) and the cyclic olefin (Z-2), the pressure of the α-olefin (Z-1) and the concentrations of the cyclic olefins (Z-2) and (Z-3) can be set arbitrarily and are not particularly limited. The pressure of the α-olefin (Z-1) is preferably the polymerization pressure.

[0134] 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.

[0135] 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.

[0136] 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]

[0137] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0138] [Measurement method] [Structure of transition metal compounds] The structure of transition metal compounds is, 1It 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) of "Alliance GPC 2000" manufactured by Waters. The operating conditions are as follows:

[0140] [Apparatus and conditions used] Measuring apparatus; Gel permeation chromatograph allianceGPC2000 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) [[ID=1〕 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. Equipment: SII Nanotechnology Co., Ltd. DSC6220 Measurement conditions: A sample held at 300°C for 5 minutes was rapidly cooled to 0°C, and then the Tg was determined during the heating process at a rate of 20°C / min to 250°C.

[0143] [Manufacturing of titanium compounds] [Synthesis Example 1] 6.22 g (20.0 mmol) of avobenzone and 30 mL of methanol were charged into a 100 mL reactor. While stirring, 1.50 g (30.0 mmol) of hydrazine monohydrate and 0.1 mL of hydrochloric acid were added, and the mixture was heated under reflux for 1 hour. After cooling to room temperature, the precipitated components were collected, washed, and dried under reduced pressure to obtain 4.42 g (72% yield) of 3-(4-tert-butylphenyl)-5-(4-methoxyphenyl)-1H-pyrazole as a colorless solid. 1 H-NMR(270MHz,CDCl3)δ 7.63-7.69(4H,m,ArH),7.45(2H,d,J=8.6Hz),6.95(2H,d,J=8.6Hz),6.74(1H,s,CH),3.85(3H,s,OCH3),1.35(9H,s,C(CH3)3)ppm

[0144] [Example A1] In a thoroughly dried, nitrogen-purged 30 mL reactor, 309 mg (1.01 mmol) of 3-(4-tert-butylphenyl)-5-(4-methoxyphenyl)-1H-pyrazole obtained in Synthesis Example 1 and 10 mL of diethyl ether 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 24 hours to obtain a colorless solution.

[0145] 279 mg (1.01 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 colorless solution was 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-brown substance 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 allowed to stand again at -30°C to separate the oily component from the supernatant. The oily component was recovered, washed, and dried under reduced pressure to obtain 387 mg (70% yield) of titanium compound (1) represented by the following formula (1) as a reddish-orange solid. 1 H-NMR(270MHz,CDCl3)δ 7.83-7.89(4H,m,ArH),7.50(2H,d,J=8.6Hz,ArH),7.26(1H,s,CH),6.98-7.02(2H,m,ArH),6.70(2H,t,J= 2.6Hz,CpH),6.51(2H,t,J=2.6Hz,CpH),3.86(3H,s,OCH3),1.37(9H,s,C(CH3)3),1.18(9H,s,C(CH3)3)ppm

[0146] [ka] [In the formula, tBu is a tert-butyl group.]

[0147] [Synthesis Example 2] 4.50 g (20.1 mmol) of dibenzoylmethane and 40 mL of methanol were charged into a 100 mL reactor. While stirring, 1.50 g (30.0 mmol) of hydrazine monohydrate and 0.1 mL of hydrochloric acid were added, and the mixture was heated under reflux for 1 hour. After cooling to room temperature, the precipitated components were collected, washed, and dried under reduced pressure to obtain 3.06 g (69% yield) of 3,5-diphenyl-1H-pyrazole as a colorless solid. 1H-NMR(270MHz,CDCl3)δ 7.73(4H,d,J=6.9Hz,ArH),7.31-7.43(6H,m,ArH),6.84(1H,s,CH)ppm

[0148] [Example A2] In a thoroughly dried, nitrogen-purged 30 mL reactor, 222 mg (1.01 mmol) of 3,5-diphenyl-1H-pyrazole obtained in Synthesis Example 2 and 10 mL of diethyl ether 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 24 hours to obtain a pale yellow solution.

[0149] 281 mg (1.02 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 pale yellow solution was 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-brown substance to prepare a suspension, and insoluble matter was removed by Celite filtration. The obtained solution was concentrated under reduced pressure, and then n-hexane was added and allowed to stand at -30°C to obtain a yellow-orange solid. The resulting solid was collected, washed, and dried under reduced pressure to obtain 230 mg (yield 50%) of titanium compound (2) represented by the following formula (2). 1 H-NMR(270MHz,CDCl3)δ 7.93(4H,d,J=6.9Hz,ArH),7.37-7.51(6H,m,ArH),7.26(1H,s,CH),6.70(2H,t,J=2.6Hz,CpH),6.55(2H,t,J=2.6Hz,CpH),1.16(9H,s,C(CH3)3)ppm

[0150] [ka] [In the formula, tBu is a tert-butyl group and Ph is a phenyl group.]

[0151] [Production of olefin polymers] [Example B1] A 2.0 L pressure-resistant autoclave with a dry internal volume was thoroughly purged with nitrogen, and 710 mL of a dehydrated and purified cyclohexane / hexane (9 / 1) mixed solution, 50 mmol of tetracyclododecene (TD), 240 mmol of benzonorbornadiene (BNBD), and 1.0 mmol of triethylaluminum in terms of aluminum atoms were sequentially inserted under a nitrogen stream. Subsequently, the temperature was raised to 50 °C, and ethylene was supplied so that the ethylene partial pressure became 0.1 MPaG, and this state was maintained. Then, 0.005 mmol of the titanium compound (1) obtained in Example A1 was added, and subsequently, 0.02 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate was added to initiate polymerization. While maintaining the internal temperature at 50 °C, ethylene was supplied so that the ethylene partial pressure remained at 0.1 MPaG, and polymerization was carried out for 5 minutes. After a predetermined time had elapsed, the supply of ethylene was stopped, and polymerization was terminated by adding a small amount of methanol. The reaction product was added to 3 L of an acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, it was dried under reduced pressure at 130 °C for 10 hours to obtain 0.620 g of an ethylene·tetracyclododecene·benzonorbornadiene copolymer. The polymerization activity and the physical property values of the ethylene·tetracyclododecene·benzonorbornadiene copolymer are as follows. Polymerization activity: 0.12 kg-polymer / mmol-Ti Glass transition temperature: 167 °C Limiting viscosity [η]: 1.41 dl / g Structural unit ratio (ethylene: TD: BNBD) = 55.7:24.8:19.5

[0152] [Example B2] The same procedure as in Example B1 was carried out except that the titanium compound (1) was changed to the titanium compound (2) obtained in Example A2, and 0.449 g of an ethylene·tetracyclododecene·benzonorbornadiene copolymer was obtained. The polymerization activity and the physical property values of the ethylene·tetracyclododecene·benzonorbornadiene copolymer are as follows. Polymerization activity: 0.09 kg-polymer / mmol-Ti Glass transition temperature: 174 °C Limiting viscosity [η]: 1.15 dl / g Structural unit ratio (ethylene:TD:BNBD) = 56.2:25.3:18.6

[0153] [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), and changing the amount of triethylaluminum to 0.5 mmol in terms of aluminum atoms, 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.

[0154] [ka] [In the formula, tBu is a tert-butyl group and iPr is an isopropyl group.] Polymerization activity: 0.38 kg-polymer / millimole-Ti Glass transition temperature: 163°C Intrinsic viscosity [η]: 2.44dl / g Structural unit ratio (ethylene:TD:BNBD) = 61.7:20.9:17.3

[0155] From the above examples and comparative examples, it can be seen that the olefin polymerization method of the present invention can efficiently produce copolymers with a high content of cyclic olefins containing aromatic structures. In particular, it can be seen that the effect is remarkable when using a transition metal compound with the structure obtained in Example A1.

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 substituent having an aromatic structure.

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. 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` One of these is 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 structure. R 6` ~R 8` At least one of them is a substituent having an aromatic structure.

5. The transition metal compound according to claim 4, wherein in the general formula [A-1] above, M is a titanium atom.

6. 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 4, wherein is a hydrogen atom.

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