Catalyst for olefin polymerization and method for producing olefin polymer

Abstract

To provide a catalyst for olefin polymerization that enables efficient production of a cyclic olefin copolymer which, preferably, exhibits a high molecular weight and a high glass transition temperature.SOLUTION: An olefin polymerization catalyst comprises (A) a transition metal compound represented by formula [A-1] and (B) a specific aluminum compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel olefin polymerization catalyst, more specifically to an olefin polymerization catalyst containing a specific transition metal compound and a specific aluminoxane compound, and a method for producing an olefin polymer using the catalyst. [Background technology]

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

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

[0004] [ka]

[0005] (In the formula, M represents a transition metal of Group 4 of the periodic table such as Ti, L represents a monovalent anionic ligand in which an element of Group 15 of the periodic table is a coordinating atom, X represents a halogen or the like, m represents an integer of 1 to 3, and R 1 ~R 5 represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, or the like. The present invention discloses a method for producing a cyclic olefin copolymer by copolymerizing ethylene and / or an α-olefin having 3 to 20 carbon atoms with at least one cyclic olefin compound in the presence of a polymerization catalyst comprising (A) and one or more activators (B) selected from organoaluminum oxy compounds and organoboron compounds. Specific examples of the transition metal compound (A) include CpTi(t-Bu2C=N)Cl2 and Cp * Ti(2,6- i Pr2PhO)Cl2 (Cp represents a cyclopentadienyl group, Cp * is η 5-pentamethylcyclopentadienyl group.

[0006] Additionally, Non-Patent Document 1 discloses a transition metal compound having the above basic skeleton.

[0007] The present applicant has also disclosed in Patent Documents 2 to 6 that a transition metal compound having the above basic skeleton serves as an olefin polymerization catalyst suitable for copolymerizing ethylene with a cyclic olefin compound, and can produce a novel cyclic olefin copolymer. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-63409 [Patent Document 2] Japanese Patent Application Publication No. 2018-150273 [Patent Document 3] Japanese Patent Application Publication No. 2019-172954 [Patent Document 4] Japanese Patent Application Publication No. 2022-125289 [Patent Document 5] Japanese Patent Publication No. 2022-154223 [Patent Document 6] Japanese Patent Publication No. 2022-155527 [Non-patent literature]

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

[0010] The olefin polymerization catalysts containing the above-mentioned transition metal compounds generally use methylaluminoxane, which is considered to be expensive, as a cocatalyst. On the other hand, there is a demand from the market for a method for efficiently producing polymers with high molecular weights and glass transition temperatures, as well as for lowering the prices of cyclic olefin copolymers and the like.

[0011] The present invention has been made in view of the above circumstances, and aims to develop an olefin polymerization catalyst that can be more efficient and reduce costs, and also to provide an olefin polymerization catalyst that can produce a polymer with a high molecular weight and a high glass transition temperature. [Means for solving the problem]

[0012] The present inventors have discovered that an olefin polymerization catalyst containing a specific transition metal compound and a specific aluminoxane compound can efficiently produce a cyclic olefin copolymer having a high molecular weight and a high glass transition temperature, and have thus completed the present invention. The present invention is characterized by the following requirements:

[0013] <1> (A) a transition metal compound represented by the following formula [A-1], (B) an aluminum compound containing a compound containing a structural unit sequence of the following formula (Al-1) and, as an optional component, a compound represented by the following formula (Al-2); 1. A catalyst for olefin polymerization comprising:

[0014] [ka]

[0015] [In formula [A-1], M is a titanium atom, a zirconium atom, or a hafnium atom; n is an integer from 1 to 4, X's each independently represent 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; R1 ~R 8 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, and R 1 ~R 5 Adjacent groups may be bonded to each other to form a ring. [ka] (Above, Al is an aluminum atom, O is an oxygen atom, R b are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and multiple R a may be the same or different, and multiple R a At least one of the groups contains a hydrocarbon group having 2 to 20 carbon atoms.)

[0016] <2> In the formula [A-1], M is a titanium atom or a zirconium atom, X's each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group; R 1 ~R 5 and R 8 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, or a silicon-containing group, and R 1 ~R 5 adjacent groups may be bonded to each other to form a ring, R 6 and R 7 are each independently a hydrocarbon group having 1 to 20 carbon atoms. <1> The olefin polymerization catalyst according to claim 1. <3> In the formula [A-1], M is a titanium atom, R 1 ~R 5 and R 8 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R1 ~R 5 adjacent groups among these can be bonded to each other to form a ring, R 6 and R 7 are each independently a hydrocarbon group having 1 to 20 carbon atoms. <1> or <2> The olefin polymerization catalyst according to claim 1. <4> The aluminum compound is the molar fraction [Ra2] of hydrocarbon groups having 2 to 20 carbon atoms in the formula (Al-1) is 50 to 100 mol %, The organoaluminum oxy compound (B-1) is an organoaluminum oxy compound (B-1) in which the molar fraction [Rb2] of hydrocarbon groups having 2 to 20 carbon atoms in the formula (Al-2) is 0 to 50 mol % (provided that the total of [Rb2] and [Rb2] is 100 mol %). <1> ~ <3> 10. The olefin polymerization catalyst according to claim 9, wherein the catalyst is a olefin polymerization catalyst having a molecular weight of 100 or more. <5> R in the formula (Al-1) a and R in the formula (Al-2). b are hydrocarbon groups having 2 to 6 carbon atoms. <1> ~ <4> 10. The olefin polymerization catalyst according to claim 9, wherein the catalyst is a olefin polymerization catalyst having a molecular weight of 100 or more. <6> <1> ~ <5> 1. A method for producing an olefin-cyclic olefin copolymer, comprising copolymerizing a linear or branched α-olefin having 2 to 30 carbon atoms with a cyclic olefin in the presence of the olefin polymerization catalyst according to any one of the above items. [Effects of the Invention]

[0017] According to one embodiment of the present invention, there is provided an olefin polymerization catalyst which can efficiently produce an olefin polymer having a high glass transition temperature and a high molecular weight, preferably in the copolymerization of ethylene and a cyclic olefin, by using an aluminoxane other than methylaluminoxane, which has conventionally been considered suitable. DETAILED DESCRIPTION OF THE INVENTION

[0018] The olefin polymerization catalyst and the process for producing an olefin polymer according to the present invention will be described in more detail below. In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" may be used to mean not only homopolymer but also copolymer.

[0019] [Transition metal compound (A)] The transition metal compound of the present invention (hereinafter also referred to as "transition metal compound (A)") is represented by the following general formula [A-1].

[0020] [ka]

[0021] [In formula [A-1], M is a titanium atom, a zirconium atom, or a hafnium atom; n is an integer from 1 to 4, X's each independently represent 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 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, and R 1 ~R 5 Adjacent groups may be bonded to each other to form a ring. The transition metal compounds will now be described in detail.

[0022] 《M》 In formula [A-1], 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.

[0023] 《R 1 ~R 8》 In formula [A-1], R 1 ~R 8 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, and R 1 ~R 5 Adjacent groups among these may be bonded to each other to form a ring.

[0024] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 20, preferably 1 to 10, carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl; a linear or branched alkenyl group having 2 to 20, preferably 2 to 10, carbon atoms, such as vinyl, allyl, or isopropenyl; linear or branched alkynyl groups having 2 to 20, preferably 2 to 10, carbon atoms, such as ethynyl and propargyl; a cyclic saturated hydrocarbon group having 3 to 20, preferably 3 to 10, carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or adamantyl; Cyclic unsaturated hydrocarbon groups having 5 to 20 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl; aryl groups having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; and Examples of alkyl-substituted aryl groups include tolyl, isopropylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl.

[0025] The hydrocarbon group may have a hydrogen atom substituted with another hydrocarbon group, such as an aryl-substituted alkyl group such as benzyl or cumyl. R1 ~R 5 Examples of the cyclopentadienyl moiety having a ring formed by bonding adjacent groups to each other include the following ring structures, which may further have a substituent.

[0026] [ka]

[0027] In some cases, it is preferable for such a cyclic structure to further have a substituent. Such a substituent 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, and adjacent groups among these may be bonded to each other to form a ring. Examples of the halogen-containing group include halogenated hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as trifluoromethyl, pentafluorophenyl, and chlorophenyl.

[0028] Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Specific examples of the hydrocarbon-substituted silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl(pentafluorophenyl)silyl. Among these, preferred are methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, and triphenylsilyl. Particularly preferred are trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

[0029] Examples of the oxygen-containing group include an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic anhydride group, and a furyl group.

[0030] Among the oxygen-containing groups, preferred examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy; Preferred examples of the aryloxy group include phenoxy, 2,6-dimethylphenoxy, and 2,4,6-trimethylphenoxy. Preferred examples of the ester group include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, and p-chlorophenoxycarbonyl. Preferred examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.

[0031] Examples of the sulfur-containing group include a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group.

[0032] Among the sulfur-containing groups, preferred examples of the thioester group include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl. Preferred examples of the alkylthio group include methylthio and ethylthio. Preferred examples of the arylthio group include phenylthio, methylphenylthio, and naphthylthio. Preferred examples of the sulfonate group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Preferred examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

[0033] Examples of the nitrogen-containing group include an amino group, an imino group, an amido group, an imido group, a pyrrolidino group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, and an amino group in the form of an ammonium salt.

[0034] Among the nitrogen-containing groups, preferred examples of the amino group include dimethylamino, ethylmethylamino, and diphenylamino; Preferred examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino; Preferred examples of the amide group include acetamide, N-methylacetamide, and N-methylbenzamide. Preferred examples of the imide group include acetimide and benzimide.

[0035] Examples of the phosphorus-containing groups include phosphido groups, phosphoryl groups, thiophosphoryl groups, and phosphato groups. R 1 As for the a linear or branched alkyl group 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, or n-hexyl; aryl groups having 6 to 20, preferably 6 to 10, carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; Preferred are hydrocarbon groups having 1 to 20 carbon atoms, such as substituted aryl groups in which one or more hydrogen atoms of these aryl groups are substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or the like. R 2 ~R 5As the group, a hydrogen atom is particularly preferred.

[0036] On the other hand, R 6 and R 7 are each independently a halogen atom or a halogen-containing group, preferably a halogen-containing group. In some cases, transition metal compounds in which Preferred examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the halogen-containing group include halogenated hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as trifluoromethyl, pentafluoroethyl, 1,1,1,3,3,3-hexafluoro-2-propyl, nonafluoro-tert-butyl, pentafluorophenyl, and chlorophenyl, and more preferably a trifluoromethyl group.

[0037] The aforementioned R 6 ~R 8 Preferably, one or more of the hydrocarbon groups are hydrocarbon groups. More preferably, two or more of the hydrocarbon groups are hydrocarbon groups. Furthermore, the hydrocarbon groups are preferably branched hydrocarbon groups, more preferably secondary or tertiary hydrocarbon groups, and even more preferably tertiary hydrocarbon groups.

[0038] 《n》 In the formula [A-1], n is an integer of 1 to 4, and is selected depending on the valence of M and the type of X so that the transition metal compound (A-1) as a whole is electrically neutral.

[0039] 《X》 In formula [A-1], each X independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a divalent diene derivative group.

[0040] 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 described in the above-mentioned R 1 ~R5 and R 8 The specific embodiments of the halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, and phosphorus-containing group as the halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, and phosphorus-containing group are the same as those of the halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, and phosphorus-containing group as ...

[0041] Examples of the boron-containing group include a boranediyl group, a boranetriyl group, a diboranyl group, as well as groups such as alkyl-substituted boron, aryl-substituted boron, boron halide, and alkyl-substituted boron halide.

[0042] Examples of the alkyl group-substituted boron include groups represented by (Et)B-, (iPr)B-, (iBu)B-, (Et)B, (iPr)B, or (iBu)B. Examples of the aryl group-substituted boron include groups represented by (C6H5)2B-, (C6H5)3B, (C6F5)3B, or (3,5-(CF3)2C6H3)3B. Examples of boron halides include groups represented by BCl2- or BCl3, Examples of alkyl-substituted boron halides include (Et)BCl-, (iBu)BCl-, and (C6H5)2BCl. Tri-substituted boron may be in a coordinate bond. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

[0043] Examples of the aluminum-containing group include alkyl group-substituted aluminum, aryl group-substituted aluminum, aluminum halide, and alkyl group-substituted aluminum halide.

[0044] Examples of alkyl-substituted aluminum include groups represented by (Et)Al-, (iPr)Al-, (iBu)Al-, (Et)Al, (iPr)Al, or (iBu)Al. Examples of aryl group-substituted aluminum include a group represented by (C6H5)2Al-. Examples of aluminum halides include groups represented by AlCl2- or AlCl3, Examples of alkyl-substituted aluminum halides include (Et)AlCl- and (iBu)AlCl-. Tri-substituted aluminum may be in a coordinate bond state. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

[0045] Examples of the diene-based divalent derivative group include a 1,3-butadienyl group, an isoprenyl (2-methyl-1,3-butadienyl) group, a piperylenyl (1,3-pentadienyl) group, a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group, a cyclopentadienyl group, and a metallocyclopentene group.

[0046] Furthermore, X may have a structure in which the groups exemplified as specific examples of X are bonded to each other, and may form a ring together with M. For example, X may be an alkylene group in which two alkyl groups are bonded, and this alkylene group may form a ring together with M.

[0047] <Aluminum Compounds (B)> The aluminum compound (B) of the present invention is an aluminum compound containing a compound having a structural unit sequence of the following formula (Al-1) and, as an optional component, a compound represented by the following formula (Al-2).

[0048] [ka]

[0049] (Above, Al is an aluminum atom, O is an oxygen atom, R b are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and multiple R a may be the same or different, and multiple R aAt least one of the groups contains a hydrocarbon group having 2 to 20 carbon atoms.)

[0050] The aforementioned R a and R b Specifically, R of the transition metal compound 1 ~R 8 It is the same as the hydrocarbon group introduced in. The aforementioned R a There are multiple R a At least one of the groups contains a hydrocarbon group having 2 to 20 carbon atoms, preferably a hydrocarbon group having 2 to 10 carbon atoms. Such a hydrocarbon group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, isohexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, or eicosyl; a linear or branched alkenyl group having 2 to 20, preferably 2 to 10, carbon atoms, such as vinyl, allyl, or isopropenyl; linear or branched alkynyl groups having 2 to 20, preferably 2 to 10, carbon atoms, such as ethynyl and propargyl; a cyclic saturated hydrocarbon group having 3 to 20, preferably 3 to 10, carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or adamantyl; Examples include cyclic unsaturated hydrocarbon groups having 5 to 20 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl; aryl groups having 6 to 20, preferably 6 to 10, carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; and alkyl-substituted aryl groups, such as tolyl, isopropylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl.

[0051] Of the above, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, isohexyl, heptyl, octyl, and decyl are preferred, and alkyl groups having 2 to 6 carbon atoms such as ethyl, isopropyl, n-butyl, isobutyl, and n-hexyl are preferred. Such an R a may be a single type or a mixture of multiple types.

[0052] Specific examples of such compounds include ethylaluminoxane, butylaluminoxane, isobutylaluminoxane, hexylaluminoxane, octylaluminoxane, and decylaluminoxane.

[0053] Also, the above R a may contain a methyl group or a hydrogen atom, but R a is a methyl group or a hydrogen atom, is preferably 30 mol % or less, more preferably 20 mol % or less, even more preferably 10 mol % or less, and particularly preferably 5 mol % or less, relative to the total number of structural units represented by formula (Al-1) (100 mol %).

[0054] The aluminum compound (B) of the present invention may contain a compound represented by the formula (Al-2) above, for example, an unreacted product of the organoaluminum compound in the reaction of the organoaluminum compound with water.

[0055] R in formula (Al-1) a , and R in (Al-2) b are each preferably a hydrocarbon group having 2 to 20 carbon atoms, more preferably a hydrocarbon group having 2 to 6 carbon atoms, even more preferably a hydrocarbon group having 3 to 6 carbon atoms, and still more preferably a hydrocarbon group having 4 to 6 carbon atoms. Although it depends on the production conditions of the aluminum compound (B) of the present invention described later, a larger number of carbon atoms in the above Ra and Rb may tend to suppress the proportion of the compound having the structure of formula (Al-2), which is preferable.

[0056] When the sum of the compound containing a structural unit sequence of the formula (Al-1) and the compound represented by the formula (Al-2) is taken as 100 mol %, the proportion of the compound containing a structural unit sequence of the formula (Al-1) is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, and particularly preferably 90 mol % or more, calculated in terms of aluminum atoms. Such a ratio may be, for example, 1 H NMR measurements and 13 By performing C NMR, the R a and the R of (Formula Al-2) b From the peak intensity derived from R a Mole fraction [Ra2] and R b The mole fraction [Rb2] can be quantified.

[0057] From the viewpoint of excellent polymerization activity and copolymerizability, the aluminum compound is preferably an organoaluminum oxy compound (B-1) in which the molar fraction [Ra2] of the hydrocarbon group having 2 to 20 carbon atoms in the formula (Al-1) is 50 to 100 mol % and the molar fraction [Rb2] of the hydrocarbon group having 2 to 20 carbon atoms in the formula (Al-2) is 0 to 50 mol %, more preferably the molar fraction [Ra2] is 80 to 100 mol % and the molar fraction [Rb2] is 0 to 20 mol %, even more preferably the molar fraction [Ra2] is 90 to 100 mol % and the molar fraction [Rb2] is 0 to 10 mol %, and particularly preferably the molar fraction [Ra2] is 90 to 99.9 mol % and the molar fraction [Rb2] is 0.1 to 10 mol %. Furthermore, it is more preferable that the molar fraction [Ra2] is 92 to 99.9 mol% and the molar fraction [Rb2] is 0.1 to 8 mol%, further preferably that the molar fraction [Ra2] is 93 to 99.9 mol% and the molar fraction [Rb2] is 0.1 to 7 mol%, and particularly preferably that the molar fraction [Ra2] is 95 to 99.9 mol% and the molar fraction [Rb2] is 0.1 to 5 mol%, provided that the sum of [Ra2] and [Rb2] is 100 mol%.

[0058] The aluminum compound (B) of the present invention can be produced by any known production method without any restrictions, and preferably by reacting the corresponding organoaluminum compound with water. Examples of the organoaluminum compound include the compounds introduced below as organoaluminum compound (B-1).

[0059] The ratio of water to the organoaluminum compound, expressed as a molar ratio of HO / Al, is preferably 0.7 to 1.5. A more preferred lower limit is 0.8, and even more preferred is 0.9. Meanwhile, a more preferred upper limit is 1.4, and even more preferred is 1.3, and particularly preferred is 1.2.

[0060] The reaction temperature between water and the organoaluminum compound is usually low, and it is preferably carried out under mild conditions. Specifically, the temperature at the contact stage between water and the organoaluminum compound is preferably -50 to 20°C. A more preferred lower limit is -30°C, and even more preferred is -20°C. On the other hand, a more preferred upper limit is 15°C, and even more preferably 10°C. The contact step between the two is preferably carried out slowly in small amounts, and controlled so as to minimize temperature changes. It is preferable to bring the two compounds into contact under the above conditions, and then gradually raise the temperature until the reaction proceeds sufficiently or is completed.

[0061] (Olefin polymerization catalyst) The olefin polymerization catalyst of the present invention is characterized by containing the transition metal compound (A) and the aluminum compound (B). The molar ratio [(Al-B) / M] of the amount of aluminum atom of the aluminum compound (B) to the amount of all transition metals (M) in the transition metal compound (A) is preferably 10 to 10,000, more preferably 20 to 8,000, and even more preferably 30 to 7,000.

[0062] The olefin polymerization catalyst of the present invention can be used in combination with other components, provided that the object of the present invention is not impaired. The most typical examples are organometallic compounds (excluding the aluminum compound (B)) used primarily as scavengers or auxiliary cocatalysts. Examples of such compounds include the following organometallic compounds (B-1), methylaluminoxane compounds (B-2), and compounds (B-3) that react with the transition metal complex (A) to form ion pairs.

[0063] 《Organometallic compound (B-1》) Examples of the organometallic compound (B-1) (hereinafter also referred to as "component (B-1)") include organometallic compounds of Groups 1, 2, 12, and 13 such as the organoaluminum compound (B-1a) represented by the general formula (B-1a), the complex alkylated product (B-1b) of Group 1 metal and aluminum represented by the general formula (B-1b), and the dialkyl compound (B-1c) of Group 2 or Group 12 metal represented by the general formula (B-1c).

[0064] (B-1a):Ra m Al(ORb) n H p X q In the formula (B-1a), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 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.

[0065] (B-1b):M2AlRa4 In the formula (B-1b), M2 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 and LiAl(C7H 15 )4.

[0066] (B-1c):RaRbM3 In formula (B-1c), Ra and Rb each independently represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and M3 represents Mg, Zn, or Cd. Examples of compound (B-1c) include dimethyl magnesium, diethyl magnesium, di-n-butyl magnesium, ethyl-n-butyl magnesium, diphenyl magnesium, dimethyl zinc, diethyl zinc, di-n-butyl zinc, and diphenyl zinc. Among the organometallic compounds (B-1), organoaluminum compounds (B-1a) are preferred. The organometallic compound (B-1) may be used alone or in combination of two or more kinds.

[0067] The organometallic compound (B-1) is preferably used as a scavenger, and is preferably brought into contact in advance with a polymerization reaction vessel, a polymerization solvent, etc. A preferred amount to be used is 2 mmol or less, more preferably 1.5 mmol or less, and even more preferably 1.2 mmol or less, calculated as metal atoms, per liter of polymerization solvent.

[0068] Methylaluminoxane (B-2) As the methylaluminoxane (B-2) (hereinafter sometimes referred to as "component (B-2)" or MAO), a conventionally known methylaluminoxane can be used as it is. Specifically, a methylaluminoxane represented by the following general formula [B2-1]

[0069] [ka] and / or the following general formula [B2-2]

[0070] [ka] (wherein R is an alkyl group which must contain a methyl group, and n is an integer of 2 or greater)

[0071] Among these, preferred examples are the benzene-insoluble organoaluminum oxy compounds described in JP-A Nos. 2-78687 and 2-167305, and the aluminoxanes having two or more types of alkyl groups described in JP-A No. 3-103407.

[0072] Further, examples of the organoaluminum oxy compound (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 of 2 or greater.)

[0074] This modified methylaluminoxane is prepared using trimethylaluminum and alkylaluminums other than trimethylaluminum. Such compounds are commonly referred to as MMAO. Such MMAOs can be prepared by the methods described in U.S. Patent Nos. 4,960,878 and 5,041,584. When the total of the above methyl groups and the substituent R is taken as 100 mol %, the proportion of methyl groups exceeds 50 mol %.

[0075] As the methylaluminoxane (B-2), commercially available methylaluminoxane and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred, and among these, MMAO, which has improved solubility in various solvents and storage stability, is particularly preferred.

[0076] (B-2) is a compound known as a co-catalyst for transition metal compounds, and when used, it is preferably used in an amount smaller than that of the compound (B).

[0077] <<Compound (B-3) that reacts with transition metal complex (A) to form an ion pair>> Examples of the compound (B-3) (hereinafter also referred to as "ionic compound (B-3)" or "component (B-3)") that reacts with the transition metal complex (A) to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and US Pat. No. 5,321,106. Heteropoly compounds and isopoly compounds are also included. However, this does not include the aforementioned (B-2) organoaluminum oxy compounds.

[0078] The ionic compound (B-3) is preferably a boron compound represented by the following general formula [B3-1].

[0079] [ka]

[0080] In the formula, R e+ As for H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, etc. f From R i may be the same or different and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and are preferably substituted aryl groups.

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

[0133] to

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

[0082] Such a compound (B3) is used in an amount of less than 10 moles, more preferably less than 5 moles, even more preferably less than 2 moles, and particularly preferably less than 1 mole, per mole of metal atom of the transition metal compound.

[0083] (Carrier (C)) The support (C) is an inorganic or organic compound, and is a granular or fine particle solid. It is possible to use a support that has been conventionally used in olefin polymerization using a transition metal complex and a support as catalyst components, such as those described in paragraphs

[0110] to

[0122] of JP 2011-122146 A.

[0084] (Organic compound component (D)) An organic compound component (D) may be used as a constituent of the olefin polymerization catalyst, if necessary. The organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the resulting polymer. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0085] [Method for producing olefin polymer] The process for producing an olefin polymer of the present invention is characterized by polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst of the present invention.

[0086] In the method for producing an olefin polymer of the present invention, an olefin homopolymer may be produced by polymerizing one type of olefin, or an olefin copolymer may be produced by copolymerizing two or more types of olefins. In this specification, polymerization and copolymerization are not particularly distinguished from each other and are also referred to as "polymerization," and olefin homopolymers and olefin copolymers are not particularly distinguished from each other and are also referred to as "olefin polymers."

[0087] The method of using each component constituting the olefin polymerization catalyst of the present invention in polymerization and the order of adding them to a polymerization vessel can be selected arbitrarily, but examples include the following. Hereinafter, the transition metal complex (A), aluminum 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 a polymerization vessel. (2) A method of adding components (A) and (B) to a polymerization vessel 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 polymerization vessel 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 polymerization vessel in any order. (5) A method of adding a catalyst component in which component (A) and component (B) are supported on component (C) to a polymerization vessel.

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

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

[0090] When olefin polymerization is carried out using the above-mentioned olefin polymerization catalyst, the transition metal compound (A) is usually used in an amount of 10 -12 ~10 -2 moles, preferably 10 -10 ~10 -3 It is used in molar amounts.

[0091] When the organometallic compound (B-1) is used, it is used in an amount such that the molar ratio of the organometallic compound (B-1) to the total transition metal atoms (M) in the transition metal compound (A) [(B-1) / M] is usually 0.01 to 50,000, preferably 0.05 to 10,000. When the organometallic compound (B-1) is used as one component of the same olefin polymerization catalyst as the compound (B), it is preferably used in an amount smaller than that of the compound (B).

[0092] The organoaluminum oxy compound (B-2) is used in an amount such that the molar ratio of aluminum atoms in the organoaluminum oxy compound (B-2) to the total transition metals (M) in the transition metal compound (A) [(B-2) / M] is generally 5 to 5,000, preferably 10 to 2,000. When the organometallic compound (B-2) is used as one component of the same olefin polymerization catalyst as the compound (B), it is preferably used in an amount smaller than that of the compound (B).

[0093] The ionizing ionic compound (B-3) is used in an amount such that the molar ratio of the ionizing ionic compound (B-3) to the transition metal atom (M) in the transition metal compound (A) [(B-3) / M] is generally 1 to 10,000, preferably 1 to 5,000. When the organometallic compound (B-3) is used as one component of the same olefin polymerization catalyst as the compound (B), it is preferably used in an amount smaller than that of the compound (B).

[0094] When the carrier (C) is used, it is used in an amount such that the weight ratio of the transition metal compound (A) to the carrier (C) [(A) / (C)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5, and even more preferably 0.001 to 0.1.

[0095] In the production method of the present invention, the polymerization temperature in the polymerization step is usually -50 to +200°C, preferably 0 to 180°C; the polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous, and continuous systems. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0096] The molecular weight of the resulting olefin polymer can be adjusted by adding hydrogen to the polymerization system, by changing the polymerization temperature, or by the amount of compound (B) used. When hydrogen is added, the amount is suitably about 0.001 to 5,000 NL per kg of the resulting olefin polymer.

[0097] Examples of the olefin to be subjected to the polymerization reaction in the process for producing an olefin polymer of the present invention include linear or branched α-olefins and cyclic olefins.

[0098] (Z-1) A linear or branched α-olefin having 2 to 30 carbon atoms The linear or branched α-olefins include linear or branched α-olefins (Z-1) having 2 to 30 carbon atoms.

[0099] The α-olefin (Z-1) preferably has 2 to 20 carbon atoms. Specific examples of the α-olefin (Z-1) include ethylene, 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) At least one cyclic olefin selected from the group consisting of compounds represented by general formula [ZI], general formula [Z-II], general formula [Z-III] or general formula [Z-IV]. The cyclic olefin may be at least one cyclic olefin (Z-2) selected from the group consisting of compounds represented by the following general formula [ZI], general formula [Z-II], general formula [Z-III] or general formula [Z-IV].

[0101] [ka] [In formula [ZI], u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R 61 ~R 78 and R a1 and R b1 are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group; R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and R 75 and R 76 and, or R 77 and R 78 may form an alkylidene group.]

[0102] [ka] [In formula [Z-II], x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2; R 81 ~R 99 are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group; R 89 and R 90 and the carbon atom to which R is bonded. 93 or the carbon atom to which R is attached 91 may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R 95 and R 92 or R 95 and R 99may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0103] [ka] [In formula [Z-III], R 100 and R 101 are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18.

[0104] [ka] [In the general formula [Z-IV], x is 0 or an integer of 1 or more, R 111 ~R 118 are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group; R 121 ~R 124 are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring. General formula [ZI], general formula [Z-II], general formula [Z-III], and general formula [Z-IV] will be explained in detail below.

[0105] 《General formula [ZI]》 In formula [ZI], u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. When w is 1, the ring represented by w is a 6-membered ring, and when w is 0, the ring is a 5-membered ring.

[0106] R 61 ~R 78 and R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0107] Examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, 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 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl, allyl, and isopropenyl; linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Examples include cycloalkyl groups having 3 to 30, preferably 3 to 20, carbon atoms, such as cyclooctyl, adamantyl, norbornyl, and tetracyclododecyl; cyclic unsaturated hydrocarbon groups having 5 to 30, carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; and alkyl-substituted aryl groups, such as tolyl, isopropylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl.

[0108] The hydrocarbon group may have a hydrogen atom substituted with a halogen, and examples thereof include halogenated alkyl groups or halogenated aryl groups having 1 to 30, preferably 1 to 20, carbon atoms, such as monotrifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, and chlorophenyl.

[0109] The hydrocarbon group may be substituted with another hydrocarbon group, for example, an aryl-substituted alkyl group such as benzyl or cumyl. Further, the hydrocarbon group may be a heterocyclic compound residue; an oxygen-containing group such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, or a carboxylic anhydride group; a nitrogen-containing group such as an amino group, an imino group, an amido group, an imido group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, or an amino group in the form of an ammonium salt; a boranediyl group, a boranetriyl group, a diboranyl group, or the like. The compound may have a boron-containing group; a sulfur-containing group such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isocyanate ester group, a sulfonate ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, or a sulfenyl group; a phosphorus-containing group such as a phosphido group, a phosphoryl group, a thiophosphoryl group, or a phosphato group; a silicon-containing group; a germanium-containing group; or a tin-containing group.

[0110] Preferred examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30, preferably 1 to 20, carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl; cycloalkyl groups having 3 to 30, preferably 3 to 20, carbon atoms, such as cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, and tetracyclododecyl; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; and substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents, such as halogen atoms, alkyl groups or alkoxy groups having 1 to 30, preferably 1 to 20, carbon atoms, or aryl groups or aryloxy groups having 6 to 30, preferably 6 to 20, carbon atoms.

[0111] Furthermore, in the above general formula [ZI], R 75 and R 76 But, R77 and R 78 But, R 75 and R 77 But, R 76 and R 78 But, R 75 and R 78 Toga or R 76 and R 77 and may be bonded to each other (together with each other) to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group thus formed may have a double bond. Specific examples of the monocyclic or polycyclic group formed here include the following:

[0112] [ka] In the above examples, the carbon atoms numbered 1 and 2 correspond to R 75 (R 76 ) or R 77 (R 78 ) represents the carbon atom to which it is attached.

[0113] Also, R 75 and R 76 and, or R 77 and R 78 and the like may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include ethylidene, propylidene, and isopropylidene.

[0114] 《General formula [Z-II]》 In formula [Z-II], x and d are 0 or a positive integer, and y and z are 0, 1, or 2.

[0115] Also, R 81 ~R 99 may be the same or different and are a hydrogen atom, a halogen atom, or a hydrocarbon group. Examples of the halogen atom and hydrocarbon group include the same as those in the above formula [ZI].

[0116] where R 89 and R 90 and the carbon atom to which R is bonded. 93 or the carbon atom to which R is attached 91 may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. That is, when the two carbon atoms are bonded via an alkylene group, R 89 and R 93 and, or, R 90 and R 91 and together form an alkylene group selected from the group consisting of a methylene group (-CH2-), an ethylene group (-CH2CH2-), or a propylene group (-CH2CH2CH2-).

[0117] Furthermore, when y=z=0, R 95 and R 92 or R 95 and R 99 may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Specifically, when y=z=0, R 95 and R 92 Examples of aromatic rings formed by the following include:

[0118] [ka] Here, l is the same as d in the above general formula [Z-II].

[0119] 《General formula [Z-III]》 In formula [Z-III], R 100 and R 101 may be the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18.

[0120] The hydrocarbon group having 1 to 5 carbon atoms is preferably an alkyl group, a halogenated alkyl group, or a cycloalkyl group. Specific examples of these groups are R in the above formula [ZI]. 61 ~R78 This is similar to the specific example above.

[0121] 《General formula [Z-IV]》 In the general formula [Z-IV], x is 0 or an integer of 1 or more. R 111 ~R 118 and R 121 ~R 124 are selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and may be the same or different.

[0122] Examples of the halogen atom and hydrocarbon group include the same as those in the above formula [ZI]. Also, R 121 ~R 124 Two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring. 121 and R 122 Specific examples of cyclic olefins in which an aromatic ring is formed by bonding include the following structures:

[0123] [ka]

[0124] [ka]

[0125] Also, R 122 and R 123 Specific examples of cyclic olefins in which an aromatic ring is formed by bonding include the following structures:

[0126] [ka]

[0127] [ka]

[0128] Also, R 121 and R 122 , R 123 and R 124 Specific examples of cyclic olefins in which an aromatic ring is formed by bonding include the following structures:

[0129] [ka] Examples also include cyclic olefins in which the aromatic ring is substituted with a substituent selected from a halogen atom, an alkyl group, and an aryl group.

[0130] Specific examples of the cyclic olefins represented by the above general formula [ZI], [Z-II], [Z-III] or [Z-IV] include tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, etc., are exemplified by the compounds exemplified in

[0176] to

[0207] of JP-A No. 2011-122146.

[0131] The cyclic olefins (Z-2) represented by the general formula [ZI], [Z-II], [Z-III] or [Z-IV] may be used singly or in combination of two or more. Further examples of the olefin to be subjected to the polymerization reaction in the process for producing an olefin polymer of the present invention include conjugated / non-conjugated polyenes and vinylcyclohexane.

[0132] The conjugated / non-conjugated polyenes include cyclic or chain hydrocarbons having preferably 4 to 30, more preferably 4 to 20, carbon atoms and two or more double bonds. Specific examples thereof include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, and vinylno Examples of suitable compounds include those listed in paragraph

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

[0133] In the method for producing an olefin polymer of the present invention, a polymerizable compound other than an olefin may be polymerized together with the above-mentioned olefin. Examples of such a polymerizable compound include a compound having a polar group and a polymerizable unsaturated bond, an aromatic vinyl compound, and a functional group-containing styrene derivative.

[0134] Specific examples of compounds having a polar group and a polymerizable unsaturated bond include the compounds exemplified as unsaturated hydrocarbons having a polar group in

[0208] to

[0211] of JP-A-2011-122146.

[0135] Specific examples of aromatic vinyl compounds and functional group-containing styrene derivatives include the compounds exemplified in

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

[0136] A preferred embodiment of the production method of the present invention is copolymerization of the α-olefin (Z-1) with the cyclic olefin (Z-2). In this embodiment, the α-olefin (Z-1) is preferably ethylene, and the cyclic olefin (Z-2) is preferably tetracyclo[4.4.0.1]. 2,5 .1 7,10 ]-3-dodecene is preferred.

[0137] When the α-olefin (Z-1) and the cyclic olefin (Z-2) are copolymerized, the pressure of the α-olefin (Z-1) and the concentration of the cyclic olefin (Z-2) can be set arbitrarily and are not particularly limited. The pressure of the α-olefin (Z-1) is preferably the polymerization pressure, and the concentration of the cyclic olefin (Z-2) is 0.001 to 100M, preferably 0.01 to 10M, and more preferably 0.1 to 1M.

[0138] When olefins are polymerized in the presence of the olefin polymerization catalyst of the present invention, high molecular weight olefin polymers tend to be obtained. Furthermore, when copolymerization of olefins containing the above-mentioned cyclic olefins is carried out, polymers having a high content of structural units derived from the cyclic olefin, i.e., a high glass transition temperature, tend to be obtained. The factors behind this tendency are not clear at present, but the present inventors speculate that the following may be the cause.

[0139] The aluminum compound (B) of the present invention is a so-called organoaluminum oxy compound, and has a structure similar to MAO. However, since the substituent is larger than the methyl group of MAO, the Lewis acidity of the compound as a whole may be low. For this reason, compared to MAO, coordination with the transition metal atom and nitrogen atom contained in the transition metal compound is weaker, and the space around the transition metal atom is relatively large. It is thought that bulky olefins such as cyclic olefins may be more likely to approach the transition metal atom (ion) (the center of the polymerization active species). Alternatively, it is thought that ion separation between the cation derived from the transition metal atom and the counter anion may be more likely to occur for a similar reason. Furthermore, as mentioned above, the aluminum compound (B) of the present invention has a lower Lewis acidity than MAO, and may be less likely to undergo chain transfer reactions. It is generally said that the smaller the alkyl group in organoaluminum compounds, which may be present as unreacted compounds during the production of aluminum oxy compounds, tends to be more likely to undergo chain transfer. For these reasons, the olefin polymerization catalyst of the present invention may be more likely to produce polymers with high molecular weights. Conventionally, methylaluminoxane has been considered to be suitable as an organoaluminum oxy-compound as a cocatalyst component of a metallocene catalyst, particularly from the viewpoint of enhancing polymerization activity. On the other hand, as shown in the experimental examples described below, the combination of the transition metal compound (A) of the present invention with the aluminum compound (B) may result in higher polymerization activity than when MAO is used. One of the reasons for this is thought to be that the aluminum compound (B) of the present invention has a relatively weaker coordination with the nitrogen of the transition metal compound (A) than MAO, and therefore tends not to excessively block the flow of electrons from the lone electron pair of nitrogen to the transition metal.

[0140] Due to these multiple factors, it is believed that the olefin polymerization catalyst of the present invention exhibits multiple effects, such as "relatively increased reactivity of cyclic olefins with linear olefins and the like, making it easier to obtain olefin polymers with a high content of structural units derived from cyclic olefins," "hardly allowing chain transfer to occur, making it easier to increase molecular weight," and "relatively high polymerization activity."

[0141] The olefin polymer, preferably the cyclic olefin copolymer, obtained by the above-described method can be used for known applications without limitation, such as materials for lenses such as optical lenses and pickup lenses, materials for packaging materials such as transparent films and shrink films, and materials for injection-molded articles that take advantage of their high heat resistance. [Example]

[0142] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. [Measurement method] [Structures of transition metal compounds and organometallic compounds (aluminoxanes)] The analysis of transition metal compounds was carried out under the following conditions. The solvent used was deuterated chloroform manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The NMR measurement device used was a GSH-270 model manufactured by JEOL Ltd., and the sample solution using the above solvent was measured. The measurement temperature was room temperature, and the observed nucleus was1 H (270 MHz), the sequence was a single pulse, 45° pulse, the repetition time was 5.5 seconds or more, and the number of accumulations was 32.

[0143] The analysis of organometallic compounds (aluminoxanes) was carried out under the following conditions. The solvent was deuterated tetrahydrofuran that had been thoroughly dehydrated using molecular sieves 3A manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Diphenylmethane was used as the internal standard substance. The NMR measurement device used was a GSH-270 model manufactured by JEOL Ltd., and the sample solution using the above solvent was measured. The measurement temperature was room temperature, and the observed nucleus was 1 H (270 MHz), sequence was single pulse, 45° pulse, repetition time was 5.5 seconds or more, and the number of accumulations was 32. The reference chemical shift was set to 3.955 ppm for the methylene hydrogen of diphenylmethane. The values ​​of [Ra2] for formula (Al-1) and [Rb2] for formula (Al-2) were determined by the ratio of the absorption intensities of methylene hydrogens bonded to Al (near 2.3 ppm and near 1.2 ppm). 1 Peaks such as H were assigned by conventional methods.

[0144] [Polymer weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC) using a Waters Alliance GPC 2000 gel permeation chromatograph (high-temperature size exclusion chromatograph) under the following operating conditions:

[0145] <Devices and conditions used> Measurement equipment: Gel permeation chromatograph Alliance GPC2000 (Waters) Analysis software: Chromatography Data System Empower (trademark, Waters) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2 (inner diameter 7.5 mm x length 30 cm, Tosoh Corporation) Mobile phase: o-Dichlorobenzene (ODCB) (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) Detector: differential refractometer (built-in) Column temperature: 140°C Flow rate; 1.0mL / min Injection volume: 400μL Sampling time: 1 second Sample concentration: 0.15% (w / v) Molecular weight calibration: A calibration curve was used using monodisperse polystyrene (Tosoh Corporation) / molecular weight #3 standard set sample (molecular weight 4.95 to 20.6 million).

[0146] [Comonomer (cyclic olefin) content of polymer] According to the description of

[0216] to

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

[0147] [Polymer Tg] Differential scanning calorimetry (DSC measurement) was carried out under the following conditions to determine the Tg (glass transition temperature) of the polymer. Measurement equipment: PerkinElmer Diamond DSC type equipment Measurement conditions: Approximately 4 to 7 mg of sample was weighed to four decimal places using a precision balance, sealed in an aluminum pan specified for the device, and heated to 300°C at a rate of 100°C / min in a nitrogen atmosphere, then held for 5 minutes. The sample was then rapidly cooled to 0°C, and the Tg was determined by a conventional method during the subsequent heating process to 250°C at a rate of 20°C / min.

[0148] [First embodiment of the present invention] <(1) Synthesis of transition metal compounds> [Synthesis Example 1-1] Titanium compound (1) was synthesized by the method described in Macromolecules 2011, 44, 1986.

[0149] [ka]

[0150] <(2) Synthesis of aluminoxane compounds> [Synthesis Example 2-1] A 500 mL glass reactor was thoroughly dried and purged with nitrogen. 100 mL (83.0 mmol) of triisobutylaluminum solution (toluene solution, 0.83 M) was placed at room temperature and stirred until the solution temperature was reduced to 0°C. Then, 1.5 mL of thoroughly degassed purified water (83.3 mmol, HO / Al = 1.0 ml) was added dropwise over 60 minutes. Stirring was continued at 0°C for 30 minutes, followed by heating to 50°C at a rate of 0.8°C / min. Stirring was continued for 1 hour at 50°C, after which the solution was cooled to room temperature to obtain the desired aluminoxane compound (Al concentration: 0.897 mol / L). NMR measurement revealed that the molar ratio of isobutyl groups derived from aluminoxane to isobutyl groups derived from isobutylaluminum was 98:2.

[0151] [Synthesis Example 2-2] The same procedure as in Synthesis Example 2-1 was carried out except that the amount of pure water added dropwise was 1.65 mL (91.6 mmol, H2O / Al = 1.1 ml), to obtain the target aluminoxane compound (Al concentration 0.932 mol / L). NMR measurement revealed that the molar ratio of isobutyl groups derived from aluminoxane to isobutyl groups derived from isobutylaluminum was 98:2.

[0152] [Synthesis Example 2-3] A thoroughly dried, nitrogen-purged 500 mL glass reactor was charged with 80.3 mL (66.6 mmol) of a 0.83 M triisobutylaluminum toluene solution and 17.4 mL (16.7 mmol) of a 0.96 M triethylaluminum toluene solution at room temperature. The solution was cooled to 0 °C with stirring, and then 1.5 mL (83.3 mmol) of thoroughly degassed pure water (HO / Al = 1.0 ml) was added dropwise over 60 minutes. Stirring was continued at 0 °C for 30 minutes, followed by heating to 50 °C at a rate of 0.8 °C / min. Stirring was continued for another 1 hour at 50 °C, after which the solution was cooled to room temperature to obtain the desired aluminoxane compound (Al concentration: 0.904 mol / L). NMR analysis revealed that the molar ratio of the alkyl group derived from the aluminoxane to the alkyl group derived from the alkylaluminum was 96:4.

[0153] <(3) Olefin Polymerization> Example 1-1 The olefin gas supply line and exhaust gas line were thoroughly replaced with nitrogen in a 1,000 mL glass reactor equipped with a stirrer, and 500 mL of dehydrated toluene was charged at room temperature. After heating to 50°C, tetracyclo[4.4.0.1 2,5 .1 7,10 5 mL (31.8 mmol) of tetracyclododecene (hereinafter also referred to simply as "tetracyclododecene") was charged, and ethylene was fed at a rate of 100 L / hr with stirring to saturate the liquid and gas phases. 2.5 mmol, in terms of aluminum atom, of the aluminoxane compound (2) obtained in Synthesis Example 2-1 was then charged, and after stirring for 5 minutes, 0.0005 mmol, in terms of titanium atom, of the titanium compound (1) obtained in Synthesis Example 1-1 was added to initiate polymerization. Ethylene was continuously fed at 100 L / hr, and the mixture was maintained at 50°C under atmospheric pressure for 15 minutes, after which a small amount of methanol was added. The resulting solution was added in small portions to 1 liter of a stirred acetone / methanol (3 / 1) mixture containing a small amount of hydrochloric acid to obtain a precipitate. The solid was separated using a glass filter, washed with the same acetone / methanol (3 / 1) mixture as above, and then dried under reduced pressure at 80°C for 10 hours to obtain 1.04 g of a white solid. The polymerization activity was 8.32 kg / mmol-Ti·hr. The weight-average molecular weight Mw of the resulting white solid was 1,740 kg / mol. The glass transition temperature measured by DSC was 149°C. Therefore, this white solid can be considered to be an ethylene / tetracyclododecene copolymer. The results are shown in Table 1.

[0154] Example 1-2 The same procedure as in Example 1-1 was repeated, except that the aluminoxane compound added was the same as that obtained in Synthesis Example 2-2. 0.49 g of ethylene-tetracyclododecene copolymer was obtained. The polymerization activity was 3.92 kg / mmol-Ti·hr, and the weight-average molecular weight Mw of the resulting ethylene-tetracyclododecene copolymer was 2,100 kg / mol. The glass transition temperature measured by DSC was 151°C. The results are shown in Table 1.

[0155] Examples 1-3 The same procedure as in Example 1-1 was repeated, except that the aluminoxane compound added was the same as that obtained in Synthesis Example 2-3. 0.93 g of ethylene-tetracyclododecene copolymer was obtained. The polymerization activity was 7.44 kg / mmol-Ti·hr, and the weight-average molecular weight Mw of the resulting ethylene-tetracyclododecene copolymer was 1,280 kg / mol. The glass transition temperature measured by DSC was 146°C. The results are shown in Table 1.

[0156] Comparative Example 1-1 The same procedure as in Example 1-1 was repeated, except that the aluminoxane compound added was modified methylaluminoxane (MMAO-3A, ​​toluene solution, manufactured by Toso Finechem Co., Ltd.), and 0.53 g of ethylene-tetracyclododecene copolymer was obtained. The polymerization activity was 4.24 kg / mmol-Ti·hr, and the weight-average molecular weight Mw of the resulting ethylene-tetracyclododecene copolymer was 924 kg / mol. The glass transition temperature measured by DSC was 140°C. The results are shown in Table 1.

[0157] [Table 1]

[0158] Example 1-1-2 The procedure was repeated as in Example 1-1, except that the amount of tetracyclododecene added was 2.5 mL (15.9 mmol). 1.27 g of ethylene-tetracyclododecene copolymer was obtained. The polymerization activity was 10.16 kg / mmol-Ti·hr, and the weight-average molecular weight (Mw) of the resulting ethylene-tetracyclododecene copolymer was 2,320 kg / mol. The glass transition temperature (Tg) measured by DSC was 103°C. The results are shown in Table 2.

[0159] Example 1-1-3 The procedure of Example 1-1 was repeated, except that the amount of tetracyclododecene added was 10 mL (63.6 mmol). 0.82 g of ethylene-tetracyclododecene copolymer was obtained. The polymerization activity was 6.56 kg / mmol-Ti·hr, and the weight-average molecular weight (Mw) of the resulting ethylene-tetracyclododecene copolymer was 1,330 kg / mol. The glass transition temperature (Tg) measured by DSC was 176°C. The results are shown in Table 2.

[0160] Comparative Example 1-1-2 The procedure was repeated as in Example 1-1, except that the aluminoxane compound added was modified methylaluminoxane (MMAO-3A, ​​toluene solution, manufactured by Toso Finechem Co., Ltd.) and the amount of tetracyclododecene added was 2.5 mL (15.9 mmol). 0.47 g of ethylene-tetracyclododecene copolymer was obtained. The polymerization activity was 3.76 kg / mmol-Ti·hr, and the weight-average molecular weight (Mw) of the resulting ethylene-tetracyclododecene copolymer was 914 kg / mol. The glass transition temperature (Tg) measured by DSC was 95°C. The results are shown in Table 2.

[0161] Comparative Example 1-1-3 The same procedure as in Example 1-1 was repeated, except that the aluminoxane compound added was modified methylaluminoxane (MMAO-3A, ​​toluene solution, manufactured by Toso Finechem Co., Ltd.) and the amount of tetracyclododecene added was 10 mL (63.6 mmol). 0.53 g of ethylene-tetracyclododecene copolymer was obtained. The polymerization activity was 4.24 kg / mmol-Ti·hr, and the weight-average molecular weight (Mw) of the resulting ethylene-tetracyclododecene copolymer was 842 kg / mol. The glass transition temperature (Tg) measured by DSC was 171°C. The results are shown in Table 2.

[0162] [Table 2]

[0163] The results shown in Table 1 show that Examples 1-1 to 1-3, which used the aluminoxane compounds synthesized in Synthesis Examples 2-1 to 2-3 as the aluminum compound (B) satisfying the requirements of the present invention (having an alkyl group with two or more carbon atoms), produced polymers with higher weight-average molecular weights Mw and glass transition temperatures (Tg) than Comparative Example 1-1, which used MMAO-3A as the aluminoxane compound. Furthermore, Examples 1-1 and 1-3 showed higher reactivity than Comparative Example 1-1.

[0164] Furthermore, as shown in Table 2, even in experimental examples in which the amount of tetracyclododecene was varied, examples in which an aluminoxane compound satisfying the requirements for the aluminum compound (B) of the present invention was used showed higher polymerization activity, weight-average molecular weight Mw of the produced polymer, and glass transition temperature (Tg) than examples in which MMAO-3A was used as the aluminoxane compound.

[0165] According to the olefin polymerization catalyst of the present invention, it is possible to increase the weight average molecular weight (Mw) and glass transition temperature (Tg) of the resulting polymer by selecting an aluminoxane compound, which can be relatively easily prepared into various structures, rather than a transition metal compound, which is considered to be relatively difficult to synthesize.

Claims

1. (A) a transition metal compound represented by the following formula [A-1], (B) an aluminum compound containing a compound containing a structural unit sequence of the following formula (Al-1) and, as an optional component, a compound represented by the following formula (Al-2); 1. A catalyst for olefin polymerization comprising: 【Chemical 1】 [In formula [A-1], M is a titanium atom, a zirconium atom, or a hafnium atom; n is an integer from 1 to 4, X's each independently represent 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 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; R １ ~R ５ Adjacent groups may be bonded to each other to form a ring. 【Chemistry 2】 (Above, Al is an aluminum atom, O is an oxygen atom, R ｂ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ａ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ａ may be the same or different, and multiple R ａ At least one of the groups contains a hydrocarbon group having 2 to 20 carbon atoms.)

2. In the formula [A-1], M is a titanium atom or a zirconium atom; X's each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group; R １ ~R ５ and R ８ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, or a silicon-containing group; R １ ~R ５ adjacent groups may be bonded to each other to form a ring, R ６ and R ７ The olefin polymerization catalyst according to claim 1, wherein each of the groups independently represents a hydrocarbon group having 1 to 20 carbon atoms.

3. In the formula [A-1], M is a titanium atom; R １ ~R ５ and R ８ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R １ ~R ５ adjacent groups among these can be bonded to each other to form a ring, R ６ and R ７ The olefin polymerization catalyst according to claim 1, wherein each of the groups independently represents a hydrocarbon group having 1 to 20 carbon atoms.

4. The aluminum compound is the molar fraction [Ra2] of hydrocarbon groups having 2 to 20 carbon atoms in the formula (Al-1) is 50 to 100 mol %, The olefin polymerization catalyst according to claim 1, wherein the organoaluminum oxy compound (B-1) is an organoaluminum oxy compound (B-1) of formula (Al-2), in which the molar fraction [Rb2] of hydrocarbon groups having 2 to 20 carbon atoms is 0 to 50 mol % (provided that the sum of [Ra2] and [Rb2] is 100 mol %).

5. R in the formula (Al-1) ａ and R in the formula (Al-2). ｂ and each represent a hydrocarbon group having 2 to 6 carbon atoms.

6. A method for producing an olefin-cyclic olefin copolymer, comprising copolymerizing a linear or branched α-olefin having 2 to 30 carbon atoms with a cyclic olefin in the presence of the olefin polymerization catalyst according to claim 1.

Images