Method for producing ethylene-α-olefin-non-conjugated polyene copolymer

Abstract

To provide a method for producing an ethylene-α-olefin-nonconjugated polyene copolymer by using a polymerization catalyst having a greater ability to copolymerize a nonconjugated polyene while maintaining copolymerizability of an α-olefin.SOLUTION: The present disclosure provides a method for producing an ethylene-α-olefin-nonconjugated polyene copolymer in the presence of an olefin polymerization catalyst containing a transition metal compound [A] of formula (I) or the like [where R1-R5 and R10-R14 each denote a hydrogen atom, a hydrocarbon group or the like].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing an ethylene-α-olefin-non-conjugated polyene copolymer by using an olefin polymerization catalyst containing a transition metal compound having a specific ligand structure. [Background technology]

[0002] Ethylene-α-olefin rubbers, such as ethylene-propylene-non-conjugated diene copolymers (EPDM), do not have unsaturated bonds in the main chain of their molecular structure, and therefore have superior heat resistance and weather resistance compared to the commonly used conjugated diene rubbers. As a result, they are widely used in a variety of applications, including automotive parts, electric wire materials, construction and civil engineering materials, industrial parts, and as modifiers for various resins.

[0003] Conventionally, ethylene-α-olefin-non-conjugated polyene copolymers such as EPDM have been produced using a catalyst system (so-called Ziegler-Natta catalyst system) that generally consists of a combination of a titanium-based catalyst or a vanadium-based catalyst and an organoaluminum compound. The biggest drawback of this catalyst system is its productivity. The catalyst has low polymerization activity and a short catalyst life, so it is necessary to carry out polymerization at a low temperature of around 0 to 50°C. When polymerization is carried out at such a low temperature, the viscosity generally increases as the temperature decreases, so the product concentration in the polymerization system is limited due to the viscosity bottleneck of the polymerization solution, and a process for decatalyzing and deashing the product is essential. Furthermore, it is difficult to control the polymerization heat due to the low-temperature polymerization. Due to the above problems, improvements were desired in terms of production and cost.

[0004] On the other hand, metallocene catalyst systems, which have been the subject of active research since the 1980s, exhibit superior polymerization activity and α-olefin copolymerization ability compared to Ziegler-Natta catalyst systems, and because they are single-site catalysts, they enable the production of new olefin copolymers with narrow molecular weight and composition distributions. There have also been reports on new production methods for ethylene-α-olefin-non-conjugated polyene copolymers.

[0005] However, even with such metallocene catalyst systems, there are many issues that prevent commercial practical use. For example, there are issues in the production of ethylene-α-olefin-non-conjugated polyene copolymers in terms of production, cost, and physical properties, such as polymerization activity that can be adapted to a non-deashing process, high molecular weight that can withstand high-temperature polymerization, non-conjugated polyene copolymerization ability that does not burden the monomer recovery process, and high monomer alternating copolymerization ability to show good low-temperature properties in terms of physical properties.

[0006] For example, Patent Documents 1, 2, 3, and 4 disclose production methods using a geometrically constrained catalyst, which has excellent copolymerizability with α-olefins and produces high molecular weight products, but has low alternating copolymerizability of monomers, resulting in a long average ethylene chain length in the ethylene-α-olefin-non-conjugated polyene copolymer, and as a result, the low-temperature properties, which are one of the important physical properties, are insufficient. In addition, production methods using a geometrically constrained catalyst often show high polymerization activity in the early stages of polymerization, making it difficult to control the polymerization heat.

[0007] In addition, Patent Documents 5, 6, 7, etc. disclose bridged metallocene catalysts having a biscyclopentadienyl group or a bisindenyl group in the ligand. Although the alternating copolymerization of monomers is relatively high, all of these catalysts have problems such as low polymerization activity and low molecular weight of the obtained ethylene-α-olefin-non-conjugated polyene copolymer.

[0008] Therefore, there is a need for a manufacturing method for more efficiently and cheaply producing ethylene-α-olefin-non-conjugated polyene copolymers with excellent heat resistance, weather resistance, and low-temperature properties. In particular, if a catalyst system with higher copolymerization ability for non-conjugated polyenes could be developed, it would be possible to reduce the amount of non-conjugated polyene fed, reducing the load on the monomer recovery process and providing a more efficient and cost-effective manufacturing method.

[0009] More recently, in response to the strengthening of legal regulations on chemical safety, it has become expected to reduce the amount of non-conjugated polyene residues in ethylene-α-olefin-non-conjugated polyene copolymer products, and polymerization catalysts are now required to have higher non-conjugated polyene copolymerization ability. However, with conventional metallocene catalysts, when attempting to increase the non-conjugated polyene copolymerization ability above a certain level, the α-olefin copolymerization ability is impaired, making it difficult to reduce the amount of non-conjugated polyene residues in the resin while maintaining product quality. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] European Patent Application Publication No. 416815 [Patent Document 2] WO 95 / 00526 [Patent Document 3] WO 98 / 27103 [Patent Document 4] Special Publication No. 2001-522398 [Patent Document 5] JP 2005-344101 A [Patent Document 6] Japanese Patent Application Publication No. 9-151205 [Patent Document 7] Special Publication No. 2000-507635 Summary of the Invention [Problem to be solved by the invention]

[0011] In view of these problems, the present invention aims to provide a method for producing an ethylene-α-olefin-non-conjugated polyene copolymer by using a polymerization catalyst having a higher copolymerization ability for a non-conjugated polyene while maintaining the copolymerizability of an α-olefin. [Means for solving the problem]

[0012] As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by copolymerizing ethylene, an α-olefin, and a non-conjugated polyene in a specific monomer charging ratio using an olefin polymerization catalyst consisting of a transition metal compound having a bidentate ligand of a specific structure, and have thus completed the present invention. The gist of the present invention is as follows. [1] [A] A transition metal compound represented by the following general formula (I), and [B] [B-1] Organometallic compound, [B-2] an organoaluminum oxy compound, and [B-3] A compound that reacts with the transition metal compound [A] to form an ion pair At least one compound selected from the group consisting of A method for producing an ethylene-α-olefin-non-conjugated polyene copolymer, comprising: a step [P] of polymerizing ethylene-α-olefin-non-conjugated polyene in the presence of an olefin polymerization catalyst comprising:

[0013] [ka] (In formula (I), M represents a transition metal atom of Groups 3 to 11 of the periodic table; m represents an integer from 1 to 6; R 1 ~R 3 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked to each other to form a ring, R 4 ,R 5 may be the same or different and each represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and may be bonded to each other to form a double bond between a carbon atom and a nitrogen atom, Z represents a structure represented by the following formula (II):

[0014] [ka] (In formula (II), the multiple R's may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be bonded to each other to form a ring, adjacent R's may be bonded to each other to form a double bond, ● represents a bonding point with a carbon atom (C), ○ represents a bonding point with a nitrogen atom (N), and p represents an integer of 1 to 6.) In addition, when m is 2 or more, R 1 ~R 3 and two of the groups represented by R may be linked together; n is a number that satisfies the valence of M, X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; when n is 2 or more, the multiple groups represented by X may be the same or different from one another, and the multiple groups represented by X may be bonded to one another to form a ring; R 10 ~R 14 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring. [2] R in the above general formula (I) 4 and R 5 are bonded to each other to form a double bond between a carbon atom and a nitrogen atom. [3] The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to item [1] or [2], wherein Z in the general formula (I) is represented by the following formula (III):

[0015] [ka] [In the formula, R 6 ~R 9 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked to each other to form a ring, ● represents a point of attachment to a carbon atom (C), and ○ represents a point of attachment to a nitrogen atom (N). [4] R in the above general formula (I) 1 ~R 3 is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. [5] R in the above general formula (I) 1 ~R 3

[0023] Item [1] to

[0024] 3. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to any one of [1] to [3], wherein is any one of hydrogen, a methyl group, and a phenyl group. [6] The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to any one of items [1] to [5], wherein M in the general formula (I) is a transition metal atom of Group 4 or 5 of the periodic table. [7] The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to any one of items [1] to [5], wherein M in the general formula (I) is a transition metal atom of Group 4 of the periodic table. [8] The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to any one of items [1] to [7], wherein the non-conjugated polyene is represented by the following general formula (IV):

[0016] [ka] [In the formula, m is an integer from 0 to 2, R 15 , R 16 , R 17 and R 18 each independently represents an atom or a substituent selected from a hydrogen atom, 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 the hydrocarbon group may have a double bond, R 15 From R 18 Any two of the substituents may be bonded to each other to form a ring, which may contain a double bond; R 15 and R 16 With or R 17 and R 18 may form an alkylidene group, R 15 and R 17 Toga or R 16 and R 18 and may be bonded to each other to form a double bond, At least one of the following requirements (i) to (iv) is met: (i)R 15 From R 18 At least one of the groups up to the end of the first group is a hydrocarbon group having one or more double bonds. do. (ii)R 15 From R 18 Any two substituents up to may be joined together to form a ring, said ring containing a double bond. (iii)R 15 and R 16 With or R 17 and R 18 and form an alkylidene group. (iv) R 15 and R 17 Toga or R16 and R 18 and are bonded to each other to form a double bond. [9] The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to item [8], wherein the non-conjugated polyene is 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB).

[10] The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to item [8] or [9], wherein the step [P] is a step of copolymerizing ethylene, an α-olefin having 3 to 10 carbon atoms, and a non-conjugated polyene.

[11] Item

[10] , the method for producing an ethylene-α-olefin-non-conjugated polyene copolymer, wherein the α-olefin is propylene.

[12] The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to any one of items [1] to

[11] , wherein the polymerization temperature in the step [P] is 80° C. or higher. Effect of the Invention

[0017] According to the present invention, an ethylene-α-olefin-non-conjugated polyene copolymer can be produced with higher non-conjugated polyene copolymerizability while maintaining the copolymerizability of α-olefin, and therefore an ethylene-α-olefin-non-conjugated polyene copolymer of the same composition can be produced with a smaller amount of non-conjugated polyene used. This not only enables process streamlining in the production process of ethylene-α-olefin-non-conjugated polyene copolymer, such as reducing the load of the demonomerization step, but is also expected to improve quality and safety, such as reducing the amount of non-conjugated polyene remaining in the product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The olefin polymerization catalyst and the process for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention will be described in detail below.

[0019] [Olefin Polymerization Catalyst] The olefin polymerization catalyst according to the present invention has, as essential components, a transition metal compound [A] and at least one compound selected from [B], [B-1] an organometallic compound, [B-2] an organoaluminum oxy compound, and [B-3] a compound that reacts with the transition metal compound [A] to form an ion pair. The above-mentioned components [A] and [B], which are the constituent elements of the olefin polymerization catalyst of the present invention, as well as other components that can be used as necessary, will now be described in detail.

[0020] [Transition metal compound [A]] In the present invention, the transition metal compound [A] is represented by the following general formula (I).

[0021] [ka] In the above general formula (I), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), preferably a metal atom of Groups 3 to 9, more preferably a transition metal atom selected from Groups 3 to 5, further preferably a transition metal atom selected from Group 4 or Group 5, and particularly preferably a transition metal atom of Group 4. Specifically, M is scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, etc., preferably scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, etc., more preferably titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum, etc., more preferably titanium, zirconium, hafnium, and particularly preferably zirconium and hafnium.

[0022] In addition, in the general formula (I), the dotted line connecting N and M generally indicates that N is coordinated to M, but in the present invention, it does not matter whether N is coordinated or not.

[0023] In the above general formula (I), m represents an integer of 1 to 6, preferably an integer of 1 to 4, and more preferably 1.

[0024] In the above general formula (I), R 1 ~R 3 may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group; R 1 ~R 3 Two or more of may be linked to each other to form a ring. The halogen atom includes fluorine, chlorine, bromine, and iodine.

[0025] Examples of the hydrocarbon group include linear or branched aliphatic hydrocarbon groups having 1 to 30 carbon atoms, cyclic hydrocarbon groups having 3 to 30 carbon atoms, and aromatic hydrocarbon groups having 6 to 30 carbon atoms. Specific examples include linear or branched alkyl groups having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20, carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group; linear or branched alkynyl groups having 2 to 30, preferably 2 to 20, and more preferably 2 to 10, carbon atoms, such as an ethynyl group or a propargyl group; cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20, and more preferably 3 to 10, carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or an adamantyl group; Cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl groups; aryl groups having 6 to 30, preferably 6 to 20, and more preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group; Alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl; etc.

[0026] The above-mentioned hydrocarbon group may have a hydrogen atom substituted with a halogen. Examples of such a hydrocarbon group in which a hydrogen atom is substituted with a halogen include halogenated hydrocarbon groups having 1 to 30, preferably 1 to 20, carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group.

[0027] In addition, the above-mentioned hydrocarbon group may be substituted with another hydrocarbon group. Examples of such a hydrocarbon group substituted with another hydrocarbon group include aryl-substituted alkyl groups such as a benzyl group and a cumyl group.

[0028] Furthermore, the hydrocarbon group may be a heterocyclic compound residue; Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, and carboxylic anhydride groups; nitrogen-containing groups such as amino groups, imino groups, amido groups, imido groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups in the form of ammonium salts; boron-containing groups such as boranediyl, boranetriyl, and diboranyl groups; sulfur-containing groups 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 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; Phosphorus-containing groups such as phosphido groups, phosphoryl groups, thiophosphoryl groups, and phosphato groups; It may have a silicon-containing group; a germanium-containing group; or a tin-containing group.

[0029] Examples of the heterocyclic compound residue include residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, as well as groups in which these heterocyclic compound residues are further substituted with a substituent having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as an alkyl group or an alkoxy group.

[0030] Examples of the silicon-containing group include silyl group, siloxy group, hydrocarbon-substituted silyl group, and hydrocarbon-substituted siloxy group, and more specifically, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, and dimethyl(pentafluorophenyl)silyl group. Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, and triphenylsilyl group are preferred, and particularly preferred are trimethylsilyl group, triethylsilyl group, triphenylsilyl group, and dimethylphenylsilyl group. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy group.

[0031] The germanium-containing group or the tin-containing group includes groups in which the silicon of the silicon-containing group is substituted with germanium or tin.

[0032] Among the groups exemplified as the groups that the hydrocarbon group may have, Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group. Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group. Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group. Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group. Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group. Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group. Specific examples of the imide group include an acetimide group and a benzimide group. Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group. Specific examples of the alkylthio group include a methylthio group and an ethylthio group. Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group. Specific examples of the sulfonate group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group. Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

[0033] 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group; Preferred are substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents such as a halogen atom, an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, or an aryl group or aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms.

[0034] R 1 ~R 3 As described above, can be a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and examples of these include the same as those exemplified in the above description of the hydrocarbon group.

[0035] As described above, R in the above general formula (I) 1 ~R 3 Two or more of the groups may be linked together to form a ring. 1 ~R 3 Two or more of these groups, preferably adjacent groups, may be linked to each other to form a ring such as an aliphatic ring, an aromatic ring, or a heterocycle containing a heteroatom such as a nitrogen atom, and these rings may further have a substituent.

[0036] R in the above general formula (I) 1 ~R 3 Of these, R 1 From the viewpoint of activity, it is preferable that is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and among these, a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, and a hydrogen atom or a methyl group is more preferable.

[0037] In the above general formula (I), R 4 ,R 5may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and may be bonded to each other to form a double bond between a carbon atom and a nitrogen atom.

[0038] The halogen atom, the hydrocarbon group, the heterocyclic compound residue, the oxygen-containing group, the nitrogen-containing group, the boron-containing group, the sulfur-containing group, the phosphorus-containing group, the silicon-containing group, the germanium-containing group, and the tin-containing group are each independently selected from the group consisting of the above-mentioned R 1 ~R 3 Examples of the examples are similar to those given in the explanation of 1.

[0039] Above R 4 ,R 5 As for the bonds, R 4 and the carbon atom to which R is bonded. 5 From the viewpoint of the structural stability of the resulting compound, it is particularly preferred that a double bond is formed between the nitrogen atom to which is bonded.

[0040] In the general formula (I), Z represents a structure represented by the following formula (II).

[0041] [ka] In the above formula (II), ● indicates the point of attachment to the carbon atom (C), and ◯ indicates the point of attachment to the nitrogen atom (N).

[0042] In the above formula (II), p represents an integer of 1 to 6, preferably an integer of 1 to 4, and more preferably 2.

[0043] In the above formula (II), the multiple Rs may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring. The halogen atom includes fluorine, chlorine, bromine, and iodine.

[0044] Examples of the hydrocarbon group include linear or branched aliphatic hydrocarbon groups having 1 to 30 carbon atoms, cyclic hydrocarbon groups having 3 to 30 carbon atoms, and aromatic hydrocarbon groups having 6 to 30 carbon atoms.

[0045] Specifically, linear or branched alkyl groups having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, or an n-hexyl group; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20, carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group; linear or branched alkynyl groups having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms, such as an ethynyl group or a propargyl group; a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20, and more preferably 3 to 10, carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or an adamantyl group; Cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl groups; aryl groups having 6 to 30, preferably 6 to 20, and more preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group; Alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl; etc.

[0046] The above-mentioned hydrocarbon group may have a hydrogen atom substituted with a halogen. Examples of such a hydrocarbon group in which a hydrogen atom is substituted with a halogen include halogenated hydrocarbon groups having 1 to 30, preferably 1 to 20, carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group.

[0047] In addition, the above-mentioned hydrocarbon group may be substituted with another hydrocarbon group. Examples of such a hydrocarbon group substituted with another hydrocarbon group include aryl-substituted alkyl groups such as a benzyl group and a cumyl group.

[0048] Furthermore, the hydrocarbon group may be a heterocyclic compound residue; Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, and carboxylic anhydride groups; nitrogen-containing groups such as amino groups, imino groups, amido groups, imido groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups in the form of ammonium salts; boron-containing groups such as boranediyl, boranetriyl, and diboranyl groups; sulfur-containing groups 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 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; Phosphorus-containing groups such as phosphido groups, phosphoryl groups, thiophosphoryl groups, and phosphato groups; It may have a silicon-containing group; a germanium-containing group; or a tin-containing group.

[0049] Examples of the heterocyclic compound residue include residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, as well as groups in which these heterocyclic compound residues are further substituted with a substituent having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as an alkyl group or an alkoxy group.

[0050] Examples of the silicon-containing group include silyl group, siloxy group, hydrocarbon-substituted silyl group, and hydrocarbon-substituted siloxy group, and more specifically, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, and dimethyl(pentafluorophenyl)silyl group. Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, and triphenylsilyl group are preferred, and particularly preferred are trimethylsilyl group, triethylsilyl group, triphenylsilyl group, and dimethylphenylsilyl group. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy group.

[0051] The germanium-containing group or the tin-containing group includes groups in which the silicon of the silicon-containing group is substituted with germanium or tin.

[0052] Among the groups exemplified as the groups that the hydrocarbon group may have, Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group. Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group. Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group. Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group. Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group. Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group. Specific examples of the imide group include an acetimide group and a benzimide group. Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group. Specific examples of the alkylthio group include a methylthio group and an ethylthio group. Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group. Specific examples of the sulfonate group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group. Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

[0053] 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group; Preferred are substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents such as a halogen atom, an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, or an aryl group or aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms.

[0054] As described above, R can be a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. Examples of these groups include those exemplified in the description of the hydrocarbon group above.

[0055] In addition, adjacent R in the formula (II) may be bonded to each other to form a double bond. When adjacent R in the Z are bonded to each other to form a double bond, specific examples of the structure represented by Z and the structure including the carbon atom and nitrogen atom to which Z is bonded include a pyrrole skeleton, a pyridine skeleton, an azepine skeleton, an azocine skeleton, an azonine skeleton, and an azecine skeleton. Of these, preferred are a pyrrole skeleton and a pyridine skeleton, and more preferred is a pyridine skeleton.

[0056] It is particularly preferable that Z has a structure represented by the following formula (III) (that is, a pyridine skeleton).

[0057] [ka] In the above formula (III), ● indicates a bonding point with a carbon atom (C), and ◯ indicates a bonding point with a nitrogen atom (N).

[0058] In the above formula (III), R 6 ~R 9may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group; R 6 ~R 9 Two or more of may be linked to each other to form a ring. The halogen atom includes fluorine, chlorine, bromine, and iodine.

[0059] Examples of the hydrocarbon group include linear or branched aliphatic hydrocarbon groups having 1 to 30 carbon atoms, cyclic hydrocarbon groups having 3 to 30 carbon atoms, and aromatic hydrocarbon groups having 6 to 30 carbon atoms. Specific examples include linear or branched alkyl groups having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20, carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group; linear or branched alkynyl groups having 2 to 30, preferably 2 to 20, and more preferably 2 to 10, carbon atoms, such as an ethynyl group or a propargyl group; cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20, and more preferably 3 to 10, carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or an adamantyl group; Cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl groups; aryl groups having 6 to 30, preferably 6 to 20, and more preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group; Alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl; etc.

[0060] The above-mentioned hydrocarbon group may have a hydrogen atom substituted with a halogen. Examples of such a hydrocarbon group in which a hydrogen atom is substituted with a halogen include halogenated hydrocarbon groups having 1 to 30, preferably 1 to 20, carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group.

[0061] In addition, the above-mentioned hydrocarbon group may be substituted with another hydrocarbon group. Examples of such a hydrocarbon group substituted with another hydrocarbon group include aryl-substituted alkyl groups such as a benzyl group and a cumyl group.

[0062] Furthermore, the hydrocarbon group may be a heterocyclic compound residue; Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, and carboxylic anhydride groups; nitrogen-containing groups such as amino groups, imino groups, amido groups, imido groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups in the form of ammonium salts; boron-containing groups such as boranediyl, boranetriyl, and diboranyl groups; sulfur-containing groups 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 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; Phosphorus-containing groups such as phosphido groups, phosphoryl groups, thiophosphoryl groups, and phosphato groups; It may have a silicon-containing group; a germanium-containing group; or a tin-containing group.

[0063] Examples of the heterocyclic compound residue include residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, as well as groups in which these heterocyclic compound residues are further substituted with a substituent having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as an alkyl group or an alkoxy group.

[0064] Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. More specific examples include a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group, a dimethyl-t-butylsilyl group, and a dimethyl(pentafluorophenyl)silyl group. Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, triphenylsilyl group, etc. are preferred, and trimethylsilyl group, triethylsilyl group, triphenylsilyl group, and dimethylphenylsilyl group are particularly preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy group.

[0065] The germanium-containing group or the tin-containing group includes groups in which the silicon of the silicon-containing group is substituted with germanium or tin.

[0066] Among the groups exemplified as the groups that the hydrocarbon group may have, Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group. Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group. Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group. Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group. Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group. Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group. Specific examples of the imide group include an acetimide group and a benzimide group. Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group. Specific examples of the alkylthio group include a methylthio group and an ethylthio group. Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group. Specific examples of the sulfonate group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group. Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

[0067] 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group; Preferred are substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents such as a halogen atom, an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, or an aryl group or aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms.

[0068] R 6 ~R 9 As described above, can be a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and examples of these include the same as those exemplified in the above description of the hydrocarbon group.

[0069] As described above, R in the above general formula (III) 6 ~R 9 Two or more of the groups may be linked together to form a ring. 6 ~R 9 Two or more of these groups, preferably adjacent groups, may be linked to each other to form a ring such as an aliphatic ring, an aromatic ring, or a heterocycle containing a heteroatom such as a nitrogen atom, and these rings may further have a substituent.

[0070] In the above general formula (I), when m is 2 or more, R 1 ~R 3 and a group represented by R (when Z is a structure represented by general formula (III), R 6 ~R 9 In particular, two of the groups R 1 Fellow, R 2 Fellow, R 3 Fellow, R 4 Fellow, R 5 R 6 Fellow, R 7 Fellow, R 8 Fellow, R 9and the like) may be bonded to each other, and, regardless of the above, the substituents present at other positions may be bonded to each other.

[0071] Furthermore, when m is 2 or more, R 1 Fellow, R 2 Fellow, R 3 Fellow, R 4 Fellow, R 5 R 6 Fellow, R 7 Fellow, R 8 Fellow, R 9 ) may be the same or different.

[0072] In the above general formula (I), X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. The halogen atom includes fluorine, chlorine, bromine, and iodine.

[0073] The hydrocarbon group is the same as the above R 1 ~R 3 Specific examples of the alkyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a nonyl group, a dodecyl group, and an eicosyl group; Cycloalkyl groups having 3 to 30 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group; Alkenyl groups such as vinyl, propenyl, and cyclohexenyl groups; Arylalkyl groups such as benzyl, phenylethyl, and phenylpropyl groups; Examples of the aryl groups include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a biphenyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, and a phenanthryl group.

[0074] However, the hydrocarbon group is not limited to these. These hydrocarbon groups also include halogenated hydrocarbon groups, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen. Among these, the halogenated hydrocarbon group is preferably a halogenated hydrocarbon group having 1 to 10 carbon atoms.

[0075] Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, an aryloxy group such as a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, or a naphthoxy group, an arylalkoxy group such as a phenylmethoxy group or a phenylethoxy group, an acetoxy group, or a carbonyl group, but the oxygen-containing group is not limited to these.

[0076] The sulfur-containing group is the above-mentioned R 1 ~R 3 Examples of the sulfonate group include the same as those exemplified in the description of the above, specifically, sulfonate groups such as a methylsulfonate group, a trifluoromethanesulfonate group, a phenylsulfonate group, a benzylsulfonate group, a p-toluenesulfonate group, a trimethylbenzenesulfonate group, a triisobutylbenzenesulfonate group, a p-chlorobenzenesulfonate group, and a pentafluorobenzenesulfonate group; Examples of the sulfur-containing group include sulfinate groups such as methylsulfinate group, phenylsulfinate group, benzylsulfinate group, p-toluenesulfinate group, trimethylbenzenesulfinate group, and pentafluorobenzenesulfinate group; alkylthio groups; and arylthio groups. However, the sulfur-containing group is not limited to these.

[0077] Specific examples of the nitrogen-containing group include the above-mentioned R 1 ~R 3 Examples of the alkyl group include the same as those exemplified in the description of the above, specifically, an amino group; Alkylamino groups, such as a methylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, or a dicyclohexylamino group; Examples of the nitrogen-containing group include arylamino groups or alkylarylamino groups such as a phenylamino group, a diphenylamino group, a ditolylamino group, a dinaphthylamino group, and a methylphenylamino group, although the nitrogen-containing group is not limited to these.

[0078] Specific examples of the boron-containing group include BR4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

[0079] Specific examples of the aluminum-containing group include AlR4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.), but are not limited thereto.

[0080] Specific examples of the phosphorus-containing group include trialkylphosphine groups such as a trimethylphosphine group, a tributylphosphine group, and a tricyclohexylphosphine group; triarylphosphine groups, such as a triphenylphosphine group and a tritolylphosphine group; Phosphite groups (phosphido groups) such as methyl phosphite groups, ethyl phosphite groups, and phenyl phosphite groups; Examples of the aryl group include, but are not limited to, a phosphonic acid group; a phosphinic acid group; and the like.

[0081] Specific examples of the halogen-containing group include fluorine-containing groups such as PF6 and BF4, chlorine-containing groups such as ClO4 and SbCl6, and iodine-containing groups such as IO4, but are not limited thereto.

[0082] The heterocyclic compound residue is preferably the above-mentioned R 1 ~R 3 Examples of the examples are similar to those given in the explanation of 1.

[0083] Specific examples of the silicon-containing group include the above-mentioned R 1 ~R 3 Specific examples of the silyl group include hydrocarbon-substituted silyl groups such as a phenylsilyl group, a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tricyclohexylsilyl group, a triphenylsilyl group, a methyldiphenylsilyl group, a tritolylsilyl group, and a trinaphthylsilyl group; Hydrocarbon-substituted silyl ether groups, such as trimethylsilyl ether groups; silicon-substituted alkyl groups such as trimethylsilylmethyl groups; Examples of the aryl group include silicon-substituted aryl groups such as trimethylsilylphenyl group.

[0084] Specific examples of the germanium-containing group include the above-mentioned R 1 ~R 3 Specific examples of the silicon-containing group include those in which silicon is substituted with germanium.

[0085] Specific examples of the tin-containing group include the above-mentioned R 1 ~R 3 Examples of the silicon-containing group include those in which the silicon atom of the silicon-containing group is substituted with tin.

[0086] In the above general formula (I), n is a number satisfying the valence of M, and is usually an integer of 0 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 1. When n is 2 or more, the multiple X's may be the same or different. Furthermore, the multiple groups represented by X may be bonded to each other to form a ring.

[0087] In the above general formula (I), R 10 ~R 14may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group; R 10 ~R 14 Two or more of may be linked together to form a ring. For a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, the same definition as above for R 1 ~R 3 The same substituents as those shown above can be exemplified.

[0088] R 10 ~R 14 As an embodiment in which two or more groups among the above are linked to each other to form a ring, preferably adjacent groups are linked to each other to form one ring or two rings, and the ring formed may form a ring such as an aromatic ring, an aliphatic ring, or a heterocycle containing a heteroatom such as a nitrogen atom, and these rings may further have a substituent.

[0089] R 10 ~R 14 Specific examples of the cyclopentadienyl group having the formula include alkyl-substituted cyclopentadienyl groups such as a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, an ethylcyclopentadienyl group, a methylethylcyclopentadienyl group, a propylcyclopentadienyl group, a methylpropylcyclopentadienyl group, a butylcyclopentadienyl group, a methylbutylcyclopentadienyl group, and a hexylcyclopentadienyl group, or an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. The hydrogen atoms of these groups may be substituted with a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom, or the like.

[0090] R in the above general formula (I) 10 ~R 14 With respect to R, from the viewpoint of protecting the central metal with a planar and sterically bulky ligand structure formed by introducing a substituent onto the cyclopentadienyl group, it is preferable that R is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 10 ~R 14 Two or more of R may be linked together to form a ring. However, from the viewpoint of imparting high copolymerizability to non-conjugated polyenes, 10 ~R 14 It is preferred that three or more of the groups are hydrogen.

[0091] Specific examples of the transition metal compound [A] represented by the above general formula (I) are shown below, but the transition metal compound [A] is not limited to these.

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] [ka] In the above examples, Me represents a methyl group and Ph represents a phenyl group. In the above examples, transition metal compounds in which at least one of the two methyl groups on the metal is replaced with a substituent exemplified as X in general formula (I) can also be mentioned as examples of the transition metal compound [A].

[0097] The method for producing such a transition metal compound [A] is not particularly limited, and it can be produced, for example, as follows.

[0098] First, the ligand can be synthesized by a previously reported method (Organic Letters, 2002, 4, 435.). Next, the obtained ligand is reacted with a compound containing a transition metal atom M to synthesize the corresponding transition metal compound. The compound containing a transition metal atom M can be synthesized by a previously reported method (Organometallics, 1982, 1, 793. J. Am. Chem. Soc. 1988, 110, 7701.). Specifically, the ligand is dissolved in a solvent, and mixed with a compound having a transition metal atom M, such as a metal alkyl compound, a metal arylate compound, or a metal aryl alkyl compound, at a temperature range of -78°C to room temperature, and stirred at a temperature range of -78°C to room temperature or under reflux conditions for about 10 minutes to 48 hours. As the solvent, a solvent generally used for such a reaction can be used, but among them, polar solvents such as ether and tetrahydrofuran (THF), and hydrocarbon solvents such as toluene are preferably used.

[0099] Furthermore, the transition metal compound obtained by such a production method can be used as it is in the reaction solution of the ligand and the metal compound for olefin polymerization without isolation.

[0100] [Compound [B] group] The following describes the compounds selected as components of the olefin polymerization catalyst of the present invention, which react with the organometallic compound [B-1], the organoaluminum oxy compound [B-2], and the transition metal compound [A] to form ion pairs.

[0101] [[B-1] Organometallic Compound] As the [B-1] organometallic compound used in the present invention, specifically, there may be mentioned an organoaluminum compound represented by the following general formula (B-1a), a complex alkylated product of a Group 1 metal and aluminum in the periodic table represented by the general formula (B-1b), and a dialkyl compound of a Group 2 or Group 12 metal in the periodic table represented by the general formula (B-1c). It should be noted that the [B-1] organometallic compound does not include the [B-2] organoaluminum oxy compound described later.

[0102] R a p Al(OR b ) q H r Y s ···(B-1a) (In the general formula (B-1a), R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Y represents a halogen atom, p is a number such that 0 < p ≤ 3, q is a number such that 0 ≤ q < 3, r is a number such that 0 ≤ r < 3, s is a number such that 0 ≤ s < 3, and m + n + p + q = 3.) M 3 AlR c 4···(B-1b) (In the general formula (B-1b), M 3 represents Li, Na or K, and R c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.) R d R e M 4 ···(B-1c) (In the general formula (B-1c), R d and R e may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. M 4 is Mg, Zn or Cd.) Examples of the organoaluminum compound represented by the general formula (B-1a) include the following compounds. R a p Al(OR b) 3-p (In the formula, R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number such that 1.5 ≦ p ≦ 3.) An organoaluminum compound represented by R a p AlY 3-p (In the formula, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably a number such that 0 < p < 3.) An organoaluminum compound represented by R a p AlH 3-p (In the formula, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number such that 2 ≦ p < 3.) An organoaluminum compound represented by R a p Al(OR b ) q Y s (In the formula, R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, p is a number such that 0 < p ≦ 3, q is a number such that 0 ≦ q < 3, s is a number such that 0 ≦ s < 3, and p + q + s = 3.) An organoaluminum compound represented by

[0103] More specifically, as the organoaluminum compound belonging to the general formula (B-1a), tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexylaluminum, and tri2-ethylhexylaluminum; Tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; Triarylaluminum such as triphenylaluminum and tritolylaluminum; Dialkylaluminum hydrides such as diisobutylaluminum hydride; (i-C4H9) x Al y (C5H 10 ) z (wherein x, y and z are positive numbers, and z≧2x), and other trialkenylaluminums, such as triisoprenylaluminum; Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, and isobutyl aluminum isopropoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide; R a 2.5 Al(OR b ) 0.5 Partially alkoxylated alkylaluminum having an average composition represented by the formula: a and R b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide; partially halogenated alkylaluminums, such as alkylaluminum dihalides, such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, and the like; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminums, such as alkylaluminum dihydrides, such as ethylaluminum dihydride, propylaluminum dihydride, etc.; Examples of the aluminum compounds include partially alkoxylated and halogenated alkylaluminum compounds such as ethylaluminum ethoxy chloride, butylaluminum butoxy chloride, and ethylaluminum ethoxy bromide.

[0104] Compounds similar to (B-1a) can also be used in the present invention, such as organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms, such as (C2H5)2AlN(C2H5)Al(C2H5)2.

[0105] The compounds belonging to the general formula (B-1b) include LiAl(C2H5)4, LiAl(C7H 15 )4 can be mentioned as examples.

[0106] Examples of the compound belonging to the general formula (B-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dimethylzinc, diethylzinc, diphenylzinc, di-n-propylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc, bis(pentafluorophenyl)zinc, dimethylcadmium, and diethylcadmium.

[0107] In addition, as the (B-1) organometallic compound, methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, etc. can also be used.

[0108] Furthermore, a compound that forms the above-mentioned organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium, can also be used as the organometallic compound (B-1). The organometallic compounds [B-1] as described above may be used singly or in combination of two or more kinds.

[0109] [B-2] Organoaluminum oxy compound The organoaluminum oxy compound [B-2] used in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. Specific examples of the organoaluminum oxy compound [B-2] include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, etc.

[0110] Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent. (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium chloride hydrate, etc., to react the adsorbed water or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or water vapor is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0111] The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the resulting aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0112] Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the general formula (B-1a) above.

[0113] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, with trimethylaluminum being particularly preferred. The above organoaluminum compounds may be used singly or in combination of two or more.

[0114] Examples of the solvent used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel; and halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorides and bromides. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred.

[0115] The benzene-insoluble organoaluminum oxy-compound used in the present invention is preferably one in which the Al component dissolved in benzene at 60°C is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less, calculated as Al atom, i.e., it is preferably insoluble or poorly soluble in benzene.

[0116] The organoaluminum oxy compound [B-2] used in the present invention may also be, for example, an organoaluminum oxy compound containing boron represented by the following general formula (V).

[0117] [ka] (In general formula (V), R 11 represents a hydrocarbon group having 1 to 10 carbon atoms, and four R 12 may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.) The boron-containing organoaluminum oxy compound represented by the general formula (V) can be produced by reacting an alkylboronic acid represented by the following general formula (VI) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

[0118] R 12-B(OH)2···(VI) (In general formula (VI), R 12 is R in the general formula (V). 12 It shows the same group as Specific examples of the alkylboronic acid represented by the general formula (V) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

[0119] Specific examples of the organoaluminum compound to be reacted with such alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the general formula (B-1a). As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferred. These compounds are used alone or in combination of two or more. The organoaluminum oxy-compounds [B-2] as described above may be used singly or in combination of two or more kinds.

[0120] [B-3] A compound that reacts with a transition metal compound [A] to form an ion pair. Examples of the compound (hereinafter sometimes referred to as "ionizing ionic compound [B-3]") used in the present invention that reacts with the transition metal compound [A] [B-3] to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Patent No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds.

[0121] Specifically, the Lewis acid includes a compound represented by BR3 (R is fluorine or a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron. The ionic compound may, for example, be a compound represented by the following general formula (VII).

[0122] [ka] (In general formula (VII), R 13 H + , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a ferrocenium cation having a transition metal, and R 14 ~R 17 may be the same or different and are a hydrocarbon group having 1 to 10 carbon atoms, preferably an aryl group or substituted aryl group having 6 to 10 carbon atoms.

[0123] Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0124] Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0125] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0126] R 13+ As the cation, a carbonium cation and an ammonium cation are preferred, and in particular, a triphenylcarbonium cation, an N,N-dimethylanilinium cation, and an N,N-diethylanilinium cation are preferred.

[0127] R 14 ~R 17is a hydrocarbon group having 1 to 10 carbon atoms, preferably an aryl group or a substituted aryl group having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a dimethylphenyl group, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, a pentafluorophenyl group, and a tolylpentafluorophenyl group. Of these, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, and a pentafluorophenyl group are preferred, and a pentafluorophenyl group is particularly preferred.

[0128] Further, examples of the ionic compound include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0129] Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

[0130] Specific examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.

[0131] Specific examples of the dialkylammonium salt include di(1-propyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, and the like.

[0132] Further examples of the ionic compound include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formula (VIII) or (IX).

[0133] [ka] (In formula (VIII), Et represents an ethyl group.)

[0134] [ka] (In formula (IX), Et represents an ethyl group.) Specific examples of the borane compound, which is an example of the ionizable ionic compound (compound [B-3]), include decaborane; Salts of anions such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate; Examples of the salt include salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydride dodecaborate) cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydride dodecaborate) nickelate(III).

[0135] Specific examples of carborane compounds, which are examples of ionizable ionic compounds, include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, and undecahydride-7,8-dimethyl-1,3-dicarbanonaborane. 1-methyl-7,8-dicarboxylic acid borane, dodecahydride-11-methyl-2,7-dicarboxylic acid borane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium ammonium 6-carbadecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 7-carbaundecaborate, tri(n-butyl)ammonium 7,8-dicaundecaborate, tri(n-butyl)ammonium 2,9-dicaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicaundecaborate Salts of anions such as undecahydride, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboxaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboxaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboxaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)ferrate salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)cobaltate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)nickelate (IV), and the like.

[0136] Heteropoly compounds, which are examples of ionized ionic compounds, are compounds that contain an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten.Specific examples include, but are not limited to, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and the salts of these acids. Examples of the salts include salts of the acids with metals of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0137] Isopoly compounds, which are examples of ionized ionic compounds, are compounds composed of metal ions of one type of atom selected from vanadium, niobium, molybdenum, and tungsten, and can be considered to be molecular ion species of metal oxides.Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids.Furthermore, examples of the salts include salts of the acids with metals of Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts. The above-mentioned ionizing ionic compounds (compounds [B-3] that react with the transition metal compound [A] to form an ion pair) may be used singly or in combination of two or more kinds.

[0138] The above-described compounds that react with the organometallic compound [B-1], the organoaluminum oxy compound [B-2], and the transition metal compound [A] to form an ion pair can be used in combination. In particular, when the transition metal compound [A] of the present invention is used, it has been revealed that high polymerization activity and high copolymerizability are exhibited when the organometallic compound [B-1] and the compound that reacts with the transition metal compound [A] to form an ion pair are used in combination. Up until now, examples have been reported that show high polymerization activity by using the organoaluminum oxy compound [B-2] such as methylaluminoxane as a cocatalyst component in combination with a known transition metal compound, but the organoaluminum oxy compound (B-2) such as methylaluminoxane is generally expensive, and depending on the amount used, this leads to high costs for the obtained olefin polymer.

[0139] On the other hand, as described above, the transition metal compound [A] in the present invention exhibits high polymerization activity and high copolymerizability even when used in combination with the organometallic compound [B-1] and the compound [B-3] that reacts with the transition metal compound [A] to form an ion pair as cocatalyst components, and since these cocatalyst components are available at very low cost, there is an advantage that it is possible to produce olefin polymers at low cost.

[0140] The olefin polymerization catalyst according to the present invention may contain the above-mentioned transition metal compound [A], at least one compound [B] selected from the group consisting of [B-1] organometallic compounds, [B-2] organoaluminum oxy compounds, and [B-3] ionizing ionic compounds, and may also contain the following support [C], if necessary.

[0141] [Carrier [C]] The olefin polymerization catalyst according to the present invention may use a carrier [C], if necessary. The carrier [C] that can be used in the present invention is an inorganic or organic compound, and is a granular or fine particle solid. By supporting the transition metal compound [A] and the compound [B] on the carrier [C], a polymer with good morphology can be obtained. The inorganic compound is preferably a porous oxide, an inorganic halide, a clay, a clay mineral, or an ion-exchangeable layered compound.

[0142] Specifically, the porous oxide may be SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or a composite or mixture containing these, and may further be, for example, natural or synthetic zeolite, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc. Among these, the porous oxide is preferably one having SiO2 and / or Al2O3 as the main component.

[0143] In addition, the above-mentioned porous oxide may contain small amounts of carbonates, sulfates, nitrates, and oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O.

[0144] The properties of such porous oxides vary depending on the type and manufacturing method, but the porous oxides preferably used in the present invention have a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of ​​50 to 1000 m. 2 / g, preferably 100 to 700m 2 / g and the pore volume is 0.3-3.0 cm 3 / g range. Such a porous oxide is calcined at 100 to 1000°C, preferably 150 to 700°C, as required, before use.

[0145] As the inorganic halide, MgCl2, MgBr2, MnCl2, MnBr2, etc. can be used. The inorganic halide can be used as it is, or can be used after being pulverized by a ball mill or a vibration mill. In addition, the inorganic halide can be dissolved in a solvent such as alcohol, and then precipitated into fine particles by a precipitating agent.

[0146] The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which the planes formed by ionic bonds are stacked in parallel with each other with weak bonding force, and the ions contained therein are exchangeable. Most clay minerals are ion-exchangeable layered compounds. The clays, clay minerals, and ion-exchangeable layered compounds are not limited to those produced in nature, and artificially synthesized compounds can also be used.

[0147] Examples of the clay, clay mineral, or ion-exchangeable layered compound include ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl2 type, and CdI2 type.

[0148] Furthermore, examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, and halloysite, and examples of ion-exchangeable layered compounds include crystalline acid salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O.

[0149] Such clay, clay mineral, or ion-exchangeable layered compound preferably has a pore volume of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, having a radius of 20 Å or more, as measured by mercury intrusion porosimetry, where the pore volume is measured for a pore radius range of 20 to 30,000 Å by mercury intrusion porosimetry using a mercury porosimeter. When a support having a pore volume of less than 0.1 cc / g and a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.

[0150] It is also preferable to subject the clay and clay minerals used in the present invention to chemical treatment. As the chemical treatment, any of surface treatments that remove impurities attached to the surface and treatments that affect the crystalline structure of the clay can be used. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. In addition to removing impurities from the surface, acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystalline structure. In alkali treatment, the crystalline structure of the clay is destroyed, resulting in a change in the structure of the clay. In addition, salt treatment and organic treatment form ion complexes, molecular complexes, organic derivatives, etc., which can change the surface area and interlayer distance.

[0151] The ion-exchangeable layered compound used in the present invention may be a layered compound in which the space between layers is expanded by utilizing the ion exchangeability and exchanging the exchangeable ions between layers with other large bulky ions. Such bulky ions play a role of supporting the layered structure and are usually called pillars. The introduction of another substance between layers of a layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (R is a hydrocarbon group, etc.), [Al 13 O4(OH) 24 ] 7+ , [Zr4(OH) 14 ] 2+ , [Fe3O(OCOCH3)6] +Metal hydroxide ions such as these can be used. These compounds can be used alone or in combination of two or more. When intercalating these compounds, polymers obtained by hydrolysis of metal alkoxides (R represents a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, Ge(OR)4, etc., and colloidal inorganic compounds such as SiO2 can also be used. Examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them with heat.

[0152] The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as is, or may be used after treatment such as ball milling or sieving. They may also be used after newly adding and adsorbing water or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more kinds. Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica are particularly preferred.

[0153] As described above, the carrier [C] is an inorganic or organic compound, and examples of the organic compound include granular or fine particle solids with a particle size in the range of 10 to 300 μm.Specific examples include (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers produced mainly from vinylcyclohexane and styrene, and their modified products.

[0154] The olefin polymerization catalyst according to the present invention contains the above-mentioned transition metal compound [A], preferably the above-mentioned compound [B], and, if necessary, a support [C]. In addition to these, if necessary, it can also contain the following specific organic compound component [D].

[0155] [Organic compound component [D]] In the present invention, the organic compound component [D] is used, if necessary, for the purpose of improving the polymerization performance (e.g., catalytic activity) of the olefin polymerization catalyst of the present invention and the physical properties of the produced polymer (e.g., increasing the molecular weight of the produced polymer). Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

[0156] The alcohols and phenolic compounds are generally selected from the group consisting of R 18 -OH, where R 18 represents a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, the number of carbon atoms is 6 to 50) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, the number of carbon atoms is 6 to 50).

[0157] Alcohols include R 18 The phenolic compound is preferably one in which the α,α'-positions of the hydroxyl group are substituted with a hydrocarbon having 1 to 20 carbon atoms.

[0158] The carboxylic acid is usually R 19 The one represented by -COOH is used. 19 represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and is particularly preferably a halogenated hydrocarbon group having 1 to 50 carbon atoms.

[0159] As the phosphorus compound, phosphoric acids having a POH bond, phosphates having a P-OR or P=O bond, and phosphine oxide compounds are preferably used. The sulfonate salt includes those represented by the following general formula (X).

[0160] [ka] (In general formula (X), M 5 is an element in groups 1 to 14 of the periodic table, and R 20is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; t is an integer from 1 to 7; u is an integer satisfying 1≦u≦7; and tu is an integer satisfying tu≧1.

[0161] [Method for producing ethylene-α-olefin-non-conjugated polyene copolymer] In the process for producing an ethylene-α-olefin-non-conjugated polyene polymer of the present invention, an ethylene-α-olefin-non-conjugated polyene polymer can be obtained by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene in the presence of the above-mentioned olefin polymerization catalyst. When copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene in the present invention, the method of using and the order of adding each component constituting the above-mentioned olefin polymerization catalyst may be selected arbitrarily, and the following method may be exemplified.

[0162] (1) A method in which the transition metal compound [A] is added alone to a polymerization reactor. (2) A method of adding the transition metal compound [A] and the compound [B] to a polymerization reactor in any order, (3) A method of adding the catalyst component in which the transition metal compound [A] is supported on a carrier [C], and the compound [B] to a polymerization reactor in any order. (4) A method in which a catalyst component in which a compound [B] is supported on a carrier [C] and a transition metal compound [A] are added to a polymerization reactor in any order. (5) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C] is added to a polymerization reactor. (6) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C], and compound [B] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different. (7) A method in which a catalyst component in which the compound [B] is supported on a carrier [C] and a transition metal compound [A] are added to a polymerization reactor in any order. (8) A method in which a catalyst component in which compound [B] is supported on a carrier [C], a transition metal compound [A], and compound [B] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different. (9) A method in which a component in which a transition metal compound [A] is supported on a carrier [C] and a component in which a compound [B] is supported on a carrier [C] are added to a polymerization reactor in any order. (10) A method in which a component in which a transition metal compound [A] is supported on a carrier [C], a component in which a compound [B] is supported on a carrier [C], and a compound [B] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different. (11) A method in which the transition metal compound [A], the compound [B], and the organic compound component [D] are added to a polymerization reactor in any order. (12) A method in which the compound [B] and the organic compound component [D], which have been contacted in advance, and the transition metal compound [A] are added to a polymerization reactor in any order. (13) A method in which the compound [B], the organic compound component [D] supported on the carrier [C], and the transition metal compound [A] are added to a polymerization reactor in any order. (14) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] have been contacted in advance, and an organic compound component [D] are added to a polymerization reactor in any order. (15) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] are previously contacted, compound [B], and an organic compound component [D] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different. (16) A method of adding a catalyst component in which a transition metal compound [A] is contacted with a compound [B] in advance, and a component in which a compound [B] is contacted with an organic compound component [D] in advance, to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different. (17) A method in which a transition metal compound [A] supported on a carrier [C], a compound [B], and an organic compound component [D] are added to a polymerization reactor in any order. (18) A method in which a component in which a transition metal compound [A] is supported on a carrier [C] and a component in which a compound [B] and an organic compound component [D] are previously contacted are added to a polymerization reactor in any order. (19) A method in which a catalyst component obtained by previously contacting a transition metal compound [A], a compound [B] and an organic compound component [D] in any order is added to a polymerization reactor. (20) A method in which a catalyst component obtained by contacting a transition metal compound [A], a compound [B] and an organic compound component [D] in any order in advance, and compound [B] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different. (21) A method in which a catalyst comprising a transition metal compound [A], a compound [B] and an organic compound component [D] supported on a carrier [C] is added to a polymerization reactor. (22) A method in which a catalyst component comprising a transition metal compound [A], a compound [B] and an organic compound component [D] supported on a carrier [C], and a compound [B] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different.

[0163] In the solid catalyst component in which the transition metal compound [A] is supported on the support [C], and in the solid catalyst component in which the transition metal compound [A] and the compound [B] are supported on the support [C], an olefin may be prepolymerized, or the transition metal compound [A] and / or the compound [B] may be further supported on the prepolymerized solid catalyst component. In each of the above methods (2) to (5), at least two of the transition metal compound [A], the compound [B] and the support [C] may be contacted in advance.

[0164] In the above methods (4) and (5) in which the compound [B] is supported, the unsupported compound [B] may be added in any order, if necessary. In this case, the compound [B] may be the same as or different from the compound [B] supported on the carrier [C].

[0165] In addition, the solid catalyst component in which the transition metal compound [A] is supported on the support [C] and the solid catalyst component in which the transition metal compound [A] and the compound [B] are supported on the support [C] may be prepolymerized with an olefin, or the prepolymerized solid catalyst component may further be supported on the solid catalyst component.

[0166] The prepolymerization is preferably a substantially homopolymerization of 95 mol% or more of olefin. The olefin used in the prepolymerization is preferably the same as that used in the main polymerization. Specifically, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-heptene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-decene, cyclopentene, and vinylcyclohexane are particularly preferred, and ethylene, propylene, 1-butene, 1-heptene, 3-methyl-1-butene, 1-hexene, and 4-methyl-1-pentene are particularly preferred.

[0167] The amount of olefin polymerized in the prepolymerization is in the range of 0.1 to 1000 g, preferably 1 to 50 g, per 1 g of the solid catalyst component. The above prepolymerization is usually preferably carried out by slurry polymerization, and as a solvent, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, or toluene can be used alone or in combination.

[0168] The prepolymerization temperature is preferably in the range of −50 to +100° C., particularly −20 to +80° C., and more preferably 0 to +40° C. The prepolymerization time may be appropriately determined depending on the prepolymerization temperature and the amount of polymerization in the prepolymerization. The pressure in the prepolymerization is not limited, but in the case of slurry polymerization, it is generally normal pressure to 50 kg / cm. 2 Each prepolymerization may be carried out in a batch, semi-batch or continuous manner. After each prepolymerization is completed, it is preferable to wash the mixture with saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, toluene, etc., either alone or in a mixture thereof, and the number of washings is usually preferably 5 to 6 times.

[0169] In the present invention, an ethylene-α-olefin-non-conjugated polyene copolymer can be suitably obtained by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene in the presence of the above-mentioned olefin polymerization catalyst.

[0170] When olefin polymerization is carried out using the above catalyst, the transition metal compound [A] is usually used in an amount of 10 -12 ~10 -2 Molar, preferably 10 -10 ~10 -8 It is used in molar amounts.

[0171] The organometallic compound [B-1] is used in an amount such that the molar ratio [[B-1] / [M]] of the organometallic compound [B-1] to the total transition metal atoms [M] in the transition metal compound [A] is usually 0.01-100,000, preferably 0.05-50,000. The organoaluminum oxy compound [B-2] is used in an amount such that the molar ratio [[B-2] / [M]] of the aluminum atoms in the organoaluminum oxy compound [B-2] to the total transition metals [M] in the transition metal compound [A] is usually 10-500,000, preferably 20-100,000. 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 1-10, preferably 1-5.

[0172] When the compound [B] is an organometallic compound [B-1], the organic compound component [D] is used in an amount such that the molar ratio [[D] / [B-1]] is usually 0.01 to 10, preferably 0.1 to 5. When the compound [B] is an organoaluminum oxy compound [B-2], the organic compound component [D] is used in an amount such that the molar ratio [[D] / [B-2]] is usually 0.01 to 2, preferably 0.005 to 1. When the compound [B] is an ionized ionic compound [B-3], the organic compound component [D] is used in an amount such that the molar ratio [[D] / [B-3]] is usually 0.01 to 10, preferably 0.1 to 5.

[0173] In the present invention, the method for producing the ethylene-α-olefin-non-conjugated polyene copolymer is not particularly limited and may be carried out by any of liquid phase polymerization methods such as solution (dissolution) polymerization and suspension polymerization, or gas phase polymerization methods, but it is preferable that the method includes a step of obtaining the following polymerization reaction liquid.

[0174] The step of obtaining a polymerization reaction liquid is a step of copolymerizing ethylene, the above-mentioned α-olefin, and the above-mentioned non-conjugated polyene using an aliphatic hydrocarbon as a polymerization solvent in the presence of an olefin polymerization catalyst medium containing the transition metal compound [A] according to the present invention, to obtain a polymerization reaction liquid of an ethylene-α-olefin-non-conjugated polyene copolymer.

[0175] If the concentration of the ethylene-α-olefin-non-conjugated polyene copolymer in the polymerization solvent exceeds the above range, the viscosity of the polymerization solution will be too high, and the solution will not be stirred uniformly, which may make it difficult to carry out the polymerization reaction.

[0176] Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specific examples 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. These can be used alone or in combination of two or more. Olefin itself can also be used as the solvent. Among these, hexane is preferred from the viewpoint of separation and purification from the resulting ethylene-α-olefin-non-conjugated polyene copolymer.

[0177] The polymerization temperature is usually in the range of -50 to +200°C, preferably 0 to +200°C, and more preferably +80 to +200°C. Although it depends on the attained molecular weight and polymerization activity of the metallocene catalyst system used, a higher temperature (+80°C or higher) is preferable from the viewpoints of catalytic activity, copolymerizability, and productivity.

[0178] The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0179] The reaction time (average residence time when copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours.

[0180] The molecular weight of the resulting ethylene-α-olefin-non-conjugated polyene copolymer can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. It can also be adjusted by the amount of compound [B] used. Specific examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the appropriate amount is about 0.001 to 100 NL per kg of olefin.

[0181] The molar ratio of ethylene to the above-mentioned α-olefin (ethylene / α-olefin) is preferably 25 / 75 to 80 / 20, and more preferably 30 / 70 to 70 / 30. The molar ratio of the charged ethylene to the non-conjugated polyene (ethylene / non-conjugated polyene) is preferably 70 / 30 to 99 / 1, and more preferably 80 / 20 to 98 / 2.

[0182] [Ethylene-α-olefin-non-conjugated polyene copolymer] The ethylene-α-olefin-non-conjugated polyene copolymer obtained by the production method of the present invention is described below.

[0183] [α-Olefin] The α-olefin constituting the ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention is usually an α-olefin having 3 to 20 carbon atoms, and examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Among these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, and 1-octene are preferred, and propylene is particularly preferred. Such α-olefins are preferred because the raw material cost is relatively low, the ethylene-α-olefin-non-conjugated polyene copolymer exhibits excellent mechanical properties, and a molded product having rubber elasticity can be obtained. These α-olefins may be used alone or in combination.

[0184] The ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention contains structural units derived from at least one type of α-olefin having 3 to 20 carbon atoms, and may contain structural units derived from two or more types of α-olefins having 3 to 20 carbon atoms.

[0185] [Non-conjugated polyenes] Specific examples of the non-conjugated polyene constituting the ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention include cyclic dienes such as 5-ethylidene-2-norbornene (ENB), 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene (VNB), 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, and norbornadiene; chain non-conjugated dienes such as 2,3-diisopropylidene-5-norbornene, 4-ethylidene-8-methyl-1,7-nonadiene, etc. Among these, 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), 5-methylene-2-norbornene, 7-methyl-1,6-octadiene, 1,4-hexadiene, and dicyclopentadiene are preferred. Among them, 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), and 7-methyl-1,6-octadiene are particularly preferred. When a composition containing an ethylene-α-olefin-non-conjugated polyene copolymer is crosslinked with sulfur, ENB, 1,4-hexadiene, and dicyclopentadiene, which have excellent mechanical strength, are preferred, and when a composition containing an ethylene-α-olefin-non-conjugated polyene copolymer is crosslinked with an organic peroxide, VNB and 5-methylene-2-norbornene, which have excellent crosslinking efficiency and heat aging resistance, are preferred. These non-conjugated polyenes may be used alone or in combination of two or more.

[0186] The ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention usually has a content of constitutional units derived from non-conjugated polyene of 0.1 to 5 mol %, preferably 2.5 to 4 mol %. The total of the constitutional units derived from ethylene, the constitutional units derived from α-olefin, and the constitutional units derived from non-conjugated polyene is 100 mol %. Within the above range, the strength, rubber elasticity, compression set, etc. of a molded article obtained from the composition containing the ethylene-α-olefin-non-conjugated polyene copolymer are excellent, and when the composition containing the ethylene-α-olefin-non-conjugated polyene copolymer contains a crosslinking agent and a foaming agent, it is preferable because it has excellent foamability, dimensional stability, etc. The content of the structural units derived from ethylene is 13 It can be determined by C NMR.

[0187] The ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention generally has an intrinsic viscosity [η] measured in decalin at 135° C. of 0.1 to 1.0 dL / g, preferably 0.2 to 0.5 dL / g. EXAMPLES

[0188] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The structure of the transition metal compound [A] is 1 The 1 H NMR spectrum (270 MHz, JEOL GSH-270), FD-mass (hereinafter FD-MS) spectrum (JEOL SX-102A), etc. were measured and determined. The physical properties of the ethylene-α-olefin-non-conjugated polyene copolymers were measured by the following methods.

[0189] [Ethylene content, propylene content, 5-ethylidene-2-norbornene (ENB) content] The measurement solvent was o-dichlorobenzene / benzene-d6 (4 / 1 {vol / vol%}) and the measurement conditions were 120°C, 250 ppm spectral width, 5.5 s pulse repetition time, and 4.7 μs pulse width (45° pulse) (100 MHz, JEOL ECX400P), or 120°C, 250 ppm spectral width, 5.5 s pulse repetition time, and 5.0 μs pulse width (45° pulse) (125 MHz, Bruker Biospin AVANCEIIIcryo-500). 13 C NMR spectra were measured and calculated.

[0190] [Intrinsic viscosity ([η])] The measurement was performed at 135°C using decalin as a solvent. Approximately 20 mg of the polymer was dissolved in 15 mL of decalin, and the specific viscosity η sp The decalin solution was diluted with 5 mL of decalin solvent, and the specific viscosity η was measured in the same manner. sp This dilution procedure was repeated two more times, and the η sp The value of / C was taken as the intrinsic viscosity. [η]=lim(η sp / C) (C→0)

[0191] [Synthesis of transition metal compound [A]] [Synthesis Example 1] In a 50mL eggplant flask that had been thoroughly dried and purged with nitrogen, 575mg (2.62mmol) of trichloro(η5-cyclopentadienyl)titanium and 20mL of ether were placed and cooled in a methanol-dry ice bath at around -30℃. To this suspension, 6.8mL (7.89mmol) of a 1.16M ether solution of methyllithium was added. To the resulting gray-green suspension, 440mg (2.55mmol) of 2-(2-pyridyl)-3,5-dimethylpyrrole in toluene (20mL) was added dropwise, and the mixture was stirred overnight while slowly warming to room temperature. The reaction solution was concentrated using a vacuum pump, and the residue was extracted with toluene and filtered through Celite. The concentrated filtrate was azeotroped with a hexane-ether mixture, and the resulting solid was washed with hexane and then pentane to obtain 500mg (dark red powder, 64% yield) of the target product shown below (hereinafter referred to as transition metal compound [A-1]). 1 H NMR (CDCl3): δ=7.56-7.44(3H,m,Ar-H), 6.70-6.65(1H,m,Ar-H), 6.50(5H,s,Cp-H), 5.85(1H,s,Ar-H ), 2.41(3H,s,Ar-Me), 2.00(3H,s,Ar-Me), 0.96(3H,d,Ti-Me,J=0.9Hz), 0.80(3H,d,Ti-Me,J=0.9Hz) FD-MS(m / z):314.1

[0192] [ka]

[0193] [Synthesis Example 2] In a 50mL eggplant flask that had been thoroughly dried and substituted with nitrogen, 480mg (2.14mmol) of trichloro(η5-cyclopentadienyl)titanium and 20mL of ether were placed and cooled in a methanol-dry ice bath at around -30℃. 5.5mL (6.38mmol) of 1.16M ether solution of methyllithium was added to this suspension. 630mg (2.13mmol) of 2-(2-pyridyl)-3,5-diphenylpyrrole in toluene (20mL) was added dropwise to the resulting gray-green suspension, and the mixture was stirred overnight while slowly warming to room temperature. The reaction solution was concentrated using a vacuum pump, and the residue was extracted with toluene and filtered through Celite. The concentrated filtrate was washed with hexane and then pentane to obtain 512mg (dark red powder, 50% yield) of the target product shown below (hereinafter referred to as transition metal compound [A-2]). 1 H NMR (CDCl3): δ=7.67-7.23(13H,m,Ar-H), 6.79-6.74(1H,m,Ar-H), 6.45(5H,s,Cp-H), 6.35(1H,s,Ar-H), 0.75(3H,broad s,Ti-Me), 0.50(3H,broad s,Ti-Me)FD-MS(m / z):438.2

[0194] [ka]

[0195] [Synthesis Example 3] In a 50mL eggplant flask that had been thoroughly dried and substituted with nitrogen, 732mg (2.60mmol) of trichloro(tert-butyl-η5-cyclopentadienyl)titanium and 30mL of ether were placed and cooled in a methanol-dry ice bath at around -30℃. To this suspension, 6.9mL (8.00mmol) of a 1.16M ether solution of methyllithium was added. To the resulting gray-green suspension, 460mg (2.67mmol) of 2-(2-pyridyl)-3,5-dimethylpyrrole in toluene (30mL) was added dropwise, and the mixture was stirred overnight while slowly warming to room temperature. The reaction solution was concentrated using a vacuum pump, and the residue was extracted with toluene and filtered through Celite. The concentrated filtrate was dissolved in a small amount of pentane and left to stand overnight in a refrigerator, and the precipitated solid was filtered off to obtain 499mg (dark red powder, 50% yield) of the target product shown below (hereinafter referred to as transition metal compound [A-3]). 1 H NMR(CDCl3):δ=7.57-7.45(3H,m,Ar-H), 7.11-7.02(1H,m,Ar-H), 6.67-6.62(1H,m,Ar-H), 6.14-6.11(1H,m ,Cp-H), 6.00-5.97(1H,m,Cp-H), 5.83(1H,s,Ar-H), 2.39(3H,s,Ar-Me), 1.99(3H,s,Ar-Me), 0.99(3H,broad s,Ti-Me), 0.81(3H,broad s,Ti-Me), 0.80(9H,s,Cp-C(CH3)3)FD-MS(m / z):370.2

[0196] [ka]

[0197] [Synthesis Example 4] In a 50mL eggplant flask that had been thoroughly dried and purged with nitrogen, 770mg (2.80mmol) of trichloro(η5-indenyl)titanium and 30mL of ether were placed and cooled in a methanol-dry ice bath at around -78℃. To this suspension, 7.25mL (8.41mmol) of a 1.16M ether solution of methyllithium was added. After the obtained brown suspension was heated to -30℃, a toluene solution (30mL) of 479mg (2.78mmol) of 2-(2-pyridyl)-3,5-dimethylpyrrole was added dropwise, and the mixture was stirred overnight while slowly heating to room temperature. The reaction solution was concentrated using a vacuum pump, and the residue was extracted with toluene and filtered through Celite. The concentrated filtrate was washed with pentane to obtain 567mg (red powder, 64% yield) of the target product shown below (hereinafter referred to as transition metal compound [A-4]). 1 H NMR(CDCl3): δ=7.94-7.90(1H,m,Ar-H), 7.58-7.52(1H,m,Ar-H), 7.43-7.39( 2H,m,Ar-H), 7.36-7.25(2H,m,Ar-H), 6.70-6.64(1H,m,Ar-H), 6.21(1H,t,Ar- H,J=3.5Hz), 6.05-6.03(1H,m,Ar-H), 5.83(1H,s,Ar-H), 2.38(3H,s,Ar-Me), 2.13(3H,s,Ar-Me), 0.89(3H,d,Ti-Me,J=1.0Hz), 0.71(3H,d,Ti-Me,J=1.0Hz) FD-MS(m / z):364.1

[0198] [ka]

[0199] [Synthesis Example 5] In a 50mL eggplant flask that had been thoroughly dried and substituted with nitrogen, 285mg (1.27mmol) of trichloro(η5-cyclopentadienyl)titanium and 20mL of toluene were placed and cooled in a methanol-dry ice bath at around -78℃. 3.60mL (3.92mmol) of 1.09M ether solution of methyllithium was added to this suspension. The resulting ocher suspension was stirred at -78℃ for 75 minutes, after which 182mg (1.26mmol) of 2-(2-pyridyl)-pyrrole in toluene (20mL) was added dropwise and stirred overnight while slowly warming to room temperature. The reaction solution was concentrated using a vacuum pump, and the residue was extracted with toluene and filtered through Celite. The concentrated filtrate was extracted and concentrated with methylcyclohexane, and the oily product obtained was washed with hexane to obtain 38.9mg (dark red oily product, 11% yield) of the target product shown below (hereinafter referred to as transition metal compound [A-5]). 1 H NMR(C7D8): δ=7.13-7.09(1H,m,Ar-H), 6.86-6.73(3H,m,Ar-H), 6.65-6.64(1H,m,Ar-H ), 6.39-6.37(1H,m,Ar-H), 6.11-6.06(1H,m,Ar-H), 5.97(5H,s,Cp-H), 1.22(6H,broad s,Ti-Me) FD-MS(m / z):286.1 [ka]

[0200] [Synthesis Example 6] According to the description in JP-A-2007-529584, the transition metal compound [A-6] shown below was synthesized. [ka]

[0201] [Production of ethylene-propylene-ENB copolymer] [Example 1-1] 1030mL of hexane and 12mL of ethylidenenorbornene (ENB) were charged into a 2L stainless steel autoclave that had been thoroughly purged with nitrogen, and the temperature in the system was raised to 95°C. Then, 0.90MPa of propylene was charged at a partial pressure, and ethylene was fed to a total pressure of 1.6MPa-G. Next, 0.3mmol of triisobutylaluminum, 0.005mmol of the transition metal compound [A-1], and 0.02mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were fed with nitrogen, and polymerization was started by setting the stirring speed to 250rpm. Then, polymerization was carried out at 95°C for 15 minutes while maintaining the total pressure at 1.6MPa-G by continuously feeding only ethylene. A small amount of ethanol was added to the system to stop the polymerization, and the unreacted ethylene was purged. The obtained polymer solution was poured into a large excess of a mixed solution of methanol / acetone and air-dried overnight. The obtained polymer was recovered by filtration and dried overnight at 120° C. under reduced pressure. As a result, 0.79 g of ethylene-propylene-ENB copolymer was obtained with an ethylene content of 63.2 mol% and an ENB content of 12.7 mass%. The polymerization activity was 0.6 kg / mmol-Ti / h.

[0202] [Comparative Example 1-2] The same procedure as in Example 1-1 was carried out, except that 0.005 mmol of the transition metal compound [A-1] was changed to 0.001 mmol of the transition metal compound [A-5]. As a result, 0.62 g of an ethylene / propylene / ENB copolymer having an ethylene content of 60.2 mol% and an ENB content of 7.4 mass% was obtained. The polymerization activity was 2.5 kg / mmol-Ti / h.

[0203] [Example 2-1] 1030mL of hexane and 4mL of ethylidenenorbornene (ENB) were charged into a stainless steel autoclave with a capacity of 2L, which had been thoroughly purged with nitrogen. After raising the temperature in the system to 95°C, 0.45MPa of propylene was charged at a partial pressure, and ethylene was fed to set the total pressure to 1.6MPa-G. Next, 0.3mmol of triisobutylaluminum, 0.0025mmol of the transition metal compound [A-1], and 0.01mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were fed with nitrogen, and polymerization was started by setting the stirring speed to 250rpm. Then, polymerization was carried out at 95°C for 15 minutes while maintaining the total pressure at 1.6MPa-G by continuously feeding only ethylene. A small amount of ethanol was added to the system to stop the polymerization, and the unreacted ethylene was purged. The obtained polymer solution was poured into a large excess of a mixed solution of methanol / acetone and air-dried overnight. The obtained polymer was recovered by filtration and dried overnight at 120° C. under reduced pressure. As a result, 1.51 g of ethylene-propylene-ENB copolymer was obtained with an ethylene content of 79.0 mol% and an ENB content of 13.1 mass%. The polymerization activity was 2.4 kg / mmol-Ti / h.

[0204] [Example 2-2] The same procedure as in Example 2-1 was carried out, except that the transition metal compound [A-1] used in Example 2-1 was changed to the transition metal compound [A-2]. As a result, 0.90 g of an ethylene / propylene / ENB copolymer having an ethylene content of 80.2 mol% and an ENB content of 11.9 mass% was obtained. The polymerization activity was 1.4 kg / mmol-Ti / h.

[0205] [Example 2-3] The same procedure as in Example 2-1 was carried out, except that the transition metal compound [A-1] used in Example 2-1 was changed to the transition metal compound [A-3]. As a result, 1.05 g of ethylene-propylene-ENB copolymer was obtained with an ethylene content of 77.0 mol% and an ENB content of 10.2 mass%. The polymerization activity was 1.7 kg / mmol-Ti / h.

[0206] [Example 2-4] The same procedure as in Example 2-1 was carried out, except that the transition metal compound [A-1] used in Example 2-1 was changed to the transition metal compound [A-4]. As a result, 3.05 g of ethylene-propylene-ENB copolymer was obtained with an ethylene content of 79.0 mol% and an ENB content of 9.5 mass%. The polymerization activity was 4.9 kg / mmol-Ti / h.

[0207] [ Comparative Example 2-5] The same procedure as in Example 2-1 was carried out, except that the transition metal compound [A-1] used in Example 2-1 was changed to the transition metal compound [A-5]. As a result, 3.63 g of ethylene-propylene-ENB copolymer was obtained with an ethylene content of 72.3 mol% and an ENB content of 6.7 mass%. The polymerization activity was 5.8 kg / mmol-Ti / h.

[0208] [Comparative Example 2-6] The same procedure as in Example 2-1 was carried out, except that the transition metal compound [A-1] used in Example 2-1 was changed to the transition metal compound [A-6]. As a result, 9.06 g of ethylene-propylene-ENB copolymer was obtained with an ethylene content of 88.5 mol% and an ENB content of 2.4 mass%. The polymerization activity was 72.5 kg / mmol-Ti / h.

Claims

1. [A] A transition metal compound represented by the following general formula (I), and [B] [B-1] Organometallic compound, [B-2] an organoaluminum oxy compound, and [B-3] A compound that reacts with the transition metal compound [A] to form an ion pair At least one compound selected from the group consisting of The present invention relates to a method for producing an ethylene-α-olefin-non-conjugated polyene copolymer, the method comprising the steps of: (P) polymerizing ethylene, an α-olefin, and a non-conjugated polyene in the presence of an olefin polymerization catalyst comprising: 【Chemistry 1】 [In the formula (I), M represents a titanium atom; m represents an integer from 1 to 6; R 1 is a methyl group or a phenyl group; R2 and R 3 may be the same or different and each represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and may be linked to each other to form a ring, R 4 , R 5 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and may be bonded to each other to form a double bond between a carbon atom and a nitrogen atom, Z represents a structure represented by the following formula (III): 【Chemistry 2】 (In formula (III), R 6 to R 9 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring, and ● represents a bonding point with a carbon atom (C), and ○ represents a bonding point with a nitrogen atom (N).) In addition, when m is 2 or more, R 1 ~R 3 and two of the groups represented by R may be linked together; n is a number that satisfies the valence of M; X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different from one another, and the multiple groups represented by X may be bonded to one another to form a ring; R 10 ~R 14 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked to each other to form a ring, and three or more of R 10 to R 14 are hydrogen.

2. R in the above general formula (I) 4 and R 5 The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to claim 1, wherein the carbon atom and the nitrogen atom form a double bond.

3. R 2 and R 3 is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

4. R 2 and R 3 The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to claim 1 or 2, wherein is any one of hydrogen, a methyl group, and a phenyl group.

5. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to any one of claims 1 to 4, wherein the non-conjugated polyene is represented by the following general formula (IV): 【Chemistry 3】 [In the formula, m is an integer from 0 to 2, R 15 , R 16 , R 17 and R 18 each independently represents an atom or a substituent selected from a hydrogen atom, 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, the hydrocarbon group optionally having a double bond, R 15 From R 18 Any two of the substituents may be bonded to each other to form a ring, which may contain a double bond; R 15 and R 16 With or R 17 and R 18 may form an alkylidene group, R 15 and R 17 Toga or R 16 and R 18 and may be bonded to each other to form a double bond, At least one of the following requirements (i) to (iv) is met: (i) R 15 From R 18 At least one of the groups up to is a hydrocarbon group having one or more double bonds. (ii) R 15 From R 18 Any two substituents up to may be joined together to form a ring, said ring including double bonds. (iii) R 15 and R 16 With or R 17 and R 18 and form an alkylidene group. (iv) R 15 and R 17 Toga or R 16 and R 18 and are bonded to each other to form a double bond.

6. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to claim 5, wherein the non-conjugated polyene is 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB).

7. The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to claim 5 or 6, wherein the step [P] is a step of copolymerizing ethylene, an α-olefin having 3 to 10 carbon atoms, and a non-conjugated polyene.

8. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to claim 7, wherein the α-olefin is propylene.

9. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to any one of claims 1 to 8, wherein the polymerization temperature in the step [P] is 80°C or higher.

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