Transition metal compounds, catalysts for olefin polymerization, and methods for producing olefin polymers

Abstract

To provide a novel transition metal compound, particularly a novel transition metal compound or the like suitable as an olefin-polymerization catalyst available for various types of olefin polymerization.SOLUTION: A transition metal compound has, for example, the following structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel transition metal compound, and more particularly to a novel transition metal compound that can be used as a catalyst for olefin polymerization, a catalyst for olefin polymerization containing the compound, and a method for producing an olefin polymer using the catalyst. [Background technology]

[0002] Titanium-based catalysts, consisting of titanium compounds and organoaluminum compounds, and vanadium-based catalysts, consisting of vanadium compounds and organoaluminum compounds, are known as catalysts used to produce olefin polymers such as ethylene polymers and ethylene-α-olefin copolymers.

[0003] Furthermore, metallocene catalysts consisting of metallocene compounds such as zirconocene and organoaluminum oxy compounds (aluminoxanes) are known as catalysts capable of producing olefin polymers with high polymerization activity. Generally, olefin polymers are lightweight, inexpensive, and possess excellent physical properties and processability, making them suitable for various applications such as molded articles. However, in recent years, the demands for olefin polymer properties have diversified, and olefin polymers with a variety of properties are desired. Improvement in productivity is also desired. Under these circumstances, there is a strong need for the emergence of olefin polymerization catalysts and methods for producing olefin polymers that possess high olefin polymerization activity and excellent properties.

[0004] For example, Patent Documents 1 and 2 disclose a catalyst for olefin polymerization containing a transition metal compound represented by the following formula (PI), and describe that this catalyst exhibits excellent polymerization activity.

[0005] [ka] (In formula (PI), M, m, R 1 ~R 5 (where , n, and X are those described in Patent Documents 1 and 2, respectively). Furthermore, Patent Document 3 discloses a catalyst for olefin polymerization containing a transition metal compound represented by the following formula (FI), and it is stated that this catalyst exhibits excellent polymerization activity.

[0006] [ka] (In formula (FI), M, m, R 1 ~R 6 n and X are those described in Patent Document 3. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2001-072706 [Patent Document 2] Japanese Patent Publication No. 2001-181333 [Patent Document 3] Japanese Patent Application Publication No. 11-315109 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] However, in order to achieve the high performance and high productivity expected of olefin polymers in recent years, there is a need to develop better-performing catalysts for olefin polymerization. In view of the above prior art, the present invention aims to provide novel transition metal compounds, in particular novel transition metal compounds that can be used as catalysts for olefin polymerization suitable for various olefin polymerizations.

[0009] Another aspect of the present invention aims to provide a catalyst for olefin polymerization that is highly active and capable of producing high molecular weight olefin polymers, and novel transition metal compounds that can be used in such olefin polymerization catalysts. [Means for solving the problem]

[0010] As a result of investigations in view of the above problems and objectives, the present inventors have found that an olefin polymerization catalyst containing a transition metal compound having a specific structure has high polymerization activity and can produce an olefin polymer having a high molecular weight, thereby completing the present invention.

[0011] The present invention relates to, for example, the following [1] to

[14] . [1] A transition metal compound (A) represented by the following general formula [I].

[0012] [Chemical formula] [In formula [I], M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of 1 to 6, Z represents a structure represented by the following formula [2] or [3],

[0013] [Chemical formula] (In formulas [2] and [3], ○ indicates the bonding point with the carbon atom to which R in general formula [I] 1 is bonded, and ● indicates the bonding point with the transition metal atom M.) A 2 represents a nitrogen atom or a phosphorus atom, A 3 represents an oxygen atom, a sulfur atom or a selenium atom, Q represents a carbon atom having a substituent R c (-(R c ))C=), a nitrogen atom (-N=), or a phosphorus atom (-P=), S represents a carbon atom having a substituent R b (-(R b ))C=), a nitrogen atom (-N=), or a phosphorus atom (-P=), T represents a carbon atom having a substituent R a (-(R a ))C=), a nitrogen atom (-N=), or a phosphorus atom (-P=), Ra ~R g , R 1 and R 2 These may be the same or different from each other, and represent a hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, R a ~R c , R 1 and R 2 Two or more of these groups may be linked to each other to form a ring, R d ~R g , R 1 and R 2 Two or more of these groups may be linked to each other to form a ring. 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. If n is 2 or greater, the multiple groups represented by X may be identical or different from each other, and the multiple groups represented by X may be bonded to each other to form a ring. R 3 ~R 5 These may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, R 3 ~R 5 Two or more of these groups may be bonded to each other to form a ring.

[0014] [2] R in the above general formula [I] 3 ~R 5 However, the transition metal compound (A) of [1] is a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0015] [3] R in the above general formula [I]3 ~R 5 However, the transition metal compound (A) of [2] is a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms.

[0016] [4] A transition metal compound (A) of any of the above [1] to [3], wherein M in the above general formula [I] is a transition metal atom of group 4 or 5 of the periodic table.

[0017] [5] The transition metal compound (A) of the above general formula [I], wherein M is a titanium atom.

[0018] [6] A transition metal compound (A) represented by the following general formula [II], one of the above [1] to [5].

[0019] [ka]

[0020] [7] A of the above general formula [II] 2 However, it is a nitrogen atom, Q is substituent R c A carbon atom having, S, substituent R b A carbon atom having, T is a substituent R a The transition metal compound (A) of [6] having carbon atoms.

[0021] [8] R in the above general formula [II] a ~R c However, the transition metal compound (A) of [6] or [7] is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0022] [9] A transition metal compound (A) represented by the following general formula [III], one of the above [1] to [5].

[0023] [ka]

[0024]

[10] A of the above general formula [III] 3 However, the transition metal compound (A) described above [9] is an oxygen atom.

[0025]

[11] R in the above general formula [III] d ~R g However, the transition metal compound (A) of [9] or

[10] is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0026]

[12] A transition metal compound (A) from any of the above [1] to

[11] , (B-1) organometallic compound, (B-2) Organic aluminum oxy compounds, and (B-3) Compounds that react with the transition metal compound to form an ion pair At least one compound (B) selected from the group consisting of and A catalyst for olefin polymerization containing [specific component].

[0027]

[13] A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst

[12] described above.

[0028]

[14] A method for producing the olefin polymer of

[13] , wherein the olefin comprises an α-olefin having 2 to 30 carbon atoms. [Effects of the Invention]

[0029] According to the present invention, it is possible to produce olefin polymers with high polymerization activity and high molecular weight. [Modes for carrying out the invention]

[0030] The present invention will be described in more detail below. [Transition metal compounds] The transition metal compound (A) of the present invention is characterized by being represented by the following general formula [I].

[0031] [ka]

[0032] 《M》 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 lanthanides), preferably a metal atom of groups 3 to 9 (group 3 also includes lanthanides), more preferably a transition metal atom selected from groups 3 to 5, even more preferably a transition metal atom selected from group 4 or 5, and particularly preferably a transition metal atom of group 4. Specifically, these include 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 titanium.

[0033] In general formula [I], the dotted line connecting N and M generally indicates that N is coordinated to M, but in the present invention, coordination may or may not occur. In the above general formula [I], m represents an integer from 1 to 6, preferably 1 or 2, and particularly preferably 1.

[0034] 《Z》 In the above general formula [I], Z represents the structure shown in formula [2] or [3] below.

[0035] [ka] (In equations [2] and [3], ○ represents R in general equation [I]) 1 The circles indicate the bonding points with carbon atoms, and the dots (●) indicate the bonding points with transition metal atoms M.

[0036] In the above general formula [2], A 2 This represents a nitrogen atom or a phosphorus atom. In the above general formula [3], A 3 This represents an oxygen atom, a sulfur atom, or a selenium atom. In the above general formula [2], Q is a substituent R c A carbon atom having (-(R c ) indicates a C=), a nitrogen atom (-N=), or a phosphorus atom (-P=), In the above general formula [2], S is a substituent R b A carbon atom having (-(R b ) indicates a C=), a nitrogen atom (-N=), or a phosphorus atom (-P=), In the above general formula [2], T is a substituent R a A carbon atom having (-(R a ) indicates a C atom (-N=), a nitrogen atom (-P=), or a phosphorus atom (-P=).

[0037] 《R a ~R g 、R 1 and R 2 》 In the above general formula [I], R a ~R g , R 1 and R 2 These may be the same or different from each other, and represent a hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, R a ~R c , R 1and R 2 Two or more of these groups may be linked to each other to form a ring, R d ~R g , R 1 and R 2 Two or more of these groups may be linked to each other to form a ring. Examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0038] 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, or aromatic hydrocarbon groups having 6 to 30 carbon atoms. Specifically, this includes linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, and more preferably 1 to 10, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl groups; Linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20, such as vinyl groups, allyl groups, and isopropenyl groups; Linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20, and more preferably 2 to 10, such as ethynyl groups and propargyl groups; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, norbornyl group, adamantyl group, and other cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20, and more preferably 3 to 12 carbon atoms; Cyclopentadienyl groups, indenyl groups, fluorenyl groups, and other cyclic unsaturated hydrocarbon groups with 5 to 30 carbon atoms; Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, and more preferably 6 to 10, such as phenyl groups, naphthyl groups, biphenyl groups, terphenyl groups, phenanthryl groups, and anthracenyl groups; Alkyl-substituted aryl groups such as tolyl group, iso-propylphenyl group, t-butylphenyl group, dimethylphenyl group, and di-t-butylphenyl group; Examples include aryl-substituted alkyl groups such as benzyl and cumyl groups.

[0039] The above hydrocarbon group may have hydrogen atoms substituted with halogens. Examples of such hydrocarbon groups with hydrogen atoms substituted with halogens include halogenated hydrocarbon groups having 1 to 30, preferably 1 to 20, carbon atoms, such as trifluoromethyl, pentafluorophenyl, and chlorophenyl groups.

[0040] The above hydrocarbon group is a heterocyclic compound residue; Oxygen-containing groups such as alkali groups, allyloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxyl groups, peroxy groups, and carboxylic acid anhydride groups; Nitrogen-containing groups such as amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and ammonium salts of amino groups; Boron-containing groups such as boranediyl groups, borantriyl groups, and diboranyl groups; Sulfur-containing groups such as mercapto groups, thioester groups, dithioester groups, alkylthio groups, arylthio groups, thioacyl groups, thioether groups, thiocyanate groups, isothianeate groups, sulfone ester groups, sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups, and sulfenyl groups; Phosphorus-containing groups such as phosphine groups, phosphoryl groups, thiophosphoryl groups, and phosphat groups; Silicon-containing group; Germanium-containing group; or It may have a tin-containing group.

[0041] Examples of the heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine; oxygen-containing compounds such as furan and pyran; sulfur-containing compounds such as thiophene; and groups obtained by further substituting these heterocyclic compound residues with substituents such as alkyl groups and alkoxy groups having 1 to 30, preferably 1 to 20, carbon atoms.

[0042] Examples of the silicon-containing group include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups. More specifically, examples include methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups, diphenylmethylsilyl groups, triphenylsilyl groups, dimethylphenylsilyl groups, dimethyl-t-butylsilyl groups, and dimethyl(pentafluorophenyl)silyl groups. Among these, methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups, dimethylphenylsilyl groups, and triphenylsilyl groups are preferred, with trimethylsilyl groups, triethylsilyl groups, triphenylsilyl groups, and dimethylphenylsilyl groups being particularly preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy groups.

[0043] Examples of the germanium-containing group or the tin-containing group include groups in which the silicon in the silicon-containing group is replaced with germanium or tin.

[0044] Of the groups listed as groups that the above hydrocarbon group may have, Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and t-butoxy groups. Examples of allyloxy groups include phenoxy group, 2,6-dimethylphenoxy group, and 2,4,6-trimethylphenoxy group. Examples of ester groups include acetyloxy group, benzoyloxy group, methoxycarbonyl group, phenoxycarbonyl group, and p-chlorophenoxycarbonyl group. Examples of acyl groups include formyl, acetyl, benzoyl, p-chlorobenzoyl, and p-methoxybenzoyl groups. Examples of amino groups include dimethylamino group, ethylmethylamino group, and diphenylamino group. Examples of imino groups include methylimino group, ethylimino group, propylimino group, butylimino group, and phenylimino group. Examples of amide groups include acetamide, N-methylacetamide, and N-methylbenzamide. Examples of imide groups include acetimide groups and benzimide groups. Examples of thioester groups include acetylthio groups, benzoylthio groups, methylthiocarbonyl groups, and phenylthiocarbonyl groups. Examples of alkylthio groups include methylthio groups and ethylthio groups. Examples of arylthio groups include phenylthio groups, methylphenylthio groups, naphthylthio groups, etc. Examples of sulfonate ester groups include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Specific examples of sulfonamide groups include phenylsulfonamide group, N-methylsulfonamide group, and N-methyl-p-toluenesulfonamide group.

[0045] The hydrocarbon groups mentioned above include, in particular, linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl groups; Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, such as phenyl groups, naphthyl groups, biphenyl groups, terphenyl groups, phenanthryl groups, and anthracenyl groups; These aryl groups are preferably substituted with 1 to 5 substituents, such as a halogen atom, an alkyl or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, or an aryl or aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms.

[0046] R a ~R g , R 1 and R 2 As mentioned above, these can be heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, or tin-containing groups. Examples of these include those exemplified in the description of hydrocarbon groups above.

[0047] 《R 3 ~R 5 》 R 3 ~R 5 These may be the same or different from each other, and include a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. Specific examples of these include the above-mentioned R a ~R g , R 1 and R 2 Examples similar to those exemplified in the explanation can be given. Note that hydrocarbon groups also include halogenated hydrocarbon groups. 3 ~R 5 Two or more of these groups may be bonded to each other to form a ring.

[0048] R 3 ~R 5Preferably, the alkyl groups are linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms, with linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms being more preferred. Examples of alkyl and aryl groups in these preferred or more preferred embodiments include t-butyl group, adamantyl group, cyclohexyl group, phenyl group, biphenyl-2-yl group, and o-tolyl group.

[0049] 《X》 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. Examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0050] The hydrocarbon group is the above R a ~R g , R 1 and R 2 Examples similar to those exemplified in the explanation include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and icosyl groups; Cycloalkyl groups with 3 to 30 carbon atoms, such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups; Alkenyl groups such as vinyl groups, propenyl groups, and cyclohexenyl groups; Arylalkyl groups such as benzyl, phenylethyl, and phenylpropyl groups; Examples include phenyl groups, tolyl groups, dimethylphenyl groups, trimethylphenyl groups, ethylphenyl groups, propylphenyl groups, biphenyl groups, naphthyl groups, methylnaphthyl groups, anthryl groups, phenanthryl groups, and other aryl groups.

[0051] These hydrocarbon groups 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, as the halogenated hydrocarbon group, a halogenated hydrocarbon group having 1 to 10 carbon atoms is preferable.

[0052] 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; a carbonyl group and the like.

[0053] Examples of the sulfur-containing group include those similar to those exemplified in the description of R a ~R g 、R 1 and R 2 Specific examples include 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, or a pentafluorobenzenesulfonate group; sulfinate groups such as a methylsulfinate group, a phenylsulfinate group, a benzylsulfinate group, a p-toluenesulfinate group, a trimethylbenzenesulfinate group, or a pentafluorobenzenesulfinate group; an alkylthio group; an arylthio group and the like.

[0054] Specific examples of the nitrogen-containing group include those similar to those exemplified in the description of R a ~R g 、R 1 and R 2 Specific examples include an amino group; Alkylamino groups such as methylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dicyclohexylamino group; Aryl amino groups or alkylaryl amino groups such as phenylamino group, diphenylamino group, ditolylamino group, dinaphthylamino group, methylphenylamino group, etc. may be mentioned.

[0055] Specific examples of the boron-containing group include BR4 (where R represents hydrogen, an alkyl group, an aryl group which may have a substituent, or a halogen atom, etc.). Specific examples of the aluminum-containing group include AlR4 (where R represents hydrogen, an alkyl group, an aryl group which may have a substituent, or a halogen atom, etc.).

[0056] Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine group, tributylphosphine group, tricyclohexylphosphine group; Triarylphosphine groups such as triphenylphosphine group, tritolylphosphine group; Phosphite groups (phosphide groups) such as methyl phosphite group, ethyl phosphite group, phenyl phosphite group; Phosphonic acid group; Phosphinic acid group and the like may be mentioned.

[0057] Specific examples of the halogen-containing group include fluorine-containing groups such as PF6, BF4, chlorine-containing groups such as ClO4, SbCl6, and iodine-containing groups such as IO4. Examples of the heterocyclic compound residue include those similar to those exemplified in the description of R a ~R g 、R 1 and R 2 The same ones as those exemplified in the description of R

[0058] Specific examples of the silicon-containing group include those of R a ~R g 、R 1 and R 2Examples similar to those exemplified in the explanation include, specifically, hydrocarbon-substituted silyl groups such as phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tritrilsilyl group, and trinaphthylsilyl group; Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether groups; Silicon-substituted alkyl groups such as trimethylsilylmethyl groups; Examples include silicon-substituted aryl groups such as trimethylsilylphenyl groups.

[0059] Specifically, the germanium-containing group is the above R a ~R g , R 1 and R 2 Examples similar to those exemplified in the explanation include, specifically, groups in which the silicon in the silicon-containing group is replaced with germanium.

[0060] Specifically, the tin-containing group is the above R a ~R g , R 1 and R 2 Examples similar to those exemplified in the explanation can be given, and more specifically, examples include groups in which the silicon in the silicon-containing group is replaced with tin. Among these, methyl groups and benzyl groups are preferred for X, with methyl groups being more preferred.

[0061] 《n》 In the above general formula [I], n is a number that satisfies the valence of M, i.e., an integer selected such that the transition metal compound (A) is electrically neutral, and is usually an integer from 0 to 5, preferably an integer from 1 to 4, more preferably an integer from 1 to 3, and particularly preferably 2. When n is 2 or greater, the multiple X groups may be the same or different from one another. Furthermore, the groups represented by the multiple X groups may bond to each other to form a ring.

[0062] A transition metal compound (A) in which Z in the general formula [I] exhibits the structure represented by formula [2] is represented by the following general formula [II].

[0063] [ka]

[0064] In the above general formula [II], A 2 This represents a nitrogen atom or a phosphorus atom, preferably a nitrogen atom.

[0065] In the above general formula [II], Q is a substituent R c A carbon atom having (-(R c )C=), a nitrogen atom (-N=), or a phosphorus atom (-P=), preferably a substituent R c It is a carbon atom. In the above general formula [II], S is a substituent R b A carbon atom having (-(R b )C=), a nitrogen atom (-N=), or a phosphorus atom (-P=), preferably a substituent R b It is a carbon atom. In the above general formula [II], T is a substituent R a A carbon atom having (-(R a )C=), a nitrogen atom (-N=), or a phosphorus atom (-P=), preferably a substituent R a It is a carbon atom.

[0066] As mentioned above, R in the general formula [II] above a ~R c , R 1 and R 2 Two or more of these groups may be linked together to form a ring. More specifically, R a ~R c , R 1 and R 2 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 substituents.

[0067] R in the above general formula [II] a ~R c From the viewpoint of olefin polymerization activity and copolymerizability, it is preferable that the group is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a silicon-containing group.

[0068] R in the above general formula [II] a It is preferably a hydrogen atom, a methyl group, a phenyl group, or a silicon-containing group, and is particularly preferably a hydrogen atom, a methyl group, or a trimethylsilyl group.

[0069] R in the above general formula [II] b and R c It is preferably a hydrogen atom, a methyl group, or a phenyl group, and is particularly preferably a hydrogen atom. Furthermore, R in the above general formula [II] a and R b However, it is also preferable for them to bond with each other to form a benzene ring.

[0070] R in the above general formula [II] 1 From the viewpoint of olefin polymerization activity and copolymerizability, it is preferably a hydrogen atom, a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and is preferably a hydrogen atom, a methyl group, or a phenyl group, and is particularly preferably a hydrogen atom.

[0071] R in the above general formula [II] 2 From the viewpoint of olefin polymerization activity and copolymerizability, it is preferable that the group is a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and is particularly preferable to be a cyclohexyl group, a cyclododecyl group, or a phenyl group.

[0072] One preferred embodiment of the transition metal compound (A) of the above general formula [II] is: A 2 This is a nitrogen atom, Q is substituent R c A carbon atom having, S, substituent R b A carbon atom having, T is a substituent R a Examples of compounds represented by the following general formula [II-1] include carbon atoms having the following properties.

[0073] [ka]

[0074] In the above general formula [II-1], it is particularly preferable that m is 1. The following are specific examples of transition metal compounds (A) represented by the general formula [II] above, but transition metal compounds (A) are not limited to these. For the sake of explanation, transition metal compounds (A) are divided into two parts: the phosphinimide moiety (α) containing the metal M and the ligand moiety (β). First, Table 1 shows specific examples of the substructure of the phosphinimide moiety (α) containing the metal M.

[0075] [Table 1]

[0076] Next, Table 2 shows specific examples of the substructure of the ligand portion (β) in the general formula [II] above. In Table 2, ● indicates a bond site with a transition metal atom M.

[0077] [Table 2]

[0078] Particularly preferred transition metal compounds (A) represented by the general formula [II] include, for example, the compounds represented by the following formulas (a1), (a2), and (a5). According to the table above, the transition metal compound (a1) represented by the following formula consists of a phosphinimide moiety (α) containing metal M as α1 and a ligand moiety (β) as β1, with the case where metal moiety M is titanium, X is a methyl group, n is 2, and m is 1 being an example. The transition metal compound (a2) represented by the following formula consists of a phosphinimide moiety (α) containing metal M as α1 and a ligand moiety (β) as β2, with the case where metal moiety M is titanium, X is a methyl group, n is 2, and m is 1 being an example. The transition metal compound (a5) represented by the following formula consists of a phosphinimide moiety (α) containing metal M as α2 and a ligand moiety (β) as β2, with the case where metal moiety M is titanium, X is a methyl group, n is 2, and m is 1 being an example.

[0079] [ka]

[0080] A transition metal compound (A) in which Z in the above general formula [I] has the structure represented by the above formula [3] is represented by the following general formula [III].

[0081] [ka]

[0082] In the above general formula [III], A 3 This represents an oxygen atom, a sulfur atom, or a selenium atom, preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

[0083] R in the above general formula [III] d ~R g From the viewpoint of olefin polymerization activity and copolymerizability, it is preferable that the elements are hydrogen atoms, linear or branched or cyclic alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms, or aryl-substituted alkyl groups.

[0084] R in the above general formula [III] dIt is more preferably a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl-substituted alkyl group, and is particularly preferably a t-butyl group, a phenyl group, or a cumyl group.

[0085] R in the above general formula [III] e and R g It is preferably a hydrogen atom, a methyl group, or a phenyl group, and is particularly preferably a hydrogen atom. R in the above general formula [III] f It is particularly preferable that this is a hydrogen atom, a t-butyl group, or a cumyl group.

[0086] R in the above general formula [III] 1 From the viewpoint of olefin polymerization activity and copolymerizability, it is preferably a hydrogen atom, a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and is preferably a hydrogen atom, a methyl group, or a phenyl group, and is particularly preferably a hydrogen atom.

[0087] R in the above general formula [III] 2 From the viewpoint of olefin polymerization activity and copolymerizability, the group is preferably selected from linear or branched hydrocarbon groups having 1 to 20 carbon atoms, alicyclic hydrocarbon groups having 3 to 20 carbon atoms, or aromatic hydrocarbon groups having 6 to 20 carbon atoms, and in particular, t-butyl groups, phenyl groups, pt-butylphenyl groups, or pentafluorophenyl groups are preferred.

[0088] One preferred embodiment of the transition metal compound (A) of the above general formula [III] is A 3 Examples of compounds represented by the following general formula [III-1], in which the atom is an oxygen atom, include the following:

[0089] [ka]

[0090] In the above general formula [III-1], it is particularly preferable that m is 1. The following are specific examples of transition metal compounds (A) represented by the general formula [III] above, but transition metal compounds (A) are not limited to these. For the sake of explanation, transition metal compounds (A) are divided into two parts: the phosphinimide sub-part (α) containing metal M and the ligand sub-part (γ). Specific examples of the substructure of the phosphinimide (α) containing metal M are the same as those exemplified in Table 1 in the explanation of the general formula [II] above.

[0091] Table 3 shows specific examples of the substructure of the ligand (γ). In Table 3, ● indicates a bond site with the transition metal atom M.

[0092] [Table 3]

[0093] Particularly preferred transition metal compounds (A) represented by the general formula [III] include, for example, the compounds represented by the following formulas (a3) ​​and (a4). According to the table above, the transition metal compound (a3) ​​represented by the following formula consists of a phosphine-imide moiety (α) containing metal M (α1) and a ligand moiety (γ) (γ1), with the case where metal moiety M is titanium, X is a methyl group, n is 2, and m is 1 being an example. The transition metal compound (a4) represented by the following formula consists of a phosphine-imide moiety (α) containing metal M (α1) and a ligand moiety (γ) (γ2), with the case where metal moiety M is titanium, X is a methyl group, n is 2, and m is 1 being an example.

[0094] [ka]

[0095] (Method for producing transition metal compound (A)) Such a transition metal compound (A) can be produced, for example, as follows. First, the ligands (pyrroleimine ligands and phenoxyimine ligands represented by the following formulas) can be synthesized by previously reported methods (Patent Documents 2 and 3).

[0096] [ka] (In the formula, R 1 , R 2 , and Z are synonymous with these signs in equation [I].

[0097] Also, compounds containing transition metal atoms M (for example, Cl n+1 MN=PR 3 R 4 R 5 Compounds having the structure represented by the formula (wherein n, M, R 3 , R 4 , and R 5 These signs are synonymous with those in formula [I]. )) can be synthesized by known methods (Organometallics 2000, 19, 2994-3000).

[0098] Next, the ligand obtained can be reacted with a compound containing a transition metal atom M to synthesize the corresponding transition metal compound. Specifically, the ligand is dissolved in a solvent and mixed with a metal compound such as a metal alkylide, metal arylide, or metal arylalkylide at a temperature range of -78°C to room temperature, and the mixture is stirred for about 10 minutes to 48 hours at a temperature range of -78°C to room temperature or under reflux conditions. As for the solvent, any solvent common to such reactions can be used, but polar solvents such as ether and tetrahydrofuran (THF), and hydrocarbon solvents such as toluene are preferably used.

[0099] As a more specific example of a method for producing the transition metal compound (A), the method for producing the compound represented by the above formula (a1) is described below, as shown in the scheme below. Step 1 involves adding a methyllithium reagent or a methylglylinial reagent to a phosphineimide titanium trichloride complex to generate a phosphineimide titanium trimethyl complex, The compound represented by formula (a1) above can be produced by a method comprising step 1, step 2, in which a ligand component (pyrroleimine) is added to the phosphineimide titanium trimethyl complex obtained in step 1.

[0100] [ka]

[0101] Furthermore, the transition metal compound (A) obtained by this manufacturing method can be used directly in the polymerization of olefins as a reaction solution of the ligand and the metal compound without isolation.

[0102] [Catalyst for olefin polymerization] The olefin polymerization catalyst of the present invention comprises a transition metal compound (A) according to the present invention, and preferably further comprises at least one compound (B) selected from the group consisting of (B-1) organometallic compounds, (B-2) organoaluminum oxy compounds, and (B-3) compounds that react with the transition metal compound (A) to form an ion pair.

[0103] The olefin polymerization catalyst of the present invention may optionally further contain (C) a support and (D) an organic compound.

[0104] <Compound (B)> 《Organometallic compound (B-1)》 Examples of organometallic compounds (B-1) (hereinafter also referred to as "component (B-1)") include organoaluminum compounds represented by general formula (B-1a) (B-1a), complex alkylates of group 1 metals and aluminum represented by general formula (B-1b) (B-1b), and dialkyl compounds of group 2 or group 12 metals represented by general formula (B-1c) (B-1c), which are organometallic compounds of groups 1, 2 and 12 and 13.

[0105] (B-1a):R a m Al(OR b ) nH p X q In formula (B-1a), R a and R b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m satisfies 0 < m ≦ 3, n satisfies 0 ≦ n < 3, p satisfies 0 ≦ p < 3, q satisfies 0 ≦ q < 3, and m + n + p + q = 3. Examples of the organoaluminum compound (B-1a) include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, and tricycloalkylaluminum.

[0106] (B-1b): M 2 AlR a 4 In formula (B-1b), M 2 is Li, Na or K, and R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the complex alkylated product (B-1b) include LiAl(C2H5)4 and LiAl(C7H 15 )4.

[0107] (B-1c): R a R b M 3 In formula (B-1c), R a and R b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 3 is Mg, Zn or Cd. Examples of the compound (B-1c) include dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, ethyl-n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, di-n-butylzinc, and diphenylzinc.

[0108] Among the organometallic compounds (B-1), the organoaluminum compound (B-1a) is preferred. The organometallic compound (B-1) may be used alone or in combination of two or more.

[0109] Organoaluminum oxy compounds (B-2) As the organoaluminum oxy compound (B-2) (hereinafter also referred to as "component (B-2)"), conventionally known aluminoxanes can be used as is. Specifically, the following general formula [B2-1]

[0110] [ka] and / or the following general formula [B2-2]

[0111] [ka] Examples include compounds represented by the formula (wherein R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more), benzene-insoluble organoaluminum oxy compounds described in Japanese Patent Publication No. 2-78687 and Japanese Patent Publication No. 2-167305, and aluminoxanes having two or more alkyl groups described in Japanese Patent Publication No. 3-103407.

[0112] Furthermore, examples of organoaluminum oxy compounds (B-2) include modified methylaluminoxanes represented by the following general formula [B2-3].

[0113] [ka] (In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represent an integer greater than or equal to 2.)

[0114] These modified methylaluminoxanes are prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such compounds are commonly referred to as MMAOs. Such MMAOs can be prepared by the methods described in U.S. Patent No. 4,960,878 and U.S. Patent No. 5,041,584.

[0115] Furthermore, as organoaluminum oxy compounds (B-2), organoaluminum oxy compounds containing boron, represented by the following general formula [B2-4], can also be mentioned.

[0116] [ka] (In the formula, R c R represents a hydrocarbon group having 1 to 10 carbon atoms. d These may be identical or different from each other, and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0117] As the organoaluminum oxy compound (B-2), methylaluminoxane, which is readily available as a commercially available product, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred. Of these, MMAO with improved solubility in various solvents and storage stability is particularly preferred.

[0118] Compounds (B-3) that react with transition metal compounds (A) to form ion pairs. Compounds (B-3) that react with transition metal compounds (A) to form ion pairs (hereinafter also referred to as "ionic compounds (B-3)" or "component (B-3)") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Application Publication No. 3-179005, Japanese Patent Application Publication No. 3-179006, Japanese Patent Application Publication No. 3-207703, Japanese Patent Application Publication No. 3-207704, and U.S. Patent No. 5321106, etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

[0119] The ionic compound (B-3) is preferably a boron compound represented by the following general formula [B3-1].

[0120] [ka]

[0121] In the formula, R e+ H + Examples include carbenium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, and ferrocenium cations containing transition metals.

[0122] R f From R i These substituents may be the same or different from each other and are selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups, and are preferably substituted aryl groups.

[0123] Examples of boron compounds represented by the general formula [B3-1] include those described in paragraphs

[0196] to

[0217] of Japanese Patent Publication No. 2012-72365, among which triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are preferred. The ionic compound (B-3) may be used alone or as a mixture of two or more types.

[0124] (Carrier (C)) The carrier (C) is an inorganic or organic compound, in the form of a granular or particulate solid, and can be one that has been conventionally used in olefin polymerization using a transition metal compound and a carrier as a catalyst component, for example, one described in paragraphs

[0220] to

[0235] of Japanese Patent Application Publication No. 2012-72365.

[0125] (Organic compound component (D)) An organic compound component (D) may be used as a component of the olefin polymerization catalyst as needed. The organic compound component (D) is used to improve polymerization performance and the physical properties of the resulting polymer. Examples of organic compound components (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0126] [Method for producing olefin polymers] The method for producing olefin polymers according to the present invention is characterized by polymerizing olefins in the presence of the olefin polymerization catalyst described above.

[0127] In the method for producing olefin polymers of the present invention, one type of olefin may be polymerized to produce an olefin homopolymer, or two or more types of olefins may be copolymerized to produce an olefin copolymer. In this specification, polymerization and copolymerization are not particularly distinguished and are also referred to as "polymerization," and olefin homopolymers and olefin copolymers are also referred to as "olefin polymers."

[0128] In polymerization, the method of using each component constituting the olefin polymerization catalyst of the present invention and the order of addition to the polymerizer can be arbitrarily selected, but the following methods are examples. Hereinafter, the transition metal compound (A), compound (B), support (C), and organic compound component (D) will also be referred to as "components (A) to (D)," respectively.

[0129] (1) A method of adding component (A) alone to the polymerizer. (2) A method of adding component (A) and component (B) to a polymerizer in any order. (3) A method of adding a catalyst component in which component (A) is supported on component (C) and component (B) to a polymerizer in any order. (4) A method of adding a catalyst component in which component (B) is supported on component (C) and component (A) to a polymerizer in any order. (5) A method of adding a catalyst component, in which components (A) and (B) are supported on component (C), to a polymerizer.

[0130] In each of the above methods, component (D) may be added at any stage. In each of the above methods, at least two of the catalyst components may be in contact with each other beforehand. In the methods described in (4) and (5) above, in which component (B) is supported, unsupported component (B) may be added in any order as needed. In this case, component (B) may be the same or different. Furthermore, the solid catalyst component in which component (A) is supported on component (C), and the solid catalyst component in which component (A) and component (B) are supported on component (C), may have the olefin prepolymerized, and further catalyst components may be supported on the prepolymerized solid catalyst component.

[0131] In the present invention, the polymerization of olefins can be carried out by either liquid-phase polymerization methods such as dissolution polymerization or suspension polymerization, or by gas-phase polymerization methods. Specifically, examples of inert hydrocarbon media used in liquid-phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof. The olefin (monomer) itself to be subjected to (co)polymerization can also be used as the solvent.

[0132] When polymerizing olefins using the above-described olefin polymerization catalyst, the transition metal compound (A) is typically present in an amount of 1 × 10⁻¹⁶ per liter of reaction volume. -12 ~1 × 10 -2 Moles, preferably 1 × 10⁻⁶ -10 ~1 × 10 -3 It is used in quantities that equal moles.

[0133] The organometallic compound (B-1) is used in an amount such that the molar ratio [(B-1) / M] of the organometallic compound (B-1) to the total transition metal atoms (M) in the transition metal compound (A) is typically 0.01 to 100,000, preferably 0.05 to 50,000.

[0134] 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 all the transition metal atoms (M) in the transition metal compound (A) is usually from 10 to 500,000, preferably from 20 to 100,000.

[0135] The ionizable ionic compound (B-3) is used in an amount such that the molar ratio [(B-3) / M] of the ionizable ionic compound (B-3) to the transition metal atoms (M) in the transition metal compound (A) is usually from 1 to 10, preferably from 1 to 5.

[0136] Moreover, the polymerization temperature of the olefin using such a catalyst for olefin polymerization is usually in the range of -50 to +200°C, preferably 0 to 170°C. The polymerization pressure is usually from atmospheric pressure to 100 kgf / cm 2 -G, preferably from atmospheric pressure to 50 kgf / cm 2 -G, and the polymerization reaction can be carried out by any of the batch, semi-continuous, and continuous methods. Further, it is also possible to carry out the polymerization in two or more steps with different reaction conditions.

[0137] The molecular weight of the obtained olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Further, it can also be adjusted by the amount of the compound (B) used.

[0138] <Olefin> The method for producing an olefin polymer of the present invention is a method for polymerizing an olefin in the presence of the catalyst for olefin polymerization of the present invention. The olefin preferably includes an α-olefin having 2 to 30 carbon atoms.

[0139] As a preferred embodiment of the method for producing an olefin polymer of the present invention, a method for polymerizing or copolymerizing (preferably, polymerizing ethylene alone) an olefin including an α-olefin having 2 to 30 carbon atoms in the presence of the catalyst for olefin polymerization of the present invention, and One method involves copolymerizing an olefin containing ethylene, an α-olefin having 3 to 30 carbon atoms (preferably propylene), and a non-conjugated polyene in the presence of the olefin polymerization catalyst of the present invention.

[0140] In the method for producing olefin polymers according to the present invention, when copolymerization is carried out, the supply amount of each monomer is appropriately set according to the composition of the olefin polymer to be produced.

[0141] The aforementioned olefin is, Linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20, more preferably 2 to 10, such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; Examples of cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20, and more preferably 3 to 10, include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4:5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene. These may be used individually or in combination of two or more types.

[0142] Furthermore, examples of the aforementioned non-conjugated polyenes include: Cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene (ENB), 5-propyridene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene (VNB), 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, norbornadiene; Chain-like non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,7-octadiene, and 7-methyl-1,6-octadiene; Examples include trienes such as 2,3-diisopropylidene-5-norbornene and 4-ethylidene-8-methyl-1,7-nonadien.

[0143] 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, with 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), and 7-methyl-1,6-octadiene being more preferred.

[0144] These may be used individually or in combination of two or more types. When olefin polymerization is carried out in the presence of the transition metal compound (A) of the present invention, polymers with higher activity and higher molecular weight can be produced compared to when conventional transition metal compounds having a pyrrolimine ligand or a phenoxyimine ligand are used.

[0145] Although the reason is not entirely clear, the inventors of this invention posit that the transition metal compound (A) represented by the above general formula [I] is stabilized as a whole due to the presence of a phosphineimide group, and that the combination of two types of ligands (pyrroleimine ligand / phosphineimide group, or phenoxyimine ligand / phosphineimide group) makes the space around the transition metal atom M suitable for increasing the molecular weight of the polymer. [Examples]

[0146] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0147] [Measurement method] Transition metal compounds are 1The organism was identified by measuring its 1H-NMR spectrum (270 MHz, JEOL GSH-270 or 400 MHz, JEOL ECZ400S), FD-mass (FD-MS) spectrum (JEOL SX-102A), etc. The physical properties / characteristics of the ethylene / propylene / ethylidene norbornene copolymer were measured by the following method.

[0148] [Comonomer content] The comonomer content of ethylene / propylene / ethylidene norbornene copolymer is measured by FT-IR (Japan Spectroscopic Instruments FT-IR410 infrared spectrophotometer) or 1 The measurement was performed by 1H-NMR.

[0149] (FT-IR measurement method) For FT-IR, the polymer obtained in the examples was heated to 135°C, dissolved and stretched using a hot press, and then cooled under pressure at room temperature. The resulting film was used as the measurement sample, and the propylene structural unit content and ethylidene norbornene structural unit content were measured using a calibration curve.

[0150] The ethylene / propylene / ethylidene norbornene copolymer samples for calibration curve creation were prepared under the following conditions: 13 The comonomer content was determined by 13C-NMR measurement. A calibration curve was obtained by selecting the peak intensity ratios of two specific absorption wavenumbers that showed a linear or nearly linear relationship with the propylene structural unit content data and ethylidene norbornene structural unit content data of these samples, and then graphing these relationships.

[0151] ( 13 C-NMR measurement method) Using o-dichlorobenzene / benzene-d6 (4 / 1 {vol / vol%}) as the measurement solvent, under the measurement conditions of a measurement temperature of 120 °C, a spectral width of 250 ppm, a pulse repetition time of 5.5 seconds, and a pulse width of 4.7 μs (45° pulse) (100 MHz, JEOL ECX400P), or under the measurement conditions of a measurement temperature of 120 °C, a spectral width of 250 ppm, a pulse repetition time of 5.5 seconds, and a pulse width of 5.0 μs (45° pulse) (125 MHz, Bruker Biospin AVANCEIII cryo-500), 13 the 13C-NMR spectrum was measured, various signals were assigned by a conventional method, and the comonomer content was quantified based on the integral value of the signal intensity.

[0152] ( 1 (1H-NMR measurement) Using o-dichlorobenzene-d4 as the measurement solvent, or under the measurement conditions of a measurement temperature of 120 °C, a spectral width of 250 ppm, a pulse repetition time of 7.0 seconds, and a pulse width of 5.0 μs (45° pulse) (500 MHz, Bruker Biospin AVANCEIII cryo-500), 1 the 1H-NMR measurement was performed. The assignment of various signals such as methyl groups and ethylidene groups was carried out based on a conventional method, and the above-mentioned comonomer content was quantified based on the integrated value of the signal intensity. The physical properties / characteristics of the ethylene / 1-octene copolymer were measured by the following method.

[0153] [1-Octene content] The comonomer content of the physical properties of the ethylene / 1-octene copolymer was measured by FT-IR (FT-IR410 type infrared spectrophotometer manufactured by JASCO).

[0154] (FT-IR measurement method) For FT-IR, the polymer obtained in the example was heated to 135 °C, dissolved and stretched by a hot press, and then a film obtained by pressurized cooling at room temperature was used as the measurement sample, and the 1-octene structural unit content was measured using a calibration curve. The sample of the ethylene / 1-octene copolymer for preparing the calibration curve was under the same conditions as the above conditions 13The comonomer content was determined by 13C-NMR measurement.

[0155] [Weight-average molecular weight (Mw), molecular weight distribution (Mw / Mn) of polymers] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). The calculations were performed from molecular weight distribution curves obtained using either a Waters Alliance GPC 2000 or a Tosoh HLC-8321 GPC / HT gel permeation chromatograph (high-temperature size exclusion chromatograph). The operating conditions were as follows:

[0156] <Equipment and conditions used> Measurement equipment: Gel permeation chromatograph allianceGPC2000 (Waters Corporation) or gel permeation chromatograph HLC-8321 GPC / HT (Tosoh Corporation) Analysis software; Chromatography data system Empower (trademark, Waters Inc.) Column; TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2 (inner diameter 7.5mm x length 30cm, Tosoh Corporation) Mobile phase: o-dichlorobenzene [ODCB] (Wako Pure Chemical Industries, Special Grade Reagent) Detector; differential refractometer (built into the device) Column temperature: 140°C Flow rate; 1.0mL / min Injection volume; 400μL Sampling time interval: 1 second Sample concentration: 0.15% (w / v) Molecular weight calibration for monodisperse polystyrene (Tosoh Corporation) / molecular weight from 495 to 20.6 million

[0157] <Production of transition metal compounds> [Synthesis Example 1] (i) Synthesis of ligand A The target substance represented by the following formula (hereinafter also referred to as "ligand A") was synthesized using the method of synthesis example 7 described in Japanese Patent Publication No. 3945559.

[0158] [ka]

[0159] (ii) Synthesis of transition metal compound A A 300 mL three-necked flask equipped with a three-way stopcock and a magnetic stirrer was thoroughly purged with nitrogen. 370 mg (1.00 mmol) of Ti(N=P(t-Bu)3)Cl3 (synthesized by the method described in Organometallics 2000, 19, 2994-3000) was added to the flask, followed by 30 mL of toluene. While cooling the flask in a dry ice / methanol bath, 2.8 mL of 1.09 M methyllithium / diethyl ether solution (3.05 mmol of methyllithium) was gradually added. The mixture was then gradually heated to room temperature and stirred under a nitrogen atmosphere at room temperature for 2 hours. To this solution, while again cooling in a dry ice / methanol bath, 40 mL of toluene solution of ligand A (176 mg, 1.00 mmol) was added over 30 minutes, washing with 5 mL of toluene. The mixture was then gradually heated to room temperature and stirred under a nitrogen atmosphere at room temperature for 18 hours to obtain a slurry. The solvent was removed under reduced pressure, and the resulting solid was extracted with hexane. The filtrate was concentrated under reduced pressure, then dissolved in pentane and recrystallized at -10°C. By washing the precipitated solid with pentane, 224 mg of the target product represented by the following formula (hereinafter also referred to as "transition metal compound A") was obtained (blackish-yellow powder, yield 48%). 1 The target substance was identified by the results of 1H-NMR (CDCl3) measurement. The measurement results are shown below.

[0160] 1 H-NMR(270MHz,CDCl3)δ 0.68(6H,s),1.19-1.91(37H,m),3.31-3.39(1H,m),6.15-6.17(1H,m),6.53-6.55(1H,m),7.01(1H,s),8.00(1H,s)ppm

[0161] [ka]

[0162] [Synthesis Example 2] (i) Synthesis of ligand B The target substance represented by the following formula (hereinafter also referred to as "ligand B") was synthesized in the same manner as in Synthesis Example 7 described in Japanese Patent Publication No. 3945559.

[0163] [ka]

[0164] (ii) Synthesis of transition metal compound B A 100 mL three-necked flask equipped with a three-way stopcock and a magnetic stirrer was thoroughly purged with nitrogen. Ti(N=P(t-Bu)3)Cl3 370 mg (1.00 mmol) was placed in the flask, and 30 mL of toluene was added. While cooling the flask in a dry ice / methanol bath, 2.65 mL of 1.16 M methyllithium / diethyl ether solution (3.07 mmol of methyllithium) was gradually added, and the temperature was gradually increased to room temperature. The mixture was stirred at room temperature under a nitrogen atmosphere for 2 hours. To this solution, while cooling again in a dry ice / methanol bath, 10 mL of toluene solution of ligand B 260 mg (1.00 mmol) was added over 30 minutes, washing with 5 mL of toluene. After gradually increasing the temperature to room temperature, the mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours to obtain a slurry. The solvent was removed under reduced pressure, and the resulting solid was extracted with hexane. The filtrate was concentrated under reduced pressure, dissolved in pentane, and recrystallized at -10°C. By washing the precipitated solid with pentane, 193 mg (yellow powder, yield 35%) of the target product represented by the following formula (hereinafter also referred to as "transition metal compound B") was obtained. 1 The target substance was identified based on the results of 1H-NMR (CDCl3) measurements.

[0165] 1 H-NMR(270MHz,CDCl3)δ 0.71(6H,s),1.35-1.78(49H,m),3.69-3.74(1H,m),6.13-6.15(1H,m),6.52-6.54(1H,m),7.00(1H,s),7.98(1H,s)ppm

[0166] [ka]

[0167] [Comparative Example 1 of Synthesis] Synthesis of transition metal compound a The target product represented by the following formula (hereinafter also referred to as "transition metal compound a") was synthesized using the method of Synthesis Example 7 described in Japanese Patent Publication No. 3945559.

[0168] [ka]

[0169] [Synthesis Example 3] (i) Synthesis of ligand C The target substance represented by the following formula (hereinafter also referred to as "ligand C") was synthesized using the same method as the ligand synthesis example described in Japanese Patent Publication No. 11-315109.

[0170] [ka]

[0171] (ii) Synthesis of transition metal compound C A 300 mL three-necked flask equipped with a three-way stopcock and a magnetic stirrer was thoroughly purged with nitrogen. Ti(N=P(t-Bu)3)Cl3 370 mg (1.00 mmol) was placed in the flask, and 30 mL of toluene was added. While cooling the flask in a dry ice / methanol bath, 2.8 mL of 1.09 M methyllithium / diethyl ether solution (3.05 mmol of methyllithium) was gradually added, and the temperature was gradually increased to room temperature. The mixture was stirred at room temperature under a nitrogen atmosphere for 2 hours. To this solution, while cooling again in a dry ice / methanol bath, 40 mL of toluene solution of ligand C 309 mg (1.00 mmol) was added over 30 minutes, washing with 5 mL of toluene. After gradually increasing the temperature to room temperature, the mixture was stirred at room temperature under a nitrogen atmosphere for 20 hours to obtain a slurry. The solvent was removed under reduced pressure, and the resulting solid was extracted with hexane using Celite. The filtrate was concentrated under reduced pressure, and the resulting solid was washed with pentane to obtain 156 mg (yellow powder, yield 26%) of the target substance represented by the following formula (hereinafter also referred to as "transition metal compound C"). 1 The target substance was identified based on the results of 1H-NMR (CDCl3) measurements.

[0172] 1 H-NMR(270MHz,CDCl3)δ 0.42(6H,s),1.35(9H,s),1.48-1.53(36H,m),7.16-7.34(6H,m),7.59(1H,d,J=2.6Hz),8.51(1H,s)ppm

[0173] [ka]

[0174] [Synthesis Example 4] (i) Synthesis of ligand D The target substance represented by the following formula (hereinafter also referred to as "ligand D") was synthesized using the method of Synthesis Example 1 described in Japanese Patent Publication No. 2004-331965.

[0175] [ka]

[0176] (ii) Synthesis of transition metal compound D A 300 mL three-necked flask equipped with a three-way stopcock and a magnetic stirrer was thoroughly purged with nitrogen. Ti(N=P(t-Bu)3)Cl3 370 mg (1.00 mmol) was placed in the flask, and 30 mL of toluene was added. While cooling the flask in a dry ice / methanol bath, 3.00 mL of 1.03 M methyllithium / diethyl ether solution (3.09 mmol of methyllithium) was gradually added. The mixture was then gradually heated to room temperature and stirred under a nitrogen atmosphere at room temperature for 2 hours. To this solution, while cooling again in a dry ice / methanol bath, 30 mL of toluene solution of ligand D3 29 mg (1.00 mmol) was added over 30 minutes, washing with 5 mL of toluene. After gradually heating to room temperature, the mixture was stirred under a nitrogen atmosphere at room temperature for 17 hours to obtain a slurry. The solvent was removed under reduced pressure, and the resulting solid was extracted with pentane using Celite. The filtrate was concentrated under reduced pressure and washed with pentane to obtain a yellow powder. This yellow powder was dissolved in dichloromethane, hexane was added, and the solvent was concentrated to 1 / 10 of its original volume. The precipitated solid was washed with hexane. The obtained solid was dissolved in dichloromethane, added dropwise to hexane, and the solvent was concentrated to 1 / 5 of its original volume. The precipitated yellow powder was recovered by filtration and washed with hexane to obtain 116 mg (yellow powder, yield 19%) of the target product represented by the following formula (hereinafter also referred to as "transition metal compound D"). 1 The target substance was identified based on the results of 1H-NMR (CDCl3) measurements.

[0177] 1 H-NMR(270MHz,CDCl3)δ 0.38(6H,s),1.33-1.38(36H,m),7.19-7.44(9H,m),7.58-7.61(1H,m),7.74(2H,d,J=7.3Hz),8.55(1H,s)ppm

[0178] [ka]

[0179] [Comparison Example 2] Synthesis of transition metal compound c The target product represented by the following formula (hereinafter also referred to as "transition metal compound c") was synthesized by the method of Synthesis Example 15 described in Japanese Patent Publication No. 11-315109.

[0180] [ka]

[0181] [Comparative Example 3 of Synthesis] Synthesis of transition metal compound d The target product represented by the following formula (hereinafter also referred to as "transition metal compound d") was synthesized by the method of Synthesis Example 1 described in Japanese Patent Publication No. 2004-331965.

[0182] [ka]

[0183] [Synthesis Example 5] (i) Synthesis of phosphineimide compound EL A 100 mL three-necked flask equipped with a three-way stopcock and a magnetic stirrer was thoroughly purged with nitrogen. Then, 2055 mg (4.71 mmol) of Tris(1-adamantyl)phosphine, 50 mL of toluene, and 800 mg (6.94 mmol) of trimethylsilyl azide were added to the flask and heated under reflux for 16 hours. After returning to room temperature and removing the solvent under reduced pressure, the mixture was washed with hexane. The resulting solid was dried under reduced pressure to obtain 2353 mg (white powder, 95% yield) of the target product represented by the following formula (hereinafter also referred to as "phosphinimide compound EL"). 1 The target substance was identified based on the results of 1H-NMR (CDCl3) measurements.

[0184] 1 H-NMR(400MHz,CDCl3)δ 0.05(9H,s),1.67-2.21(45H,m)ppm

[0185] [ka]

[0186] (ii) Synthesis of phosphineimide titanium trichloride complex E-0 A 100 mL three-necked flask equipped with a three-way stopcock and a magnetic stirrer was thoroughly purged with nitrogen. Then, 2353 mg (4.49 mmol) of the phosphine imide compound EL obtained in the previous reaction and 45 mL of toluene were added to the flask. Subsequently, 4.5 mL (4.5 mmol of TiCl4) of 1.0 M TiCl4 / toluene solution was gradually added, and the mixture was heated under reflux for 17 hours. After cooling to room temperature, another 4.5 mL (4.5 mmol of TiCl4) of 1.0 M TiCl4 / toluene solution was added to this solution, and the mixture was heated under reflux for 22 hours. After cooling to room temperature, the solvent was removed under reduced pressure, and the mixture was washed with hexane. The resulting solid was added to a 100 mL three-necked flask equipped with a three-way stopcock and a magnetic stirrer, and 40 mL of toluene was added. A solution of 380 mg (2.00 mmol) of TiCl4 dissolved in 2 mL of toluene was added, and the mixture was heated under reflux for 18 hours. After cooling to room temperature, the solvent was removed under reduced pressure, and the mixture was washed twice with hexane. The obtained solid was dried under reduced pressure to obtain 2502 mg (yellow powder, yield 92%) of the target product represented by the following formula (hereinafter also referred to as "complex E-0"). 1 The target substance was identified based on the results of 1H-NMR (CDCl3) measurements.

[0187] 1 H-NMR(400MHz,CDCl3)δ 1.76-2.67(45H,m)ppm

[0188] [ka]

[0189] (iii) Synthesis of transition metal compound E After thoroughly purging a 100 mL Schlenk flask with nitrogen, 605 mg (1.0 mmol) of complex E-0 obtained in the previous reaction and 30 mL of toluene were added to the Schlenk flask. While cooling in a dry ice / methanol bath, 3.05 mL of 1.01 M methyllithium / diethyl ether solution (3.05 mmol of methyllithium) was gradually added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 3 hours. To this solution, while still cooling in a dry ice / methanol bath, a solution of 260 mg (1.0 mmol) of ligand B dissolved in 15 mL of toluene was added over 15 minutes while washing with 10 mL of toluene. After gradually raising the temperature to room temperature, the mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours to obtain a slurry. The solvent was removed under reduced pressure, and the resulting solid was extracted with hexane and filtered by Celite. The concentrate of the filtrate was dissolved in hexane and recrystallized at -35°C. The precipitated solid was washed with hexane and then dried under reduced pressure to obtain 228 mg (yellow powder, yield 36%) of the target product represented by the following formula (hereinafter also referred to as "transition metal compound E"). 1 The target substance was identified based on the results of 1H-NMR (CDCl3) measurements.

[0190] 1 H-NMR(400MHz,CDCl3)δ 0.73(6H,s),1.28-2.40(67H,m),3.74-3.80(1H,m),6.13-6.14(1H,m),6.52-6.53(1H,m),7.02(1H,s),7.98(1H,s)ppm

[0191] [ka]

[0192] <Production of ethylene polymers> [Polymerization Example 1-1] A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 250 mL of toluene, and the liquid and gas phases were saturated with ethylene at a rate of 100 L / hr. Then, 0.5 mmol of triisobutylaluminum (in terms of aluminum atoms), 0.001 mmol of transition metal compound A, and subsequently 0.004 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were added to initiate polymerization. Ethylene was continuously supplied at a rate of 100 L / hr, and polymerization was carried out at atmospheric pressure and 50°C for 5 minutes. Polymerization was then stopped by adding a small amount of methanol. After polymerization, the reaction mixture was added to 750 mL of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 80°C for 10 hours to obtain 1.555 g of ethylene polymer. The physical properties of the obtained polymer are shown in Table 4.

[0193] [Polymerization Examples 1-2] Polymerization was carried out in the same manner as in Polymerization Example 1-1, except that 0.001 mmol of transition metal compound B was used instead of transition metal compound A, and 1.975 g of ethylene polymer was obtained. The physical properties of the polymer are shown in Table 4.

[0194] [Polymerization Examples 1-3] Polymerization was carried out in the same manner as in Polymerization Example 1-1, except that 0.001 mmol of transition metal compound E was used instead of transition metal compound A, and 0.610 g of ethylene polymer was obtained. The physical properties of the polymer are shown in Table 4.

[0195] [Polymerization Comparative Example 1-1] Polymerization was carried out in the same manner as in Polymerization Example 1-1, except that 0.001 mmol of transition metal compound a was used instead of transition metal compound A, and 0.067 g of ethylene polymer was obtained. The physical properties of the obtained polymer are shown in Table 4.

[0196] [Table 4]

[0197] [Polymerization Example 2-1] Polymerization was carried out in the same manner as in Polymerization Example 1-1, except that 0.001 mmol of transition metal compound C was used instead of transition metal compound A, and 0.724 g of ethylene polymer was obtained. The physical properties of the polymer are shown in Table 5.

[0198] [Polymerization Example 2-2] Polymerization was carried out in the same manner as in Polymerization Example 2-1, except that 0.001 mmol of transition metal compound D was used instead of transition metal compound C, and 1.285 g of ethylene polymer was obtained. The physical properties of the polymer are shown in Table 5.

[0199] [Polymerization Comparative Example 2-1] Polymerization was carried out in the same manner as in Polymerization Example 2-1, except that 0.001 mmol of transition metal compound c was used instead of transition metal compound C, and 0.051 g of ethylene polymer was obtained. The physical properties of the polymer are shown in Table 5.

[0200] [Polymerization Comparative Example 2-2] Polymerization was carried out in the same manner as in Polymerization Example 2-1, except that 0.002 mmol of transition metal compound d was used instead of transition metal compound C, 0.1 mmol of triisobutylaluminum (calculated on an aluminum atom basis), and 0.008 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate was used, yielding 0.666 g of ethylene polymer. The physical properties of the polymer are shown in Table 5.

[0201] [Table 5]

[0202] <Production of ethylene / 1-octene copolymer> [Polymerization Example 3-1] A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 250 mL of toluene, and the liquid and gas phases were saturated with ethylene at a rate of 100 L / hr. Then, 10 mL of 1-octene, 1.0 mmol of triisobutylaluminum (calculated as aluminum atoms), 0.002 mmol of transition metal compound A, and subsequently 0.008 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were added to initiate polymerization. Ethylene was continuously supplied at a rate of 100 L / hr, and polymerization was carried out at atmospheric pressure and 60°C for 10 minutes. Polymerization was then stopped by adding a small amount of methanol. After polymerization, the reaction mixture was added to a 1000 mL mixed solvent of methanol and acetone (2:1) containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the solvent, the polymer was dried under reduced pressure at 120°C for 10 hours to obtain 1.100 g of ethylene / 1-octene copolymer. The physical properties of the obtained polymer are shown in Table 6.

[0203] [Polymerization Example 3-2] Polymerization was carried out in the same manner as in Polymerization Example 3-1, except that 0.002 mmol of transition metal compound B was used instead of transition metal compound A, yielding 0.925 g of ethylene / 1-octene copolymer. The physical properties of the polymer are shown in Table 6.

[0204] [Polymerization Comparative Example 3-1] Polymerization was carried out in the same manner as in Polymerization Example 3-1, except that 0.005 mmol of transition metal compound a and 0.02 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were used instead of transition metal compound A, yielding 0.124 g of ethylene / 1-octene copolymer. The physical properties of the polymer are shown in Table 6. The 1-octene content was less than 1.5%, which is below the detection limit of the IR calibration curve.

[0205] [Table 6]

[0206] <Production of ethylene / propylene / ethylidene norbornene copolymer> [Polymerization Example 4-1] In a 2 L stainless steel autoclave that had been thoroughly purged with nitrogen, 1030 mL of hexane and 12 mL of 5-ethylidene-2-norbornene (hereinafter also referred to as "ENB") were charged. After raising the temperature of the system to 95°C, propylene was charged at a partial pressure of 0.9 MPa-G. Subsequently, the total pressure was increased to 1.6 MPa-G by supplying ethylene. Next, 0.3 mmol of triisobutylaluminum, 0.0002 mmol of the transition metal compound A obtained above as the main catalyst, and 0.0008 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate as a co-catalyst were injected under nitrogen pressure, and polymerization was started by increasing the stirring speed to 250 rpm. Subsequently, the total pressure was maintained at 1.6 MPa-G by continuously supplying only ethylene, and polymerization was carried out at 95°C for 15 minutes. After stopping the polymerization by adding a small amount of ethanol to the system, unreacted ethylene was purged. The obtained polymer solution was added to a large excess methanol / acetone mixture to precipitate the polymer. The polymer was recovered by filtration and dried overnight under reduced pressure at 120°C to produce an ethylene / propylene / ethylidene norbornene copolymer. The analytical results of the obtained polymer are shown in Table 7.

[0207] [Polymerization Example 4-2] Polymerization was carried out in the same manner as in Polymerization Example 4-1, except that 0.0002 mmol of transition metal compound B was used instead of transition metal compound A. The analysis results of the obtained polymer are shown in Table 7.

[0208] [Polymerization Example 4-3] Polymerization was carried out in the same manner as in Polymerization Example 4-1, except that 0.0004 mmol of transition metal compound E was used instead of transition metal compound A, and 0.0016 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate was used as a co-catalyst. The analysis results of the obtained polymer are shown in Table 7.

[0209] [Polymerization Comparative Example 4-1] Polymerization was carried out in the same manner as in Polymerization Example 4-1, except that 0.0025 mmol of transition metal compound a and 0.01 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were used instead of transition metal compound A. The analysis results of the obtained polymer are shown in Table 7.

[0210] [Table 7]

Claims

1. A transition metal compound (A) represented by the following general formula [I]. 【Chemistry 1】 [In formula [I], M represents a transition metal atom from groups 3 to 11 of the periodic table. m represents an integer from 1 to 6. Z represents a structure that can be expressed by the following formulas [2] or [3], 【Chemistry 2】 (In equations [2] and [3], ○ represents R in general equation [I]) 1 The symbol (●) indicates the bond point with the carbon atom to which it is bonded, and the black (●) indicates the bond point with the transition metal atom M. A 2 This represents a nitrogen atom. A 3 This represents an oxygen atom. Q is a substituent R c A carbon atom having (-(R c ) shows C = ), S is a substituent R b A carbon atom having (-(R b ) shows C = ), T is a carbon atom having a substituent R a (-(R a )C=), and R a ~R g , R 1 and R 2 These may be the same or different from each other, and represent a hydrogen atom, a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, R a ~R c , R 1 and R 2 Adjacent groups among them may be linked to each other to form an aliphatic ring or an aromatic ring. n is a number that satisfies the valence of M, X represents a hydrogen atom, a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms. If n is 2 or more, the multiple groups represented by X may be the same or different from each other. R 3 ~R 5 These elements may be identical or different from each other, and are linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms.

2. The transition metal compound (A) according to claim 1, wherein M in the general formula [I] is a transition metal atom of group 4 or 5 of the periodic table.

3. The transition metal compound (A) according to claim 2, wherein M in the general formula [I] is a titanium atom.

4. A transition metal compound (A) according to any one of claims 1 to 3, represented by the following general formula [II]. 【Transformation 3】

5. R in the above general formula [II] a ~R c The transition metal compound (A) according to claim 4, wherein the A is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

6. The transition metal compound according to any one of claims 1 to 3, represented by the following general formula [III] (A). 【Chemistry 4】

7. R in the above general formula [III] d ~R g The transition metal compound (A) according to claim 6, wherein the A is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

8. A transition metal compound (A) according to any one of claims 1 to 7, (B-1) organometallic compound, (B-2) Organoaluminum oxy compounds, and (B-3) Compounds that react with the transition metal compound (A) to form ion pairs At least one compound (B) selected from the group consisting of and A catalyst for olefin polymerization containing [specific component].

9. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst described in claim 8.

10. The method for producing an olefin polymer according to claim 9, wherein the olefin comprises an α-olefin having 2 to 30 carbon atoms.

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