Group 13 element-containing compound, catalyst for olefin polymerization, and method for producing olefin polymer

Abstract

To provide a new compound containing the group XIII element.SOLUTION: A compound containing the group XIII element is represented by the following formula (A). [α]γ+{β}γ- (A) [γ is an integer of 2-100. [α]γ+ is a cation represented by the following formula (α). {β}γ- is one or two or more anions (β) having the total valence of γ valence. At least one anion (β) is an anion represented by the following formula (β'-I) or the like. (R1 is a hydrocarbon group or the like, R2 is a hydrogen atom, a hydrocarbon group or the like). [M'(R3)4]- (β'-I) (M' is an atom of the group XIII element, R3 is an aryl group having a substituent at the ortho position)].SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a Group 13 element-containing compound, more particularly a Group 13 element-containing compound useful as a cocatalyst in an olefin polymerization catalyst, and an olefin polymerization catalyst using the same and a method for producing an olefin polymer.

Background Art

[0002] In the polymerization of olefins, borate compounds are widely used as cocatalysts for activating transition metal complexes as main catalysts. Although these borate compounds have high cocatalyst performance in solution polymerization, they are difficult to be immobilized on carriers such as silica gel, so it has been difficult to apply them to slurry polymerization and gas-phase polymerization.

[0003] In order to solve such problems, many techniques have been reported in which a specific functional group is introduced into the cation or anion of a borate compound and the borate compound is immobilized by reacting it with a functional group such as a silanol group in a carrier (for example, Patent Documents 1 to 7).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the conventional borate compounds still had room for further improvement from the viewpoints of catalyst immobilization and activation. In view of such prior art, the present invention aims to provide a novel Group 13 element-containing compound that is useful as a cocatalyst in an olefin polymerization catalyst and preferably also excellent in catalyst immobilization and activation performance, an olefin polymerization catalyst using the same, and a method for producing an olefin polymerization.

Means for Solving the Problems

[0006] The present invention relates to, for example, the following [1] to [5]. [1] A Group 13 element-containing compound (A) represented by the following general formula (A). [α] γ+ {β} γ- …(A) (In the general formula (A), γ is an integer of 2 to 100.) [α] γ+ is a cation represented by the following general formula (α).

[0007]

Chemical Formula

[0008] {β} γ- represents one or more anions (β), and the total valence of the anions (β) is γ valence. The anion (β) is an anion (β') represented by the following general formula (β'-I), (β'-II) or (β'-III), or an anion (β") other than the anion (β'), and at least one of the anions (β) is the anion (β'). When a plurality of the anions (β) are present, they may be the same as or different from each other.

[0009] [Chemical formula] (In the general formulas (β'-I), (β'-II) and (β'-III), M' is an atom of a Group 13 element. A plurality of R 3 are each independently an aryl group having 6 to 20 carbon atoms represented by the following general formula (R3), and a plurality of R 3 may be bonded to each other to form a ring.

[0010] [Chemical formula] (In the general formula (R3), * is a bond to M'. A plurality of R are each independently a substituent (r3) selected from the group consisting of a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heteroatom-containing hydrocarbon group and a hydrocarbon-substituted silyl group, or a hydrogen atom, and at least one of the R adjacent to * is the substituent (r3). When a plurality of the substituents (r3) are present, the plurality of substituents (r3) may be the same as or different from each other, and may be bonded to each other to form an aromatic ring which may have a substituent.)

[0011] A plurality of R 4 are each independently an arylene group having 6 to 20 carbon atoms represented by the following general formula (R4), (R5) or (R6), and a plurality of R4 They may be bonded to each other to form a ring, and R 4 is R 3 and may be bonded to form a ring.

[0012] [Chemical formula] (In general formulas (R4), (R5), and (R6), * represents a bond to M'. R has the same meaning as R in the general formula (R3).))

[0013] [2] In the general formulas (β'-I), (β'-II), and (β'-III), M' is a boron or aluminum atom, and all Rs 3 each independently have, as at least one of the Rs adjacent to * in the general formula (R3), a halogen atom or a halogen atom-containing hydrocarbon group, the Group 13 element-containing compound (A) of [1] above. [2A] A cocatalyst for olefin polymerization comprising the Group 13 element-containing compound (A) of [1] or [2] above.

[0014] [3] A catalyst for olefin polymerization comprising the Group 13 element-containing compound (A) of [1] or [2] above or the cocatalyst for olefin polymerization of [2A] above, and a transition metal complex (B).

[0015] [4] The catalyst for olefin polymerization of [3] above, further comprising a porous material (S). [5] A method for producing an olefin polymer by polymerizing an olefin in the presence of the catalyst for olefin polymerization of [3] or [4] above. [Advantages of the Invention]

[0016] According to the present invention, there are provided a novel Group 13 element-containing compound useful as a cocatalyst in an olefin polymerization catalyst, preferably also excellent in catalyst immobilization and activation performance, an olefin polymerization catalyst using the same, and a method for producing an olefin polymerization.

Embodiments for Carrying Out the Invention

[0017] Hereinafter, the present invention will be described in more detail. [Group 13 element-containing compound (A)] The Group 13 element-containing compound (A) according to the present invention (hereinafter, also simply referred to as "compound (A)" or "component (A)") is characterized by being represented by the following general formula (A).

[0018] [α] γ+ {β} γ- …(A) 〔In the general formula (A), γ is an integer of 2 to 100. [α] γ+ is a predetermined cation. {β} γ- is one or more predetermined anions having a total valence of γ valences.〕

[0019] <γ> In the general formula (A), γ is an integer of 2 to 100, and preferably an integer of 2 to 20. γ may be, for example, 2, or may be an integer of 3 to 20. <[α] γ+ > In the general formula (A), [α] γ+ is a cation represented by the following general formula (α).

[0020]

Chemical formula

[0021] 《γ》 γ is as described above. 《R 1 》 In general formula (α), R 1 is a hydrocarbon group having 1 to 100 carbon atoms or a heteroatom-containing hydrocarbon group.

[0022] Hydrocarbon group: Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The alicyclic hydrocarbon group may contain an aliphatic hydrocarbon moiety, and the aromatic hydrocarbon group may contain an aliphatic hydrocarbon moiety and / or an alicyclic hydrocarbon moiety.

[0023] The hydrocarbon group may or may not have an unsaturated bond. The aliphatic hydrocarbon group may be linear or may have a branch. Examples of the saturated aliphatic hydrocarbon group include a methylene group and an alkylene group (e.g., an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a 2-methylpropylene group, a pentamethylene group, a 2-methylbutylene group, a 2-ethylpropylene group, a hexamethylene group, a 2-ethylbutylene group, a heptamethylene group, a 2-ethylpentylene group, a 2-methylhexylene group, an octamethylene group, a 2-ethylhexylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a tetradecamethylene group, a hexadecamethylene group, an octadecamethylene group, a 2-ethyloctadecene group, an icosene group).

[0024] The number of carbon atoms of the alkylene group is 2 to 100, preferably 2 to 40, more preferably 2 to 20, and even more preferably 2 to 6. Examples of the unsaturated aliphatic hydrocarbon group include those in which some or all of the carbon-carbon single bonds in the above-described alkylene group are replaced with double bonds, for example, groups represented by -CH=CH-, -CH2CH=CH-, -CH2CH2CH=CH-, -CH2CH=CHCH2-, -CH2C(CH3)=CH-, -CH2-C(=CH2)-CH2-, -CH(CH2CH3)-CH2CH2CH=CH-, -CH2CH2CH=CH-CH=CH-, -CH2CH=CH-CH(CH3)-CH=CH-CH2-.

[0025] The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples thereof include a cyclopropylene group, a cyclobutane-1,2-diyl group, a cyclobutane-1,3-diyl group, a cyclopentane-1,2-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group, a cyclohexane-1,4-diyl group, a 3-cyclohexene-1,2-diyl group, a 2,5-cyclohexadiene-1,4-diyl group, a cycloheptane-1,4-diyl group, a cyclooctane-1,4-diyl group, a spiro[3,4]octane-2,7-diyl group, and a spiro[4,5]deca-1,6-diene-3,9-diyl group. Further, examples of the group having an aliphatic hydrocarbon group include a group represented by the following formula.

[0026]

Chemical formula

[0027] The number of carbon atoms of the alicyclic hydrocarbon group is 3 to 100, preferably 3 to 40, more preferably 3 to 20, and still more preferably 3 to 6. The aromatic hydrocarbon group may be monocyclic or polycyclic. Examples thereof include an o-phenylene group, a p-phenylene group, an m-phenylene group, a 1,5-naphthylene group, a 2,6-naphthylene group, a 2,7-naphthylene group, a biphenyl-4,4'-diyl group, a 1,5-anthrylene group, a 2,6-anthrylene group, an o-terphenyl-4,4'-diyl group, a p-terphenyl-4,4"-diyl group, an m-terphenyl-4,4'-diyl group, a 2,7-phenanthrylene group, and a 1,6-pyrenylene group. Further, examples of the group having an aliphatic hydrocarbon group include a group represented by the following formula.

[0028] [Chemical formula] The number of carbon atoms of the aromatic hydrocarbon group is 6 to 100, preferably 6 to 40, more preferably 6 to 20, and even more preferably 6.

[0029] Heteroatom-containing hydrocarbon group: One example of the heteroatom-containing hydrocarbon group is a group in which some or all of the hydrogen atoms in the hydrocarbon group are replaced with a heteroatom-containing group.

[0030] Examples of the heteroatom-containing group include a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, and a sulfur-containing group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0031] Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, a pentafluoroethyl group, a pentachloroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, a 3,3,3-trifluoropropyl group, a nonafluorobutyl group, a nonachlorobutyl group, a 4,4,4-trifluorobutyl group, a dodecafluorohexyl group, 6,6,6-trifluorohexyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, iodophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentaiodophenyl group, bis(trimethylsilyl)trifluorophenyl group, bis(triisopropylsilyl)trifluorophenyl group, bis(tert-butyldimethylsilyl)trifluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, bis(trifluoromethyl)fluorophenyl group, bis(trifluoromethyl)trifluorophenyl group, pentafluorobenzyl group, trifluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, perfluorobiphenyl-2-yl group, perfluorobiphenyl-3-yl group, di-tert-butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoromethylenedioxyphenyl group, bistrifluoromethylphenyliminomethyl group, trifluoromethylthio group, α-perfluoronaphthyl group, β-perfluoronaphthyl group may be mentioned.,

[0032] Among the halogen-containing groups, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a pentafluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group, a bistrifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a difluoromethylenedioxyphenyl group, a trifluoromethylthio group are preferable, and a trifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group are more preferable.

[0033] Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a cyclopentadienyldimethylsilyl group, a di-n-butyl(cyclopentadienyl)silyl group, a cyclopentadienyldiphenylsilyl group, an indenylmethylsilyl group, a di-n-butyl(indenyl)silyl group, an indenylphenylsilyl group, a fluorenyldimethylsilyl group, a di-n-butyl(fluorenyl)silyl group, a fluorenyldiphenylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-iso-propylsilylphenyl group, a 4-tert-butyldiphenylsilylphenyl group, a 4-triphenylsilylphenyl group, a 4-tris(trimethylsilyl)silylphenyl group, a 3,5-bis(trimethylsilyl)phenyl group.

[0034] Among the silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl group, indenyl dimethylsilyl group, indenyl diphenylsilyl group, fluorenyl dimethylsilyl group, fluorenyl diphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-triphenylsilylphenyl group, 3,5-bis(trimethylsilyl)phenyl group and the like are preferable, and trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 3,5-bis(trimethylsilyl)phenyl group are more preferable.

[0035] Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a methallyloxy group, a prenyl oxy group, an octyloxy group, a tert-octyloxy group, a decyloxy group, a dodecyloxy group, an octadecyloxy group, a benzyloxy group, a methoxymethoxy group, a methoxyethoxy group, a phenoxy group, a naphthoxy group, a tolyloxy group, an iso-propylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, an iso-propoxyphenoxy group, an allyloxyphenoxy group, a biphenyloxy group, a binaphthyloxy group, a methoxymethyl group, an allyloxymethyl group, a benzyloxymethyl group, a phenoxymethyl group, a methoxyethyl group, an allyloxyethyl group, a benzyloxyethyl group, a phenoxyethyl group, a methoxypropyl group, an allyloxypropyl group, a benzyloxypropyl group, a phenoxypropyl group, a methoxyvinyl group, an allyloxyvinyl group, a benzyloxyvinyl group, a phenoxyvinyl group, a methoxyallyl group, an allyloxyallyl group, a benzyloxyallyl group, a phenoxyallyl group, a dimethoxymethyl group, a di-iso-propoxymethyl group, a dioxolanyl group, a tetramethyldioxolanyl group, a dioxanyl group, a methoxyphenyl group, an iso-propoxyphenyl group, an allyloxyphenyl group, a phenoxyphenyl group, a methylenedioxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a tetrahydrofuryl group, a pyranyl group, a tetrahydropyranyl group, a furofuryl group, a benzofuryl group, and a dibenzofuryl group.

[0036] Among these oxygen-containing groups, methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyl-oxy group, octyloxy group, tert-octyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, benzyloxy group, phenoxy group, naphthoxy group, toluoyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-(2-ethoxyethoxy)ethoxy group, methoxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydropyranyl group, furofuryl group, benzofuryl group, dibenzofuryl group, etc. are preferable, and methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, benzofuryl group, dibenzofuryl group are more preferable.

[0037] Examples of the nitrogen-containing group include an amino group, dimethylamino group, diethylamino group, allylamino group, diallylamino group, N,N-dihexylamino group, N,N-didecylamino group, N,N-didodecylamino group, N,N-dioctadecylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, azepinyl group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinylethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidinylvinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyldi julolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenylpyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, isoquinolyl group, tetrahydro-isoquinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group.

[0038] Among the nitrogen-containing groups, amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyldujolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, etc. are preferable, and amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyldujolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, imidazolyl group are more preferable.

[0039] Examples of the sulfur-containing group include a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group, a phenylthiomethyl group, a naphthylthiomethyl group, a methylthioethyl group, a benzylthioethyl group, a phenylthioethyl group, a naphthylthioethyl group, a methylthiovinyl group, a benzylthiovinyl group, a phenylthiovinyl group, a naphthylthiovinyl group, a methylthiopropyl group, a benzylthiopropyl group, a phenylthiopropyl group, a naphthylthiopropyl group, a methylthioallyl group, a benzylthioallyl group, a phenylthioallyl group, a naphthylthioallyl group, a mercaptophenyl group, a methylthiophenyl group, a thienylphenyl group, a methylthienylphenyl group, a benzothienylphenyl group, a dibenzothienylphenyl group, a benzodithienylphenyl group, a thienyl group, a tetrahydrothienyl group, a methylthienyl group, a thienofuryl group, a thienothienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a dithiolanyl group, a dithianyl group, an oxathiolanyl group, an oxathianyl group, a thiazolyl group, a benzothiazolyl group, and a thiazolidinyl group.

[0040] Among the sulfur-containing groups, a thienyl group, a methylthienyl group, a thienofuryl group, a thienothienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a thiazolyl group, and a benzothiazolyl group are preferable.

[0041] Other examples of the heteroatom-containing hydrocarbon group include a group in which a part of the methylene group in the hydrocarbon group is replaced with a structure represented by -CO-, -CH(OH)-, -NR- (R is a hydrogen atom or a hydrocarbon group (the number of carbon atoms is, for example, 1 to 4)), -O-, -S-, or -SO2-, and a group in which a part of the methine group in the hydrocarbon group is replaced with a nitrogen atom or a structure represented by ≡SiH.

[0042] As another example of the heteroatom-containing hydrocarbon group, there is further a residue obtained by removing two hydrogen atoms from a polymer having a heteroatom. Examples of such polymers include polyaniline, polypyrrole, polyacrylonitrile, polyethyleneimine, polyamide, and the like. Protons may be coordinately bonded to part or all of the heteroatoms (preferably nitrogen atoms) contained in the heteroatom-containing hydrocarbon group within a range where γ is within the above range.

[0043] 《R 2 》 In general formula (α), the four Rs 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 100 carbon atoms, or a heteroatom-containing hydrocarbon group.

[0044] Hydrocarbon group: Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The alicyclic hydrocarbon group may contain an aliphatic hydrocarbon moiety, and the aromatic hydrocarbon group may contain an aliphatic hydrocarbon moiety and / or an alicyclic hydrocarbon moiety.

[0045] The hydrocarbon group may or may not have an unsaturated bond. The aliphatic hydrocarbon group may be linear or branched. Specific examples of the hydrocarbon group include Linear or branched alkyl groups having 1 to 40 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-icosyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group, tert-pentyl group (1,1-dimethylpropyl group), sialyl group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group (2-methylpentan-2-yl group), 3-methylpentan-2-yl group, 4-methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, 3,3-dimethylbutan-2-yl group, hexan-3-yl group, 2-methylpentan-3-yl group, heptan-4-yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,3,3-trimethylbutan-2-yl group, 2,4,4-trimethylpentan-2-yl group; A vinyl group, an allyl group, a propenyl group, an iso-propenyl group, an arylenyl group, a but-3-en-1-yl group, a crotyl group, a but-3-en-2-yl group, a methallyl group, a buta-1,3-dienyl group, a penta-4-en-1-yl group, a penta-3-en-1-yl group, a penta-2-en-1-yl group, an iso-pentenyl group, a 2-methylbut-3-en-1-yl group, a penta-4-en-2-yl group, a prenyl group, a 2-methyl-but-2-en-1-yl group, a penta-3-en-2-yl group, a 2-methyl-but-3-en-2-yl group, a penta-1-en-3-yl group, a penta-2,4-dien-1-yl group, a penta-1,3-dien-1-yl group, a penta-1,4-dien-3-yl group, an iso-prenyl group (2-methyl-but-1,3-dien-1-yl group), a penta-2,4-dien-2-yl group, a hexa-5-en-1-yl group, a hexa-4-en-1-yl group, a hexa-3-en-1-yl group, a hexa-2-en-1-yl group, a 4-methyl-penta-4-en-1-yl group, a 3-methyl-penta-4-en-1-yl group, a 2-methyl-penta-4-en-1-yl group, a hexa-5-en-2-yl group, a 4-methyl-penta-3-en-1-yl group, a 3-methyl-penta-3-en-1-yl group, a 2,3-dimethyl-but-2-en-1-yl group, a 2-methylpenta-4-en-2-yl group, a 3-ethylpenta-1-en-3-yl group, a hexa-3,5-dien-1-yl group, a hexa-2,4-dien-1-yl group, a 4-methylpenta-1,3-dien-1-yl group, a 2,3-dimethyl-but-1,3-dien-1-yl group, a hexa-1,3,5-trien-1-yl group, a 2-(cyclopentadienyl)propan-2-yl group, a 2-(cyclopentadienyl)ethyl group, or other linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms; An alkynyl group or an unsaturated triple bond-containing group having 2 to 40 carbon atoms in a linear or branched form, such as an ethynyl group, a prop-2-yn-1-yl group, a propargyl group, a but-1-yn-1-yl group, a but-2-yn-1-yl group, a but-3-yn-1-yl group, a pent-1-yn-1-yl group, a pent-2-yn-1-yl group, a pent-3-yn-1-yl group, a pent-4-yn-1-yl group, a 3-methyl-but-1-yn-1-yl group, a pent-3-yn-2-yl group, a 2-methyl-but-3-yn-1-yl group, a pent-4-yn-2-yl group, a hex-1-yn-1-yl group, a 3,3-dimethyl-but-1-yn-1-yl group, a 2-methyl-pent-3-yn-2-yl group, a 2,2-dimethyl-but-3-yn-1-yl group, a hex-4-yn-1-yl group, a hex-5-yn-1-yl group; benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl group (2-phenylpropan-2-yl group), 2-(4-methylphenyl)propan-2-yl group, 2-(3,5-dimethylphenyl)propan-2-yl group, 2-(4-tert-butylphenyl)propan-2-yl group, 2-(3,5-di-tert-butylphenyl)propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenylpropan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3-en-1-yl group, 1,1,2-triphenylethyl group, trityl group (triphenylmethyl group), tri-(4-methylphenyl)methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2-(2-methylphenyl)ethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,Aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, such as 5-di-tert-butylphenyl)ethyl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group (3-phenylallyl group), neophyl group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(tetrahydro-1-indacenyl)propan-2-yl group, (tetrahydro-1-indacenyl)diphenylmethyl group, 2-(tetrahydro-1-indacenyl)ethyl group, 2-(1-benzindenyl)propan-2-yl group, (1-benzindenyl)diphenylmethyl group, 2-(1-benzindenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, 2-(1-azulenyl)propan-2-yl group, (1-azulenyl)diphenylmethyl group, 2-(1-azulenyl)ethyl group;, Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, cyclooctatrienenyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octan-1-yl group, bicyclo[2.2.2]octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl), 1-(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl), 1-(3,5,7-triphenyladamantyl), pentalenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, azulienyl group and other cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms; Aromatic substituents having 6 to 40 carbon atoms such as phenyl group, tolyl group (o-tolyl group, m-tolyl group, p-tolyl group), xylyl group (2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group), mesityl group, cumenyl group, duryl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, (buta-3-en-1-yl)phenyl group, (buta-2-en-1-yl)phenyl group, methallylphenyl group, prenylphenyl group, 4-adamantylphenyl group, 3,5-di-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthylenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, etc. can be mentioned.

[0046] Among the linear or branched alkyl groups having 1 to 40 carbon atoms, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-octadecyl group, an iso-propyl group, a sec-butyl group, a tert-butyl group, an iso-butyl group, an iso-pentyl group, a neopentyl group, a tert-pentyl group, a pentan-3-yl group, an iso-hexyl group, a 1,1-dimethylbutyl group, a 3,3-dimethylbutyl group, a texyl group, a 3-methylpentan-3-yl group, a heptan-4-yl group, a 2,4-dimethylpentan-2-yl group, a 3-ethylpentan-3-yl group, a 4,4-dimethylpentyl group, a 4-methylheptan-4-yl group, a 4-propylheptan-4-yl group, a 2,4,4-trimethylpentan-2-yl group, etc. are preferable, and hydrocarbon groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, a tert-butyl group, a neopentyl group, a 2,4-dimethylpentan-2-yl group, a 2,4,4-trimethylpentan-2-yl group, a tert-octyl group, etc. are more preferable. When the number of carbon atoms of the hydrocarbon group is small, the compound (A) of the present invention has a low affinity with the hydrocarbon medium when used in the hydrocarbon medium as a catalyst component, and the immobilization and activation performance of the catalyst tend to improve.

[0047] Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, a vinyl group, an allyl group, a but-3-en-1-yl group, a crotyl group, a methallyl group, a pent-4-en-1-yl group, a prenyl group, a pent-1,4-dien-3-yl group, a hex-5-en-1-yl group, a 2-methylpent-4-en-2-yl group, a 2-(cyclopentadienyl)propan-2-yl group, a 2-(cyclopentadienyl)ethyl group, etc. are preferable, and a vinyl group, an allyl group, a but-3-en-1-yl group, a pent-4-en-1-yl group, a prenyl group, a hex-5-en-1-yl group are more preferable.

[0048] Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, ethynyl group, prop-2-yn-1-yl group, propargyl group, but-2-yn-1-yl group, but-3-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1-yl group, 3-methyl-but-1-yn-1-yl group, 3,3-dimethyl-but-1-yn-1-yl group, hex-4-yn-1-yl group, hex-5-yn-1-yl group, etc. are preferable, and prop-2-yn-1-yl group, propargyl group, but-2-yn-1-yl group, but-3-yn-1-yl group are more preferable.

[0049] Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neophyl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, etc. are preferable, and benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, cinnamyl group are more preferable.

[0050] Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, pentalenyl group, indenyl group, fluorenyl group, etc. are preferable, and cyclopentyl group, cyclopentenyl group, 1-methylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-adamantyl group are more preferable.

[0051] Among the aromatic substituents having 6 to 40 carbon atoms, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group, etc. are preferable, and phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group are more preferable.

[0052] Heteroatom-containing hydrocarbon group: Examples of the heteroatom-containing hydrocarbon group include R 2 wherein some or all of the hydrogen atoms in the hydrocarbon group as 1 are replaced with the heteroatom-containing groups mentioned in the description of R 2 a group in which a part of the methylene group in the hydrocarbon group as R 2 is replaced with a structure represented by -CO-, -CH(OH)-, -NR- (R is a hydrogen atom or a hydrocarbon group (having, for example, 1 to 4 carbon atoms)), -O-, -S-, or -SO2-;

[0053] Examples of such polymers include the polymers mentioned in the description of 1 R A proton may be coordinately bonded to some or all of the heteroatoms (preferably nitrogen atoms) contained in the heteroatom-containing hydrocarbon group.

[0054] Ring formation: A plurality of 2 Rs may be bonded to each other to form a ring or may not be bonded to each other.

[0055] R 1 and one or more 2 Rs may be bonded to each other to form a ring or may not be bonded to each other. Examples of the structure in which a plurality of 2 Rs are bonded to each other to form a ring include, for example, the structures represented by the following formulas (α-1) and (α-2).

[0056]

Chemical formula

[0057] For example, R2 All four are methyl groups, and R 1 is an ethylene group. When the ring represented by the above formula (α-2) is formed, the structure is represented by the following formula.

[0058] [Chemical formula]

[0059] R 1 and a plurality of R 2 are bonded to each other to form a ring. Examples of such structures include the structures represented by the following formulas (α-3) and (α-4).

[0060] [Chemical formula]

[0061] For example, when two of R 2 are hydrogen atoms and two are propylene groups, and R 1 is an ethylene group, and the ring represented by the above formula (α-3) is formed, the structure is represented by the following formula.

[0062] [Chemical formula]

[0063] 《[α] γ+ Examples of》 [α] γ+ Specific examples of [α] include the cations represented by the following formula.

[0064] [Chemical formula] [α] γ+ As further specific examples of [α], the cations represented by the following formula are also included.

[0065] [Chemical formula]

[0066] <{β} γ- > In general formula (A), {β} γ- represents one or more anions (β), and the total valence of the anions (β) is γ valence.

[0067] The anion (β) is an anion (β') represented by the following general formula (β'-I), (β'-II) or (β'-III), or an anion (β") other than the anion (β'), and at least one of the anions (β) is the anion (β'). When a plurality of the anions (β) are present, they may be the same as or different from each other.

[0068] 《Anion (β')》 The anion (β') is represented by the following general formula (β'-I), (β'-II) or (β'-III).

[0069]

Chemical formula

[0070] (M') In general formulas (β'-I), (β'-II) and (β'-III), M' is an atom of Group 13 element, preferably a boron atom or an aluminum atom, more preferably a boron atom.

[0071] (R 3 ) In general formulas (β'-I), (β'-II) and (β'-III), a plurality of R 3 are each independently an aryl group having 6 to 20 carbon atoms represented by the following general formula (R3). A plurality of R 3 may be bonded to each other to form a ring, or may not be bonded to each other.

[0072] [Chemical formula] 〔In the general formula (R3), * represents a bond to M'. A plurality of Rs are each independently a substituent (r3) selected from the group consisting of a halogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group, and a hydrocarbon-substituted silyl group, or a hydrogen atom, and at least one of the Rs adjacent to * (i.e., the R at the ortho position with respect to the bond to M') is the substituent (r3). When there are a plurality of the substituents (r3), the plurality of substituents (r3) may be the same as or different from each other. The plurality of substituents (r3) may be bonded to each other to form an aromatic ring which may have a substituent, or may not be bonded to each other.〕

[0073] Examples of the halogen atom as the R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include the hydrocarbon group exemplified as R in the general formula (α) above 2 (however, it is selected within the range where the number of carbon atoms of the aryl group represented by the general formula (R3) is 20 or less).

[0074] Examples of the heteroatom-containing hydrocarbon group include the heteroatom-containing hydrocarbon group exemplified as R in the general formula (α) above 2 (however, it is selected within the range where the number of carbon atoms of the aryl group represented by the general formula (R3) is 20 or less), and preferably a halogen atom-containing hydrocarbon group. The halogen atom in this halogen atom-containing hydrocarbon group is preferably a fluorine atom.

[0075] Examples of the halogen atom-containing hydrocarbon group include a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, and a pentafluorophenyl group. Among these, perfluorinated hydrocarbon groups such as a trifluoromethyl group, a pentafluoroethyl group, and a pentafluorophenyl group are preferable.

[0076] Examples of the hydrocarbon-substituted silyl group preferably include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyldimethylsilyl group. R is preferably a halogen atom or a heteroatom-containing hydrocarbon group, and particularly preferably a fluorine atom, a trifluoromethyl group, or a perfluorophenyl group (pentafluorophenyl group).

[0077] The substituent (r3) at at least one ortho position (ortho position with respect to the bond with M') of the aryl group is preferably an electron-withdrawing group, more preferably a halogen atom or a halogen atom-containing hydrocarbon group, and even more preferably a halogen atom. When the ortho position has an electron-withdrawing group, the compound (A) of the present invention is excellent in performance as a cocatalyst in an olefin polymerization catalyst.

[0078] Examples of the aromatic ring formed by bonding a plurality of substituents (r3) to each other include naphthalene, anthracene, and phenanthrene. This aromatic ring may have a substituent, and this substituent is preferably a halogen atom or a halogenated alkyl group, and more preferably a fluorine atom or a trifluoromethyl group.

[0079] (R 4 ) R in the general formula (β'-II) 4 , and a plurality of Rs in the general formula (β'-III)4 is, independently of each other, an arylene group having 6 to 20 carbon atoms represented by the following general formula (R4), (R5) or (R6).

[0080]

Chemical formula

[0081] In the general formula (β'-III), two Rs 4 may be bonded to each other to form a ring, or may not be bonded to each other. In the general formula (β'-II), R 4 may be bonded to one or more Rs 3 to form a ring, or may not be bonded.

[0082] In the general formula (β'-III), one or two Rs 4 may be bonded to one or more Rs 3 to form a ring, or may not be bonded. From the viewpoint of ease of production, the anion (β') is preferably a compound represented by the general formula (β'-I).

[0083] (Examples of anion (β')) Specific examples of the anion (β') include tetrakis(2,4-dimethylphenyl)borate ion, tetrakis(2,4,6-trifluorophenyl)borate ion, tris(pentafluorophenyl)(1-naphthyl)borate ion, tetrakis(pentafluorophenyl)borate ion (hereinafter also referred to as "[B(C6F5)4] - "). tetrakis(3,5-bis(trimethylsilyl)trifluorophenyl)borate ion, Tetrakis(3,5-bis(triisopropylsilyl)pentafluorophenyl)borate ion, Tetrakis(3,5-bis(tert-butyldimethylsilyl)pentafluorophenyl)borate ion, Tetrakis(3,5-bis(trifluoromethyl)pentafluorophenyl)borate ion, Tetrakis(perfluorobiphenyl-2-yl)borate ion, (Pentafluorophenyl)tris(perfluorobiphenyl-2-yl)borate ion, Bis(pentafluorophenyl)bis(perfluorobiphenyl-2-yl)borate ion, Tris(pentafluorophenyl)(perfluorobiphenyl-2-yl)borate ion, Tetrakis(perfluorobiphenyl-3-yl)borate ion, (Pentafluorophenyl)tris(perfluorobiphenyl-3-yl)borate ion, Bis(pentafluorophenyl)bis(perfluorobiphenyl-3-yl)borate ion, Tris(pentafluorophenyl)(perfluorobiphenyl-3-yl)borate ion, Tetrakis(α-perfluoronaphthyl)borate ion, (Pentafluorophenyl)tris(α-perfluoronaphthyl)borate ion, Bis(pentafluorophenyl)bis(α-perfluoronaphthyl)borate ion, Tris(pentafluorophenyl)(α-perfluoronaphthyl)borate ion, Tetrakis(β-perfluoronaphthyl)borate ion, (Pentafluorophenyl)tris(β-perfluoronaphthyl)borate ion, Bis(pentafluorophenyl)bis(β-perfluoronaphthyl)borate ion, Tris(pentafluorophenyl)(β-perfluoronaphthyl)borate ion, Bis(3,4,5,6,3',4',5',6'-octafluorobiphenyl-2,2'-diyl)borate ion, Hexakis(pentafluorophenyl)[μ-(2,3,5,6-tetrafluoro-1,4-phenylene)]diborate ion (anion represented by the following formula (β'-II-1)

[0084] [Chemical formula] ), and 1,2,3,4,6,7,8,9-octafluoro-5,10-tetrakis(pentafluorophenyl)-boranthene-diate ion (anion represented by the following formula (β'-III-1)

[0085] [Chemical formula] ), as well as those obtained by replacing the fluorine atoms in these anions with other halogen atoms such as chlorine atoms and bromine atoms, and those obtained by replacing the boron atoms in these anions with aluminum atoms are included.

[0086] Among these, [B(C6F5)4] - , tetrakis(3,5-bis(trifluoromethyl)trifluorophenyl)borate ion, tetrakis(perfluorobiphenyl-3-yl)borate ion, tris(pentafluorophenyl)(perfluorobiphenyl-3-yl)borate ion, tetrakis(2-perfluorobiphenyl)borate ion, tetrakis(α-perfluoronaphthyl)borate ion, tetrakis(β-perfluoronaphthyl)borate ion, and bis(3,4,5,6,3',4',5',6'-octafluorobiphenyl-2,2'-diyl)borate ion is preferred, [B(C6F5)4] - , tetrakis(α-perfluoronaphthyl)borate ion, and tetrakis(β-perfluoronaphthyl)borate ion are particularly preferred.

[0087] 《Anion (β")》 As the anion (β") (that is, an anion other than the anion (β') among the anions (β)), carboxylic acid ion, benzoic acid ion, amide, sulfate ester ion, sulfonic acid ion, phosphate ester ion, phosphonic acid ion, fluoride ion, chloride ion, bromide ion, iodide ion, particularly chloride ion is preferred.

[0088] As the anion (β"), the general formula: [MQ n - 〔M is an atom of a metal element or a metalloid element selected from Groups 5 to 15 of the periodic table. n is an integer selected so that the charge of [MQ n becomes -1. Q is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group. When n is an integer of 2 or more, a plurality of (n) Qs may be the same as or different from each other, may be bonded to each other to form a ring, or may not be bonded to each other. 〕 The anion represented by (however, excluding the anion represented by the general formula (β'-I)) is also included.

[0089] Examples of the halogen atom as Q include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred examples of the hydrocarbon group having 1 to 20 carbon atoms as Q include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a naphthyl group, and a biphenyl group.​

[0090] Preferred examples of the heteroatom-containing hydrocarbon group as Q include a pentafluorophenyl group, a perfluorobiphenyl-2-yl group, a perfluorobiphenyl-3-yl group, an α-perfluoronaphthyl group, and a β-perfluoronaphthyl group.

[0091] When there are a plurality of anions (β"), they may be the same as or different from each other, and from the viewpoint of ease of production method, it is preferable that they are the same as each other. Specific examples of the anion (β") include fluoride ion, chloride ion, bromide ion, iodide ion, formate ion, hydrogen sulfate ion, methyl sulfate ion, ethyl sulfate ion, octyl sulfate ion, 2-(2-methoxyethoxy)ethyl sulfate ion, methanesulfonate ion, ethanesulfonate ion, allylsulfonate ion, trifluoromethanesulfonate ion, nonafluorobutanesulfonate ion, heptadecafluorooctanesulfonate ion, p-toluenesulfonate ion, bis(fluorosulfonyl)imide ion, bis(trifluoromethylsulfonyl)imide ion, bis(pentafluoroethylsulfonyl)imide ion, tris(trifluoromethylsulfonyl)methide ion, thiocyanate ion, dicyanamide ion, nitrate ion, acetate ion, trifluoroacetate ion, 2-methoxyacetate ion, propionate ion, butyrate ion, valerate ion, caproate ion, enanthate ion, caprylate ion, pelargonate ion, caprate ion, undecylate ion, laurate ion, tridecylate ion, myristate ion, pentadecanoate ion, palmitate ion, margarate ion, stearate ion, arachidate ion, henicosanoate ion, behenate ion, lignocerate ion, cerotate ion, montanate ion, melissate ion, benzoate ion, thiosalicylate ion, dimethyl phosphate ion, bis(2,4,4-trimethylpentyl)phosphinate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion, tetrachloroborate ion, tetrakis(1-butyl)borate ion, tetrakis(1-dodecyl)borate ion, tetrakis(1-octadecyl)borate ion, tetrakisphenylborate ion, tetrakis(p-tolyl)borate ion, tri(p-tolyl)(phenyl)borate ion, tris(pentafluorophenyl)(phenyl)borate ion, tris(2,4-dimethylphenyl)(phenyl)borate ion, tetrakis(3,5-dimethylphenyl)borate ion, tris(3,5-dimethylphenyl)(phenyl)borate ion, tetrakis(3,5-di-trifluoromethylphenyl)borate ion, tris(3,5-di-trifluoromethylphenyl)(phenyl)borate ion, tris(pentafluorophenyl)(cyclohexyl)borate ion, tetrakis(bis(trifluoromethyl)phenyl)borate ion, tetrakis(bis(trifluoromethyl)fluorophenyl)borate ion, triphenyl(hydroxyphenyl)borate ion, diphenyl-di(hydroxyphenyl)borate ion, triphenyl(2,4-dihydroxyphenyl)borate ion, tri(p-tolyl)(hydroxyphenyl)borate ion, tris(pentafluorophenyl)(hydroxyphenyl)borate ion, tris(2,4-dimethylphenyl)(hydroxyphenyl)borate ion, tris(3,5-dimethylphenyl)(hydroxyphenyl)borate ion, tris(3,5-di(trifluoromethyl)phenyl)(hydroxyphenyl)borate ion, tris(pentafluorophenyl)(2-hydroxyethyl)borate ion, tris(pentafluorophenyl)(4-hydroxybutyl)borate ion, tris(pentafluorophenyl)(4-hydroxy-cyclohexyl)borate ion, tris(pentafluorophenyl)(4-(4'-hydroxyphenyl)phenyl)borate ion, tris(pentafluorophenyl)(6-hydroxy-2-naphthyl)borate ion, tris(pentafluorophenyl)(4-hydroxyphenyl)borate ion, tetrakis(3,5-di(trifluoromethyl)-4-fluorophenyl)borate ion, those obtained by replacing the fluorine atoms in these borate ions with other halogen atoms such as chlorine atoms and bromine atoms, and those obtained by replacing the boron atoms in these borate ions with aluminum atoms (for example, tetrafluoroaluminate, tetrachloroaluminate) and iron(III) tetrachloride ion are mentioned., General formula [MQ n - Among the anions represented by, tetrakis(bis(3,5-di(trifluoromethyl)-4-fluorophenyl)borate ion is preferred.

[0092] ​<Specific Examples of Group 13 Element-Containing Compound (A)> Specific examples of the Group 13 element-containing compound (A) of the present invention include compounds represented by the following formulas (A-1), (A-2), (A-5) to (A-10).

[0093]

Chemical formula

[0094]

Chemical formula

[0095]

Chemical formula

[0096]

Chemical formula

[0097] Specific examples of the Group 13 element-containing compound (A) of the present invention further include compounds represented by the following formulas (A-11) to (A-13).

[0098]

Chemical formula

[0099] The compounds represented by formulas (A-1), (A-2), (A-5) to (A-8) each have two anions (β) (two anions (β')), and the total valence is 2. The compound represented by formula (A-9) has three anions (β) (one anion (β") and two anions (β')), and the total valence is 3. The compound represented by formula (A-10) has four anions (β) (three anions (β") and one anion (β')), and the total valence is 4.

[0100] <Method for Producing Group 13 Element-Containing Compound (A)> Examples of the method for producing the Group 13 element-containing compound (A) according to the present invention include methods using the method described in US Patent Application Publication No. 2019 / 0330392, the method described in US Patent No. 5493056, and the like. Specifically, the compound (A) can be mainly produced by a method consisting of the following two steps.

[0101] In the first step, an amine having a structure in which two protons are removed from the above [α] γ+ is dissolved in a solvent (dichloromethane, diethyl ether, hexane, cyclohexane, methylcyclohexane, toluene, etc.), and hydrogen chloride in an amount of 2 equivalents or more is added to synthesize a dihydrochloride. The obtained hydrochloride is isolated by filtration.

[0102] In the second step, the hydrochloride, 2 equivalents of an alkali metal, a salt containing the above M' (atom of Group 13 element) and the above anion (β') (lithium borate salt, sodium aluminate salt, etc.), and optionally a salt of the above anion (β") are mixed in a solvent (cyclohexane, dichloromethane, methylcyclohexane, etc.) to synthesize the target borate and aluminate and the by-product alkali metal chloride, and the latter can be removed by filtration to isolate the compound (A). The above is the method when γ is 2, but when γ is 3 to 100, the compound (A) can also be produced by appropriately adjusting this method according to the value of γ.

[0103] [Olefin polymerization catalyst] The olefin polymerization catalyst of the present invention contains the above-described compound (A) and transition metal complex (B) of the present invention.

[0104] (Transition metal complex (B)) The transition metal complex (B) is not particularly limited, and examples thereof include transition metal complexes used in conventionally known olefin polymerization catalysts.

[0105] Examples of the transition metal complex (B) include at least one metallocene compound selected from a compound represented by the following general formula (B1) (non-bridged metallocene compound) and a compound represented by the general formula (B2) (bridged metallocene compound).

[0106] [Chemical formula]

[0107] In the formulas (B1) and (B2), M represents an atom of Group 4 or Group 5 of the periodic table. Specific examples of M include a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a niobium atom, and a tantalum atom, preferably a titanium atom, a zirconium atom, and a hafnium atom.

[0108] In the formulas (B1) and (B2), Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group (i.e., a group in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom), a neutral conjugated or non-conjugated diene, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons.

[0109] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms; an alicyclic hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms; and an aromatic hydrocarbon group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.

[0110] Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, 1,1-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, 1,1-dimethylbutyl group, 1,1,3-trimethylbutyl group; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, such as vinyl group, allyl group, isopropenyl group; linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, such as ethynyl group, propargyl group.

[0111] Examples of the alicyclic hydrocarbon group include cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-methyl-1-cyclohexyl group, adamantyl group; cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl group, indenyl group, fluorenyl group.

[0112] Examples of the aromatic hydrocarbon group include unsubstituted aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group; aryl groups substituted with an alkyl group, such as tolyl group, dimethylphenyl group, isopropylphenyl group, t-butylphenyl group, di-t-butylphenyl group.

[0113] The hydrocarbon group may have at least one hydrogen atom substituted by another hydrocarbon group. Examples of the hydrocarbon group having at least one hydrogen atom substituted by another hydrocarbon group include aryl group-substituted alkyl groups such as benzyl group and cumyl group, and cyclic saturated hydrocarbon group-substituted alkyl groups such as cyclohexylmethyl group.

[0114] Examples of the halogenated hydrocarbon group include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms, such as trifluoromethyl group, pentafluorophenyl group, and chlorophenyl group.

[0115] Examples of the neutral conjugated or non-conjugated diene include neutral conjugated or non-conjugated dienes having 4 to 20 carbon atoms. Specifically, s-cis- or s-trans-η 4 -1,3-butadiene, s-cis- or s-trans-η 4 -1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η 4 -3-methyl-1,3-pentadiene, s-cis- or s-trans-η 4 -1,4-dibenzyl-1,3-butadiene, s-cis- or s-trans-η 4 -2,4-hexadiene, s-cis- or s-trans-η 4 -1,3-pentadiene, s-cis- or s-trans-η 4 -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η 4 -1,4-bis(trimethylsilyl)-1,3-butadiene.

[0116] Examples of the anionic ligand include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; and sulfonate groups such as mesylate and tosylate.

[0117] Examples of neutral ligands capable of coordinating with lone pairs of electrons include, for example, organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; and ethers such as tetrahydrofuran, dioxane, diethyl ether, 1,2-dimethoxyethane.

[0118] In formulas (B1) and (B2), j represents an integer from 1 to 4, preferably an integer from 2 to 4, more preferably 2 or 3. When j is an integer of 2 or more, a plurality of Qs may be the same or different from each other.

[0119] In formulas (B1) and (B2), Cp 1 and Cp 2 may be the same as or different from each other, and represent a cyclopentadienyl group or a substituted cyclopentadienyl group capable of forming a sandwich structure with M. The substituted cyclopentadienyl group is a group in which at least one hydrogen atom of the cyclopentadienyl group is substituted with a substituent.

[0120] Examples of the substituent in the substituted cyclopentadienyl group include, for example, a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms, hereinafter may be referred to as "hydrocarbon group (f1)") or a silicon-containing group (preferably a silicon-containing group having 1 to 20 carbon atoms, hereinafter may be referred to as "silicon-containing group (f2)"). In addition, examples of the substituent in the substituted cyclopentadienyl group include heteroatom-containing groups such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups (excluding the silicon-containing group (f2)).

[0121] The hydrocarbon group (f1) is preferably a hydrocarbon group having 1 to 20 carbon atoms. Examples thereof include linear or branched hydrocarbon groups (e.g., alkyl group, alkenyl group, alkynyl group), cyclic saturated hydrocarbon groups (e.g., cycloalkyl group), and cyclic unsaturated hydrocarbon groups (e.g., aryl group). The hydrocarbon group (f1) also includes a group in which any two hydrogen atoms bonded to adjacent carbon atoms among the above-exemplified groups are simultaneously substituted to form an alicyclic or aromatic ring.

[0122] Specific examples of the hydrocarbon group (f1) include linear aliphatic hydrocarbon groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, and allyl group; branched aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, 3-methylpentyl group, neopentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, and 1-methyl-1-isopropyl-2-methylpropyl group; cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, and adamantyl group; cyclic unsaturated hydrocarbon groups such as phenyl group, naphthyl group, biphenyl group, phenanthryl group, and anthracenyl group and nuclear alkyl-substituted products thereof; and groups in which at least one hydrogen atom of a saturated hydrocarbon group is substituted with an aryl group, such as benzyl group and cumyl group.

[0123] The silicon-containing group (f2) is preferably a silicon-containing group having 1 to 20 carbon atoms. Examples thereof include a group in which a silicon atom is directly covalently bonded to a ring carbon of a cyclopentadienyl group. Specific examples thereof include alkylsilyl groups (e.g., trimethylsilyl group) and arylsilyl groups (e.g., triphenylsilyl group).

[0124] Examples of the heteroatom-containing group (excluding the silicon-containing group (f2)) specifically include a methoxy group, an ethoxy group, a phenoxy group, an N-methylamino group, a trifluoromethyl group, a tribromomethyl group, a pentafluoroethyl group, and a pentafluorophenyl group.

[0125] Among the hydrocarbon groups (f1), linear or branched aliphatic hydrocarbon groups having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, etc. are cited as preferred examples.

[0126] The substituted cyclopentadienyl group includes an indenyl group, a fluorenyl group, an azulenyl group, and a group in which one or more hydrogen atoms they have are substituted with the above hydrocarbon group. In the case of an indenyl group, a fluorenyl group, or an azulenyl group, part or all of the double bonds of the unsaturated ring condensed to the cyclopentadienyl group may be hydrogenated.

[0127] In formula (B2), Y is a divalent hydrocarbon group having 1 to 30 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O-, -CO-, -S-, -SO-, -SO2-, -Ge-, -Sn(tin)-, -NR a -, -P(R a )-, -P(O)(R a )-, -BR a - or -AlR a -. However, R a is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom, or a nitrogen compound residue (-NRH or -NR2; R is a hydrocarbon group having 1 to 20 carbon atoms) in which one or two hydrocarbon groups having 1 to 20 carbon atoms are bonded to a nitrogen atom.

[0128] As the metallocene compound represented by the general formula (B1) or (B2), a compound represented by the general formula (B2) is preferable, and a bridged metallocene compound represented by the general formula (I) (hereinafter also referred to as "bridged metallocene compound (B2a)") as disclosed in WO 01 / 27124 pamphlet is more preferable.

[0129] [Chemical formula]

[0130] The bridged metallocene compound (B2a) structurally has the following characteristics [m1] to [m3]. [m1] Of the two ligands, one is a cyclopentadienyl group which may have a substituent, and the other is a fluorenyl group which may have a substituent. [m2] The two ligands are bonded by a covalent bond bridging moiety composed of a carbon atom or a silicon atom (hereinafter also referred to as "bridging moiety"). [m3] The transition metal (M) constituting the metallocene compound is an atom of Group 4 of the periodic table, specifically, a titanium atom, a zirconium atom or a hafnium atom. Hereinafter, the cyclopentadienyl group, fluorenyl group, bridging moiety and other characteristics of the bridged metallocene compound (B2a) will be sequentially described.

[0131] (Cyclopentadienyl group) In the formula (B2a), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group, a hydrogen atom, a hydrocarbon group or a silicon-containing group is preferable, and two adjacent groups may be bonded to each other to form a ring.

[0132] For example, R 1 , R 2 , R 3 and R 4 are all hydrogen atoms, or R1 、R 2 、R 3 and R 4 One or more of them are a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms) or a silicon-containing group (preferably a silicon-containing group having 1 to 20 carbon atoms). In addition, heteroatom-containing groups such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups can also be mentioned.

[0133] R 1 、R 2 、R 3 and R 4 When two or more of them are substituents other than hydrogen atoms, the substituents may be the same or different from each other; R 1 、R 2 、R 3 and R 4 Two adjacent groups among them may be bonded to each other to form an alicyclic ring or an aromatic ring.

[0134] R 1 ~R 4 Examples and preferred groups of the hydrocarbon group in are the hydrocarbon groups (f1) defined at the position of the above-mentioned substituted cyclopentadienyl group. R 1 ~R 4 Examples and preferred groups of the silicon-containing group in are the silicon-containing groups (f2) defined at the position of the above-mentioned substituted cyclopentadienyl group. R 1 ~R 4 Examples of the heteroatom-containing group in are the groups exemplified at the position of the above-mentioned substituted cyclopentadienyl group.

[0135] (Fluorenyl group) In formula (B2a), R 5 、R 8 、R 9 and R 12 each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group, and a hydrogen atom, a hydrocarbon group or a silicon-containing group is preferred. R 6 and R 11is the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, and a hydrogen atom, a hydrocarbon group, and a silicon-containing group are preferred; R 7 and R 10 is the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, and a hydrogen atom, a hydrocarbon group, and a silicon-containing group are preferred; R 6 and R 7 may be bonded to each other to form a ring, and R 10 and R 11 may be bonded to each other to form a ring.

[0136] From the perspective of polymerization activity, it is preferred that neither R 6 nor R 11 is a hydrogen atom, and it is more preferred that neither R 7 nor R 10 is a hydrogen atom. Further, it is more preferred that none of R 6 , R 7 , R 10 and R 11 is a hydrogen atom. Also, it is particularly preferred that R 6 and R 11 are the same group selected from a hydrocarbon group and a silicon-containing group, or that R 7 and R 10 are the same group selected from a hydrocarbon group and a silicon-containing group. Furthermore, it is most preferred that R 6 and R 7 are bonded to each other to form an alicyclic or aromatic ring, and that R 10 and R 11 are bonded to each other to form an alicyclic or aromatic ring.

[0137] Examples and preferred groups of the hydrocarbon group in R 5 ~R 12 include the hydrocarbon group (f1) defined in the section of the above substituted cyclopentadienyl group. R 5 ~R 12Examples and preferred groups of the silicon-containing group in [description] include the silicon-containing group (f2) defined at the position of the above-mentioned substituted cyclopentadienyl group. R 5 ~R 12 Examples of the heteroatom-containing group in [description] include the groups exemplified at the position of the above-mentioned substituted cyclopentadienyl group.

[0138] R 6 and R 7 (R 10 and R 11 ) When they are bonded to each other to form an alicyclic or aromatic ring, examples of the substituted fluorenyl group include groups having a structure derived from the compounds represented by the general formulas [I] to [V] described later.

[0139] (Crosslinking part) In formula (B2a), R 13 and R 14 each independently represent an alkyl group or an aryl group, and Y represents a carbon atom or a silicon atom. An alkyl group or an aryl group [R 13 and R 14 which may be the same or different from each other is bonded to the crosslinking atom Y of the crosslinking part. Furthermore, R 13 and R 14 may be bonded to each other to form a ring structure.

[0140] Examples of the alkyl group include the hydrocarbon group (f1) defined at the position of the above-mentioned substituted cyclopentadienyl group. R 13 and R 14 Examples of the ring structure formed by bonding to each other include a cyclohexyl group, a cyclopentyl group, etc. when Y 1 is a carbon atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and groups in which one or more of the aromatic hydrogens (sp2-type hydrogens) they have are substituted with substituents. Examples of the substituent include the hydrocarbon group (f1) and the silicon-containing group (f2) defined at the position of the above-mentioned substituted cyclopentadienyl group, a halogen atom, and a halogenated hydrocarbon group.

[0141] Specific examples of the aryl group include unsubstituted aryl groups having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl group, naphthyl group, anthracenyl group, biphenyl group, etc.; alkyl group-substituted aryl groups such as tolyl group, dimethylphenyl group, isopropylphenyl group, n-butylphenyl group, t-butylphenyl group, etc.; cycloalkyl group-substituted aryl groups such as cyclohexylphenyl group, etc.; halogenated aryl groups such as chlorophenyl group, bromophenyl group, dichlorophenyl group, dibromophenyl group, etc.; halogenated alkyl group-substituted aryl groups such as (trifluoromethyl)phenyl group, bis(trifluoromethyl)phenyl group, etc. The position of the substituent is preferably the meta position and / or the para position. Among these, substituted phenyl groups in which the substituent is located at the meta position and / or the para position are more preferred.

[0142] (Other features of the bridged metallocene compound) In formula (B2a), Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with an unshared electron pair, j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different from each other.

[0143] Examples of the halogen atom, hydrocarbon group, halogenated hydrocarbon group, neutral conjugated or non-conjugated diene having 4 to 20 carbon atoms, anionic ligand, or neutral ligand capable of coordinating with an unshared electron pair in Q include the same atoms or groups as Q in formulas (B1) and (B2).

[0144] (Examples of preferred bridged metallocene compound (B2a)) Specific examples of the crosslinked metallocene compound (B2a) are shown below, but the scope of the present invention is not particularly limited thereby. In the exemplified compounds, octamethyloctahydrodibenzofluorenyl refers to a group derived from a compound having the structure represented by formula [I], octamethyltetrahydrodicyclopentapentafluorenyl refers to a group derived from a compound having the structure represented by formula [II], dibenzofluorenyl refers to a group derived from a compound having the structure represented by formula [III], 1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentapentafluorenyl refers to a group derived from a compound having the structure represented by formula [IV], and 1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentapentafluorenyl refers to a group derived from a compound having the structure represented by formula [V].

[0145]

Chemical formula

[0146] Specific examples of the metallocene compound represented by general formula (B1), (B2) or (B2a) include the compounds listed in

[0078] to

[0079] of International Publication No. 2013 / 161833 and the compounds listed in

[0259] to

[0262] of International Publication No. 2014 / 123212. Examples of the transition metal complex (B) also include a compound (B3) represented by the following general formula (B3).

[0147]

Chemical formula

[0148] 〈R 1 from R 16 〉 In formula (B3), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and among the substituents from R 1 to R 16 , any two substituents may be bonded to each other to form a ring.

[0149] R 1 to R 16 as the hydrocarbon group, heteroatom-containing hydrocarbon group and silicon-containing group in R 1 to R 14 in the above formula (B2a) include the hydrocarbon group, heteroatom-containing hydrocarbon group and silicon-containing group exemplified.

[0150] R 1 to R 16 among the substituents, two adjacent substituents (e.g., R 1 and R 2 , R 2 and R 3 , R 4 and R 6 , R 4 and R 7 , R 5 and R 6 , R 5 and R 7 , R 6 and R 8 , R 7 and R 8 , R 9 and R 10 , R 10 and R 11 , R 11 and R 12 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 ) may be bonded to each other to form a ring, and R 4 and R 5may be bonded to each other to form a ring, and R 6 and R 7 may be bonded to each other to form a ring, and R 1 and R 8 may be bonded to each other to form a ring, and R 3 and R 4 may be bonded to each other to form a ring, and R 3 and R 5 may be bonded to each other to form a ring. The ring formation may be present at two or more positions in the molecule.

[0151] In this specification, examples of the ring (additional ring) formed by bonding two substituents to each other include an alicyclic ring, an aromatic ring, and a heterocyclic ring. Specifically, a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; a heterocyclic ring such as a furan ring and a thiophene ring, and a hydrogenated heterocyclic ring corresponding thereto can be mentioned, and preferably a cyclohexane ring; a benzene ring and a hydrogenated benzene ring. Further, such a ring structure may further have a substituent such as an alkyl group on the ring.

[0152] R 1 and R 3 are preferably hydrogen atoms. R 2 is preferably a hydrocarbon group, a hydrocarbon group containing a heteroatom, or a silicon-containing group, more preferably a hydrocarbon group, still more preferably a hydrocarbon group having 1 to 20 carbon atoms, still more preferably not an aryl group, particularly preferably a linear hydrocarbon group, a branched hydrocarbon group, or a cyclic saturated hydrocarbon group, and particularly preferably a substituent in which the carbon atom having a free valence (the carbon atom bonded to the cyclopentadienyl ring) is a tertiary carbon atom.

[0153] R 2Specific examples thereof include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group. More preferably, they are substituents in which the carbon atom having a free valence such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, or a 1-adamantyl group is a tertiary carbon atom. Particularly preferred are a 1-adamantyl group and a tert-butyl group.

[0154] R 4 When the transition metal complex (3) is represented by the following general formula (B3'), it is preferably in the form of a hydrogen atom.

[0155]

Chemical formula

[0156] In this case, the transition metal complex (3) includes all enantiomers of the transition metal complex represented by the general formula (B3') without departing from the spirit of the present invention. For example, it includes the transition metal complex represented by the general formula (B3").

[0157]

Chemical formula

[0158] In the notations of the formulas (B3') and (B3"), it is assumed that the MQ j part is in front of the paper plane and the cross-linked part is on the back side of the paper plane. That is, in these transition metal complexes, a hydrogen atom (R 4 ) facing the central metal side exists at the α-position of the cyclopentadiene ring (based on the carbon atom substituted by the cross-linked site).

[0159] On the other hand, in the above-mentioned general formula (B3), whether the MQ j part and the cross-linked part are in front of the paper plane or on the back side of the paper plane is not specified. That is, the compound (B3) represented by the general formula (B3) includes a transition metal compound with a specific structure and its enantiomers.

[0160] R 4 、R 5 、R 6 and R 7 At least one selected from R 4 、R 5 is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and R 5 、R 4 is more preferably a hydrogen atom or a hydrocarbon group, and R 5 is more preferably an alkyl group such as a linear alkyl group or a branched alkyl group, a cycloalkyl group or a cycloalkenyl group, and particularly preferably an alkyl group having 1 to 10 carbon atoms. Further, from the viewpoint of synthesis, it is also a preferable form that R 6 、R 7 are both alkyl groups, and an alkyl group having 1 to 10 carbon atoms is particularly preferable. Similarly, from the viewpoint of synthesis, it is also preferable that R 5 and R 7 are hydrogen atoms. It is more preferable that R 5 and R 7 are bonded to each other to form a ring, and the ring is particularly preferably a 6-membered ring such as a cyclohexane ring.

[0161] R 8 is preferably a hydrocarbon group, and particularly preferably an alkyl group such as a methyl group. In the general formula (B3), the fluorene ring moiety is not particularly limited as long as it is a structure obtained from a known fluorene derivative. R 9 、R 12 、R 13 and R 16 are preferably hydrogen atoms.

[0162] R 10 、R 11 、R 14 and R 15is preferably a hydrogen atom, a hydrocarbon group, a hydrocarbon group containing an oxygen atom or a hydrocarbon group containing a nitrogen atom, more preferably a hydrocarbon group, still more preferably a hydrocarbon group having 1 to 20 carbon atoms. For example, 2,7-di-tert-butylfluorenyl group, 3,6-di-tert-butylfluorenyl group, 2,7-diphenyl-3,6-di-tert-butylfluorenyl group can be mentioned, and particularly preferably 2,7-di-tert-butylfluorenyl group.

[0163] R 10 and R 11 are bonded to each other to form a ring, and R 14 and R 15 may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include a benzofluorenyl group, a dibenzofluorenyl group, an octahydrodibenzofluorenyl group, a 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group, a 1,1,3,3,6,6,8,8-octamethyl-2,3,6,7,8,10-hexahydro-1H-dicyclopenta[b,h]fluorenyl group, and a 1',1',3',6',8',8'-hexamethyl-1'H,8'H-dicyclopenta[b,h]fluorenyl group. Particularly preferably, a 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group can be mentioned.

[0164] 〈M, Q, j〉 In formula (B3), M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.

[0165] Q is a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair of electrons. Examples of the halogen atom, hydrocarbon group, anionic ligand, and neutral ligand capable of coordinating with an unshared electron pair in Q include those exemplified as the halogen atom, hydrocarbon group, anionic ligand, and neutral ligand capable of coordinating with an unshared electron pair in the above-described formula (B2a).

[0166] j is an integer of 1 to 4, preferably 2. When j is an integer of 2 or more, Q may be selected in the same or different combinations. Specific examples of the compound (B3) include the compounds listed on pages 11 to 15 of International Publication No. 2006 / 68308, the compounds listed in

[0075] to

[0086] of International Publication No. 2014 / 50816, and the compounds listed in

[0072] to

[0084] of JP-A No. 2008 / 045008.

[0167] Examples of the transition metal complex (B) also include a compound (B4) represented by the following general formula (B4) as described in JP-A No. 11-315109, JP-A No. 2000-239312, International Publication No. 2001 / 55231, and Chemical Review, Vol. 111, No. 23, 2363 - 2449 (2011).

[0168] [Chemical formula]

[0169] In the general formula (B4), M represents a transition metal atom of Groups 4 to 10 of the periodic table. m represents an integer of 1 to 6. R 19 ~R 24 may be the same as or different from each other, 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. Two or more of these may be linked to each other to form a ring. When m is 2 or more, two of the groups represented by R 19 ~R 24 may be linked to each other. 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 plurality of groups represented by X may be the same as or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring.

[0170] Specific examples include bis{N-(5-adamantyl-3-methylsalicylidene)-2-methylcyclohexylaminato}zirconium(IV) dichloride and bis{N-(3-tert-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinato}titanium(IV) dichloride.

[0171] Examples of the transition metal complex (B) also include a compound (B5) represented by the following general formula (B5) as described in International Publication No. 2009 / 5003, JP-A-2011-178682, and JP-A-2011-195584.

[0172]

Chemical formula

[0173] In the general formula (B5), R 25 ~R 30 may be the same as or different from each other, 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, an aluminum-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. Further, R 25 may be linked to Z.

[0174] M represents a transition metal atom selected from Groups 3 to 10 of the periodic table. n represents 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. The atoms or groups represented by X may be the same as or different from each other, and the groups represented by X may be bonded to each other to form a ring.

[0175] Y represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom. Z represents a hydrocarbon group or a heterocyclic compound residue which may have a substituent, and the shortest number of bonds connecting Y and N is 4 to 6.

[0176] The bond connecting Y and Z may be a double bond or a triple bond, and the bond connecting Y and R 25 may also be a double bond or a triple bond. In the formula, the dotted line indicates a coordination bond. Examples of the compound (B5) represented by the general formula (B5) include trichloro{6-[(2'-methoxy-κO 1 -biphenyl-2-yl)imino-κN 1 -methyl]-4-methyl-2-(tricyclo[3.3.1.1 3,7 decane-1-yl)phenolato}titanium(IV).

[0177] Examples of the transition metal complex (B) include the compound (B6) represented by the following general formula (B6) described in, for example, US Patent No. 5272236. L 1 M 1 X n …(B6) In the general formula (B6), M 1 is a metal of Group 4 of the periodic table or a lanthanide series metal, L 1 is a derivative of a delocalized π-bonding group, which imparts a constrained geometry to the metal M 1 active site, X is independently hydrogen, halogen, or a hydrocarbon group, silyl group or germyl group having 1 to 20 carbon atoms.

[0178] n is an integer of 1 to 2 and is selected so that the entire compound (B6) is electrically neutral according to the valence of M and the type of X. Among the compounds (B6), compounds represented by the following general formula (B6a) are preferable.

[0179]

Chemical formula

[0180] In formula (B6a), M 1 is titanium, zirconium or hafnium, and X is the same as above. Cp is a substituted cyclopentadienyl group that is π-bonded to M 1 and has a substituent Z. Z is oxygen, sulfur, boron or an element of Group 14 of the periodic table (for example, silicon, germanium or tin), Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y may form a condensed ring.

[0181] Specific examples of the compound represented by the general formula (B6a) include compounds described in

[0062] of Tokuhei 2017-511396 such as [dimethyl(t-butylamide)(tetramethyl-η 5 -cyclopentadienyl)silane]titanium dichloride, and in these compounds, compounds in which titanium is replaced with zirconium or hafnium, and in these compounds, two Xs in the above formula (B6a) are replaced with one conjugated or non-conjugated diene (for example, s-cis- or s-trans-η 4 -1,3-pentadiene)), etc. The transition metal complex (B) may be used alone or in combination of two or more.

[0182] (Compound (C)) The olefin polymerization catalyst of the present invention preferably contains the following compound (C). Compound (C) (hereinafter sometimes referred to as "component (C)") is (C-1) An organometallic compound (hereinafter also referred to as "component (C-1)"), preferably an organoaluminum compound (C-1a) represented by the following general formula (C-1a), a complex alkylated product (C-1b) of a Group 1 metal and aluminum represented by the following general formula (C-1b), or a dialkyl compound (C-1c) of a Group 2 or Group 12 metal represented by the following general formula (C-1c), R a m Al(OR b ) n H p X q … (C-1a) 〔In the general formula (C-1a), R a and R b each represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3.〕 M a AlR a 4… (C-1b) 〔In the general formula (C-1b), M a represents Li, Na or K, and R a represents a hydrocarbon group having 1 to 15 (preferably 1 to 4) carbon atoms.〕 R a r M b R b s X t … (C-1c) 〔In the general formula (C-1c), R a and R b each represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, M b is selected from Mg, Zn and Cd, X represents a halogen atom, r is a number where 0 < r ≦ 2, s is a number where 0 ≦ s ≦ 1, t is a number where 0 ≦ t ≦ 1, and r + s + t = 2.〕, and (C-2) An organoaluminum oxy compound (hereinafter also referred to as "component (C-2)") is at least one compound selected from the group consisting of

[0183] 《Organometallic compound (C-1)》 Examples of the organoaluminum compound (C-1a) include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum, tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum, triarylaluminums such as triphenylaluminum and tri(4-methylphenyl)aluminum, dialkylaluminum hydrides such as diethylaluminum hydride, diisopropylaluminum hydride, and diisobutylaluminum hydride, the general formula (i-C4H9) x Al y (C5H 10 ) z (wherein x, y, and z are positive numbers and z ≤ 2x) alkenylaluminums such as isoprenylaluminum, alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide, dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide, alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, the general formula R a 2.5 Al(OR b ) 0.5 partially alkoxylated alkylaluminums having an average composition represented by etc. Alkylaluminum aryloxides such as diethylaluminum phenoxide and diethylaluminum(2,6-di-t-butyl-4-methylphenoxide), Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, Alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride and other partially hydrogenated alkylaluminums, Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, etc. can be exemplified. Further, compounds similar to the compound represented by the general formula R a m Al(OR b ) n H p X q can also be used. For example, organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom can be mentioned. Specific examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2.

[0184] Examples of the complex alkylate (C-1b) of a Group 1 metal and aluminum include LiAl(C2H5)4 and LiAl(C7H 15 )4. Examples of the dialkyl compounds (C-1c) of Group 2 or Group 12 metals include dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, ethyl n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, di-n-butylzinc, and diphenylzinc. Among these, the organic aluminum compound (C-1a) is preferred. The organometallic compound (C-1) may be used alone or in combination of two or more.

[0185] 《Organoaluminum oxy compound (C-2)》 Examples of the organoaluminum oxy compound (C-2) may be a conventionally known aluminoxane, or an organoaluminum oxy compound insoluble or hardly soluble in benzene as exemplified in JP-A-2-78687. The conventionally known aluminoxane can be produced, for example, by the following methods (1) to (4) and is usually obtained as a solution in a hydrocarbon solvent.

[0186] (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 crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium (I) chloride hydrate, etc., to react the adsorbed water or crystal water with the organoaluminum compound.

[0187] (2) A method in which water, ice or steam is directly allowed to act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether, tetrahydrofuran.

[0188] (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, toluene.

[0189] (4) A method of subjecting a compound formed by reacting an organoaluminum such as trialkylaluminum with an organic compound having a carbon-oxygen bond such as a tertiary alcohol, a ketone, and a carboxylic acid to a non-hydrolytic conversion such as a thermal decomposition reaction.

[0190] Incidentally, the above aluminoxane may contain a small amount of an organometallic component. Further, after distilling and removing the solvent or the unreacted organoaluminum compound from the recovered solution of the aluminoxane, it may be redissolved in a solvent or suspended in a poor solvent for aluminoxane.

[0191] Specific examples of the organoaluminum compound used when preparing aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound (C-1a). Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

[0192] In addition, examples of the organoaluminum oxy compound (C-2) include modified methylaluminoxane. Modified methylaluminoxane is an aluminoxane prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound is generally called MMAO. MMAO can be prepared by the methods described in U.S. Patent No. 4,960,878 and U.S. Patent No. 5,041,584. Further, aluminoxane in which R is an isobutyl group, prepared using trimethylaluminum and triisobutylaluminum, is commercially produced under names such as MMAO and TMAO by Tosoh Finechem Corporation and others.

[0193] Such MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, unlike those insoluble or hardly soluble in benzene as described above, it has the characteristic of dissolving in aliphatic hydrocarbons and alicyclic hydrocarbons.

[0194] Furthermore, examples of the organoaluminum oxy compound (C-2) include an organoaluminum oxy compound containing a boron atom, an aluminoxane containing a halogen as exemplified in International Publication No. 2005 / 066191 and International Publication No. 2007 / 131010, and an ionic aluminoxane as exemplified in International Publication No. 2003 / 082879. The organoaluminum oxy compound (C-2) may be used alone or in combination of two or more.

[0195] 〈Porous material (S)〉 The olefin polymerization catalyst of the present invention may further contain a porous material (S). The porous material is a granular or particulate inorganic compound or organic compound. As the inorganic compound, for example, oxides such as SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or composites or mixtures containing these can be used. For example, natural or synthetic zeolite, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO can be used. Among these, porous oxides mainly containing SiO2 and / or Al2O3 are preferred. Furthermore, inorganic chlorides, clay minerals or ion-exchangeable layered compounds can also be used. Also, a solid component obtained by insolubilizing the compound (C) by the methods described in JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, International Publication No. 2010 / 55652, etc. can be used as the porous material [S]. As the organic compound, for example, polymers or reactants mainly composed of olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, polymers mainly composed of vinylcyclohexane, styrene, divinylbenzene, and modified products thereof can be used.

[0196] The porous material (S) preferably used in the present invention is The particle size is preferably 1 to 300 μm, more preferably 3 to 100 μm; The specific surface area is preferably 50 to 1300 m 2 / g, more preferably 150 to 1200 m 2 / g; The pore volume is preferably 0.3 to 3.0 cm 3 / g, more preferably 0.5 to 2.0 cm 3 / g. Such a porous material (S) is used after being dried and / or calcined at 100 to 1000 °C, preferably 150 to 700 °C as needed. The particle shape of the porous material [S] is not particularly limited, but is preferably spherical.

[0197] 〈Organic compound component (D)〉 The catalyst for olefin polymerization of the present invention may further contain an organic compound component (D). The organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer as needed. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0198] 〈Usage and addition order of each component〉 In olefin polymerization, the usage method and the addition order of each component can be arbitrarily selected, and the following methods are exemplified. Hereinafter, the compound (A), transition metal complex (B), compound (C), and porous material (S) of the present invention are described as "component (A)", "component (B)", "component (C)", and "component (S)", respectively. (1) A method of adding component (A) and component (B) to the polymerization reactor in an arbitrary order. (2) A method of adding component (A), component (B), and component (C) to the polymerization reactor in an arbitrary order. (3) A method of adding a catalyst component in which component (A) is supported on component (S) and component (B) to the polymerization reactor in an arbitrary order. (4) A method of adding a catalyst component in which component (A) is supported on component (S), component (B), and component (C) to the polymerization reactor in an arbitrary order.

[0199] [Method for producing olefin polymer] The method for producing an olefin polymer of the present invention is characterized by having a step [P] of polymerizing an olefin (such as ethylene, an α-olefin having 3 to 20 carbon atoms, etc.) in the presence of the above-described catalyst for olefin polymerization. Here, "polymerization" is a general term for homopolymerization and copolymerization. Further, "polymerizing an olefin in the presence of a catalyst for olefin polymerization" includes a mode in which each component of the catalyst for olefin polymerization is added to a polymerization vessel by an arbitrary method as in each of the above-described methods (1) to (4) to polymerize the olefin.

[0200] In the present invention, the polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more. Further, a so-called bulk polymerization method in which the liquefied olefin itself that can be supplied to the polymerization is used as a solvent can also be used.

[0201] By the compound (A) of the present invention, the transition metal complex (B) can be fixed to the compound (A) or fixed to the porous material (S) via the compound (A) at a higher ratio than when using a Group 13 element-containing compound conventionally used as a cocatalyst in olefin polymerization instead of the compound (A). Therefore, according to the method for producing an olefin polymer of the present invention, it is possible to produce an olefin polymer with high activity even in a suspension polymerization method and a gas phase polymerization method, which were difficult when using a conventional borate compound.

[0202] When carrying out the polymerization of olefins using a catalyst for olefin polymerization, the amounts of the respective components that can constitute the catalyst for olefin polymerization are as follows. Further, in the catalyst for olefin polymerization, the content of each component can be adjusted as follows.

[0203] The compound (A) (component (A)) of the present invention can be used in an amount such that the molar ratio [(A) / (M)] of component (A) to all transition metal atoms (M) in component (B) is usually 1 to 100, preferably 1 to 20. When the molar ratio is within the above range, the proportion of component (A) having two or more sites in contact with component (B) is low, and since component (A) has low affinity with the hydrocarbon medium when the catalyst for olefin polymerization is used in a hydrocarbon medium, it is excellent in the immobilization and activation performance of the catalyst.

[0204] Component (B) is usually 1×10 per liter of reaction volume -10 ~1×10 -2 moles, preferably 1×10 -8 ~1×10 -3 moles and is used in such an amount. Component (C-1) can be used in an amount such that the molar ratio [(C-1) / M] of component (C-1) to all transition metal atoms (M) in component (B) is usually 1 to 50,000, preferably 10 to 20,000, particularly preferably 50 to 10,000.

[0205] Component (C-2) can be used in an amount such that the molar ratio [Al / M] of the aluminum atom in component (C-2) to all transition metal atoms (M) in component (B) is usually 10 to 5,000, preferably 20 to 2,000.

[0206] When component (S) is used, it can be used in an amount such that the weight ratio [(B) / (S)] of component (B) to component (S) is preferably 0.0001 to 1, more preferably 0.0005 to 0.5, and even more preferably 0.001 to 0.1.

[0207] In the production method of the present invention, the polymerization temperature is usually -50 to +200°C, preferably 0 to 200°C, more preferably 40 to 150°C, and the polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out by any of the batch, semi-continuous, and continuous methods. Furthermore, the polymerization can also be carried out in two or more stages with different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by the presence of hydrogen or the like in the polymerization system, by changing the polymerization temperature, or by the amount of component (C) used.

[0208] In particular, hydrogen can sometimes obtain the effects of improving the polymerization activity of the catalyst and increasing or decreasing the molecular weight of the polymer, and can be said to be a preferred additive. When adding hydrogen to the system, the appropriate amount is about 0.00001 to 100 NL per mole of olefin. In addition to adjusting the supply amount of hydrogen, the hydrogen concentration in the system can also be adjusted by carrying out a reaction that generates or consumes hydrogen in the system, by using a membrane to separate hydrogen, or by discharging a part of the gas containing hydrogen out of the system.

[0209] For the olefin polymer (for example, ethylene / α-olefin / non-conjugated polyene copolymer) obtained by the production method of the present invention, after synthesizing the olefin polymer by the above method, post-treatment steps such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step may be carried out as necessary.

[0210] 〈Olefin〉 In one embodiment of the production method of the present invention, examples of the olefin supplied to the polymerization reaction include ethylene and α-olefins having 3 to 20 carbon atoms.

[0211] In this embodiment, ethylene may be homopolymerized, ethylene and an α-olefin having 3 to 20 carbon atoms may be copolymerized, or an α-olefin having 3 to 20 carbon atoms may be homopolymerized or copolymerized.

[0212] Examples of the α-olefin include linear or branched α-olefins having 3 to 20 carbon atoms such as 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, and vinylcyclohexane. As the α-olefin, α-olefins having 3 to 10 carbon atoms, for example, linear or branched α-olefins having 3 to 10 carbon atoms are preferable, propylene, 1-butene, 1-hexene, and 1-octene are more preferable, and propylene is even more preferable. These α-olefins can be used alone or in combination of two or more.

[0213] Further, it may be copolymerized with ethylene or an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. When the compound (A) according to the present invention is brought into contact with the transition metal complex (B), since the cation constituting the compound (A) can form ion pairs at two positions, the transition metal complex (B) as the main catalyst is activated at one of them, and it is considered that the transition metal complex (B) can be immobilized on the compound (A) by the amine moiety coordinating to the polymerization active species. Further, since the other ion pair remains, the low solubility of the compound (A) in the polymerization solvent is maintained, and thus the olefin polymerization catalyst of the present invention is considered to function as a solid catalyst.

[0214] Therefore, when the compound (A) of the present invention is used as a cocatalyst for an olefin polymerization catalyst, in the two anions represented by [β] - constituting the compound (A), if one is the anion (β'), the other anion may be other than the anion (β').

[0215] The above was the explanation when [α] γ+ constituting the compound (A) is a dication, but even if [α] γ+ is a polyvalent cation having a valence of 3 or more, it is considered that the above functions are exhibited. In a method for producing an olefin polymer by polymerizing an olefin in the presence of a catalyst for olefin polymerization obtained by contacting a transition metal complex with a Group 13 element-containing compound (such as a borate compound), when the Group 13 element-containing compound (A) of the present invention is used as the Group 13 element-containing compound, the polymerization active species becomes less likely to dissolve and dissociate (leach) into a polymerization solvent or the like, and a solid catalyst component (X) can be obtained in which many metal species (transition metal complexes) are immobilized by the solid content (Group 13 element-containing compound (A)). In addition, by performing a polymerization reaction using the obtained solid catalyst component (X), a powdery polymer can be obtained with high catalytic activity.

[0216] The factor that exhibits the above advantages is not clear at present, but the present inventors speculate as follows. One method for forming a polymerization active species is to contact an ion pair component having an organic cation such as a tertiary ammonium that donates a proton to convert a transition metal compound (B) into a metal cation and a Group 13 element-containing anion that stabilizes the generated metal cation with the transition metal compound (B). However, after proton donation, ammonium becomes a non-ionic amine and is likely to dissolve in a polymerization solvent or the like. Also, the polymerization active species containing the metal cation is often likely to dissolve in a polymerization solvent or the like.

[0217] Therefore, in order to impart the function as a solid catalyst component, many of the prior arts have immobilized a conventional Group 13 element-containing compound by chemically reacting with a support such as silica gel.

[0218] A preferred embodiment of the Group 13 element-containing compound (A) of the present invention has a chemical structure in which two or more organic cations are connected by an alkyl chain or the like, and thus is a component having an ion pair even after proton donation, and dissolution into a polymerization solvent or the like can be suppressed. Also, the generated polymerization active species can suppress dissolution into a polymerization solvent or the like due to ionic interaction with the Group 13 element-containing compound (A) and coordination of the amine part to the polymerization active species, and many metal species can be retained in the solid content as the solid catalyst component (X).

Examples

[0219] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[0220] <Measurement method> [Identification of Group 13 element-containing compound (A)] The structure of the transition metal compound was measured and determined according to a conventional method using 270 MHz 1 1H-NMR (GSH-270 manufactured by JEOL Ltd.) and the like.

[0221] [Specific surface area and pore volume of porous material (S)] The specific surface area and pore volume of the porous material (S) were measured by the nitrogen gas adsorption method (BELSORP-max manufactured by MicrotracBEL) at liquid nitrogen temperature to measure the adsorption / desorption isotherm. As an analysis method, the BET method was used to obtain the specific surface area, and the BJH method was used to obtain the pore volume.

[0222] [Metal concentration in the supernatant during the preparation of solid catalyst component (X)] The concentrations of metals (Zr, Ti, Hf) in the supernatant during the preparation of the solid catalyst component (X) described in the following examples were analyzed by ICP emission spectrometry (720-ES manufactured by Agilent Technologies).

[0223] [Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of polymer] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymers produced in the following examples and the like were determined by gel permeation chromatography (GPC). It was calculated from the molecular weight distribution curve obtained by a Waters Alliance GPC 2000 gel permeation chromatograph (high-temperature size exclusion chromatograph), and the operating conditions are as follows: Operating conditions Analysis software; Chromatography Data System Empower (Waters) Column; TSKgel GMH6-HT×2 + TSKgel GMH6-HT×2 (inner diameter 7.5 mm × length 30 cm, Tosoh Corporation) Mobile phase; o-dichlorobenzene [=ODCB] Detector; differential refractometer (built into the device) Column temperature; 140 °C Flow rate; 1.0 mL / min Injection volume; 400 μL Sampling time interval; 1 second Sample concentration; 0.15% (w / v) Molecular weight calibration: monodisperse polystyrene (Tosoh Corporation) / molecular weight from 495 to 20.6 million

[0224] <Synthesis of Group 13 Element-Containing Compound (A)> [Example A1] (Synthesis of Group 13 Element-Containing Compound (A-1)) In Example A1, N,N,N',N'-tetramethyl-1,4-phenylenediamine dihydrochloride and lithium tetrakis(pentafluorophenyl)borate ethyl ether complex, purchased from Tokyo Chemical Industry Co., Ltd., were used as they were.

[0225] 3.7 g of lithium tetrakis(pentafluorophenyl)borate ethyl ether complex and 18 mL of dichloromethane were added to a 50 mL reactor that had been sufficiently dried and purged with nitrogen, and the mixture was stirred. Then, 0.3 g of N,N,N',N'-tetramethyl-1,4-phenylenediamine dihydrochloride was added, and stirring was continued overnight at room temperature. Insoluble matter in the resulting suspension was removed by passing it through celite on a glass filter, and the solvent was distilled off. After washing the residue with water, it was filtered, the solvent was removed, it was dissolved in a large amount of dichloromethane, and when left standing overnight at -25 °C, a white solid precipitated. This was filtered and dried under reduced pressure to obtain 390 mg of the Group 13 element-containing compound represented by the following formula (A-1). 1 H NMR (CD3OD) δ 3.15 (12H, s), 7.22 (4H, s) ppm

[0226] [Chemical formula]

[0227] [Example A2] (Synthesis of Group 13 Element-Containing Compound (A-2)) A 1M hydrogen chloride diethyl ether solution was purchased from Tokyo Chemical Industry Co., Ltd., and 1,4-diazabicyclo[2.2.2]octane was purchased from Fujifilm Wako Pure Chemical Corporation and used as it was.

[0228] To a sufficiently dried and nitrogen-purged 50 mL reactor, 560 mg of 1,4-diazabicyclo[2.2.2]octane and 7 mL of diethyl ether were added and stirred. Then, 15 mL of a 1M hydrogen chloride diethyl ether solution was added dropwise under an ice bath, and after returning to room temperature, stirring was continued for 2 hours. The insoluble matter in the obtained suspension was collected by filtration and dried under reduced pressure to obtain 320 mg of 1,4-diazabicyclo[2.2.2]octane dihydrochloride represented by the following formula (A-2'). 1 H NMR (CD3OD) δ 3.75 (12H, s) ppm

[0229] [Chemical formula]

[0230] Subsequently, to a sufficiently dried and nitrogen-purged 50 mL reactor, 100 mg of 1,4-diazabicyclo[2.2.2]octane dihydrochloride and 20 mL of dichloromethane were added and stirred. Then, 1.1 g of lithium tetrakis(pentafluorophenyl)borate ethyl ether complex was added, and stirring was continued overnight at room temperature. The insoluble matter in the obtained suspension was collected by filtration. This was dissolved in the minimum amount of methanol and reprecipitated with water, and the obtained solid was collected by filtration and dried under reduced pressure to obtain 230 mg of a Group 13 element-containing compound represented by the following formula (A-2). 1 H NMR (CD3OD) δ 3.16 (12H, s) ppm

[0231] [Chemical formula]

[0232] [Comparative Example A3] (Synthesis of Group 13 Element-Containing Compound (a-3)) N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate represented by the following formula (a-3) was used as purchased from Tokyo Chemical Industry Co., Ltd. without further treatment.

[0233] [Chemical Formula]

[0234] [Comparative Example A4] Synthesis of Group 13 Element-Containing Compound (a-4) Trimethylammonium chloride was used as purchased from Fujifilm Wako Pure Chemical Corporation without further treatment.

[0235] 770 mg of lithium tetrakis(pentafluorophenyl)borate ethyl ether complex and 20 mL of dichloromethane were added to a thoroughly dried and nitrogen-substituted 50 mL reactor, and the mixture was stirred. Then, 75 mg of trimethylammonium chloride was added, and stirring was continued overnight at room temperature. The insoluble matter in the resulting suspension was removed by passing it through celite on a glass filter, and the solvent was distilled off. The residue was washed with hexane and water and then dried under reduced pressure to obtain 400 mg of a Group 13 element-containing compound represented by the following formula (a-4). 1 H NMR (CDCl3) δ 1.65 (9H, s) ppm

[0236] [Chemical Formula]

[0237] [Example A5] (Synthesis of Group 13 Element-Containing Compound (A-5)) Into a sufficiently dried and nitrogen-substituted 50 mL reactor, 200 mg of 1,4-diazabicyclo[2.2.2]octane dihydrochloride synthesized in Synthesis Example 2 and 20 mL of dichloromethane were added and stirred. Then, 1.0 g of lithium tetrakis(pentafluorophenyl)borate ethyl ether complex was added, and stirring was continued at room temperature for 24 hours. Insoluble matter in the obtained suspension was removed by passing through celite on a glass filter, and the solvent was distilled off. The residue was washed with water, hexane, and CH2Cl2 respectively, the insoluble matter was recovered by filtration, and dried under reduced pressure to obtain 230 mg of a Group 13 element-containing compound represented by the following formula (A-5). 1 H NMR(CD3OD)δ 3.57(12H,s)ppm

[0238]

Chemical formula

[0239] [Example A6] (Synthesis of Group 13 element-containing compound (A-6)) N,N,N',N'-tetramethyl-1,6-diaminohexane purchased from Tokyo Chemical Industry Co., Ltd. was used as it was. Into a sufficiently dried and nitrogen-substituted 100 mL reactor, 1.4 g of N,N,N',N'-tetramethyl-1,6-diaminohexane and 20 mL of diethyl ether were added and stirred. Then, after dropping 25 mL of 1M hydrogen chloride diethyl ether solution under an ice bath, the mixture was returned to room temperature and stirring was continued for 2 hours. The solvent in the obtained suspension was distilled off, and the residue was dried under reduced pressure to obtain 2.0 g of N,N,N',N'-tetramethyl-1,6-diaminohexane dihydrochloride represented by the following formula (A-6'). 1 H NMR(CD3OD)δ 1.46(4H,m),1.77(4H,m),2.88(12H,s),3.13(4H,m)ppm

[0240]

Chemical formula

[0241] Subsequently, 2.5 g of lithium tetrakis(pentafluorophenyl)borate ethyl ether complex and 100 mL of dichloromethane were added to a thoroughly dried and nitrogen-substituted 200 mL reactor, and the mixture was stirred. Then, 310 mg of N,N,N',N'-tetramethyl-1,6-diaminohexane dihydrochloride was added, and stirring was continued overnight at room temperature. The insoluble matter in the resulting suspension was collected by filtration. After washing this with hexane and water, 1.8 g of a Group 13 element-containing compound represented by the following formula (A-6) was obtained by drying under reduced pressure. 1 H NMR (CD3OD) δ 1.44 (4H, m), 1.73 (4H, m), 2.86 (12H, s), 3.09 (4H, m) ppm

[0242] [Chemical Formula]

[0243] [Example A7] (Synthesis of Group 13 Element-Containing Compound (A-7)) N,N-Dimethyl-1,3-propanediamine dihydrochloride purchased from Tokyo Chemical Industry Co., Ltd. was used as it was.

[0244] 600 mg of lithium tetrakis(pentafluorophenyl)borate ethyl ether complex and 25 mL of dichloromethane were added to a thoroughly dried and nitrogen-substituted 50 mL reactor, and the mixture was stirred. Then, 54 mg of N,N-dimethyl-1,3-propanediamine dihydrochloride was added, and stirring was continued overnight at room temperature. The insoluble matter in the resulting suspension was collected by filtration. After washing this with hexane and water, 150 mg of a Group 13 element-containing compound represented by the following formula (A-7) was obtained by drying under reduced pressure. 1 H NMR (CD3OD) δ 3.21 (2H, m), 3.03 (2H, m), 2.92 (6H, s), 2.06 (2H, m) ppm

[0245] [Chemical Formula]

[0246] [Example A8] (Synthesis of Group 13 Element-Containing Compound (A-8)) (S,S)-N,N-Bis(1-hydroxy-2-butyl)ethylenediamine dihydrochloride was used as purchased from Tokyo Chemical Industry Co., Ltd.

[0247] 600 mg of lithium tetrakis(pentafluorophenyl)borate ethyl ether complex and 25 mL of dichloromethane were added to a sufficiently dried and nitrogen-substituted 50 mL reactor and stirred. Then, 87 mg of (S,S)-N,N-bis(1-hydroxy-2-butyl)ethylenediamine dihydrochloride was added, and stirring was continued overnight at room temperature. Insoluble matter in the resulting suspension was removed by passing through celite on a glass filter, and the solvent was distilled off. The residue was washed with hexane and water and then dried under reduced pressure to obtain 420 mg of a Group 13 element-containing compound represented by the following formula (A-8). 1 H NMR (CD3OD) δ 3.86 (2H, m), 3.73 (2H, m), 3.43 (4H, s), 3.23 (2H, m), 1.75 (4H, m), 1.06 (6H, t) ppm

[0248] [Chemical Formula]

[0249] [Example A9] (Synthesis of Group 13 Element-Containing Compound (A-11)) N,N,N’,N’’,N’’-Pentamethyldiethylenetriamine was used as purchased from Tokyo Chemical Industry Co., Ltd. 400 mg of N,N,N’,N’’,N’’-pentamethyldiethylenetriamine and 15 mL of diethyl ether were added to a thoroughly dried and nitrogen-substituted 100 mL reactor, followed by stirring. Subsequently, 8 mL of a 1 M hydrogen chloride diethyl ether solution was added dropwise under an ice bath, and then the mixture was returned to room temperature and stirring was continued for 2 hours. The solvent in the resulting suspension was distilled off, and the residue was dried under reduced pressure to obtain 600 mg of N,N,N’,N’’,N’’-pentamethyldiethylenetriamine trihydrochloride represented by the following formula (A-11’). 1 H NMR(CD3OD)δ 2.54(3H,s),2.94(12H,m),3.15(4H,m),3.48(4H,m)ppm

[0250]

Chemical formula

[0251] Subsequently, 1.1 g of lithium tetrakis(pentafluorophenyl)borate ethyl ether complex and 20 mL of deionized water were added to a thoroughly dried and nitrogen-substituted 100 mL reactor, followed by stirring. Then, 200 mg of N,N,N’,N’’,N’’-pentamethyldiethylenetriamine trihydrochloride was added, and stirring was continued at room temperature for 2 hours. The insoluble matter in the resulting suspension was collected by filtration. After washing this with hexane and water, it was dried under reduced pressure to obtain 700 mg of a Group 13 element-containing compound represented by the following formula (A-11). 1 H NMR(CD3OD)δ 2.36(3H,s),2.83(4H,m), 2.93(12H,s),3.27(4H,m)ppm

[0252]

Chemical formula

[0253] [Example A10] (Synthesis of Group 13 element-containing compound (A-12)) Hexamethylenetetramine purchased from Kanto Chemical Co., Inc. was used as it was. To a sufficiently dried and nitrogen-substituted 100 mL reactor, 0.4 g of hexamethylenetetramine and 15 mL of diethyl ether were added and stirred. Then, 13 mL of a 1 M hydrogen chloride diethyl ether solution was added dropwise under an ice bath, and then the mixture was returned to room temperature and stirring was continued for 2 hours. The solvent in the obtained suspension was distilled off, and the residue was dried under reduced pressure to obtain 820 mg of hexamethylenetetramine tetrahydrochloride represented by the following formula (A-12’). 1 H NMR (CD3OD) δ 4.86 (12H, s) ppm

[0254]

Chemical formula

[0255] Subsequently, to a sufficiently dried and nitrogen-substituted 100 mL reactor, 580 mg of lithium tetrakis(pentafluorophenyl)borate ethyl ether complex and 20 mL of deionized water were added and stirred. Then, 170 mg of hexamethylenetetramine tetrahydrochloride dihydrochloride was added, and stirring was continued at room temperature for 2 hours. The insoluble matter in the obtained suspension was collected by filtration. This was washed with water and hexane and then dried under reduced pressure to obtain 450 mg of a Group 13 element-containing compound represented by the following formula (A-12). 1 H NMR (CD3OD) δ 4.94 (12H, s) ppm

[0256]

Chemical formula

[0257] [Example A11] (Synthesis of Group 13 element-containing compound (A-13)) 1,3-Diaminopropane dihydrochloride purchased from Tokyo Chemical Industry Co., Ltd. was used as it was. 600 mg of lithium tetrakis(pentafluorophenyl)borate ethyl ether complex and 50 mL of deionized water were added to a 100 mL reactor that had been sufficiently dried and purged with nitrogen, and the mixture was stirred. Then, 45 mg of 1,3-diaminopropane dihydrochloride was added, and stirring was continued at room temperature for 2 hours. The insoluble matter in the resulting suspension was collected by filtration. After washing this with water and hexane, it was dried under reduced pressure to obtain 320 mg of a Group 13 element-containing compound represented by the following formula (A-13). 1 H NMR (CD3OD) δ 1.99 (2H, m), 3.01 (4H, m) ppm

[0258]

Chemical formula

[0259] (Supported catalyst and polymerization) <Transition metal compound (B)> As the transition metal compound (B), transition metal compounds represented by the following formulas (B-1) to (B-4) produced by a conventionally known method were used.

[0260]

Chemical formula

[0261] <Porous material (S)> As the porous material (S-1), silica gel (manufactured by Fuji Silysia Chemical, average particle diameter: 70 μm, specific surface area: 340 m 2 / g, pore volume: 1.3 cm 3 / g), As the porous material (S-2), silica gel (Sunsphere H-122 manufactured by AGC Si-Tech, average particle diameter 12 μm, specific surface area: 700 m 2 / g, pore volume: 2 cm 3 / g), As the porous material (S-3), mesoporous aluminosilicate (MCM-41 (hexagonal) purchased from Sigma-Aldrich, specific surface area: 1,000 m 2 / g, pore volume: 1 cm3 / g), As the porous material (S-4), γ-alumina (purchased from STREM, specific surface area: 200 m 2 / g, pore volume: 0.5 cm 3 / g) was used.

[0262] <Preparation of the solid catalyst component (X) immobilizing the transition metal compound (B) and polymerization of olefins> [Example X1] To a 30 mL reactor that had been sufficiently dried and purged with nitrogen, 30.5 mg (20.0 μmol) of the Group 13 element-containing compound (A-1) obtained in Example A1 and 15.0 mL of heptane were added and stirred. To this, a mixed solution (5.00 mL) prepared in another reactor by mixing the transition metal compound (B-1), triisobutylaluminum, and heptane so that the Zr concentration was 1.00 μmol / mL and the Al concentration was 30.0 μmol / mL was added, and stirring was continued at room temperature for 30 minutes.

[0263] After stopping the stirring and allowing the solid content of the suspension to settle sufficiently, a part of the supernatant liquid not containing the solid content was collected and analyzed. As a result, the Zr concentration was 0.211 μmol / mL. Thereafter, decantation of the supernatant liquid and addition of heptane were repeated to prepare a 20.0 mL suspension of the solid catalyst component (X-1).

[0264] To a 1 L SUS autoclave with a sufficient nitrogen substitution, 500 mL of heptane was added under a nitrogen atmosphere, and then ethylene was passed through to saturate the inside of the reactor with ethylene. Next, 0.38 mmol of triisobutylaluminum and 10.0 mL of the suspension of the solid catalyst component (X-1) withdrawn with stirring were charged, and then the temperature and pressure were raised to 80 °C and 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the content, it was vacuum dried at 80 °C for 10 hours to obtain 1.98 g of polymer powder.

[0265] [Example X2] Instead of the Group 13 element-containing compound (A-1), a suspension of the solid catalyst component (X-2) was prepared in the same manner as in Example X1, except that 29.4 mg (20.0 μmol) of the Group 13 element-containing compound (A-2) obtained in Synthesis Example 2 was used. At this time, the Zr concentration in the supernatant was 0.181 μmol / mL.

[0266] A polymerization reaction was carried out in the same manner as in Example X1, except that 10.0 mL of the suspension of the solid catalyst component (X-2) was used instead of the solid catalyst component (X-1). After filtering the contents, the polymer powder (16.3 g) was obtained by vacuum drying at 80 °C for 10 hours.

[0267] [Comparative Example X1] A suspension of the solid catalyst component (x-3) was prepared in the same manner as in Example X1, except that 16.0 mg (20.0 μmol) of the Group 13 element-containing compound (a-3) obtained in Comparative Example A1 was used instead of the Group 13 element-containing compound (A-1). At this time, the Zr concentration in the supernatant was 0.243 μmol / mL.

[0268] A polymerization reaction was carried out in the same manner as in Example X1, except that 10.0 mL of the suspension of the solid catalyst component (x-3) was used instead of the solid catalyst component (X-1). After filtering the contents, the polymer powder (0.06 g) was obtained by vacuum drying at 80 °C for 10 hours.

[0269] [Comparative Example X2] A suspension of the solid catalyst component (x-4) was prepared in the same manner as in Example X1, except that 14.8 mg (20.0 μmol) of the Group 13 element-containing compound (a-4) obtained in Comparative Example A2 was used instead of the Group 13 element-containing compound (A-1). At this time, the Zr concentration in the supernatant was 0.241 μmol / mL.

[0270] A polymerization reaction was carried out in the same manner as in Example X1, except that 10.0 mL of a suspension of the solid catalyst component (x-4) was used instead of the solid catalyst component (X-1). After filtering the content, it was dried in vacuo at 80 °C for 10 hours to obtain 0.10 g of polymer powder. Table 1 shows the evaluation results and the like of Examples X1 to X2 and Comparative Examples X1 to X2.

[0271] [Table 1]

[0272] In the examples using the Group 13 element-containing compound (A) of the present invention, the Zr concentration in the supernatant after contact with the transition metal compound (B) is lower than that in the comparative examples. This indicates that more Zr was immobilized in the solid content as the solid catalyst component (X). In addition, when a polymerization reaction was carried out using the solid catalyst component (X), more polymer could be obtained in a powder state than in the comparative examples.

[0273] <Preparation and Polymerization Evaluation of Solid Catalyst Component (X) Containing Porous Material (S)> [Example X3] 150 mg of the porous material (S-1) was added to a sufficiently dried and nitrogen-substituted 30 mL reactor, and a solution prepared by dissolving 22.8 mg of the Group 13 element-containing compound (A-1) obtained in Example A1 in 0.18 mL of methanol was added dropwise thereto. Thereafter, vacuum drying was carried out at 50 °C for 3 hours to obtain a powder of the porous material (S-1) impregnated with the Group 13 element-containing compound (A-1). 11.0 mL of heptane was added thereto and stirred, and 0.25 mL of a triisobutylaluminum solution (heptane solution, 1.0 M) was added dropwise thereto, and stirring was continued for 30 minutes. Next, in another reactor, the transition metal compound (B-1), triisobutylaluminum, and heptane were mixed, and 3.75 mL of a mixed solution prepared to have a Zr concentration of 1.00 μmol / mL and an Al concentration of 30.0 μmol / mL was added, and stirring was further continued at room temperature for 30 minutes.

[0274] After stopping the stirring and allowing the solid content of the suspension to settle sufficiently, a part of the supernatant liquid containing no solid content was collected and analyzed. As a result, the Zr concentration was less than the detection limit (0.011 μmol / mL).

[0275] Thereafter, decantation of the supernatant liquid and addition of heptane were repeated to prepare a 15.0 mL suspension of the solid catalyst component (X-5). 500 milliliters of heptane was added to a 1-liter SUS autoclave with a sufficient nitrogen substitution under a nitrogen atmosphere. After that, ethylene was passed through to saturate the inside of the reactor with ethylene. Next, 0.38 mmol of triisobutylaluminum and 6.0 mL of the suspension of the solid catalyst component (X-5) withdrawn with stirring were charged. Then, the temperature and pressure were raised to 80 °C and 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the content, it was vacuum dried at 80 °C for 10 hours to obtain 24.2 g of polymer powder. The Mw of the obtained polymer was 3,740,000, and Mw / Mn was 3.0.

[0276] [Examples X4 to X8] The addition of the transition metal compound (B-1), the analysis of the supernatant liquid, etc. were carried out in the same manner as in Example X3 except that the Group 13 element-containing compound (A) described in Table 2 was used instead of the Group 13 element-containing compound (A-1), and suspensions of the solid catalyst components (X-6) to (X-10) were prepared. The Zr concentration in the supernatant liquid at this time is shown in Table 2.

[0277] A polymerization reaction was carried out in the same manner as in Example X3 except that 6.0 mL of the suspension of the solid catalyst component (X) described in Table 2 was used instead of the solid catalyst component (X-5). The weight of the obtained polymer powder is shown in Table 2.

[0278] [Example X8'] After adding 500 milliliters of heptane to a 1-liter SUS autoclave with sufficient nitrogen substitution under a nitrogen atmosphere, ethylene was passed through to saturate the reactor with ethylene. Next, 0.38 mmol of triisobutylaluminum and 6.0 mL of a suspension of the solid catalyst component (X-10) prepared in Example X8, which was withdrawn while stirring, were charged. Then, using an ethylene-hydrogen mixed gas with a hydrogen concentration of 0.10 vol%, the temperature and pressure were raised to 80 °C and 0.8 MPaG, and a polymerization reaction was carried out for 90 minutes. After filtering the contents, they were dried under vacuum at 80 °C for 10 hours to obtain 116.8 g of polymer powder.

[0279] [Comparative Examples X3, X4] Instead of the Group 13 element-containing compound (A-1), the Group 13 element-containing compound (A) described in Table 2 was used. In the same manner as in Example X3, the addition of the transition metal compound (B-1), the analysis of the supernatant, etc. were carried out to prepare suspensions of solid catalyst components (x-11) to (x-12). The Zr concentration in the supernatant at this time is shown in Table 2.

[0280] A polymerization reaction was carried out in the same manner as in Example X3, except that 6.0 mL of a suspension of the solid catalyst component (X) described in Table 2 was used instead of the solid catalyst component (X-5). The weight of the obtained polymer powder is shown in Table 2.

[0281] Even when the porous material (S) is impregnated with the Group 13 element-containing compound (A), in the examples using the Group 13 element-containing compound (A) of the present invention, the Zr concentration in the supernatant after contact with the transition metal compound (B) is lower than that in the comparative examples, and more Zr is immobilized in the solid content as the solid catalyst component (X). In addition, when a polymerization reaction is carried out using the solid catalyst component (X), more polymer powder can be obtained compared to the comparative examples.

[0282] [Example X9] In a sufficiently dried and nitrogen-substituted 30 mL reactor, 150 mg of a porous material (S-1) was added, and a solution prepared by dissolving 12.4 mg of a Group 13 element-containing compound (A-5) in 0.18 mL of methanol was added dropwise thereto. Thereafter, vacuum drying was performed at 50 °C for 3 hours to obtain a powder of the porous material (S-1) impregnated with the Group 13 element-containing compound (A-5). To this, 11.0 mL of heptane was added and stirred, and 0.25 mL of a triisobutylaluminum solution (heptane solution, 1.0 M) was added dropwise while stirring, and stirring was continued for 30 minutes. Next, in another reactor, a transition metal compound (B-2), triisobutylaluminum, and heptane were mixed, and 3.75 mL of a mixed solution prepared to have a Zr concentration of 1.00 μmol / mL and an Al concentration of 150.0 μmol / mL was added, and stirring was further continued at room temperature for 30 minutes.

[0283] After stopping the stirring and allowing the solid content of the suspension to settle sufficiently, a part of the supernatant liquid not containing the solid content was collected and analyzed. As a result, the Zr concentration was 0.064 μmol / mL. Thereafter, decantation of the supernatant liquid and addition of heptane were repeated to prepare a 15.0 mL suspension of the solid catalyst component (X-13).

[0284] In a 1-liter SUS autoclave with a sufficiently nitrogen-substituted internal volume, 500 milliliters of heptane was added under a nitrogen atmosphere, and then ethylene was passed through to saturate the inside of the reactor with ethylene. Next, 0.38 mmol of triisobutylaluminum and 6.0 mL of a suspension of the solid catalyst component (X-13) withdrawn while stirring were charged, and then the temperature and pressure were raised to 80 °C and 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the content, vacuum drying was performed at 80 °C for 10 hours to obtain 12.8 g of a polymer powder.

[0285] [Example X10] 150 mg of the porous material (S-1) that had been sufficiently dried and purged with nitrogen was added to a 30 mL reactor. While dropping a solution prepared by dissolving 12.4 mg of the Group 13 element-containing compound (A-5) in 0.18 mL of methanol, it was added. Thereafter, vacuum drying was performed at 50 °C for 3 hours to obtain a powder of the porous material (S-1) impregnated with the Group 13 element-containing compound (A-5). 11.0 mL of heptane was added thereto and stirred, and 0.25 mL of a triisobutylaluminum solution (heptane solution, 1.0 M) was added dropwise while stirring, and stirring was continued for 30 minutes. Next, in another reactor, a transition metal compound (B-3) and heptane were mixed, and 3.75 mL of a mixed solution prepared to have a Ti concentration of 1.00 μmol / mL was added, and stirring was continued at room temperature for 30 minutes.

[0286] After stopping the stirring and allowing the solid content of the suspension to settle sufficiently, a part of the supernatant liquid not containing the solid content was collected and analyzed. As a result, the Ti concentration was less than the detection lower limit (0.021 μmol / mL).

[0287] Thereafter, decantation of the supernatant liquid and addition of heptane were repeated to prepare a 15.0 mL suspension of the solid catalyst component (X-14). 500 milliliters of heptane was added to a 1-liter SUS autoclave with a sufficient nitrogen substitution under a nitrogen atmosphere, and then ethylene was passed through to saturate the inside of the reactor with ethylene. Next, 0.38 mmol of triisobutylaluminum and 6.0 mL of the suspension of the solid catalyst component (X-14) withdrawn while stirring were charged, and then the temperature and pressure were raised to 80 °C and 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the contents, vacuum drying was performed at 80 °C for 10 hours to obtain 106.2 g of a polymer powder. The Mw of the obtained polymer was 2,520,000 and Mw / Mn was 4.6.

[0288] [Example X10'] Into a 1-liter SUS autoclave with sufficient nitrogen replacement, 500 milliliters of heptane was added under a nitrogen atmosphere. Then, ethylene was passed through to saturate the inside of the reactor with ethylene. Next, 3.0 mL of 1-hexene, 0.38 mmol of triisobutylaluminum, and 6.0 mL of a suspension of the solid catalyst component (X-14) prepared in Example X10, which was withdrawn while stirring, were charged. After that, the temperature and pressure were raised to 80 °C and 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the contents, vacuum drying was performed at 80 °C for 10 hours to obtain 99.4 g of polymer powder. The Mw of the obtained polymer was 2,330,000, and the Mw / Mn was 3.3.

[0289] [Example X11] To a 30 mL reactor that had been sufficiently dried and nitrogen-replaced, 150 mg of a porous material (S-2) was added, and a solution in which 12.4 mg of a Group 13 element-containing compound (A-5) was dissolved in 0.30 mL of methanol was added dropwise. Then, vacuum drying was carried out at 50 °C for 3 hours to obtain a powder of the porous material (S-2) impregnated with the Group 13 element-containing compound (A-5). 10.9 mL of heptane was added thereto and stirred, and 0.37 mL of a triisobutylaluminum solution (heptane solution, 1.0 M) was added dropwise while stirring, and stirring was continued for 30 minutes. Next, in another reactor, a transition metal compound (B-4), triisobutylaluminum, and heptane were mixed, and 3.75 mL of a mixed solution prepared to have an Hf concentration of 1.00 μmol / mL and an Al concentration of 4.00 μmol / mL was added, and stirring was continued at room temperature for 30 minutes.

[0290] After stopping the stirring and allowing the solid content of the suspension to settle sufficiently, a part of the supernatant liquid without the solid content was sampled and analyzed. As a result, the Hf concentration was less than the detection limit (0.006 μmol / mL).

[0291] Thereafter, decantation of the supernatant liquid and addition of heptane were repeated to prepare a 15.0 mL suspension of the solid catalyst component (X-15). After adding 500 milliliters of heptane to a 1-liter SUS autoclave with sufficient nitrogen substitution in a nitrogen atmosphere, ethylene was passed through to saturate the reactor with ethylene. Next, 0.38 mmol of triisobutylaluminum and 6.0 mL of a suspension of the solid catalyst component (X-15) withdrawn with stirring were charged. Then, the temperature and pressure were raised to 80 °C and 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the contents, vacuum drying was performed at 80 °C for 10 hours to obtain 3.55 g of polymer powder.

[0292] [Example X12] 150 mg of a porous material (S-3) was added to a 30 mL reactor that had been sufficiently dried and nitrogen-substituted. A solution prepared by dissolving 14.6 mg of a Group 13 element-containing compound (A-5) in 0.15 mL of methanol was added dropwise thereto. Thereafter, vacuum drying was carried out at 50 °C for 3 hours to obtain a powder of the porous material (S-3) impregnated with the Group 13 element-containing compound (A-5). 10.9 mL of heptane was added thereto and stirred, and 0.25 mL of a triisobutylaluminum solution (heptane solution, 1.0 M) was added dropwise while stirring, and stirring was continued for 30 minutes. Next, in another reactor, a transition metal compound (B-1), triisobutylaluminum, and heptane were mixed, and 3.75 mL of a mixed solution prepared to have a Zr concentration of 1.00 μmol / mL and an Al concentration of 30.0 μmol / mL was added, and stirring was further continued at room temperature for 30 minutes.

[0293] After stopping the stirring and allowing the solid content of the suspension to settle sufficiently, a part of the supernatant liquid containing no solid content was collected and analyzed. As a result, the Zr concentration was 0.158 μmol / mL. Thereafter, decantation of the supernatant liquid and addition of heptane were repeated to prepare a 15.0 mL suspension of the solid catalyst component (X-16).

[0294] After adding 500 milliliters of heptane to a 1-liter SUS autoclave with sufficient nitrogen substitution in a nitrogen atmosphere, ethylene was passed through to saturate the inside of the reactor with ethylene. Next, 0.38 mmol of triisobutylaluminum and 6.0 mL of a suspension of the solid catalyst component (X-16) withdrawn with stirring were charged. Then, the temperature and pressure were raised to 80 °C and 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the contents, the polymer powder (3.43 g) was obtained by vacuum drying at 80 °C for 10 hours.

[0295] [Example X13] 300 mg of a porous material (S-4) was added to a 30 mL reactor that had been sufficiently dried and nitrogen-substituted. A solution prepared by dissolving 9.74 mg of a Group 13 element-containing compound (A-5) in 0.12 mL of methanol was added dropwise thereto. Then, vacuum drying was carried out at 50 °C for 3 hours to obtain a powder of the porous material (S-4) impregnated with the Group 13 element-containing compound (A-5). 11.9 mL of heptane was added thereto and stirred, and 0.12 mL of a triisobutylaluminum solution (heptane solution, 1.0 M) was added dropwise while stirring, and stirring was continued for 30 minutes. Next, in another reactor, a transition metal compound (B-1), triisobutylaluminum, and heptane were mixed, and 2.94 mL of a mixed solution prepared to have a Zr concentration of 1.00 μmol / mL and an Al concentration of 30.0 μmol / mL was added, and stirring was continued at room temperature for 30 minutes.

[0296] After stopping the stirring and allowing the solid content of the suspension to settle sufficiently, a part of the supernatant liquid containing no solid content was collected and analyzed. As a result, the Zr concentration was 0.122 μmol / mL. Thereafter, decantation of the supernatant liquid and addition of heptane were repeated to prepare a 15.0 mL suspension of the solid catalyst component (X-17).

[0297] 500 mL of heptane was added to a 1 L SUS autoclave with sufficient nitrogen substitution under a nitrogen atmosphere, and then ethylene was passed through to saturate the reactor with ethylene. Next, 0.38 mmol of triisobutylaluminum and 7.5 mL of a suspension of the solid catalyst component (X-17) withdrawn with stirring were charged. Then, the temperature and pressure were raised to 80 °C and 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the content, it was dried in vacuo at 80 °C for 10 hours to obtain 1.52 g of polymer powder. Table 2 shows the evaluation results and the like of Examples X3 to X13 and Comparative Examples X3 to X4.

[0298] [Table 2]

[0299] [Examples X14 to X16] The addition of the transition metal compound (B-1), the analysis of the supernatant, etc. were carried out in the same manner as in Example X3, except that the Group 13 element-containing compound (A) described in Table 3 was used instead of the Group 13 element-containing compound (A-1), and suspensions of solid catalyst components (X-18) to (X-20) were prepared. The Zr concentration in the supernatant at this time is shown in Table 3. A polymerization reaction was carried out in the same manner as in Example X3, except that 6.0 mL of a suspension of the solid catalyst component (X) described in Table 3 was used instead of the solid catalyst component (X-5). The weight of the obtained polymer powder is shown in Table 3.

[0300] [Table 3]

Claims

**Claim 1**: A catalyst for olefin polymerization comprising a Group 13 element-containing compound (A) represented by the following general formula (A) and a transition metal complex (B). [α]γ+ {β}γ- … (A) 〔In the general formula (A), γ is an integer of 2 to 100. [α]γ+ is a cation represented by the following general formula (α). 【Chemical 1】 (In the general formula (α), γ is an integer of 2 to 100. R1 is a hydrocarbon group having 1 to 100 carbon atoms or a hydrocarbon group containing a heteroatom. The four R2s are each independently a hydrogen atom, a hydrocarbon group having 1 to 100 carbon atoms, or a hydrocarbon group containing a heteroatom. A plurality of R2s may be bonded to each other to form a ring. R1 and one or more of the R2s may be bonded to each other to form a ring.) {β}γ- represents one or two or more anions (β), and the total valence of the anions (β) is γ valent. The anion (β) is an anion (β') represented by the following general formula (β'-I), (β'-II) or (β'-III), or an anion (β'') other than the anion (β'), and at least one of the anions (β) is the anion (β'). When a plurality of the anions (β) are present, they may be the same as or different from each other. 【Chemical 2】 (In the general formulas (β'-I), (β'-II) and (β'-III), M' is an atom of a Group 13 element. A plurality of R3s are each independently an aryl group having 6 to 20 carbon atoms represented by the following general formula (R3), and a plurality of R3s may be bonded to each other to form a ring. 【Chemical 3】 (In the general formula (R3), * is a bond to M'. A plurality of Rs are each independently a substituent (r3) selected from the group consisting of a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing a heteroatom, and a hydrocarbon-substituted silyl group, or a hydrogen atom, and at least one of the Rs adjacent to * is the substituent (r3). When a plurality of the substituents (r3) are present, the plurality of substituents (r3) may be the same as or different from each other, and may be bonded to each other to form an aromatic ring which may have a substituent.) A plurality of R4s are each independently an arylene group having 6 to 20 carbon atoms represented by the following general formula (R4), (R5) or (R6), and the plurality of R4s may be bonded to each other to form a ring, and R4 may be bonded to R3 to form a ring. 【Chemical Formula 4】 (In the general formulas (R4), (R5) and (R6), * is a bond to M'. R has the same meaning as R in the general formula (R3).))

2. In the general formulas (β'-I), (β'-II) and (β'-III), M' is an atom of boron or aluminum, and all Rs 3 each independently has a halogen atom or a halogen atom-containing hydrocarbon group as at least one of the Rs adjacent to * in the general formula (R3). The olefin polymerization catalyst according to claim 1.

3. The olefin polymerization catalyst according to claim 1 or 2, further comprising a porous material (S).

4. A method for producing an olefin polymer by polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 3.

Images