Olefin polymerization catalyst component and method for producing olefinic polymer

Abstract

To provide: a highly active catalyst component used for the production of olefinic (particularly propylene) polymers and copolymers without a decrease in molecular weight compared to conventional catalysts; and a method for producing olefinic (particularly propylene) polymers and copolymers employing the same.SOLUTION: The olefin polymerization catalyst component comprises: a metal complex (D), which is a product of reaction of a compound (A) represented by a specific general formula [1] or a compound (B) represented by a specific general formula [2] with a transition metal compound (C) containing at least one of nickel and palladium; and a compound (E) represented by a specific general formula [3].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a catalyst component for olefin polymerization and a method for producing an olefin polymer. [Background technology]

[0002] Copolymers of olefins and vinyl monomers containing polar functional groups are industrially useful polymers. These copolymers are generally produced by high-pressure radical polymerization. Although high-pressure radical polymerization is effective for the polymerization of ethylene, it cannot polymerize olefins having a large number of carbon atoms such as propylene. Coordination polymerization is also widely known as a method for producing ethylene and olefin polymers. Ziegler catalysts and metallocene catalysts are widely used in coordination polymerization, but these catalysts are deactivated by vinyl monomers containing polar functional groups. Therefore, it has been difficult to obtain copolymers with polar functional groups introduced by coordination polymerization using these catalysts. In recent years, it has become clear that in the coordination polymerization of ethylene and a polar functional group-containing vinyl monomer, the use of a late transition metal complex catalyst makes it difficult for deactivation caused by the polar functional group-containing vinyl monomer to occur, and copolymerization proceeds. Specific examples include a palladium complex having a diimine ligand reported by Brookhart et al. (Non-Patent Document 1) and a nickel complex having a salicylaldimine ligand reported by Grubbs et al. (Non-Patent Document 2). It has also been disclosed that a nickel complex having a phosphinophenolate ligand can be applied to the copolymerization of ethylene and (meth)acrylate (Patent Document 1). It has been reported that the addition of a Lewis base to a nickel complex having a phosphinophenolate ligand improves the polymerization performance in ethylene polymerization (Patent Document 2). Compared to ethylene, there are only a limited number of reports on the polymerization of olefins such as propylene using late transition metal complex catalysts. For example, it has been disclosed that nickel complexes having phosphinophenolate ligands are useful for producing polypropylene with a relatively high molecular weight (Patent Document 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6913051 [Patent Document 2] Patent No. 5232718 [Patent Document 3] International Publication No. 2018 / 021446 [Non-patent literature]

[0004] [Non-Patent Document 1] M. Brookhart et al., "J. Am. Chem. Soc.", 1996, 118, 267-268. [Non-Patent Document 2] RH Grubbs et al., Science, 2000, 287, 460-462. Summary of the Invention [Problem to be solved by the invention]

[0005] In industrially producing a copolymer of an olefin having 3 or more carbon atoms, such as propylene, and a vinyl monomer containing a polar functional group, the catalytic activity of the metal complex disclosed in Patent Document 3 is not sufficient, and there is a demand for the development of a complex catalyst with higher activity. One method for improving the activity of a complex catalyst is the addition of a Lewis base, as disclosed in Patent Document 2. However, no effective combination of catalyst components has been found for the polymerization of olefins such as propylene using a nickel complex having a phosphinophenolate ligand.

[0006] In view of the above-mentioned problems of the conventional technology, an object of the present invention is to provide a highly active catalyst component for use in the production of olefin (particularly propylene)-based polymers and copolymers that is not accompanied by a decrease in molecular weight as compared with conventional catalysts, and a method for producing an olefin (particularly propylene)-based polymer and copolymer using the same. [Means for solving the problem]

[0007] That is, the present invention includes the following aspects. <1> A catalyst component for olefin polymerization, comprising: a metal complex (D) which is a reaction product of a compound (A) represented by the following general formula [1] or a compound (B) represented by the following general formula [2] with a transition metal compound (C) containing at least one of nickel and palladium; and a compound (E) represented by the following general formula [3].

[0008] [ka]

[0009] [In formula [1] and formula [2], R 1 , R 2 , R 3 and R 4 each independently represents an atom or group selected from the group consisting of the following (i) to (iv): (i) Hydrogen atom (ii) Halogen atom (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom. (iv) OR 10 , CO2R 10 , CO2M, C(O)N(R 11 )2, C(O)R 10 , O.C.(O)R 10 , S.R. 10 , SO2R 10 , OSO2R 10 , P(O)(OR 10 ) 2-y (R 10 )y , C.N., N.R. 10 (R 11 ), Si(OR 11 ) 3-x (R 11 ) x , OSi(OR 11 ) 3-x (R 11 ) x , NO2, SO3M, PO3M2, P(O)(OR 11 )2M, or an epoxy-containing group. R 10 represents a hydrocarbon group having 1 to 20 carbon atoms, R 11 R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 10 and R 11 If there are multiple R 10 and R 11 may be the same or different. M represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer of 0 to 3, and y represents an integer of 0 to 2. 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring. R 5 and R 6 each independently represents an alkyl group having 1 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a condensed polycyclic hydrocarbon group having 8 to 30 carbon atoms, which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; 10 (R 11 ), or SiR 10 (R 11 )2 (where R 11 may be the same or different. E 1 represents a phosphorus atom, an arsenic atom, or an antimony atom. X 1 represents an oxygen atom or a sulfur atom. Z 1 represents a hydrogen atom or a leaving group, m represents Z 1 represents the valence of . [In formula [3], R 7 , R 8 and R 9 are each independently N(R 10 )2 (where R 10 may be the same or different.) and an oxygen atom, an alkyl group having 1 to 20 carbon atoms which may have at least one selected from the group consisting of an aryl group having 7 to 20 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 20 carbon atoms. 10 has the same definition as above, except that R 7 , R 8 and R 9 If any two of R are aryl groups having 6 to 20 carbon atoms, the remaining one cannot be an aryl group having 6 to 20 carbon atoms. 7 , R 8 and R 9 may be bonded to each other to form an alicyclic structure.

[0010] <2> R 7 , R 8 and R 9 are each independently, N(R 10 )2 (where R 10 may be the same or different.) and an oxygen atom, an alkyl group having 1 to 12 carbon atoms which may have at least one selected from the group consisting of an arylalkyl group having 7 to 12 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 12 carbon atoms (wherein R 7 , R 8 and R 9 When any two of the above are aryl groups having 6 to 12 carbon atoms, the remaining one cannot be an aryl group having 6 to 12 carbon atoms. <1> 1. The olefin polymerization catalyst component according to claim 1 .

[0011] <3> The total number of nitrogen atoms contained in the compound (E) is 3 or less. <1> 1. The olefin polymerization catalyst component according to claim 1 .

[0012] <4> R 5 and R 6are each independently an alkyl group having 1 to 20 carbon atoms or a condensed polycyclic hydrocarbon group having 8 to 30 carbon atoms, which may have at least one selected from the group consisting of a hetero atom and a group containing a hetero atom. <1> 1. The olefin polymerization catalyst component according to claim 1 .

[0013] <5> R 5 and R 6 each independently represents a branched acyclic alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms which may have a side chain, or a condensed polycyclic hydrocarbon group having 8 to 15 carbon atoms, which may have at least one selected from the group consisting of a hetero atom and a group containing a hetero atom. <1> 1. The olefin polymerization catalyst component according to claim 1 .

[0014] <6> A method for producing an olefin polymer, comprising mixing a compound (A) represented by the following general formula [1] or a compound (B) represented by the following general formula [2], a transition metal compound (C) containing at least one of nickel and palladium, a compound (E) represented by the following general formula [3], and an olefin, and polymerizing or copolymerizing the olefin.

[0015] [ka]

[0016] [In formulas [1], [2] and [3], R 1 ~R 9 , E 1 , X 1 , Z 1 and m is the above <1> As defined in.

[0017] <7> R 7 , R 8 and R 9 are each independently, N(R 10 )2 (where R 10may be the same or different.) and an alkyl group having 1 to 12 carbon atoms which may have at least one selected from the group consisting of an oxygen atom, an arylalkyl group having 7 to 12 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 12 carbon atoms (wherein R 7 , R 8 and R 9 When any two of the R are aryl groups having 6 to 12 carbon atoms, the remaining one cannot be an aryl group having 6 to 12 carbon atoms. 10 The above <1> As defined above. <6> 2. A method for producing an olefin polymer according to claim 1 .

[0018] <8> The total number of nitrogen atoms contained in the compound (E) is 3 or less. <6> 2. A method for producing an olefin polymer according to claim 1 .

[0019] <9> R 5 and R 6 are each independently an alkyl group having 1 to 20 carbon atoms or a condensed polycyclic hydrocarbon group having 8 to 30 carbon atoms, which may have at least one selected from the group consisting of a hetero atom and a group containing a hetero atom. <6> 2. A method for producing an olefin polymer according to claim 1 .

[0020] <10> R 5 and R 6 each independently represents a branched acyclic alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms which may have a side chain, or a condensed polycyclic hydrocarbon group having 8 to 15 carbon atoms, which may have at least one selected from the group consisting of a hetero atom and a group containing a hetero atom. <6> 2. A method for producing an olefin polymer according to claim 1 .

[0021] <11> The olefin is ethylene or propylene. <6> 2. A method for producing an olefin polymer according to claim 1 .

[0022] <12> mixing the compound (A) or the compound (B), the transition metal compound (C), the compound (E), an olefin, and a polar group-containing comonomer, and copolymerizing the olefin and the polar group-containing comonomer; <6> 2. A method for producing an olefin polymer according to claim 1 . Effect of the Invention

[0023] According to the present invention, it is possible to provide a highly active olefin polymerization catalyst component used for producing an olefin (particularly propylene) polymer and copolymer without a decrease in molecular weight compared to conventional catalysts, and a method for producing an olefin (particularly propylene) polymer and copolymer using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] The present invention provides a catalyst component for olefin polymerization comprising a metal complex (D) which is a reaction product of a compound (A) represented by the following general formula [1] or a compound (B) represented by the following general formula [2] with a transition metal compound (C) containing at least one of nickel and palladium, and a compound (E) represented by the following general formula [3]; a catalyst containing the same as the catalyst component; and a method for producing an olefin polymer or copolymer in the presence of the catalyst. In the present invention, "polymerization" refers collectively to homopolymerization of one type of monomer and copolymerization of multiple types of monomers, and when there is no need to distinguish between the two, they are collectively referred to simply as "polymerization." In addition, in the present invention, "(meth)acrylic acid ester" includes both acrylic acid ester and methacrylic acid ester. In addition, in this specification, the use of "to" indicating a numerical range is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, "Me" is methyl, "Et" is ethyl, "Pr" is propyl, "Bu" is butyl, "Cy" is cyclohexyl, "Ph" is phenyl, "4-MeOPh" is 4-methoxyphenyl, "OMe" is methoxy, "OEt" is ethoxy, "OiPr" is isopropoxy, "SMe" is methylthio, "NMe2" is dimethylamino, "NEt2" is diethylamino, and "SiMe3" is trimethoxysilyl. Furthermore, in the prefixes of structural isomers of alkyl groups, "i" stands for iso, "n" stands for normal, "s" stands for secondary, and "t" stands for tertiary. When no prefix of structural isomer is given to an alkyl group, it indicates that it is a normal structure.

[0025] 1. Olefin polymerization catalyst components According to the present invention, there is provided a catalyst component for olefin polymerization, characterized by comprising a metal complex (D) which is a reaction product of a compound (A) represented by the following general formula [1] or a compound (B) represented by the following general formula [2] with a transition metal compound (C) containing at least one of nickel and palladium, and a compound (E) represented by the following general formula [3]:

[0026] [ka]

[0027] [In formula [1] and formula [2], R 1 , R 2 , R 3 and R 4 each independently represents an atom or group selected from the group consisting of the following (i) to (iv): (i) Hydrogen atom (ii) Halogen atom (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom. (iv) OR 10 , CO2R 10 , CO2M, C(O)N(R 11 )2, C(O)R10 , O.C.(O)R 10 , S.R. 10 , SO2R 10 , OSO2R 10 , P(O)(OR 10 ) 2-y (R 10 ) y , C.N., N.R. 10 (R 11 ), Si(OR 11 ) 3-x (R 11 ) x , OSi(OR 11 ) 3-x (R 11 ) x , NO2, SO3M, PO3M2, P(O)(OR 11 )2M, or an epoxy-containing group. R 10 represents a hydrocarbon group having 1 to 20 carbon atoms, R 11 R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 10 and R 11 If there are multiple R 10 and R 11 may be the same or different. M represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer of 0 to 3, and y represents an integer of 0 to 2. 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring. R 5 and R 6 each independently represents an alkyl group having 1 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a condensed polycyclic hydrocarbon group having 8 to 30 carbon atoms, which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; 10 (R 11 ), or SiR 10 (R 11 )2 (where R 11 may be the same or different. E 1 represents a phosphorus atom, an arsenic atom, or an antimony atom. X 1 represents an oxygen atom or a sulfur atom. Z 1 represents a hydrogen atom or a leaving group, m represents Z 1 represents the valence of . [In formula [3], R 7 , R 8 and R 9 are each independently N(R 10 )2 (where R 10 may be the same or different.) and an oxygen atom, an alkyl group having 1 to 20 carbon atoms which may have at least one selected from the group consisting of an aryl group having 7 to 20 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 20 carbon atoms. 10 has the same definition as above, except that R 7 , R 8 and R 9 If any two of R are aryl groups having 6 to 20 carbon atoms, the remaining one cannot be an aryl group having 6 to 20 carbon atoms. 7 , R 8 and R 9 may be bonded to each other to form an alicyclic structure.

[0028] By using the catalyst component for olefin polymerization of the present invention, olefin (co)polymers, particularly propylene (co)polymers, can be obtained with high activity. When a tertiary amine compound (E), which is a basic compound with low π-acceptance, no proton, and moderate coordination power with a nitrogen atom that is not sterically bulky, and is represented by the general formula [3], is used as one of the catalyst components for olefin polymerization, the tertiary amine acts as an auxiliary ligand to prevent the decomposition of the complex, while during the polymerization reaction, it is easily detached from the central metal, making it easier for the activation reaction to proceed, and it is presumed that the initiation efficiency of polymerization is increased, resulting in high activation.

[0029] [Compound (A) or Compound (B)] The compound (A) is represented by the above general formula [1]. The compound (B) is represented by the above general formula [2]. R 1 , R 2 , R 3 and R 4 each independently represents an atom or group selected from the group consisting of the following (i) to (iv): (i) Hydrogen atom (ii) Halogen atom (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom. (iv) OR 10 , CO2R 10 , CO2M, C(O)N(R 11 )2, C(O)R 10 , O.C.(O)R 10 , S.R. 10 , SO2R 10 , OSO2R 10 , P(O)(OR 10 ) 2-y (R 10 ) y , C.N., N.R. 10 (R 11 ), Si(OR 11 ) 3-x (R 11 ) x , OSi(OR 11 ) 3-x (R 11 ) x , NO2, SO3M, PO3M2, P(O)(OR 11 )2M, or an epoxy-containing group. R 10 represents a hydrocarbon group having 1 to 20 carbon atoms, R 11 R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 10 and R 11 If there are multiple R 10 and R 11 may be the same or different. M represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer of 0 to 3, and y represents an integer of 0 to 2. 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring.

[0030] (ii) Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferred.

[0031] Examples of the hydrocarbon group having 1 to 30 carbon atoms in (iii) include linear, branched, and cyclic saturated or unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. Specific examples of the hydrocarbon group having 1 to 30 carbon atoms include linear alkyl groups having 1 to 30 carbon atoms, branched acyclic alkyl groups having 3 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms which may have a side chain, arylalkyl groups having 7 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, cycloalkenyl groups having 3 to 30 carbon atoms which may have a side chain, aryl groups having 6 to 30 carbon atoms, and alkylaryl groups having 7 to 30 carbon atoms.

[0032] Examples of the linear alkyl group having 1 to 30 carbon atoms include 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, and an n-decyl group, and may be a linear alkyl group having 1 to 20 carbon atoms.

[0033] Examples of the branched acyclic alkyl group having 3 to 30 carbon atoms include a branched acyclic alkyl group having 3 to 20 carbon atoms, such as an i-propyl group, an i-butyl group, a t-butyl group, an s-butyl group, an i-pentyl group (3-methylbutyl group), a t-pentyl group (1,1-dimethylpropyl group), an s-pentyl group (1-methylbutyl group), a 2-methylbutyl group, a neopentyl group (2,2-dimethylpropyl group), a 1,2-dimethylpropyl group, an i-hexyl group (4-methylpentyl group), and a 2-heptyl group, and may be a branched acyclic alkyl group having 3 to 8 carbon atoms.

[0034] Examples of the cycloalkyl group having 3 to 30 carbon atoms and optionally having a side chain include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decahydronaphthyl group (bicyclo[4,4,0]decyl group), a 5-tricyclo[3.3.1.13,7]dec-1-yl group (1-adamantyl group), a 5-methyl-2-(propan-2-yl)cyclohexyl group (menthyl group), and a bicyclo-[2.2.1]-hept-2-yl group. The cycloalkyl group may have a side chain having 3 to 20 carbon atoms, or may have a side chain having 3 to 6 carbon atoms.

[0035] Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, a phenethyl group (2-phenylethyl group), a 9-fluorenyl group, a naphthylmethyl group, and a 1-tetralinyl group. The arylalkyl group may be an arylalkyl group having 7 to 15 carbon atoms, or an arylalkyl group having 7 to 10 carbon atoms.

[0036] Examples of the alkenyl group having 2 to 30 carbon atoms include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a styryl group, and a cinnamyl group. The alkenyl group may have 3 to 8 carbon atoms, or may have 4 to 8 carbon atoms. Examples of the cycloalkenyl group having 3 to 30 carbon atoms and optionally having a side chain include a cyclopentenyl group, a cyclohexenyl group, and a bicyclo[2.2.1]hept-5-en-2-yl group. The cycloalkenyl group may have a side chain having 3 to 10 carbon atoms, or may have a side chain having 5 to 7 carbon atoms.

[0037] Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a naphthyl group, an azulenyl group, a biphenyl group, an anthracenyl group, a terphenyl group, a phenanthrenyl group, a triphenylenyl group, a chrysenyl group, a pyrenyl group, and a tetracenyl group. The aryl group may have 6 to 18 carbon atoms, or may have 6 to 12 carbon atoms.

[0038] The alkylaryl group having 7 to 30 carbon atoms may be an aryl group substituted with one or more linear or branched acyclic alkyl groups having 1 to 10 carbon atoms, and examples thereof include alkylaryl groups in which at least one of the linear alkyl groups having 1 to 10 carbon atoms and the branched acyclic alkyl groups having 3 to 10 carbon atoms is substituted on the aryl group having 6 to 18 carbon atoms, and may be an alkylaryl group in which at least two of the linear alkyl groups having 1 to 10 carbon atoms and the branched acyclic alkyl groups having 3 to 10 carbon atoms are substituted on the aryl group having 6 to 18 carbon atoms. Specific examples of the alkylaryl group having 7 to 30 carbon atoms include alkylaryl groups having 7 to 20 carbon atoms, such as a tolyl group, a xylyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group, an undecylphenyl group, and a dodecylphenyl group.

[0039] Examples of the heteroatom used in (iii) include an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom, a selenium atom, a silicon atom, a halogen atom, and a boron atom. Among these heteroatoms, a fluorine atom and a chlorine atom are preferred. Specific examples of the "group containing a heteroatom" used in (iii) include the same groups as the heteroatom-containing substituents listed in (iv) below. Examples of the "group containing a heteroatom" include an alkoxy group (OR 10 ), ester group (COR 10 ) and others. 10 is as stated above.

[0040] In (iii) above, R1 , R 2 , R 3 or R 4 The total number of carbon atoms of the substituents corresponding to the above may preferably have an upper limit of 30 or less, 25 or less, 20 or less, or 15 or less. The lower limit of the total number of carbon atoms may preferably be 1 or more, 2 or more, or 4 or more. In light of the above, (iii) "a specific group which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom" refers to (iii-A) a linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an arylalkyl group having 7 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an alkylaryl group having 7 to 30 carbon atoms, (iii-B) a group in which each of the groups in (iii-A) is substituted with one or more of the heteroatoms, (iii-C) a group in which each of the groups in (iii-A) is substituted with one or more of the "groups containing a heteroatom", and (iii-D) a group in which each of the groups in (iii-A) is substituted with one or more of the heteroatoms and one or more of the "groups containing a heteroatom". Examples of (iii-C) include an alkyl group substituted with an alkoxy group, an aryl group substituted with an alkoxy group, and an aryl group substituted with an ester group.

[0041] (iv) The heteroatom-containing substituent is specifically, OR 10 , CO2R 10 , CO2M, C(O)N(R 11 )2, C(O)R 10 , O.C.(O)R 10 , S.R. 10 , SO2R 10 , OSO2R 10 , P(O)(OR 10 ) 2-y (R 10 ) y , C.N., N.R. 10 (R 11 ), Si(OR 11 )3-x (R 11 ) x , OSi(OR 11 ) 3-x (R 11 ) x , NO2, SO3M, PO3M2, P(O)(OR 11 )2M, or epoxy-containing group. R 10 represents a hydrocarbon group having 1 to 20 carbon atoms, R 11 R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 10 and R 11 If there are multiple R 10 and R 11 and may be the same or different. In the present invention, the hydrocarbon group includes saturated and unsaturated aliphatic hydrocarbons and aromatic hydrocarbons, and examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned linear alkyl groups, branched non-cyclic alkyl groups, cycloalkyl groups which may have a side chain, arylalkyl groups, alkenyl groups, aryl groups, and alkylaryl groups, each having 1 to 20 carbon atoms. R 10 and R 11 The number of carbon atoms in the hydrocarbon group may be 1 to 10, 1 to 6, or 1 to 4. M represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium, or a phosphonium; x represents an integer from 0 to 3; and y represents an integer from 0 to 2.

[0042] R 1 , R 2 , R 3 and R 4are each independently preferably (i) a hydrogen atom; (ii) a fluorine atom, a chlorine atom, or a bromine atom; (iii) a methyl group, an ethyl group, an i-propyl group, an i-butyl group, a t-butyl group, an s-butyl group, a phenyl group, a trifluoromethyl group, a pentafluorophenyl group, a naphthyl group, an anthracenyl group, or an adamantyl group; and (iv) a methoxy group, an ethoxy group, a phenoxy group, a nitrile group, a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a trimethoxysilyl group, a triethoxysilyl group, a trimethylsilyloxy group, a trimethoxysiloxy group, a cyclohexylamino group, sodium sulfonate, potassium sulfonate, sodium phosphate, potassium phosphate, or the like. Among these, particularly preferred ones include (i) a hydrogen atom; (iii) a methyl group, an ethyl group, an i-propyl group, an i-butyl group, a t-butyl group, an s-butyl group, a trifluoromethyl group, and a pentafluorophenyl group; and (iv) a methoxy group, a trimethylsilyl group, a trimethylsilyloxy group, and a cyclohexylamino group. R 1 , R 2 , R 3 and R 4 are each independently more preferably a hydrogen atom, a fluorine atom, a methyl group, a t-butyl group, a trifluoromethyl group, a pentafluorophenyl group, a methyl acetate group, a phenyl group, a 2,6-dimethylphenyl group, a 2,6-diisopropylphenyl group, a 2,4,6-triisopropylphenyl group, a 2,6-dicyclohexylphenyl group, a 2,6-diphenylphenyl group (a terphenyl group), a 2,6-dimethoxyphenyl group, a 2,6-diethoxyphenyl group, a 9-anthracenyl group, or a trimethylsilyl group.

[0043] Also, R 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring. That is, R 1 , R 2 , R 3 and R 4Adjacent substituents may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from the group consisting of oxygen, nitrogen, and sulfur. In this case, the number of ring members is 5 to 8, and the ring may or may not have a substituent. The substituent may be at least one of the above (ii), (iii), and (iv).

[0044] R 5 and R 6 each independently represents (v) an alkyl group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom, an arylalkyl group having 7 to 30 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom, or a condensed polycyclic hydrocarbon group having 8 to 30 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; (vi) NR 10 (R 11 ), or SiR 10 (R 11 )2 (where R 11 may be the same or different. R 5 and R 6 The heteroatom and the group containing a heteroatom used in may be the same as those explained in the above (iii). R 5 and R 6 In the above, the alkyl group having 1 to 30 carbon atoms may be a linear alkyl group having 1 to 30 carbon atoms, a branched non-cyclic alkyl group having 3 to 30 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain. The linear alkyl group having 1 to 30 carbon atoms, the branched acyclic alkyl group having 3 to 30 carbon atoms, the cycloalkyl group which may have a side chain having 3 to 30 carbon atoms, or the arylalkyl group having 7 to 30 carbon atoms may be the same as those explained in (iii) above. The condensed polycyclic hydrocarbon group having 8 to 30 carbon atoms may be a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptalenyl group, an octalenyl group, an indacenyl group, a biphenylenyl group, an acenaphthylenyl group, a fluorenyl group, a phenalenyl group, a phenanthrenyl group, an anthracenyl group, or the like. R 5 and R 6 NR in 10 (R 11 ), or SiR 10 (R 11 )2 may be the same as that described in (iv) above.

[0045] Also, R 5 and R 6 may each independently be an alkyl group having 1 to 20 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or a condensed polycyclic hydrocarbon group having 8 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom. In addition, R 5 and R 6 may each independently be a branched non-cyclic alkyl group having 3 to 20 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, a cycloalkyl group having 3 to 20 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom and which may have a side chain, or a condensed polycyclic hydrocarbon group having 8 to 15 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom. R 5 and R 6 may be, among others, a t-butyl group, a menthyl group, an adamantyl group, a benzyl group, a 9-fluorenyl group, or a 9-methyl-9-fluorenyl group.

[0046] E 1 represents a phosphorus atom, an arsenic atom, or an antimony atom. 1is preferably a phosphorus atom in terms of its coordination power to metals. X 1 represents an oxygen atom or a sulfur atom. 1 is preferably an oxygen atom in terms of acidity for deprotonation. Z 1 represents a hydrogen atom or a leaving group, m represents Z 1 represents the valence of Z. 1 Specifically, R is a hydrogen atom, a halogen atom, 10 SO2 group (where R 10 The halogen atom may be a bromine atom or an iodine atom, and R 10 Specific examples of the SO2 group include a tosyl group (p-toluenesulfonyl group) and a mesyl group (methanesulfonyl group).

[0047] The general formula [2] is expressed in the form of an anion, but any counter cation can be used as long as it does not inhibit the reaction with the transition metal compound in the present invention. Specific examples of the counter cation include ammonium, quaternary ammonium or phosphonium, and metal ions of Groups 1 to 14 of the periodic table. Of these, NH4 + , R 10 4N + (where R 10 is as mentioned above, and the four R 10 may be the same or different. The same applies below.) R 10 4P + , Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+ and more preferably, R 10 4N + , Li + , Na + , K + It is.

[0048] Compound (A) represented by general formula [1] or compound (B) represented by general formula [2], i.e., the compound represented by general formula [1] or [2], can be synthesized based on a known synthesis method.

[0049] Specific combinations of substituents in the general formulas [1] and [2] according to the present invention are shown in Table 1 below. 1 and m relate only to the general formula [1]. However, the specific examples are not limited to the following examples. In Table 1, No. 19 is ligand A, which will be described later, No. 32 is ligand C, which will be described later, and No. 47 is ligand B, which will be described later. In Table 1, "*" indicates E 1 Represents a bond with.

[0050] [Table 1]

[0051] Compound (A) and compound (B) are R 2 and R 3 may be a compound represented by general formula [1-1] or general formula [2-1] in which

[0052] [ka]

[0053] Specific combinations of substituents in the general formulae [1-1] and [2-1] of the present invention are shown in Table 2 below. 1 and m relate only to the general formula [1-1]. However, specific examples are not limited to the following examples.

[0054] [Table 2]

[0055] Compound (A) and compound (B) are R1 and R 2 may be a compound represented by general formula [1-2] or general formula [2-2] in which

[0056] [ka]

[0057] Specific combinations of substituents in the general formulas [1-2] and [2-2] of the present invention are shown in Table 3 below. 1 and m relate only to the general formula [1-2]. However, specific examples are not limited to the following examples.

[0058] [Table 3]

[0059] [Transition metal compound (C)] The transition metal compound (C) containing nickel or palladium used in the present invention is one that can react with the compound represented by the general formula [1] or [2] to form a complex having polymerization ability. These are sometimes called precursors.

[0060] Among the transition metal compounds used, examples of transition metal compounds containing nickel atoms include bis(1,5-cyclooctadiene)nickel(0) (hereinafter, may be referred to as Ni(COD)2), (N,N,N,N-tetramethylethylenediamine)nickeldimethyl(II) (hereinafter, (TMEDA)NiMe2) (hereinafter, TMEDA stands for tetramethylethylenediamine), diacetylacetonenickel(II) (hereinafter, Ni(acac)2) (hereinafter, acac stands for acetylacetone), bis(cyclopentadienyl)nickel(II), NiPhCl(PEt3)2 (hereinafter, Ph stands for phenyl, Et stands for ethyl), and NiPhCl(PPh3). 2、Examples of preferred transition metal compounds include NiPhCl(TMEDA), NiArBr(TMEDA) (wherein Ar represents, for example, 4-fluorophenyl or 4-biphenyl), Ni(CH2CHCH2)2, Ni(CH2CMeCH2)2, Ni(CH2SiMe3)2(pyridine)2 (hereinafter, Py represents pyridine), Ni(CH2SiMe3)2(2,6-lutidine)2 (hereinafter, Lut represents 2,6-lutidine), NiPh2(Py)2, and NiPh2(Lut)2. Examples of preferred transition metal compounds containing palladium atoms include Pd(dibenzylideneacetone)2 (hereinafter, Pd(dba)2) (hereinafter, dba represents dibenzylideneacetone), Pd2(dba)3, Pd3(dba)4, Pd(OCOCH3)2, and (1,5-cyclooctadiene)Pd(methyl)(chloride).

[0061] The reaction product of the present invention can be obtained by contacting the compound (A) represented by the above-mentioned general formula [1] or the compound (B) represented by the general formula [2] with the above-mentioned transition metal compound (C) at, for example, (A) + (B): (C) = 1: 99 to 99: 1 (molar ratio) in an organic solvent such as toluene or benzene at 0 to 100 ° C. under reduced pressure to pressure for 1 to 86400 seconds. This reaction may be carried out in the presence of an olefin, a (meth)acrylic acid ester monomer, and a vinyl monomer, and in this case, a mixed solution of each of the above compounds may be used, or each individual solution of each compound may be added to the above monomer. In addition, in the case of using individual solutions, a monomer may be added to any of the solutions and then the other solution may be further added, and the order of addition may be arbitrary. The reaction product may also be obtained by adding each solution in which each of the above compounds is dissolved using the above-mentioned organic solvent to the olefin, the (meth)acrylic acid ester monomer, and the vinyl monomer. The amount ratio of each of the above compounds, the mixing temperature, and the mixing time at this time may be the same as those described above.

[0062] After this reaction, a part of the components constituting the transition metal compound other than the transition metal in the compound is replaced by the part excluding Z in the general formula [1] or the compound of the general formula [2], and a metal complex (D) which is a reaction product between the compound represented by the general formula [1] or [2] and the transition metal compound (C) is generated. It is preferable that this substitution reaction proceeds quantitatively, but in some cases it may not proceed completely. After the reaction is completed, other components derived from the general formula [1], [2], and the transition metal compound (C) may coexist in addition to the metal complex (D), but these other components may or may not be removed when performing the polymerization reaction or copolymerization reaction of the present invention. In general, it is preferable to remove these other components because high activity can be obtained.

[0063] [Metal complex (D)] The reaction product of the metal complex (D), which is the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2], and the transition metal compound (C) containing nickel or palladium, can be obtained, for example, by contacting the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] with the transition metal compound (C) containing nickel or palladium. In the present invention, "contact" refers to the E 1 can form a coordinate bond with the transition metal, and / or X in these general formulas 1 means that the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] and the transition metal compound (C) are present in sufficient proximity to each other so that a covalent bond can be formed with the transition metal. And, contacting the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] with the transition metal compound (C) means mixing these compounds so that they are present in sufficient proximity to each other and at least one of the two types of bonds can be formed. The conditions for mixing the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] with the transition metal compound (C) are not particularly limited. These compounds may be mixed directly or may be mixed using a solvent. In particular, it is preferable to use a solvent from the viewpoint of achieving uniform mixing. In the obtained metal complex (D), the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] becomes a ligand. When the obtained metal complex (D) is more thermodynamically stable than the transition metal compound (C), the ligand exchange reaction proceeds by mixing the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] with the transition metal compound (C) at room temperature (15 to 30°C). On the other hand, when the obtained metal complex (D) is more thermodynamically unstable than the transition metal compound (C), it is preferable to heat the mixture appropriately in order to sufficiently proceed with the ligand exchange reaction. The reaction may be promoted by adding an olefin, a (meth)acrylic acid ester monomer, or a vinyl monomer.

[0064] The metal complex (D) obtained by contacting the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] with the transition metal compound (C) is a 1:1 reaction product of the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] with the transition metal compound (C), but it is possible to obtain a reaction product with a different composition ratio depending on the type of transition metal compound. For example, it is possible that two or more molecules of the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] form a complex with one transition metal, and it is also possible that one molecule of the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] reacts with two or more transition metals to form a polynuclear complex. Therefore, the metal complex (D) may be a mixture containing two or more reaction products, or may be a metal complex composition.

[0065] [Carrier] The metal complex (D) may be supported on a carrier, which may be carried out in a reactor used for the polymerization or copolymerization of olefins in the presence or absence of monomers, or in a vessel separate from the reactor.

[0066] Any carrier can be used as long as it does not impair the gist of the present invention. In general, inorganic oxides and polymer carriers can be used. Specifically, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc. or mixtures thereof can be mentioned, and mixed oxides such as SiO2-Al2O3, SiO2-V2O5, SiO2-TiO2, SiO2-MgO, and SiO2-Cr2O3 can also be used, and inorganic silicates, polyethylene carriers, polypropylene carriers, polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic acid ester carriers, polyester carriers, polyamide carriers, and polyimide carriers can be used. There are no particular limitations on the particle size, particle size distribution, pore volume, specific surface area, etc. of these carriers, and any carrier can be used.

[0067] As the inorganic silicate, clay, clay minerals, zeolite, diatomaceous earth, etc. can be used. These may be synthetic products or naturally occurring minerals. Specific examples of clay and clay minerals include allophane group such as allophane, kaolin group such as dickite, nacrite, kaolinite, anoxicite, halloysite group such as metahaloysite, halloysite, serpentine group such as chrysotile, lizardite, antigorite, smectite such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, glauconite, attapulgite, sepiolite, pyrogorskite, bentonite, kibushi clay, gairome clay, hisingerite, pyrophyllite, ryokudeite group, etc. These may form a mixed layer. Examples of artificially synthesized substances include synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, etc. Among these specific examples, preferred are kaolin group such as dickite, nacrite, kaolinite, anoxite, etc., halloysite group such as metahaloysite, halloysite, etc., serpentine group such as chrysotile, lizardite, antigorite, etc., smectite such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, etc., vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, glauconite, etc., synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, etc., and particularly preferred are smectite such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, etc., vermiculite minerals such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite.

[0068] These carriers may be used as they are, or may be treated with an acid such as hydrochloric acid, nitric acid, or sulfuric acid, and / or a salt such as LiCl, NaCl, KCl, CaCl2, MgCl2, Li2SO4, MgSO4, ZnSO4, Ti(SO4)2, Zr(SO4)2, or Al2(SO4)3. In this treatment, the corresponding acid and base may be mixed to generate a salt in the reaction system. Shape control such as pulverization or granulation, or drying treatment may be performed.

[0069] [Compound (E)] The compound (E) is represented by the above general formula [3]. R 7 , R 8 and R 9 are each independently N(R 10 )2 (where R 10 may be the same or different.) and an oxygen atom, an alkyl group having 1 to 20 carbon atoms which may have at least one selected from the group consisting of an aryl group having 7 to 20 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 20 carbon atoms. 10 has the same definition as above, except that R7 , R 8 and R 9 If any two of R are aryl groups having 6 to 20 carbon atoms, the remaining one cannot be an aryl group having 6 to 20 carbon atoms. 7 , R 8 and R 9 may be bonded to each other to form an alicyclic structure.

[0070] R 7 , R 8 and R 9 In the above, the alkyl group having 1 to 20 carbon atoms may be a linear alkyl group having 1 to 20 carbon atoms, a branched non-cyclic alkyl group having 3 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms which may have a side chain. R 7 , R 8 and R 9 In the formula (iii), the linear alkyl group having 1 to 20 carbon atoms, the branched acyclic alkyl group having 3 to 20 carbon atoms, the cycloalkyl group having 3 to 20 carbon atoms which may have a side chain, the arylalkyl group having 7 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms may each be any of those described in the above (iii) that satisfy the condition of having 1 to 20 carbon atoms.

[0071] R 7 , R 8 and R 9 are each independently N(R 10 )2 (where R 10 may be the same or different.) and an oxygen atom, and may be an alkyl group having 1 to 12 carbon atoms which may have at least one selected from the group consisting of an aryl group having 7 to 12 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 12 carbon atoms. However, R 7 , R 8 and R 9 When any two of the above are aryl groups having 6 to 12 carbon atoms, the remaining one cannot be an aryl group having 6 to 12 carbon atoms. R 7 , R 8 and R 9In the above, the alkyl group having 1 to 12 carbon atoms may be a linear alkyl group having 1 to 12 carbon atoms, a branched acyclic alkyl group having 3 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms which may have a side chain. R 7 , R 8 and R 9 In the formula (iii), the linear alkyl group having 1 to 12 carbon atoms, the branched acyclic alkyl group having 3 to 12 carbon atoms, the cycloalkyl group having 3 to 12 carbon atoms which may have a side chain, the arylalkyl group having 7 to 12 carbon atoms, and the aryl group having 6 to 12 carbon atoms may each be any of those described in (iii) above that satisfy the condition of having 1 to 12 carbon atoms.

[0072] The total number of nitrogen atoms contained in compound (E) may be 3 or less. The amount of the compound (E) may be 0.001 to 5000 equivalents, 0.01 to 1000 equivalents, 0.3 to 500 equivalents, or 1 to 100 equivalents relative to the transition metal in the catalyst component present in the polymerization system. There is no particular limitation on the method of adding the compound (E), and any method can be used. For example, the compound (E) may be added by mixing with the compound (A) or compound (B) used in the present invention, by mixing with the transition metal compound (C), by mixing with the monomer, or by adding to the polymerization system independently of these. In addition, a plurality of compounds (E) may be used in combination, and the method of adding the compounds (E) in the case of using a plurality of compounds in combination may not be the same, and each of them may be added by the above-mentioned different methods.

[0073] Specific combinations or structures of the substituents and the like in the general formula [3] in the present invention are shown in the following Table 4. However, the specific examples are not limited to the following examples.

[0074] [Table 4]

[0075] 2. Olefin polymerization catalysts The olefin polymerization catalyst of the present invention is characterized by comprising the following components (F) and, optionally, (G): Component (F): The olefin polymerization catalyst component of the present invention Component (G): Organoaluminum compound

[0076] Component (F) is the above-mentioned olefin polymerization catalyst component of the present invention, and only one type of olefin polymerization catalyst component may be used, or two or more types of olefin polymerization catalyst components may be used in combination.

[0077] An example of an organoaluminum compound used as component (G) is represented by the following general formula: Al(R p ) a X (3-a) In the general formula, R p represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrogen atom, a halogen atom, an alkoxy group or a siloxy group, and a represents a number greater than 0 and equal to or less than 3. Specific examples of the organoaluminum compound represented by the general formula include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and tri-normal-octylaluminum, and halogen atom- or alkoxy-containing alkylaluminums such as diethylaluminum monochloride and diethylaluminum monomethoxide.

[0078] Among these, triisobutylaluminum or tri-n-octylaluminum is preferred. Two or more of the above-mentioned organoaluminum compounds may be used in combination. The above-mentioned aluminum compounds may be modified with alcohol, phenol, or the like. Examples of these modifying agents include methanol, ethanol, 1-propanol, isopropanol, butanol, phenol, 2,6-dimethylphenol, and 2,6-di-t-butylphenol, and preferred specific examples are 2,6-dimethylphenol and 2,6-di-t-butylphenol.

[0079] In the method for preparing the olefin polymerization catalyst according to the present invention, the method for contacting component (F) and component (G) is not particularly limited. The contact may be carried out not only during the preparation of the catalyst but also during the prepolymerization with an olefin or during the polymerization of an olefin. The contact of the above components (F) and (G) is preferably carried out in an inert gas such as nitrogen, in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene, or in a monomer such as an olefin using a solution of the above component (F) in the inert hydrocarbon solvent. The contact can be carried out at a temperature between -20°C and the boiling point of the solvent, and is particularly preferably carried out at a temperature between room temperature and the boiling point of the solvent.

[0080] 3. Method for producing olefin polymer According to the present invention, there is provided a method for producing an olefin polymer, which comprises mixing a compound (A) represented by the general formula [1] or a compound (B) represented by the general formula [2], a transition metal compound (C) containing nickel or palladium, a compound (E) represented by the general formula [3], and an olefin, and polymerizing or copolymerizing the olefin. In addition, the compound (A) or the compound (B), the transition metal compound (C), the compound (E), an olefin, and a polar group-containing comonomer may be mixed together to copolymerize the olefin and the polar group-containing comonomer.

[0081] The order of mixing the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2], the transition metal compound (C) containing nickel or palladium, the compound (E) represented by the general formula [3], and the olefin may be arbitrary. 1) The compound (E) represented by the general formula [3] may be added to a mixed solution of the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] and a transition metal compound (C) containing nickel or palladium, and the mixed solution of the three components may be added to a polymerization reactor containing an olefin. 2) A mixed solution of the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] and a transition metal compound (C) containing nickel or palladium may be added to a polymerization reactor containing the compound (E) represented by the general formula [3] and an olefin. 3) A transition metal compound (C) containing nickel or palladium may be added to a mixed solution of the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] and the compound (E) represented by the general formula [3], and the mixed solution of the three components may be added to a polymerization reactor containing an olefin. 4) The compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] may be added to a mixed solution of the transition metal compound (C) containing nickel or palladium and the compound (E) represented by the general formula [3], and the mixed solution of the three components may be added to a polymerization reactor containing an olefin. 5) A mixed solution of the compound (A) represented by the general formula [1] or the compound (B) represented by the general formula [2] and the compound (E) represented by the general formula [3] may be added to a polymerization reactor containing an olefin, and then a solution of the transition metal compound (C) containing nickel or palladium may be added to the polymerization reactor.

[0082] One embodiment of the process for producing an olefin polymer of the present invention is to polymerize or copolymerize an olefin in the presence of the above-mentioned catalyst component for olefin polymerization or catalyst for olefin polymerization of the present invention. The olefin in the present invention has the general formula: CH2=CHR 20 where R 20 R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may have a branch, a ring, and / or an unsaturated bond. 20 If the carbon number of R is more than 20, sufficient polymerization activity tends not to be exhibited. 20 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. More preferred olefins include ethylene, propylene, α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene, vinylcyclohexene, and styrene. A single olefin may be used, or multiple olefins may be used in combination. In the process for producing an olefin polymer and the process for producing an olefin copolymer of the present invention, it is particularly preferable that the olefin is ethylene or propylene.

[0083] Another embodiment of the method for producing an olefin polymer of the present invention comprises copolymerizing (a) an olefin with (b) a (meth)acrylic acid ester monomer, a vinyl monomer or an allyl monomer in the presence of the above-mentioned olefin polymerization catalyst component or olefin polymerization catalyst.

[0084] The (meth)acrylic acid ester monomer in the present invention is represented by the general formula: CH2=C(R 21 )CO2(R 22 ), where R 21 R is a hydrogen atom or a methyl group. 22 is a hydrocarbon group having 1 to 30 carbon atoms, which may have a branch, a ring, and / or an unsaturated bond. 22 It may contain a heteroatom at any position within the group. R 22 If the carbon number of R exceeds 30, the polymerization activity tends to decrease. 22 The number of carbon atoms in R is 1 to 30. 22 preferably has 1 to 12 carbon atoms, and more preferably has 1 to 8 carbon atoms. Also, R 22 Examples of the heteroatom that may be contained within R include an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen atom, a silicon atom, a fluorine atom, and a boron atom. Among these heteroatoms, an oxygen atom, a silicon atom, and a fluorine atom are preferred, and an oxygen atom is more preferred. 22 It is also preferred that the group does not contain a heteroatom.

[0085] More preferred (meth)acrylic acid ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate. , hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, glycidyl (meth)acrylate, ethylene oxide (meth)acrylate, trifluoromethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, (meth)acrylamide, (meth)acryldimethylamide, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. In addition, a single (meth)acrylic acid ester may be used, or multiple (meth)acrylic acid esters may be used in combination.

[0086] The vinyl monomer in the present invention is a vinyl monomer having a polar group such as a halogen atom, a nitrogen atom, an oxygen atom, or a sulfur atom, and in particular a vinyl monomer containing a halogen atom, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a formyl group, an ester group, an epoxy group, a nitrile group, or the like. Specifically, 5-hexen-1-ol, 2-methyl-3-buten-1-ol, ethyl 10-undecenoate, 10-undecen-1-ol, 12-tridecen-2-ol, 10-undecanoic acid, methyl 9-decenate, t-butyl-10-undecenate, 1,1-dimethyl-2-propen-1-ol, 9-decen-1-ol, 3-butenoic acid, 3-buten-1-ol, N-(3-buten-1-yl)phthalimide, 5-hexenoic acid, methyl 5-hexenoate, 5-hexen-2-one, acrylonitrile, methacrylonitrile, vinyl acetate, etc. are mentioned. Among these, 3-buten-1-ol, ethyl 10-undecenoate, and 10-undecen-1-ol are particularly preferable.

[0087] The allyl monomer in the present invention is exemplified by an allyl monomer having 3 carbon atoms (propenyl monomer) and an allyl-based monomer having 4 or more carbon atoms and an allyl group. The allyl monomer is an allyl monomer having a polar group of an atom containing a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, etc., and is particularly a vinyl monomer containing a halogen atom, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a formyl group, an ester group, an epoxy group, a nitrile group, etc. Preferred specific examples include allyl acetate, allyl alcohol, allylamine, N-allylaniline, Nt-butoxycarbonyl-N-allylamine, N-benzyloxycarbonyl-N-allylamine, N-allyl-N-benzylamine, allyl chloride, allyl bromide, allyl ether, diallyl ether, etc. Among these, allyl acetate and allyl alcohol are particularly preferred, and allyl acetate, allyl ether, and diallyl ether are more preferred.

[0088] The polymerization reaction of the present invention is carried out in the presence or absence of a liquid such as a hydrocarbon solvent, such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, or methylcyclohexane, or a liquid α-olefin, or a polar solvent, such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, or acetonitrile. A mixture of the liquid compounds described herein may also be used as a solvent. Furthermore, an ionic liquid may also be used as a solvent. In order to obtain a high polymerization activity and a high molecular weight, the above-mentioned hydrocarbon solvents and ionic liquids are more preferable.

[0089] In the present invention, the polymerization reaction can be carried out in the presence or absence of known additives. As the additive, a polymerization inhibitor that inhibits radical polymerization or an additive that has the effect of stabilizing the resulting copolymer is preferable. For example, quinone derivatives and hindered phenol derivatives are examples of preferable additives. Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), a reaction product of trimethylaluminum and BHT, a reaction product of alkoxide of tetravalent titanium and BHT, etc. can be used. In addition, inorganic and / or organic fillers may be used as additives, and polymerization may be carried out in the presence of these fillers. Furthermore, the compound (E) according to the present invention or an ionic liquid may be used as an additive.

[0090] The amount of the additive is 0.0001 to 1000 equivalents, preferably 0.1 to 100 equivalents, more preferably 0.3 to 30 equivalents, relative to the transition metal in the catalyst component present in the polymerization system. There is no particular limitation on the method of adding the additive to the polymerization system, and any method can be used. For example, the additive may be added by mixing with the olefin polymerization catalyst component of the present invention, or may be added by mixing with a monomer, or may be added to the polymerization system independently of the olefin polymerization catalyst component or the monomer. In addition, a plurality of additives may be used in combination. In addition, the same compound as the compound (E) according to the present invention may be used, or may be different.

[0091] In the present invention, there is no particular restriction on the polymerization type. Slurry polymerization in which at least a part of the polymer produced becomes a slurry in a medium, bulk polymerization in which the liquefied monomer itself is the medium, gas phase polymerization in a vaporized monomer, or high pressure ion polymerization in which at least a part of the polymer produced is dissolved in a monomer liquefied at high temperature and high pressure are preferably used. In addition, any of batch polymerization, semi-batch polymerization, and continuous polymerization types may be used.

[0092] The unreacted monomers and the medium may be separated from the resulting copolymer and recycled. In recycling, these monomers and media may be reused after purification or without purification. The resulting copolymer can be separated from the unreacted monomers and media by a conventional method. For example, filtration, centrifugation, solvent extraction, reprecipitation using a poor solvent, etc. can be used. The polymerization temperature, polymerization pressure and polymerization time are not particularly limited, but can usually be optimally set within the following ranges, taking into consideration productivity and process capacity: The polymerization temperature can usually be selected from the ranges of -20°C to 290°C, and preferably 0°C to 250°C, the copolymerization pressure from 0.1 MPa to 300 MPa, and preferably 0.3 MPa to 250 MPa, and the polymerization time from the ranges of 0.1 minute to 10 hours, and preferably 0.5 minutes to 7 hours, and more preferably 1 minute to 6 hours.

[0093] In the present invention, the polymerization is generally carried out under an inert gas atmosphere. For example, a nitrogen, argon, or carbon dioxide atmosphere can be used, and a nitrogen atmosphere is preferably used. A small amount of oxygen or air may be mixed in. There is no particular restriction on the supply of catalyst and monomer to the polymerization reactor, and various supply methods can be used depending on the purpose. For example, in the case of batch polymerization, a method can be used in which a predetermined amount of monomer is supplied to the polymerization reactor in advance and a catalyst is supplied thereto. In this case, additional monomer or additional catalyst may be supplied to the polymerization reactor. In addition, in the case of continuous polymerization, a method can be used in which a predetermined amount of monomer and catalyst are supplied to the polymerization reactor continuously or intermittently to perform the polymerization reaction continuously.

[0094] Regarding the control of the copolymer composition, a method of controlling by supplying a plurality of monomers to a reactor and changing the supply ratio can be generally used. Other methods include a method of controlling the copolymer composition by utilizing the difference in monomer reactivity ratio due to the difference in catalyst structure, and a method of controlling the copolymer composition by utilizing the polymerization temperature dependency of the monomer reactivity ratio. When it is necessary to control the molecular weight of the polymer, a conventionally known method can be used. That is, a method of controlling the molecular weight by controlling the polymerization temperature, a method of controlling the molecular weight by controlling the monomer concentration, a method of controlling the molecular weight by using a chain transfer agent, a method of controlling the molecular weight by controlling the ligand structure in a transition metal complex, etc. can be mentioned. When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used.

[0095] In particular, the copolymer with the polar group-containing monomer obtained by the present invention exhibits good coating properties, printability, antistatic properties, inorganic filler dispersibility, adhesion to other resins, and compatibility with other resins due to the effects based on the polar groups of the copolymer. By utilizing these properties, the copolymer of the present invention can be used in various applications. For example, it can be used as a film, sheet, adhesive resin, binder, compatibilizer, wax, etc. EXAMPLES

[0096] The present invention will be described in more detail in the following examples and comparative examples, but the present invention is not limited thereto. In the following synthesis examples, unless otherwise specified, operations were carried out under a purified nitrogen atmosphere, and solvents used were dehydrated and deoxygenated. In addition, the abbreviations used in the description are as follows. MOM: Methoxymethyl group (-CH2OCH3) EtOAc: ethyl acetate THF: tetrahydrofuran DMF: Dimethylformamide dba: dibenzylideneacetone s-Phos: 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl DPEPhos: Bis[2-(diphenylphosphino)phenyl]ether

[0097] 1. Evaluation method (1) Weight average molecular weight Mw, number average molecular weight Mn and molecular weight distribution Mw / Mn The weight average molecular weight Mw, number average molecular weight Mn and molecular weight distribution Mw / Mn of the polymer were determined by the following GPC measurement. A sample (about 10 mg) was collected in a vial for the high-temperature GPC pretreatment device PL-SP 260VS manufactured by Polymer Laboratory Co., Ltd., and o-dichlorobenzene containing BHT as a stabilizer (BHT concentration = 0.5 g / L) was added to adjust the polymer concentration to 0.05 (wt%). The polymer was dissolved by heating to 135 ° C in the high-temperature GPC pretreatment device PL-SP 260VS, and filtered through a glass filter to prepare a measurement sample. In the GPC measurement in the present invention, no polymer was captured by the glass filter. Next, GPC measurement was performed using a column manufactured by Tosoh Corporation TSKgel GMH6-HT (30 cm × 4 columns) and a Tosoh Corporation HLC-8321GPC / HT equipped with an RI detector. The measurement conditions were as follows: sample solution injection amount: about 300 μL, column temperature: 135 ° C, solvent: o-dichlorobenzene, flow rate: 1.0 mL / min. The molecular weight was calculated as follows. That is, a commercially available monodisperse polystyrene was used as a standard sample, and a calibration curve relating to retention time and molecular weight was created from the viscosity equation of the polystyrene standard sample and the propylene-based polymer, and the molecular weight was calculated based on the calibration curve. Note that the viscosity equation used was [η]=K×Mα, where K=1.38E-4 and α=0.70 were used for polystyrene, and K=1.03E-4 and α=0.78 were used for the propylene-based polymer.

[0098] (2) Comonomer content in copolymer The comonomer content in the propylene copolymer is measured by 1 The measurement was carried out using a H-NMR measurement device (Bruker's "Ascend 400") according to the following procedure. 35 mg of the polymer was dissolved in o-dichlorobenzene-d4 solvent, and measurements were performed at 25° C. for 64 cumulative measurements. 1 The comonomer content was calculated from the integral ratio of the H-NMR chemical shifts. The comonomer content in the ethylene copolymer was measured using a Fourier transform infrared spectrophotometer ("FT / IR-4600" manufactured by JASCO Corporation) according to the following procedure. The copolymer was molded into a film by hot pressing, and the film was used for the measurement by the transmission method with 16 cumulative measurements. 680.7cm -1 ~780.1cm -1 and an area of ​​1680.7 cm -1 ~1800.2cm -1 The area ratio of the comonomers was calculated and input to a calibration curve prepared from the IR spectra of polymer samples with known comonomer contents.

[0099] (3) Structure assignment by NMR The assignment of the ligand and complex structures was carried out using an NMR measurement device (Bruker's "Ascend 400") according to the following procedure. The ligand was dissolved in a deuterated solvent, and measurements were performed at 25°C for 16 cumulative measurements.

[0100] 2. Synthesis of the ligand (Synthesis Example 1): Synthesis of Ligand A The following ligand A was synthesized according to the following scheme.

[0101] [ka]

[0102] (i) Synthesis of Compound 2 Synthesized according to Patent No. 6913051. (ii) Synthesis of Compound 4 It was synthesized according to Patent No. 6913051. (iii) Synthesis of Compound 5 Compound 4 (6.31 g, 21.1 mmol) was added dropwise to a solution of THF (40 ml) at 0° C., and the mixture was heated to 30° C. and stirred for 2 hours. CuCl (2.30 g, 23.3 mmol) was added to this suspension at 0° C., and the mixture was heated to 30° C. and stirred for 1 hour. The reaction solution was cooled to −78° C., and t-Bu2PCl (3.82 g, 21.1 mmol) was slowly added and stirred at 66° C. for 12 hours to obtain a blue suspension. The solvent was further removed under reduced pressure, and the mixture was purified with a silica gel column to obtain a pink solid. Dichloromethane (DCM) (80 ml) and aqueous ammonia (100 ml) were added to this pink solid, and the mixture was stirred at 30° C. for 1 hour. The organic layer obtained after the liquid separation operation was concentrated to obtain a crude product. This was purified by a silica gel column (using petroleum ether (PE):ethyl acetate (EtOAc):DCM=50:1:1 as a developing solvent) to obtain 2.40 g of compound 5. (iv) Synthesis of Ligand A A solution of hydrochloric acid / EtOAc (4M, 80ml) was added to a solution of compound 5 (2.65g, 5.99mmol) in DCM (10ml) at 0°C, and the mixture was stirred at 30°C for 3 hours to obtain a colorless, transparent solution. After the solvent was removed under reduced pressure, the mixture was dissolved again in DCM (100ml) and washed with a saturated aqueous NaHCO3 solution (100ml). The organic layer obtained after the liquid separation operation was concentrated to obtain 2.10g of ligand A. 1 H NMR (400MHz, CDCl3,δ,ppm):1.09(dd,12H),1.23(s,18H),2.62(m,2H),6.93 (t,1H),7.07(dd,1H),7.22(d,2H),7.35(t,1H),7.60(m,1H),7.83(dd,1H). 31 P NMR (162MHz, CDCl3,δ,ppm):-5.48(s).

[0103] (Synthesis Example 2): Synthesis of Ligand B According to the following scheme, ligand B having the following structure was synthesized.

[0104] [ka]

[0105] (i) Synthesis of compound 6 To a solution of compound 4 (5.50 g, 18.4 mmol) in THF (70 ml), nBuLi (2.5 M, 8.11 mL) was added dropwise at 0° C., and the mixture was stirred at 20° C. for 2 hours. The reaction solution was cooled to −78° C., stirred for 30 minutes, and PCl3 (7.59 g, 55.3 mmol) was added at −78° C. The mixture was stirred at 20° C. for 1 hour to obtain a yellow suspension. After distilling off the solvent under reduced pressure, 7.36 g of compound 6 was obtained as a yellow oily compound. Compound 6 was used in the next reaction without further purification. (ii) Synthesis of compound 8 To a solution of compound 7 (8 g, 48 mmol) in THF (100 ml), n-BuLi (2.5 M, 25.8 mL) was added at -60°C, and the mixture was stirred at 25°C for 2 hours. Then, methyl iodide (10.3 g, 72.2 mmol) was slowly added dropwise at -60°C. The mixture was stirred at 25°C for 14 hours to obtain a yellow suspension. The reaction was stopped by adding 80 ml of water, and the mixture was extracted three times with 50 ml of EtOAc. The obtained organic layer was washed with a saturated aqueous solution of sodium bicarbonate, filtered, and the filtrate was concentrated to obtain a crude product. This was purified using a silica gel column (PE was used as the developing solvent) to obtain compound 8 (4 g, 22.2 mmol, yield 46%). (iii) Synthesis of Compound 9 To a solution of compound 8 (6.1 g, 33.8 mmol) in THF (60 ml), n-BuLi (2.5 M, 14.9 mL) was added at -78°C, and the mixture was stirred at 20°C for 16 hours to obtain a red suspension. After the solvent was distilled off under reduced pressure, 6.3 g of red oily compound 6 was obtained. Compound 9 was used in the next reaction without further purification. (iv) Synthesis of compound 10 A solution of compound 6 (6.76 g, 16.9 mmol, 0.5 eq) in toluene (70 ml) and a solution of compound 9 (6.3 g, 33.8 mmol, 1 eq) in toluene (60 ml) were mixed at -78 ° C and stirred at 20 ° C for 2 hours. The mixture was further heated to 80 ° C and stirred for 14 hours to obtain a yellow suspension. The solvent was distilled off under reduced pressure to obtain an oily crude product. Purification was performed twice using a silica gel column (PE:DCM = 100:1 was used as the developing solvent) under an argon atmosphere, and washing with diethyl ether (15 ml) was performed to obtain 2.2 g (3.1 mmol, yield 9.3%) of compound 10. (v) Synthesis of Ligand B A solution of hydrochloric acid / EtOAc (4M, 150 ml) was added to a solution of compound 10 (2.1 g, 2.98 mmol) in DCM (10 ml) at 0° C., and the mixture was stirred at 20° C. for 3.5 hours to obtain a colorless, transparent solution. The solvent was removed under reduced pressure, and the mixture was neutralized with a saturated aqueous solution of sodium bicarbonate (150 ml) bubbled with nitrogen. The mixture was then extracted three times with DCM (150 ml) bubbled with nitrogen. The organic layer obtained after the separation operation was concentrated to obtain a yellow crude product. The mixture was washed with diethyl ether (15 ml) under an argon atmosphere to obtain 1.1 g (1.71 mmol, 57% yield) of ligand B. 1 H NMR (400MHz, CDCl3,δ,ppm):0.92(dd,12H),1.05(d,6H),2.13(m,2H),5.78(m,1H),6.31(t ,1H),6.78(d,1H),6.85(d,2H),7.02(t,2H),7.10(t,4H),7.24-7.29(m,7H),7.61(t,4H). 31 P NMR (162MHz, CDCl3,δ,ppm):8.26(s).

[0106] (Synthesis Example 3): Synthesis of Ligand C According to the following scheme, ligand C having the following structure was synthesized.

[0107] [ka]

[0108] (i) Synthesis of compounds 12, 13, and 14 Synthesized according to Patent No. 6938264. (ii) Synthesis of compound 15 9-Bromoanthracene (14.8 g, 57.5 mmol), compound 2 (11.5 g, 63.2 mmol), Pd(PPh3)4 (6.64 g, 5.74 mmol), Na2CO3 (15.2 g, 143 mmol), toluene (150 mL), EtOH (90 mL), and water (60 mL) were mixed, and nitrogen replacement was repeated three times. The reaction solution was stirred at 90 ° C for 18 hours to obtain a yellow suspension solution. After cooling to room temperature and filtration, the obtained solid was dissolved in DCM (150 ml) and washed three times with water (100 ml). The organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain compound 15 (8.0 g, 25.5 mmol, 44.3%). Compound 15 was used in the next reaction without further purification. (iii) Synthesis of compound 16 To a solution of compound 15 (8.0 g, 25.5 mmol) in THF (80 ml), n-BuLi (2.5 M, 12.2 mL) was added at 0° C., and the mixture was allowed to react at 18° C. for 2 hours. To the resulting suspension, iodine (9.69 g, 38.2 mmol) was added at −78° C., and the mixture was stirred at 18° C. for 16 hours to obtain a yellow suspension. The reaction solution was washed with saturated sodium hydrogen sulfate (100 ml) and extracted with AcOEt (10 ml). The resulting organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled under reduced pressure to obtain a crude product. The mixture was purified using a silica gel column (developing solvent: PE: AcOEt: DCM = 100: 1: 3), and 1.0 g (2.27 mmol, yield 8.9%) of compound 16 was obtained. (iv) Synthesis of Ligand C Compound 16 (870 mg, 1.98 mmol), compound 14 (682 mg, 1.98 mmol, 1 eq), Pd(dba)2 (114 mg, 198 umol), DPEPhos (213 mg, 395 umol), and t-BuONa (380 mg, 4.0 mmol) were dissolved in 100 ml of toluene and refluxed for 12 hours to obtain a black suspension. The solution was purified using a silica gel column (PE:AcOEt:DCM = 100:5:1 to 100:5:5 was used as the developing solvent) to obtain ligand C (0.36 g, 578 umol, yield 29%) as a yellow solid. 31 P NMR (162MHz, CDCl3,δ,ppm):-43.76(s).

[0109] (Comparative Synthesis Example 1): Synthesis of Ligand D According to the examples of Japanese Patent No. 5232718, ligand D having the following structure was synthesized.

[0110] [ka]

[0111] (Comparative Synthesis Example 2): Synthesis of Ligand E According to the examples of Japanese Patent No. 5232718, ligand E having the following structure was synthesized.

[0112] [ka]

[0113] 3. Polymerization Evaluation Example 1: Polymerization of propylene using ligand A (1) Preparation of catalyst components The following operations were all carried out under a nitrogen atmosphere. Hereinafter, bis-1.5-cyclooctadiene nickel(0) will be referred to as Ni(COD)2. Ni(COD)2 (27.5 mg, 0.10 mmol) was weighed into a two-necked eggplant flask, and toluene was added to prepare a solution. This toluene solution of Ni(COD)2 was added to the two-necked eggplant flask containing the ligand A (39.9 mg, 0.10 mmol) obtained in Synthesis Example 1 to obtain a mixture.

[0114] (2) Polymerization of propylene Propylene (1000 mL) was introduced into an induction stirring autoclave with an internal volume of 2 L. The mixture of ligand A and Ni(COD)2 obtained in (1) above and TMEDA (11.6 mg, 0.10 mmol) as compound (E) were fed into the autoclave. The autoclave was heated to 50°C while stirring to start polymerization. After polymerization for 2 hours, the remaining propylene was removed to stop the reaction. The autoclave was then opened to obtain a polymer. The polymerization results are shown in Table 5. The activity represents the polymer yield (kg) per mol of nickel complex used in the polymerization. The results of GPC for the obtained polymer are also shown in Table 5. The activity was calculated assuming that ligand A and Ni(COD)2 reacted in a 1:1 ratio to form a nickel complex.

[0115] (Examples 2 to 5, Comparative Examples 1 to 2): (Co)polymerization of propylene using ligand A A polymer was obtained in the same manner as in Example 1 except that the conditions were changed as shown in Table 5.

[0116] [Table 5]

[0117] Example 6: Copolymerization of ethylene with ligand A (1) Preparation of catalyst components All of the following operations were carried out under a nitrogen atmosphere. Hereafter, nickel diacetylacetonate (II) is referred to as Ni(acac)2. Ni(acac)2 (0.02 mmol) was weighed into a two-necked eggplant flask, and toluene was added to make a solution. This toluene solution of Ni(acac)2 was added to the two-necked eggplant flask containing Ligand A (0.02 mmol) obtained in Synthesis Example 1, and stirred at room temperature for 30 minutes. A solution of a mixture of Ligand A and Ni(acac)2 was obtained.

[0118] (2) Copolymerization of ethylene Toluene (1 L), methyl acrylate (40 mmol) as a comonomer, TMEDA (0.10 mmol) as compound (E), and tri-n-octylaluminum (0.2 mmol) were introduced into an induction stirring autoclave having an internal volume of 2 L to obtain a mixture. The temperature of the autoclave was raised to 110° C. while stirring the mixture, and then ethylene was supplied to the autoclave to adjust the ethylene partial pressure in the autoclave to 3.0 MPa. The solution of the mixture of ligand A and Ni(acac)2 obtained in (1) above was fed to an autoclave to initiate polymerization. After polymerization for 1 hour, 1,2-butanediol was introduced into the autoclave to terminate the reaction. After removing unreacted gas from the autoclave, the autoclave was opened and ethanol was added to the autoclave to precipitate the copolymer. The precipitate was filtered, washed, and dried by heating to obtain the copolymer. The polymerization results are shown in Table 6. The activity represents the polymer yield (g) per mol of nickel complex used in the copolymerization. The results of GPC for the obtained copolymer are also shown in Table 6. The activity was calculated assuming that ligand A and Ni(acac)2 reacted in a 1:1 ratio to form a nickel complex.

[0119] Comparative Example 3: Copolymerization of ethylene using ligand A A copolymer was obtained in the same manner as in Example 6, except that the conditions were changed as shown in Table 6.

[0120] [Table 6]

[0121] (Examples 7 to 14): Polymerization of propylene using ligand A when compound (E) is of different type A polymer was obtained in the same manner as in Example 1, except that the conditions were changed as shown in Table 7. The polymerization results are shown in Table 7. In addition, the abbreviations used in the description are as follows. TMMDA: N,N,N′,N′-tetramethylmethanediamine PMDETA: N,N,N′,N″,N″-Pentamethyldiethylenetriamine TMPDA: N,N,N′,N′-tetramethyl-1,3-propanediamine DMBA: N,N-Dimethylbenzylamine NEt3: Triethylamine DABCO: 1,4-diazabicyclo[2.2.2]octane ABCO: 1-Azabicyclo[2.2.2]octane

[0122] [Table 7]

[0123] (Comparative Examples 4 to 12): Polymerization of propylene using ligand A when the Lewis base described in Patent Document 1 is used as compound (E) A polymer was obtained in the same manner as in Example 1, except that the conditions were changed as shown in Table 8. The polymerization results are shown in Table 8. In addition, the abbreviations used in the description are as follows. DMAP: N,N-dimethyl-4-aminopyridine DMSO: Dimethyl sulfoxide NPh3: Triphenylamine THF: tetrahydrofuran PPh3: Triphenylphosphine POPh3: Triphenylphosphine oxide

[0124] [Table 8]

[0125] (Examples 15-16, Comparative Examples 13-18): Polymerization of propylene using different types of ligands A polymer was obtained in the same manner as in Example 1, except that the conditions were changed as shown in Table 9. The polymerization results are shown in Table 9.

[0126] [Table 9]

[0127] 4. Discussion As shown in Tables 5 to 9, it was confirmed that the olefin polymerization catalyst components containing the compound (E) specified in the present invention shown in Examples 1 to 16 serve as highly active olefin polymerization catalysts in olefin (co)polymerization, compared with the olefin polymerization catalyst components not containing the compound (E) specified in the present invention shown in Comparative Examples 1 to 3 and 13 to 14, and the olefin polymerization catalyst components containing a conventional Lewis base such as that disclosed in Patent Document 1 as compound (E) shown in Comparative Examples 4 to 12. Furthermore, the olefin polymerization catalyst component containing a metal complex having a phosphinophenolate ligand disclosed in Patent Document 2, in which the substituent on P is a substituted phenyl group, and the compound (E) specified in the present invention, as shown in Comparative Examples 16 and 18, did not have the activity improving effect in propylene polymerization, compared to the olefin polymerization catalyst components not containing the compound (E) shown in Comparative Examples 15 and 17. Therefore, it was confirmed that the combination of a specific ligand structure (particularly the substituent on P) and a tertiary amine results in high activity of the olefin polymerization catalyst. In addition, although Patent Document 2 discloses that the molecular weight tends to decrease depending on the amount of Lewis base added, it was confirmed that the molecular weight is maintained in the present invention. [Industrial Applicability]

[0128] By using the metal complex of the present invention, it is possible to produce olefin polymers, particularly propylene polymers, with high activity while maintaining the molecular weight of the polymer, and therefore the metal complex is extremely useful industrially and is of great industrial utility.

Claims

1. A catalyst component for olefin polymerization, comprising: a metal complex (D) which is a reaction product of a compound (A) represented by the following general formula [1] or a compound (B) represented by the following general formula [2] with a transition metal compound (C) containing at least one of nickel and palladium; and a compound (E) represented by the following general formula [3]: 【Chemistry 1】 [In formula [1] and formula [2], R １ , R ２ , R ３ and R ４ each independently represents an atom or group selected from the group consisting of the following (i) to (iv): (i) a hydrogen atom (ii) a halogen atom (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms; (iv) OR １０ , CO ２ R １０ , CO ２ M, C(O)N(R １１ ) ２ , C(O)R １０ , O.C.(O)R １０ , S.R. １０ , S.O. ２ R １０ , OSO ２ R １０ , P(O)(OR １０ ) ２－ｙ (R １０ ) ｙ , C.N., N.R. １０ (R １１ ), Si(OR １１ ) ３－ｘ (R １１ ) ｘ , OSi(OR １１ ) ３－ｘ (R １１ ) ｘ , NO ２ , S.O. ３ M., P.O. ３ M ２ , P(O)(OR １１ ) ２ M, or an epoxy-containing group. １０ represents a hydrocarbon group having 1 to 20 carbon atoms; R １１ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. １０ and R １１ When there are multiple R １０ and R １１ may be the same or different. M represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer of 0 to 3, and y represents an integer of 0 to 2. １ , R ２ , R ３ and R ４ may be bonded to each other to form a ring. R ５ and R ６ each independently represents an alkyl group having 1 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a condensed polycyclic hydrocarbon group having 8 to 30 carbon atoms, which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; NR １０ (R １１ ), or SiR １０ (R １１ ) ２ (Here, two R １１ may be the same or different. E １ represents a phosphorus atom, an arsenic atom, or an antimony atom. X １ represents an oxygen atom or a sulfur atom. Z １ represents a hydrogen atom or a leaving group; m represents Z １ represents the valence of [In formula [3], R ７ , R ８ and R ９ Each independently represents N(R １０ ) ２ (Here, two R １０ may be the same or different.) and an oxygen atom, an alkyl group having 1 to 20 carbon atoms which may have at least one selected from the group consisting of an aryl group having 7 to 20 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 20 carbon atoms. １０ has the same definition as above. ７ , R ８ and R ９ When any two of R are aryl groups having 6 to 20 carbon atoms, the remaining one cannot be an aryl group having 6 to 20 carbon atoms. ７ , R ８ and R ９ may be bonded to each other to form an alicyclic structure.

2. The R ７ , R ８ and R ９ Each independently represents N(R １０ ) ２ (Here, two R １０ may be the same or different.) and an oxygen atom, an alkyl group having 1 to 12 carbon atoms which may have at least one selected from the group consisting of an arylalkyl group having 7 to 12 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 12 carbon atoms (provided that R ７ , R ８ and R ９ The olefin polymerization catalyst component according to claim 1, wherein when any two of the above are aryl groups having 6 to 12 carbon atoms, the remaining one is not an aryl group having 6 to 12 carbon atoms.

3. 2. The olefin polymerization catalyst component according to claim 1, wherein the total number of nitrogen atoms contained in said compound (E) is 3 or less.

4. The R ５ and R ６ are each independently an alkyl group having 1 to 20 carbon atoms or a condensed polycyclic hydrocarbon group having 8 to 30 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom.

5. The R ５ and R ６ each independently represents a branched acyclic alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms which may have a side chain, or a condensed polycyclic hydrocarbon group having 8 to 15 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom.

6. A method for producing an olefin polymer, comprising mixing a compound (A) represented by the following general formula [1] or a compound (B) represented by the following general formula [2], a transition metal compound (C) containing at least one of nickel and palladium, a compound (E) represented by the following general formula [3], and an olefin, and polymerizing or copolymerizing the olefin. 【Chemistry 2】 [In formula [1], [2] and formula [3], R １ ~R ９ , E １ , X １ , Z １ and m are as defined in claim 1.

7. The R ７ , R ８ and R ９ Each independently represents N(R １０ ) ２ (Here, two R １０ may be the same or different.) and an alkyl group having 1 to 12 carbon atoms which may have at least one selected from the group consisting of an oxygen atom, an arylalkyl group having 7 to 12 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 12 carbon atoms (wherein R ７ , R ８ and R ９ When any two of the groups are aryl groups having 6 to 12 carbon atoms, the remaining group cannot be an aryl group having 6 to 12 carbon atoms. Here, the R １０ The method for producing an olefin polymer according to claim 6, wherein is as defined in claim 1.

8. The process for producing an olefin polymer according to claim 6, wherein the total number of nitrogen atoms contained in the compound (E) is 3 or less.

9. The R ５ and R ６ each independently represents an alkyl group having 1 to 20 carbon atoms or a condensed polycyclic hydrocarbon group having 8 to 30 carbon atoms, which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom.

10. The R ５ and R ６ each independently represents a branched acyclic alkyl group having 3 to 20 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom, a cycloalkyl group having 3 to 20 carbon atoms which may have a side chain, or a condensed polycyclic hydrocarbon group having 8 to 15 carbon atoms.

11. The method for producing an olefin polymer according to claim 6, wherein the olefin is ethylene or propylene.

12. The method for producing an olefin polymer according to claim 6, further comprising mixing the compound (A) or the compound (B), the transition metal compound (C), the compound (E), an olefin, and a polar group-containing comonomer, and copolymerizing the olefin and the polar group-containing comonomer.

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