JP2024052628A - Compound, metal complex, catalyst composition for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Abstract

To provide: a novel ligand and a metal complex that enable copolymerization of olefin and vinyl monomers; a catalyst composition for olefin polymerization containing the same; and a method for producing an olefin polymer.SOLUTION: A catalyst composition for olefin polymerization contains a compound represented by the general formula (A) in the figure, and a transition metal compound represented by the general formula (E) or (F) in the figure.SELECTED DRAWING: None

Description

The present invention relates to a polymerization catalyst for producing olefin polymers. In particular, the present invention relates to a novel compound that can be used as a ligand, a metal complex using the novel compound, a catalyst composition for olefin polymerization, and a catalyst for olefin polymerization. The present invention also relates to a method for producing an olefin polymer using the catalyst.

Copolymers of olefins such as non-polar monomers, such as ethylene and propylene, and polar group-containing monomers have functions and properties that are not found in non-polar polyethylene and polypropylene. From this perspective, research has been actively conducted into imparting functionality to polyethylene and polypropylene by copolymerizing ethylene or propylene with polar group-containing monomers.
As a transition metal catalyst capable of copolymerizing ethylene or propylene with a polar group-containing monomer, a catalyst containing a palladium complex using an α-diimine ligand has been reported (Non-Patent Document 1). As a transition metal catalyst capable of copolymerizing ethylene with an acrylic acid ester, so-called SHOP-based catalysts containing a nickel complex using a ligand with phosphorus and oxygen atoms as coordinating atoms (Patent Document 1, Patent Document 2, Non-Patent Document 2, Non-Patent Document 3) and catalysts containing a palladium complex having a phosphinosulfonic acid ligand (Patent Document 3, Non-Patent Document 4, Non-Patent Document 5) have been reported.

Patent Document 4 and Non-Patent Document 6 report that a linear ethylene and (meth)acrylic acid ester copolymer with few branches can be obtained by using a nickel catalyst in which a ligand having phosphorus and oxygen atoms as coordinating atoms is reacted with bis-1,5-cyclooctadiene nickel (Ni(cod) ₂ ) as a transition metal compound. Patent Document 5 reports copolymerization of ethylene and a polar group-containing monomer using a catalyst containing a nickel complex in which a monovalent anionic bidentate ligand having phosphorus and oxygen atoms as coordinating atoms, and nickel allyl chloride dimer is reacted with the ligand skeleton having an alkylene as a non-aromatic skeleton.
Non-Patent Document 7 reports the oligomerization of ethylene by using a nickel catalyst obtained by reacting a monovalent anionic bidentate ligand having an alkylene as a non-aromatic skeleton as a ligand skeleton and having phosphorus and oxygen atoms as coordinating atoms with bis-1,5-cyclooctadiene nickel.
Non-Patent Document 8 reports the oligomerization of ethylene using a nickel catalyst obtained by reacting a nickel complex with a monovalent anionic bidentate ligand having a non-aromatic skeleton and containing a phosphorus atom and a sulfur atom as coordinating atoms.

U.S. Pat. No. 4,698,403 Japanese Patent Application Laid-Open No. 64-14217 US Patent Application Publication No. 2007/0049712 International Publication No. 2010/050256 International Publication No. 2001/092342

Mecking, S. ;Johnson, L. K. ;Wang, L. Brookhart, M. J. Am. Chem. Soc. 1998, 120, 888-899. Ittel, S. D. ;Johnson, L. K. Brookhart, M. , Chem. Rev. 2000,100,1169-1203. Gibson, V. C. ;Tomov, A. ;White, A. J. P. ;Williams, D. J. , Chem. Commun. 2001, 719-720. Drent, E. ;van Dijk, R. ;van Ginkel, R. ;van Oort, B. ;Pugh, R. I. , Chem. Commun. 2002, 744-745. Kochi, T.; Yoshimura, K.; Nozaki, K., Dalton Trans. 2006, 25-27. Xin. B. S.; Sato, N.; Tanna, A.; Oishi, Y.; Konishi, Y.; Shimizu, F. J. Am. Chem. Soc. 2017, 139, 3611-3614. Mueller, U. ;Keim, W. ;Krueger, C. ; Betz, P. Angew. Chem. Int. Ed. Engl. 1989, 28, 1011-1013. H. -F. Klein et al. , Inorganica Chimica Acta 358 (2005) 4394-4402

As mentioned above, many olefin-based polymerization catalysts are known. However, the skeleton of the ligand used in Patent Document 4 and Non-Patent Document 6 is aromatic, and there is room for improvement in the molecular weight of the copolymer in copolymerization with acrylic ester. In addition, the catalyst in Patent Document 5 has room for improvement in catalytic performance such as activity and molecular weight. In Non-Patent Document 7, only oligomers are obtained, and the polymerization activity is unknown. It is disclosed that the isolated complex does not show polymerization performance, although the complex is isolated. The catalyst in Non-Patent Document 8 is only known to produce low-density polyethylene oligomers.
In this situation, the problem to be solved by the present invention is to provide a novel compound having improved catalytic performance such as activity and molecular weight and usable as a ligand of a catalyst capable of polymerizing or copolymerizing olefins, particularly a novel compound usable as a ligand of a catalyst capable of copolymerizing at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins with a non-cyclic olefin, a metal complex using the novel compound, an olefin polymerization catalyst composition, and an olefin polymerization catalyst, as well as a method for producing an olefin polymer using the catalyst.

The present inventors have discovered an olefin polymerization catalyst that has a high level of at least activity or molecular weight by combining a monovalent anionic bidentate ligand having an alkylene with a specific structure as the ligand skeleton, with Group 15 and Group 16 elements, particularly nitrogen atoms or phosphorus atoms and oxygen atoms as coordinating atoms, and specific substituents, with a specific nickel compound and/or palladium compound, and have arrived at the present invention.

That is, the present invention relates to the following [1] to [16].
[1] A compound represented by the following general formula (A):

[In the formula (A),
^X1 represents an oxygen atom or a sulfur atom;
^E1 represents a nitrogen atom, a phosphorus atom, an arsenic atom, or an antimony atom;
Z represents a hydrogen atom, a leaving group, or a cation having a valence of 1 to 4,
m is an integer from 1 to the valence of Z,
n is 0, 1, 2, 3 or 4, and when n is 0, E ¹ is directly bonded to the carbon atom to which X ¹ , R ⁵ and R ⁶ are bonded;
R ¹ represents a hydrocarbon group represented by the following general formula (B) or (C):
^R2 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom and which is different from the hydrocarbon group represented by the following general formula (B) or (C),
l is 1 or 2, and when l is 2, ^R2 is absent.
R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent 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 contain at least one heteroatom; (iv) OR ^b , C(O)OR ^b , C(O)OM', C(O)N(R ^a ) ₂ , C(O)R ^b , OC(O)R ^b , SR ^b , S(O) ₂ R ^b , S(O)R ^b , OS(O) ₂ R ^b , SF ₅ , P(O)(OR ^b ) _2-y (R ^a ) _y , CN, N(H)R ^a , N(R ^b ) ₂ , Si(OR ^a ) _3-x (R ^a ) _x , OSi(OR ^a ) _3-x (R ^a ) _x , NO ₂ , S(O) ₂ OM', P(O)(OM') ₂ , P(O)(OR ^b ) ₂ M', or an epoxy-containing group (wherein R ^a each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ^b each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents 0, 1, 2 or 3, and y represents 0, 1 or 2). Adjacent substituents of R ³ , R ⁴ , R ⁵ and R ⁶ may be linked together to form a 5-8 membered alicyclic ring or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom. ]

[In formula (B) and formula (C),
* represents a bond to ^E1 ;
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent an atom or group selected from the group consisting of (i) to (iv) defined in formula (A), and adjacent substituents of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be bonded to each other to form a 5- to 8-membered alicyclic ring, aromatic ring, or heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom;
A ¹ , A ² , A ³ and A ⁴ each independently represent an oxygen atom, a sulfur atom, -C(R) ₂ -, -S(O)-, -S(O) ₂ -, -N(R)-, -P(R)- or -P(O)(R)- (wherein each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom).
however,
In formula (B), at least three of A ¹ , A ² , A ³ and A ⁴ are other than —C(R) ₂ —;
In formula (C), ^A3 and ^A4 are both other than -C(R) _2- , and at least one of ^R12 and ^R13 is an atom or group selected from the group consisting of (ii) and (iv) (excluding epoxy-containing groups).
W ¹ and W ² each independently represent a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O) ₂ -; when W 1 and W 2 represent a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R ⁸ and R ¹⁰ do not exist; and when W 1 and W 2 represent an oxygen atom or -S(O) ₂ -, R ⁷ and R ⁸ as well as R ⁹ and R ¹⁰ do not exist.
h and i each independently represent an integer of 1 to 6, and when a plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are present, the plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different.]

[2] A metal complex represented by the following general formula (D):

[In the formula (D),
^X1 represents an oxygen atom or a sulfur atom;
^E1 represents a nitrogen atom, a phosphorus atom, an arsenic atom, or an antimony atom;
n is 0, 1, 2, 3 or 4, and when n is 0, E ¹ is directly bonded to the carbon atom to which X ¹ , R ⁵ and R ⁶ are bonded;
R ¹ represents a hydrocarbon group represented by the following general formula (B) or (C):
^R2 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom and which is different from the hydrocarbon group represented by the following general formula (B) or (C),
l is 1 or 2, and when l is 2, ^R2 is absent.
R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent 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 contain at least one heteroatom; (iv) OR ^b , C(O)OR ^b , C(O)OM', C(O)N(R ^a ) ₂ , C(O)R ^b , OC(O)R ^b , SR ^b , S(O) ₂ R ^b , S(O)R ^b , OS(O) ₂ R ^b , SF ₅ , P(O)(OR ^b ) _2-y (R ^a ) _y , CN, N(H)R ^a , N(R ^b ) ₂ , Si(OR ^a ) _3-x (R ^a ) _x , OSi(OR ^a ) _3-x (R ^a ) _x , NO ₂ , S(O) ₂ OM', P(O)(OM') ₂ , P(O)(OR ^b ) ₂ M' or an epoxy-containing group (wherein R ^a each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ^b each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents 0, 1, 2 or 3, y represents 0, 1 or 2). Adjacent substituents of R ³ , R ⁴ , R ⁵ and R ⁶ may be linked together to form a 5-8 membered alicyclic ring or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom.
^M1 represents a nickel atom or a palladium atom;
^L1 and ^L2 each independently represent a ligand coordinated to ^M1 ;
^L1 and ^L2 may be bonded to each other to form a ring containing ^M1 .

[In formula (B) and formula (C),
* represents a bond to ^E1 ;
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent an atom or group selected from the group consisting of (i) to (iv) defined in formula (A), and adjacent substituents of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be bonded to each other to form a 5- to 8-membered alicyclic ring, aromatic ring, or heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom;
A ¹ , A ² , A ³ and A ⁴ each independently represent an oxygen atom, a sulfur atom, -C(R) ₂ -, -S(O)-, -S(O) ₂ -, -N(R)-, -P(R)- or -P(O)(R)- (wherein each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom).
however,
In formula (B), at least three of A ¹ , A ² , A ³ and A ⁴ are other than —C(R) ₂ —;
In formula (C), ^A3 and ^A4 are both other than -C(R) _2- , and at least one of ^R12 and ^R13 is an atom or group selected from the group consisting of (ii) and (iv) (excluding epoxy-containing groups).
W ¹ and W ² each independently represent a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O) ₂ -; when W 1 and W 2 represent a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R ⁸ and R ¹⁰ do not exist; and when W 1 and W 2 represent an oxygen atom or -S(O) ₂ -, R ⁷ and R ⁸ as well as R ⁹ and R ¹⁰ do not exist.
h and i each independently represent an integer of 1 to 6, and when a plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are present, the plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different.]

[3] A catalyst composition for olefin polymerization, comprising a compound represented by the general formula (A) described in [1] above and a transition metal compound represented by the following general formula (E) or (F):

[In the formula (E) and the formula (F),
^M1 represents a nickel atom or a palladium atom;
^L1 and ^L2 each independently represent a ligand coordinated to ^M1 ;
^L1 and ^L2 may be bonded to each other to form a ring containing ^M1 .
^M2 and ^M3 each independently represent a nickel atom or a palladium atom;
^L3 , ^L4 , ^L5 , ^L6 , ^L9 and ^L10 each independently represent a ligand coordinated to ^M1 , ^M2 or ^M3 ; ^L7 and ^L8 each independently represent a ligand coordinated to ^M2 and ^M3 ;
q is 0, 1 or 2;
^L3 and ^L4 may be bonded to each other to form a ring containing ^M1 ;
^L5 and ^L6 may be bonded to each other to form a ring containing ^M2 ;
^L9 and ^L10 may be bonded to each other to form a ring including ^M3 .

[4] The compound according to [1], wherein at least one of ^R5 and ^R6 is an atom or group selected from the group consisting of (i), (iii) and (iv).
[5] The metal complex according to [2] above, wherein at least one of ^R5 and ^R6 is an atom or group selected from the group consisting of (i), (iii) and (iv).
[6] At least one of ^R5 and ^R6 is an atom or group selected from the group consisting of (i), (iii) and (iv), according to the olefin polymerization catalyst composition described in [3].

[7] The compound according to [1] above, characterized in that R ⁵ is an atom or group selected from the group consisting of (i) and (iii), and R ⁶ is an atom or group selected from the group consisting of (i), (iii), C(O)OR ^b , C(O)N(R ^a ) ₂ , C(O)R ^b , S(O) ₂ R ^b and P(O)(OR ^b ) _2-y (R ^a ) _y (wherein R ^a , R ^b and y are as defined in [1] above).
[8] The metal complex according to [2] above, characterized in that R ⁵ is an atom or group selected from the group consisting of (i) and (iii), and R ⁶ is an atom or group selected from the group consisting of (i), (iii), C(O)OR ^b , C(O)N(R ^a ) ₂ , C(O)R ^b , S(O) ₂ R ^b and P(O)(OR ^b ) _2-y (R ^a ) _y (wherein R ^a , R ^b and y are as defined in [2] above).
[9] The catalyst composition for olefin polymerization according to [3] above, characterized in that R ⁵ is an atom or group selected from the group consisting of (i) and (iii), and R ⁶ is an atom or group selected from the group consisting of (i), (iii), C(O)OR ^b , C ⁽ O)N(R ^a ) ₂ , C(O)R ^b , S(O) ₂ R b and P(O)(OR ^b ) _2-y (R ^a ) _y (wherein R ^a , R ^b and y are as defined in [1] above).

[10] At least one of ^R3 and ^R4 is an atom or group selected from the group consisting of (i), (iii) and (iv). The compound according to any one of [1], [4] and [7].
[11] At least one of ^R3 and ^R4 is an atom or group selected from the group consisting of (i), (iii) and (iv). The metal complex according to any one of [2], [5] and [8].
[12] At least one of ^R3 and ^R4 is an atom or group selected from the group consisting of (i), (iii) and (iv). The catalyst composition for olefin polymerization according to any one of [3], [6] and [9].

[13] An olefin polymerization catalyst comprising the olefin polymerization catalyst composition according to any one of [3], [6], [9] and [12].
[14] An olefin polymerization catalyst comprising the metal complex according to any one of [2], [5], [8] and [11].

[15] A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to [13] or [14] above.
[16] A method for producing an olefin polymer according to the above [15], comprising copolymerizing a non-cyclic olefin with at least one monomer selected from the group consisting of a polar group-containing monomer and a cyclic olefin.

According to the present invention, it is possible to provide a novel compound that has improved catalytic performance such as activity and molecular weight and can be used as a ligand of a catalyst capable of polymerizing or copolymerizing olefins, particularly a novel compound that can be used as a ligand of a catalyst capable of copolymerizing at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins with a non-cyclic olefin, a metal complex using the novel compound, a catalyst composition for olefin polymerization, and a catalyst for olefin polymerization, as well as a method for producing an olefin-based polymer using the catalyst.

Hereinafter, the novel compound that can be used as a ligand of the present invention, the metal complex using the novel compound, the olefin polymerization catalyst composition, and the olefin polymerization catalyst, as well as the process for producing an olefin polymer using the catalyst will be described in detail for each item.
In this specification, "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 specification, "(meth)acrylic acid ester" includes both acrylic acid ester and methacrylic acid ester.
In addition, in this specification, the use of "to" indicating a range of values is used to mean that the values before and after it are included as the lower limit and upper limit.
In this specification, "Ph" stands for phenyl, "Me" stands for methyl, "Et" stands for ethyl, "Pr" stands for propyl, "Bu" stands for butyl, "Py" stands for pyridyl or pyridine, "acac" stands for acetylacetonate, "DMP" stands for 2,6-dimethoxyphenyl, and "TMS" stands for trimethylsilyl.
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 a normal structure.

1. Compound The compound of the present invention is a compound represented by the following general formula (A).

[In formula (A), each symbol is as defined above.]
R ¹ to R ⁶ , E ¹ , X ¹ , Z, l, n and m in formula (A) will be explained below.

In the general formula (A), X ¹ represents an oxygen atom or a sulfur atom. That is, the compound represented by the general formula (A) can be used as a ligand having one Group 16 element as a monovalent anionic coordinating atom. Since there are a wide variety of compounds that can be used as a ligand, X ¹ is preferably an oxygen atom.

In the general formula (A), ^E1 represents a nitrogen atom, a phosphorus atom, an arsenic atom, or an antimony atom. That is, the compound represented by the general formula (A) can be used as a ligand having one Group 15 element as a neutral coordinating atom. Since there are a wide variety of compounds that can be used as a ligand and they have good coordination with late transition metal elements such as nickel or palladium, ^E1 is preferably a nitrogen atom or a phosphorus atom.

In the above general formula (A), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent 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 contain at least one heteroatom; (iv) OR ^b , C(O)OR ^b , C(O)OM', C(O)N(R ^a ) ₂ , C(O)R ^b , OC(O)R ^b , SR ^b , S(O) ₂ R ^b , S(O)R ^b , OS(O) ₂ R ^b , SF ₅ , P(O)(OR ^b ) _2-y (R ^a ) _y , CN, N(H)R ^a , N(R ^b ) ₂ , Si(OR ^a ) _3-x (R ^a ) _x , OSi(OR ^a ) _3-x (R ^a ) _x , NO ₂ , S(O) ₂ OM', P(O)(OM') ₂ , P(O)(OR ^b ) ₂ M' or an epoxy-containing group (wherein R ^a each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ^b each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents 0, 1, 2 or 3, y represents 0, 1 or 2). Adjacent substituents of R ³ , R ⁴ , R ⁵ and R ⁶ may be linked together to form a 5-8 membered alicyclic ring or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom.

(ii) Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Of these, fluorine atoms are preferred.

(iii) Examples of the hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom include a hydrocarbon group and a hydrocarbon group in which at least one hydrogen atom is substituted with a heteroatom-containing substituent.
Examples of the heteroatom in (iii) include an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom, a silicon atom, a halogen atom, etc. The heteroatom as a substituent may be a halogen atom, and the halogen atom may be the same as in (ii) above.
The heteroatom-containing substituent in (iii) may be the same as the heteroatom-containing substituent in (iv) described below. The heteroatom-containing substituent used in (iii) may be an alkoxy group, an aryloxy group, an alkoxycarbonyl group, or an acyloxy group.

In (iii), examples of the hydrocarbon group having 1 to 30 carbon atoms include linear, branched, and cyclic saturated or unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. More specific examples of the hydrocarbon group having 1 to 30 carbon atoms include linear alkyl groups having 1 to 30 carbon atoms, branched non-cyclic alkyl groups having 3 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms that may have a side chain, aryl groups having 6 to 30 carbon atoms, arylalkyl groups having 7 to 30 carbon atoms, and alkylaryl groups having 7 to 30 carbon atoms.

The linear alkyl group having 1 to 30 carbon atoms may be a linear alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, or an n-decyl group, or may be a linear alkyl group having 1 to 4 carbon atoms.
The branched non-cyclic alkyl group having 3 to 30 carbon atoms may be a branched non-cyclic alkyl group having 3 to 10 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, or an i-hexyl group (4-methylpentyl group), or may be a branched non-cyclic alkyl group having 3 to 8 carbon atoms.

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 be an alkenyl group having 3 to 8 carbon atoms, such as an allyl group, a butenyl group, a pentenyl group, a hexenyl group, or a styryl group, or may be an alkenyl group having 4 to 8 carbon atoms, such as a butenyl group, a pentenyl group, a hexenyl group, or a styryl group.
The cycloalkyl group which may have a side chain having 3 to 30 carbon atoms may be a cycloalkyl group which may have a side chain having 3 to 10 carbon atoms, such as 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 cyclooctyl group, or a decahydronaphthyl group (bicyclo[4,4,0]decyl group), or may be a cycloalkyl group which may have a side chain having 3 to 6 carbon atoms.

The aryl group having 6 to 30 carbon atoms may be an aryl group having 6 to 18 carbon atoms, such as 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, or a tetracenyl group, or may be an aryl group having 6 to 12 carbon atoms.
The arylalkyl group having 7 to 30 carbon atoms may be an arylalkyl group having 7 to 15 carbon atoms, such as a benzyl group, a phenethyl group (2-phenylethyl group), a 9-fluorenyl group, a naphthylmethyl group, or a 1-tetralinyl group, or may be an arylalkyl group having 7 to 10 carbon atoms.
The alkylaryl group having 7 to 30 carbon atoms may be an alkylaryl group 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, or a dodecylphenyl group, or may be an alkylaryl group having 7 to 15 carbon atoms, such as a tolyl group, a xylyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, or a pentylphenyl group.

In (iii), the total number of carbon atoms in the substituents corresponding to R ³ to R ⁶ is preferably 1 to 30, more preferably 2 to 25, and even more preferably 4 to 20.
Examples of (iii) include (iii-A) a linear alkyl group having 1 to 30 carbon atoms, a branched non-cyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 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 heteroatoms containing substituents, 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 heteroatom-containing substituents. Examples of (iii-C) include an alkyl group substituted with an alkoxy group, an aryl group substituted with an alkoxycarbonyl group, or an acyloxy group.

(iii) Examples of hydrocarbon groups having 1 to 30 carbon atoms and which may contain at least one heteroatom include a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, a 2,4,6-triphenylphenyl group, a 2,6-diisopropylphenyl group, a 9-anthracenyl group, a pentafluoroethyl group, a pentafluorophenyl group, a phenyl group, and a benzyl group.

(iv) is a heteroatom-containing substituent, such as OR ^b , C(O)OR ^b , C(O)OM', C(O)N(R ^a ) ₂ , C(O)R ^b , OC(O)R ^b , SR ^b , S(O) ₂ R ^b , S(O)R ^b , OS(O) ₂ R ^b , SF ₅ , P(O)(OR ^b ) _2-y (R ^a ) _y , CN, N(H)R ^a , N(R ^b ) ₂ , Si(OR ^a ) _3-x (R ^a ) _x , OSi(OR ^a ) _3-x (R ^a ) _x , NO ₂ , S(O) ₂ OM', P(O)(OM') ₂ , P(O)(OR ^b ₂ ) M' or an epoxy-containing group (wherein each R ^a independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, each R ^b independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents 0, 1, 2 or 3, and y represents 0, 1 or 2).

Examples of the (iv) include a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, a phenoxy group, a p-methylphenoxy group, a p-methoxyphenoxy group, an ethoxycarbonyl group, a t-butoxycarbonyl group, a phenoxycarbonyl group, a dimethylamido group, an acetyl group, a benzoyl group, an acetoxy group, a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, a t-butylthio group, a phenylthio group, a methylsulfonyl group, a phenylsulfonyl group, a methylsulfonyloxy group, a phenylsulfonyloxy group, a pentafluorosulfanyl group (SF ₅ ), a dimethylphosphate group, a cyano group, an amino group (NH ₂ ), methylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, cyclohexylamino group, methylethylamino group, methyl-n-propylamino group, methylcyclohexylamino group, carbazolyl group, piperidyl group, trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, trimethoxysilyl group, triethoxysilyl group, trimethylsilyloxy group, trimethoxysiloxy group, sodium carboxylate, sodium sulfonate, potassium sulfonate, sodium phosphate, potassium phosphate, and the like.

In addition, adjacent substituents of R ³ , R ⁴ , R ⁵ , and R ⁶ may be linked to each other to form a 5- to 8-membered alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom. In the ring structure formed, an aromatic ring may be included in the condensed ring. Examples of ring-forming groups include 1,2-cyclopentylene, 1,2-cyclohexylene, 1-oxo-2,3-cyclopentylene, 1-oxo-2,3-cyclohexylene, 1,2-dihydroacenaphthylene, and 9,10-dihydroanthracenylene.

Among these, from the viewpoint of the stability of the ligand, it is preferable that at least one of R ⁵ and R ⁶ is an atom or group selected from the group consisting of (i), (iii) and (iv), and it is more preferable that R ⁵ is an atom or group selected from the group consisting of (i) and (iii) and R ⁶ is an atom or group selected from the group consisting of (i), (iii), C(O)OR ^b , C(O)N(R ^a ) ₂ , C(O)R ^b , S(O) ₂ R ^b , and P(O)(OR ^b ) _2-y (R ^a ) _y .

In particular, it is preferable that at least one of ^R5 and ^R6 adjacent to ^X1 is an electron-withdrawing group, since this further improves the performance as an olefin polymerization catalyst. Both ^R5 and ^R6 adjacent to ^X1 may be electron-withdrawing groups. As the electron-withdrawing group, a trifluoromethyl group, a pentafluorophenyl group, a methoxycarbonyl group, a phenoxycarbonyl group, _SF5 , a tosyl group, a mesyl group, a nitro group, a methylcarbonyl group, a phenylcarbonyl group, and the like are preferably used.

In addition, from the viewpoint of the degree of difficulty in synthesis and economic rationality, at least one of ^R3 and ^R4 may be an atom or group selected from the group consisting of (i), (iii) and (iv), and at least one of ^R3 and ^R4 may be a hydrogen atom.

n is 0, 1, 2, 3 or 4, and when n is 0, ^E1 is directly bonded to the carbon atom to which ^X1 , ^R5 and ^R6 are bonded. The value of n is related to the number of carbon atoms in the carbon chain connecting ^E1 and ^X1 . From the viewpoint of the stability of the complex structure, the n may be 0, 1 or 2. It is preferable that n is 1 because it becomes a 5-membered ring and the complex structure is stable.

In the above general formula (A), R ¹ represents a hydrocarbon group represented by the following general formula (B) or (C).

[In formula (B) and formula (C),
* represents a bond to ^E1 ;
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent an atom or group selected from the group consisting of (i) to (iv) defined in formula (A), and adjacent substituents of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be bonded to each other to form a 5- to 8-membered alicyclic ring, aromatic ring, or heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom;
A ¹ , A ² , A ³ and A ⁴ each independently represent an oxygen atom, a sulfur atom, -C(R) ₂ -, -S(O)-, -S(O) ₂ -, -N(R)-, -P(R)- or -P(O)(R)- (wherein each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom).
however,
In formula (B), at least three of A ¹ , A ² , A ³ and A ⁴ are other than —C(R) ₂ —;
In formula (C), ^A3 and ^A4 are both other than -C(R) _2- , and at least one of ^R12 and ^R13 is an atom or group selected from the group consisting of (ii) and (iv) (excluding epoxy-containing groups).
W ¹ and W ² each independently represent a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O) ₂ -; when W 1 and W 2 represent a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R ⁸ and R ¹⁰ do not exist; and when W 1 and W 2 represent an oxygen atom or -S(O) ₂ -, R ⁷ and R ⁸ as well as R ⁹ and R ¹⁰ do not exist.
h and i each independently represent an integer of 1 to 6, and when a plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are present, the plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different.]

In formula (B) and formula (C), A ¹ , A ² , A ³ and A ⁴ each independently represent an oxygen atom, a sulfur atom, -C(R) ₂ -, -S(O)-, -S(O) ₂ -, -N(R)-, -P(R)- or -P(O)(R)- (wherein R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom). The hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom represented by R may be the same as the hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom in (iii) above. From the standpoint of synthesis difficulty and economic rationality, R may be a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, or a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

In formula (B) and formula (C), W ¹ and W ² each independently represent a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O) ₂ -; when W 1 and W 2 represent a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R ⁸ and R ¹⁰ do not exist, and when W 1 and W 2 represent an oxygen atom or -S(O) ₂ -, R ⁷ and R ⁸ as well as R ⁹ and R ¹⁰ do not exist.
In formula (B) and formula (C), W ¹ and W ² may each independently be a carbon atom or a silicon atom, or may be a carbon atom, in terms of the stability of the ligand.

In formula (B) and formula (C), R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent an atom or group selected from the group consisting of (i) to (iv) defined in formula (A).
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ may each independently be an atom or group selected from the group consisting of (i) and (iii) from the viewpoints of synthesis difficulty and economic rationality. Among them, (iii) in R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ may be an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms from the viewpoints of synthesis difficulty and economic rationality.
Furthermore, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may each independently be such that adjacent substituents are linked to each other and, together with the W ¹ or W ² to which they are bonded, form a 5-8 membered alicyclic ring, aromatic ring, or heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom. For example, when h or i is 2 and there are two W ¹ or W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may each independently be such that adjacent substituents are linked to each other and, together with the two W ¹ or the two W ² to which they are bonded, form a 5-8 membered alicyclic ring, aromatic ring, or heterocycle.

R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may form an alicyclic ring together with W ¹ or W ² to which they are bonded, or may be an alkylene group having 4 to 7 carbon atoms in which adjacent substituents are bonded to each other. For example, adjacent R ⁷ and R ⁸ may be an alkylene group having 5 carbon atoms that forms a 6-membered ring together with W ¹ to which they are bonded. R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may each independently be a ring in which aryl groups of adjacent substituents are bonded to each other to form a ring together with W ¹ or W ² to which they are bonded. For example, adjacent R ⁷ and R ⁸ may be a biphenylene group that forms a 5-membered ring together with W ¹ to which they are bonded. In this case, when W ¹ is a carbon atom, W ¹ , R ⁷ and R ⁸ form a fluorenylidene.
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may form an alicyclic ring together with the two W ¹ or two W ² to which they are bonded, may be an alkylene group having 3 to 6 carbon atoms in which adjacent substituents are bonded to each other, or may be an alkylene group having 3 or 4 carbon atoms that forms a 5- or 6-membered ring. R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may form an aromatic ring having 6 to 12 carbon atoms together with the two W ¹ or two W ² to which they are bonded.

Furthermore, it may be a heterocycle in which at least one carbon atom of the alicyclic ring or aromatic ring is replaced with a heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom.
In addition, the alicyclic ring, aromatic ring, or heterocyclic ring formed by R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may further have an atom or group selected from the group consisting of (ii) to (iv) defined in the above formula (A) as a substituent, and the substituent may be a halogen atom.
From the viewpoint of synthesis difficulty and economic rationality, R ¹¹ may be a hydrogen atom.

R ¹² and R ¹³ may each independently be an atom or group selected from the group consisting of (i), (iii) and (iv) from the viewpoints of synthesis difficulty and economic rationality. The (iii) in R ¹² and R ¹³ may be an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, from the viewpoints of synthesis difficulty and economic rationality. In terms of synthesis difficulty and economic rationality, the (iv) in R ¹² and R ¹³ may be OR ^b , C(O)OR ^b , C(O)N(R ^a ) ₂ , C(O)R ^b , OC(O)R ^b , SR ^b , S(O) _2R ^b , S(O)R ^b , OS(O) _2R ^b , SF ₅ , P(O)(OR ^b ) _2-y (R ^a ) _y , CN, N(H)R ^a , N(R ^b ) ₂ , Si(OR ^a ) _3-x (R ^a ) _x , OSi(OR ^a ) _3-x (R ^a ) _x , or NO ₂ , etc.

In formula (B) and formula (C), h and i are each independently an integer of 1 to 6, and when a plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are present, the plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different.
In terms of the ease of synthesis and economic rationality, h and i may each independently be an integer of 1 to 3, may be 1 or 2, or may be 1.

However, in formula (B), at least three of A ¹ , A ² , A ³ and A ⁴ are other than -C(R) ₂ -. That is, in formula (B), at least three of A ¹ , A ² , A ³ and A ⁴ are an oxygen atom, a sulfur atom, -S(O)-, -S(O) ₂ -, -N(R)-, -P(R)- or -P(O)(R)-.
In formula (B), other than -C(R) ₂ -, from the viewpoint of synthesis difficulty and economic rationality, it may be an oxygen atom, a sulfur atom or -N(R)-, or it may be an oxygen atom.
In particular, in formula (B), four of A ¹ , A ² , A ³ and A ⁴ may be groups other than —C(R) ₂ —, and four may be oxygen atoms.

In formula (C), A ³ and A ⁴ are both other than -C(R) ₂ -, and at least one of R ¹² and R ¹³ is an atom or group selected from the group consisting of (ii) and (iv) (excluding epoxy-containing groups). That is, in formula (C), A ³ and A ⁴ are both oxygen atoms, sulfur atoms, -S(O)-, -S(O) ₂ -, -N(R)-, -P(R)-, or -P(O)(R)-, and at least one of R ¹² and R ¹³ is an atom or group selected from the group consisting of (ii) and (iv) (excluding epoxy-containing groups).
In formula (C), other than -C(R) ₂ -, from the viewpoint of synthesis difficulty and economic rationality, it may be an oxygen atom, a sulfur atom, or -N(R)-, or it may be an oxygen atom.
In formula (C), the atom or group selected from the group consisting of (ii) and (iv) (excluding epoxy-containing groups) in R ¹² and R ¹³ may be, from the viewpoint of activity, a fluorine atom, OR ^b , SR ^b , N(H)R ^a , N(R ^b ) ₂ , or OSi(OR ^a ) _3-x (R ^a ) _x , or may be OR ^b . Furthermore, OR ^b in R ¹² and R ¹³ may be, for example, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, or a phenoxy group.

Among these, from the viewpoint of activity, in the general formula (C), ^A3 and ^A4 may both be an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom, and ^R12 may be an atom or group selected from the group consisting of (ii) and (iv) (excluding epoxy-containing groups), and in the general formula (C), ^A3 and ^A4 may both be an oxygen atom, and ^R12 may be an atom or group selected from the group consisting of (ii) and (iv) (excluding epoxy-containing groups).

In the general formula (A), ^R2 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom and is different from the hydrocarbon group represented by the general formula (B) or (C), l is 1 or 2, and when l is 2, ^R2 does not exist.
The hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom for ^R2 may be the same as the hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom among the above (iii).
^R2 may be a hydrocarbon group having 3 to 20 carbon atoms, and examples of such groups that are preferably used include an n-propyl group, an isopropyl group, an isobutyl group, a t-butyl group, a 3-pentyl group, a 2,6-dimethyl-4-heptyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, an adamantyl group, a (1R,2S,5R)-2-isopropyl-5-methylcyclohexan-1-yl group (menthyl group), a phenyl group, a 2-methoxyphenyl group, a 2,6-diethylphenyl group (DEP), a 2,6-dimethoxyphenyl group (DMP), a 2',6'-dimethoxy[1,1'-biphenyl]-2-yl group, and a (1R,2S,5R)-2-isopropyl-5-methylcyclohexan-1-yl group.
From the viewpoint of the degree of difficulty in synthesis and economic rationality, l may be 2.

In the general formula (A), Z is a hydrogen atom, a leaving group, or a cation having a valence of 1 to 4, and m is an integer of 1 to 4, and when m is 1, Z is exemplified by a hydrogen atom, a lithium ion, a sodium ion, a potassium ion, and the like. When m is 2, Z is exemplified by a magnesium ion, a calcium ion, a zinc ion, and the like. Examples of the leaving group include a hydrogen atom, an R ^b S(O) ₂ group (wherein R ^b represents a hydrocarbon group having 1 to 20 carbon atoms), a C(F) ³ S(O) ₂ group, an R ^b S(O) ₂ group, and a TiOR ^b group. Specific examples of the cation include ammonium, quaternary ammonium or phosphonium, and metal ions of groups 1 to 14 of the periodic table. Among these, preferred are a hydrogen atom, NH4 ⁺ , ( ^Rb ) _4N ⁺ (wherein ^Rb is as defined above, and the four ^Rb may be the same or different; the same applies below), ( ^Rb ) _4P ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Cu ⁺ , Ag ⁺ , Au ⁺ , ^Mg2+ , Ca2 ⁺ , and Al3 ⁺ , and more preferred are a hydrogen atom, ( ^Rb ) _4N ⁺ , Li ⁺ , Na ⁺ , K ⁺ , and Ag ⁺ .

Specific examples of compounds represented by general formula (A) include, but are not limited to, the following compounds:

（式中、Ｒは、水素原子またはヘテロ原子を少なくとも１つ含んでいてもよい炭素数１～２０の炭化水素基を表す。）

(In the formula, R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom.)

The compound represented by the general formula (A) can be synthesized based on a known synthesis method. For example, the compound represented by the general formula (A) can be synthesized by using E ¹ H(R ¹ ) _l (R ² ) _2-l or the like and reacting E ¹ H(R ¹ ) _l (R ² ) 2 _-l with an epoxy in the presence of a base or an acid. The compound represented by the general formula (A) can also be synthesized by reacting E ¹ CH ₃ (R ¹ ) _l (R ² ) _2-l with a ketone in the presence of a base. Representative reference documents include Patent Document 5, Non-Patent Document 7, Journal of Fluorine Chemistry 2002, 117, P121-129.
The compound represented by E ¹ H(R ¹ ) _l (R ² ) _2-l may be appropriately selected and used as a commercially available product. When a commercially available product is not available, it can be synthesized by reacting a halogenated phosphine with a nucleophile such as an organolithium or an organomagnesium to synthesize E ¹ X(R ¹ ) _l (R ² ) _2-l (X is a halogen atom), and then reacting with a hydride reducing agent such as lithium aluminum hydride. Representative reference documents include JP 2021-113174 and the like.
The compound for introducing the substituent represented by the general formula (B) or (C) into R ¹ may be appropriately selected from commercially available products. When a commercially available product is not available, it can be synthesized by an intermolecular or intramolecular cyclization reaction. Examples of such cyclization reactions include nucleophilic substitution reactions of dihalogen molecules, Friedel-Crafts reactions, and cyclization reactions using transition metals. Representative reference documents include RSC Advances 2014, 4, P16312-16319, Bioorg. Med. Chem. Lett. 2014, 24, P2379-2382., Chem. Eur. J. 2013, 19, P17349-17357., Org. Biomol. Chem.2018, 16, P8976-8983., etc.

The compound represented by the general formula (A) functions as a ligand capable of forming a complex with a transition metal compound represented by the general formula (E) or (F) described later. In particular, a compound represented by the general formula (A) in which ^X1 is an oxygen atom and ^E1 is a phosphorus atom has a structure in which phosphorus and oxygen are bonded via an alkylene group, and such a compound group is sometimes called an alkylene linked phosphine alkoxide (ALPHA) ligand.

2. Catalyst Composition for Olefin Polymerization The catalyst composition for olefin polymerization of the present invention contains a compound represented by the above general formula (A) and a transition metal compound represented by the following general formula (E) or (F).

[In the formula (E) and the formula (F),
M ¹ , M ² and M ³ each independently represent a nickel atom or a palladium atom; L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁹ and L ¹⁰ each independently represent a ligand coordinated to M ¹ , M ² or M ³ ; L ⁷ and L ⁸ each independently represent a ligand coordinated to M ² and M ³ ;
q is 0, 1 or 2;
^L1 and ^L2 may be bonded to each other to form a ring containing ^M1 ;
^L3 and ^L4 may be bonded to each other to form a ring containing ^M1 ;
^L5 and ^L6 may be bonded to each other to form a ring containing ^M2 ;
^L9 and ^L10 may be bonded to each other to form a ring including ^M3 .

In the catalyst composition for olefin polymerization of the present invention, the compound represented by the general formula (A) may be the same as that described above, and therefore, description thereof will be omitted here.
In the compound represented by the general formula (A), at least one hydrocarbon group represented by the general formula (B) or (C) is bonded as R ¹ to E ¹ such as a phosphorus atom. In the hydrocarbon group represented by the general formula (B) or (C), the substituents (A ¹ and A ³ ) at the ortho positions relative to the carbon atom bonded to E ¹ such as a phosphorus atom form a cyclic structure, so that the free rotation of the ortho-positioned substituent is suppressed. On the other hand, the hydrocarbon group represented by the general formula (B) or (C) has a moderate bulkiness. When a phenyl group having freely rotatable substituents at two ortho positions is bonded to E 1, if the compound is used as a ligand, it is considered that the activity is likely to decrease because the steric hindrance near the transition metal, which is the active center, becomes too high. In addition, when an unsubstituted phenyl group is bonded to E ¹ , it is considered that the compound is difficult to increase the molecular weight due to insufficient steric hindrance near the transition metal when used as a ligand. It is believed that the compound represented by the general formula (A) can maintain a suitable degree of steric hindrance in the vicinity of the transition metal when used as a ligand of a transition metal compound, thereby increasing the activity of the catalyst while maintaining the molecular weight at a high level.
In addition, in the compound represented by the general formula (A), it is considered that the coordination force of the ^heteroatom such as an oxygen atom with respect to the central metal of the catalyst is further improved by the substituent of the phenyl group bonded to E1 such as a phosphorus atom being a substituent containing a heteroatom such as an oxygen atom in its ring structure, the catalyst is highly activated, and the obtained polymer has a high molecular weight.

In the general formula (E) or (F), M ¹ , M ² and M ³ are each independently a nickel atom or a palladium atom. Here, the valence of the metal M means the formal oxidation number used in organometallic chemistry.
In other words, it refers to the number of charges remaining on an atom of an element when the electron pairs in a bond involving that element are assigned to an element with a higher electronegativity. Nickel atoms are preferred because they are inexpensive and readily available.

In the general formula (E) or (F), L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁹ and L ¹⁰ each independently represent a ligand coordinated to M ¹ , M ² or M ³ , and represent a -1-valent electron-donating ligand or a neutral electron-donating ligand.
The electron donating ligand with a valence of -1 is a ligand that is electrically negative and forms a σ bond with the central metal M, or donates delocalized π electrons to three or more carbon atoms. One example of a neutral electron donating ligand is a ligand that is electrically neutral and can form a coordinate bond by coordinating an unpaired electron to M. The ligand is a molecule having an atom with an unpaired electron, and examples of the atom having an unpaired electron include a nitrogen atom, a phosphorus atom, an arsenic atom, an oxygen atom, a sulfur atom, and selenium. Another example of a neutral electron donating ligand is a molecule such as ethylene or cyclooctadiene (cod) that forms a π donating bond by donating a π electron, and a molecule such as dibenzylideneacetone (dba) that has both an olefin and a heteroatom that coordinate to a metal. Examples of ligands that can be used for L ¹ to L ⁶ , L ⁹ , and L ¹⁰ include acetonitrile, isonitrile, carbon monoxide, ethylene, tetrahydrofuran, and other ligands known as neutral ligands for metal complexes, and ligands that donate π electrons, such as allyl and cyclopentadienyl. A molecule represented by E ² R'R''R''' or X ² R'R'' can also be used as a ligand. Here, E ² represents N, P, or As, X ² represents O, S, or Se, and R', R'' and R'' each independently represent a hydrogen atom; an alkyl group, an alicyclic group, an alkoxy group, an aryl group, or an aryloxy group having 1 to 30 carbon atoms which may be substituted; or an amino group or a silyl group in which at least one hydrogen atom is substituted with a hydrocarbon having 1 to 30 carbon atoms, and R' and R'' may be linked together to form a heterocyclic structure, and R', R'' and R'' may be linked together to include E ² to form an aromatic heterocyclic structure. Furthermore, ^L1 and ^L2 , ^L3 and ^L4 , ^L5 and ^L6 , and ^L9 and ^L10 may be bonded to each other to form a ring containing ^M2 or ^M3 , and when these groups form a ring, the minimum number of ring members, including M, is a 5-membered ring to 10-membered ring.
Although L ¹ to L ⁶ , L ⁹ and L ¹⁰ may each have a −1-valent electron-donating ligand, in order to facilitate the reaction for producing a metal complex, it is preferable that the valence of the metal complex is selected to be 1 or 2. Therefore, the number of −1-valent electron-donating ligands among L ¹ to L ⁶ , L ⁹ and L ¹⁰ is preferably 0 to 2.

The -1-valent electron donor ligands L ¹ to L ⁶ , L ⁹ , and L ¹⁰ each include a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom, and the structure of the hydrocarbon portion may be linear, branched, or cyclic, and may form a ring containing a heteroatom. The number of carbon atoms is preferably 1 to 16, and more preferably 1 to 10.
Specific examples of the -1-valent electron donating ligands L ¹ to L ⁶ , L ⁹ , and L ¹⁰ each independently include a hydride group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a neopentyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a trimethylsilylmethyl group, a phenyl group, a p-methylphenyl group, a p-fluorophenyl group, a fluoride group, a chloride group, a bromide group, and an iodine group. Preferred examples include a hydride group, a methyl group, a neopentyl group, a benzyl group, a trimethylsilylmethyl group, a phenyl group, a p-fluorophenyl group, a chloride group, a bromide group, and an iodine group.

Other preferred examples of L ¹ to L ⁶ , L ⁹ , and L ¹⁰ include phosphines, pyridines, piperidines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkylnitrile derivatives, arylnitrile derivatives, alcohols, amides, aliphatic esters, aromatic esters, amines, and cyclic unsaturated hydrocarbons. More preferred examples include phosphines, pyridines, cyclic ethers, aliphatic esters, aromatic esters, and cyclic olefins. Particularly preferred examples include trialkylphosphines, triarylphosphines, pyridine, lutidine (dimethylpyridine), picoline (methylpyridine), and R ^b C(O)O ⁻ (wherein R ^b is as defined above). Incidentally, ^L1 and ^L2 , ^L3 and ^L4 , ^L5 and ^L6 , and ^L9 and ^L10 may be bonded to each other to form a ring containing ^M2 or ^M3 . Examples of such a ring include a cyclooct-1-enyl group, an acetylacetonate group, a tetramethylethylenediamine group, and a 1,2-dimethoxyethane group, which is also a preferred embodiment.

^L7 and ^L8 represent ligands coordinated to metal atoms ^M2 and ^M3 , and are bonded to ^M2 and ^M3 in a manner called a three-center four-electron bond, respectively. Examples of the ligands of ^L7 or ^L8 include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkoxy group having 1 to 6 carbon atoms, an amino group substituted with a hydrocarbon group having 1 to 6 carbon atoms, and an acetyl group. Preferred examples of ^L7 and ^L8 include a fluoride group, a chloride group, a bromide group, an iodide group, a methyl group, an ethyl group, a propyl group, a methoxy group, a phenoxy group, a dimethylamide group, a hydride group, a thiomethoxy group, a thiophenoxy group, and an acetyl group, more preferred examples include a fluoride group, a chloride group, a bromide group, an iodide group, a methyl group, a methoxy group, a phenoxy group, a hydride group, a thiomethoxy group, a thiophenoxy group, and an acetyl group, and even more preferred examples include a chloride group, a bromide group, an iodide group, a methoxy group, a phenoxy group, and an acetyl group.

In the general formula (E), q is 0, 1, or 2.

Specific examples of the compound represented by the general formula (E) or (F) include, but are not limited to, the following compounds. In addition, Ni(CH ₂ C(H)CH ₂ ) ₂ , Ni(CH ₂ C(Me)CH ₂ ) ₂ , Ni(CH ₂ Si(Me) ₃ ) ₂ (Py) ₂ (hereinafter, Py represents pyridine), Ni(CH ₂ Si(Me) ₃ ) ₂ (Lut) ₂ (hereinafter, Lut represents 2,6-lutidine), NiPh ₂ (Py) ₂ , NiPh ₂ (Lut) ₂ , Pd(OC(O)CH ₃ ) ₂ , etc.
These compounds are believed to form complexes with the compound represented by formula (A).

The compound represented by the general formula (A) can be used as a catalyst for the polymerization reaction of olefins in the form of a composition with the transition metal compound represented by the general formula (E) or (F) or in the form of a metal complex which is a reaction product with the transition metal compound. In the polymerization reaction of olefins, the product used as a catalyst may be isolated after the reaction of the compound represented by the general formula (A) with the transition metal compound represented by the general formula (E) or (F), or the product may be directly used in the polymerization reaction without isolating or washing it from the reaction system. The method for reacting these compounds can be a method known in the synthesis of metal complexes. It is preferable to carry out all operations under an inert gas. The reaction is carried out in a homogeneous solvent, and a general hydrocarbon reaction solvent can be used as the solvent, preferably toluene. The concentration of the transition metal compound in the reaction solvent can be freely set with the saturation concentration as the upper limit, but is preferably in the range of 1 mM to 50 mM. The order of mixing the compound (ligand) represented by the general formula (A) and the transition metal compound represented by the general formula (E) or (F) is not limited. A solvent can be added to the mixture of the solid ligand and the solid transition metal compound, or a transition metal compound dissolved in the solid ligand can be added. The mixing ratio of the ligand and the transition metal compound is preferably in the range of ligand:metal = 1:1 to 1:10. The mixing temperature can be appropriately set to 20°C or higher with the boiling point of the solvent as the upper limit. The mixing temperature is preferably in the range of 35°C to 45°C. The time required for mixing can preferably be in the range of 1 minute to 24 hours, and more preferably 10 minutes to 30 minutes. One aspect of the present invention is a method for producing an olefin polymerization catalyst, which includes a step of reacting a compound represented by the general formula (A) with a transition metal compound represented by the general formula (E) or (F).

3. Metal Complex In another aspect, the present invention provides a metal complex represented by the following general formula (D):

[In the formula (D),
^X1 , ^E1 , n, ^R1 , ^R2 , l, ^R3 , ^R4 , ^R5 , and ^R6 are as defined in the compound represented by formula (A),
M ¹ , L ¹ and L ² are as defined in the transition metal compound represented by the general formula (E) or (F).

Specific examples of the metal complex represented by the general formula (D) include the following complexes. However, these are merely examples and the complexes in the method of the present invention are not limited to these specific examples.

（式中、Ｒは、水素原子または炭素数１～２０の炭化水素基を表す。）

(In the formula, R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

The metal complex represented by the general formula (D) of the present invention can be prepared by a method including a step of reacting a compound represented by the general formula (A) with a transition metal compound represented by the general formula (E) or (F), or by a known method. A person skilled in the art can prepare the metal complex represented by the general formula (D) of the present invention by making appropriate modifications, such as changing the raw materials, based on the known complex preparation method.

For example, in producing a metal complex represented by the general formula (D), when the compound represented by the general formula (A) is reacted with the transition metal compound represented by the general formula (E) or (F), a coordinating compound or a covalent compound for substituting ^L1 or ^L2 in the general formula (D) may be coexisted.
When nickel or palladium is used as M in the present invention, the stability of the generated metal complex may be increased by allowing a Lewis basic coordination compound to coexist in the system. In such a case, the coordination compound may be allowed to coexist as long as it does not inhibit the polymerization reaction or copolymerization reaction of the present invention.
The coordinating compound used in the present invention may be a hydrocarbon compound having 1 to 20 carbon atoms and having at least one atom selected from the group consisting of oxygen atom, nitrogen atom, phosphorus atom, arsenic atom, sulfur atom, and selenium atom as an atom capable of forming a coordinate bond, or a hydrocarbon compound which may contain a heteroatom having a carbon-carbon unsaturated bond capable of coordinating to a transition metal, and may have the same meaning as the neutral electron-donating ligand among the above-mentioned ^L1 , etc.

The covalent compound used in the present invention is a compound capable of substituting a ligand derived from a transition metal compound with a −1-valent electron donor ligand such as ^L1 in the metal complex represented by general formula (D). The covalent compound may be an organometallic compound.
As a -1-valent electron donating ligand, a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom is incorporated into a polymer as an initiation terminal of the polymerization reaction and can greatly contribute to the initial rate of the polymerization reaction. Therefore, when producing a metal complex represented by the general formula (D), it is preferable to use a covalent compound for introducing a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom depending on the situation.
The covalent compound may be an organolithium compound, which may be R ¹⁴ Li (wherein R ¹⁴ is a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom), or an organolithium compound having a hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom. Examples of organolithium compounds having a hydrocarbon group having 1 to 10 carbon atoms include methyllithium, n-butyllithium, phenyllithium, neopentyllithium, benzyllithium, trimethylsilylmethyllithium, p-fluorophenyllithium, and the like. Among these, methyllithium and phenyllithium are preferred, and methyllithium is more preferred.

4. Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention comprises the above-mentioned olefin polymerization catalyst composition of the present invention.
The olefin polymerization catalyst of the present invention contains a metal complex represented by the above general formula (D).
The olefin polymerization catalyst of the present invention contains, during the olefin polymerization reaction, a metal complex which is a product of a compound represented by the general formula (A) and a transition metal compound represented by the general formula (E) or (F), or a metal complex represented by the general formula (D) (hereinafter, these may be collectively referred to simply as a "metal complex catalyst").
In the olefin polymerization catalyst of the present invention, the olefin polymerization catalyst composition of the present invention and the metal complex represented by the general formula (D) may be the same as those described above, and therefore, description thereof will be omitted here.
In the olefin polymerization catalyst of the present invention, as shown in the examples described later, the olefin polymerization catalyst composition of the present invention or the metal complex represented by the general formula (D) may be used as it is as an olefin polymerization catalyst without particular purification.

In the olefin polymerization catalyst of the present invention, the compound represented by the general formula (A) and the transition metal compound represented by the following general formula (E) or (F) of the olefin polymerization catalyst composition may be used alone or in combination of two or more kinds of components. The olefin polymerization catalyst composition may also contain a metal complex represented by the general formula (D).
The metal complex represented by the general formula (D) contained in the olefin polymerization catalyst of the present invention may be a single type alone or a mixture of two or more types.

In the olefin polymerization catalyst of the present invention, in addition to the metal complex catalyst, a cocatalyst may be further added. Examples of the cocatalyst include organometallic compounds containing an element of Group 1, 2 or 13 of the periodic table. In particular, the cocatalyst may include a compound represented by the following general formula (1), a compound represented by the following general formula (2) or an organoaluminum oxy compound. A plurality of types of these compounds may be included in the catalyst composition.

General formula (1): Q( ^R20 )( ^R21 ) ^R22
The compound represented by the general formula (1) is a boron or aluminum compound represented by Q(R ²⁰ )(R ²¹ )R ^22. (In the formula, Q represents boron (B) or aluminum (Al), and R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom; an alkyl group, an alicyclic group, an alkoxy group, an aryl group or an aryloxy group having 1 to 30 carbon atoms which may be substituted; or an amino group or a silyl group in which one or more hydrogen atoms have been substituted by a hydrocarbon having 1 to 30 carbon atoms.)
^R to R ²² may be any of the examples given in the description of R ³ etc., but from the standpoint of ease of preparation and availability of the compound, they are preferably hydrocarbon groups such as alkyl groups and aryl groups, or alkyl or aryl groups substituted with halogen (particularly fluorine), such as trifluoromethyl and perfluorophenyl groups.

Examples of the compound represented by the general formula (1) include, but are not limited to, trimethylborane, trimethoxyborane, perfluoromethylborane, triphenylborane, tris(perfluorophenyl)borane, triphenoxyborane, tris(dimethylamino)borane, tris(diphenylamino)borane, trimethylaluminum, triethylaluminum, tri(n-propyl)aluminum, tri(n-butyl)aluminum, triisobutylaluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, tri(n-decyl)aluminum, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, and diisobutylaluminum hydride.

The general formula (2): [C(R ²³ )(R ²⁴ )R ²⁵ ] ⁺ [Q(R ²⁶ )(R ²⁷ )(R ²⁸ )R ²⁹ ] ⁻
The compound represented by the general formula (2) is a salt with a carbocation of boron or aluminum, represented by [C(R ²³ )(R ²⁴ )R ²⁵ ] ⁺ [Q(R ²⁶ )(R ²⁷ )(R ²⁸ )R ²⁹ ] ^- . (In the formula, Q is as defined in the general formula (2), and R ²³ to R ²⁹ each independently have the same meaning as R ^20. )
^R to R ²⁹ may be any of the examples given in the description of R ³ , etc., but from the standpoint of ease of compound preparation and availability, they are preferably hydrocarbon groups such as alkyl groups and aryl groups, and more preferably bulky hydrocarbon groups such as t-butyl groups and aryl groups, because a carbocation can be easily obtained.

Examples of the compound represented by the general formula (2) include, but are not limited to, trityl tetramethylborate, trityl tetrakis(perfluoromethyl)borate, trityl tetraphenylborate, trityl tetrakis(perfluorophenyl)borate, and trityl tetrakis(di(trifluoromethyl)phenyl)borate.

The compound represented by the general formula (1) or (2) may be commercially available, or may be obtained by appropriately modifying a known method depending on the substituents of the compound.

In addition to the compounds represented by the general formula (1) or (2), an organoaluminum oxy compound can also be added to the olefin polymerization catalyst of the present invention. Examples of organoaluminum compounds include methylaluminoxane (MAO) and modified methylaluminoxane (MMAO), and commercially available products can be used. MMAO is preferred because it is easily available and easy to handle. MAO and MMAO can be commercially available, and there are no restrictions on the grade, etc.

In addition to the compounds containing Group 13 elements exemplified above, organometallic compounds that are conventionally known as promoters, such as Group 1 metal-containing compounds including alkyllithiums such as methyllithium and n-butyllithium, and Group 2 metal-containing compounds such as Grignard reagents, can also be used as promoters. These compounds can also be commercially available, and there are no restrictions on the grade, etc.

These co-catalysts can be used under the same conditions as the metal complex catalysts, but it is preferable to use them under an inert gas atmosphere and avoiding oxygen and moisture. If added, the amount to be used can be appropriately determined by a person skilled in the art.

Furthermore, the contact of the metal complex catalyst with the co-catalyst 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 metal complex catalyst with the co-catalyst is preferably carried out in an inert gas such as nitrogen, in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene, etc. 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.

5. Method for Producing Olefin Polymer One embodiment of the method for producing an olefin polymer of the present invention is characterized in that an olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst of the present invention.

The olefin in the present invention may be either acyclic or cyclic olefin, and may be at least one selected from the group consisting of acyclic olefins having 2 to 22 carbon atoms and cyclic olefins having 4 to 20 carbon atoms.
The non-cyclic olefin in the present invention may be an α-olefin represented by the general formula: CH ₂ ═CHR ^30. Here, R ³⁰ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may have a branch, ring, and/or unsaturated bond. If R ³⁰ has more than 20 carbon atoms, sufficient polymerization activity tends not to be exhibited. For this reason, particularly preferred olefins include olefins in which R ³⁰ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
Examples of non-cyclic olefins other than α-olefins include 2-butene, 2-pentene, and 2-hexene.
Examples of the cyclic olefin having 4 to 20 carbon atoms include cyclobutene, cyclopentene, cyclohexene, cycloheptene, norbornene, and norbornadiene.
Preferred olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, vinylcyclohexene, styrene, 4-methylstyrene, and norbornene. From the viewpoint of the production efficiency of the polymer, it is preferable to use one or more olefins selected from the group consisting of ethylene, propylene, 1-butene, and norbornene, and more preferably ethylene. It is to be noted that only one type of olefin may be used, or two or more types of olefins may be used simultaneously.

Examples of the polar group-containing monomer include non-cyclic olefins and monomers in which a functional group having polarity (polar group) is introduced into a cyclic olefin. Among non-cyclic olefins, examples of monomers in which a polar group is introduced into an α-olefin include polar group-containing monomers represented by the general formula: CH ₂ ═C(R ³⁰ )(R ³¹ ). A preferred example of the polar group-containing monomer is a (meth)acrylic acid ester. Here, R ³⁰ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ³¹ represents -C(O)OR ³² (wherein R ³² represents a hydrocarbon group having 1 to 20 carbon atoms), -C(O)N(-R ^32' ) ₂ (wherein R ^32' each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms), a cyano group, or an aryl group which may be substituted. R ³⁰ is preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, since it is possible to develop a more sufficient polymerization activity. More preferably, R ³⁰ is a hydrogen atom or a methyl group. There are no particular limitations on R ³¹ as long as it is the above-mentioned substituent, but since there are a wide variety of applications when it is made into a copolymer, it is preferably -C(O)OR ³² or an aryl group. In this case, if the carbon number of R ³² exceeds 20, the polymerization activity tends to decrease. Therefore, R ³² is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 8 carbon atoms.
In addition, R ³² is preferably composed of carbon atoms and hydrogen atoms, but R ³² may contain heteroatoms such as oxygen atoms, sulfur atoms, selenium atoms, phosphorus atoms, nitrogen atoms, silicon atoms, fluorine atoms, and boron atoms. Among these heteroatoms, oxygen atoms, silicon atoms, and fluorine atoms are preferred, and oxygen atoms are more preferred. When R ^32' is not a hydrogen atom, the preferred range and examples are the same as those of R ³² .

Examples of monomers in which a functional group having polarity has been introduced into acyclic olefins other than α-olefins or cyclic olefins include compounds in which the substituent represented by ^R31 has been introduced into any position of the exemplary compounds of acyclic olefins other than α-olefins or cyclic olefins.
The polar group-containing monomer may also be vinylene carbonate (1,3-dioxol-2-one).

Further preferred examples of polar group-containing 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, benzyl (meth)acrylate, hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, glycidyl (meth)acrylate, trifluoromethyl (meth)acrylate, 3,3,3-trifluoropropyl (meth)acrylate, perfluoroethyl (meth)acrylate, (meth)acrylamide, (meth)acryldimethylamide, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acrylonitrile, methyl 10-undecenoate, 4-acetoxystyrene, vinylanisole, methyl 5-norbornene-2-carboxylate, t-butyl 5-norbornene-2-carboxylate, 5-norbornene-2-methanol, 5-norbornene-2-methylamine, 5-norbornene-2-methylpivalamide, 5-norbornene-2-yl acetate, vinylene carbonate, and the like. More preferably, it is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, t-butyl methacrylate, acrylonitrile, methyl 10-undecenoate, 4-acetoxystyrene, 4-nitrostyrene, vinyl anisole, methyl 5-norbornene-2-carboxylate, t-butyl 5-norbornene-2-carboxylate, 5-norbornene-2-methylpivalamide, 5-norbornene-2-yl acetate, and vinylene carbonate.

As the comonomer used in copolymerization of acyclic olefins such as ethylene, at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins is suitably used.
More preferred examples include at least one selected from the group consisting of t-butyl acrylate, methyl acrylate, methyl methacrylate, methyl 10-undecenoate, 4-methylstyrene, 4-acetoxystyrene, norbornene, t-butyl 5-norbornene-2-carboxylate, 9-decenyl acetate, 1,2-epoxy-9-decene, and vinylene carbonate.
These monomers may be used alone or in combination of two or more kinds.

The types of monomers mentioned above can be appropriately selected according to the physical properties required for the resulting polymer. In some cases, it is also possible to copolymerize a composition of two or more types of monomers, and it is also possible to copolymerize a composition consisting of two or more types of polar group-containing monomers. The amount of monomers to be mixed and the ratio between the amounts of each monomer can be appropriately set according to the physical properties required for the resulting copolymer.

The process for producing an olefin polymer of the present invention is suitably used as a production process for copolymerizing at least one monomer selected from the group consisting of a polar group-containing monomer and a cyclic olefin with a non-cyclic olefin, since the polymerization is performed in the presence of the olefin polymerization catalyst of the present invention.
As the copolymerization reaction of the present invention, copolymerization of an olefin with a (meth)acrylic acid ester is a preferred embodiment in terms of polymerization activity.

In the method for producing an olefin polymer of the present invention, an olefin polymerization catalyst containing the metal complex catalyst is used as a catalyst for the polymerization or copolymerization of olefins. Each metal complex catalyst may be used in an isolated form or may be supported on a carrier. Such support may be performed in a reactor used for the polymerization of olefins or the copolymerization of olefins with (meth)acrylic esters or the like, in the presence or absence of these monomers, or may be performed in a vessel separate from the reactor.

Any carrier can be used as long as it does not interfere with the gist of the present invention. In general, inorganic oxides and polymer carriers are preferably used. Specific examples of inorganic oxides include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , and mixtures thereof. Mixed oxides such as SiO ₂ -Al ₂ O ₃ , SiO ₂ -V ₂ O ₅ , SiO ₂ -TiO ₂ , SiO ₂ -MgO, and SiO ₂ -Cr ₂ O ₃ can also be used. In addition, 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 also be used as carriers. 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.

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, anoxite, 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 the artificially synthesized substances include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic taeniolite.

Among these specific examples, preferred are kaolin group such as dickite, nacrite, kaolinite, and anoxite, halloysite group such as metahaloysite and halloysite, serpentine group such as chrysotile, lizardite, and antigorite, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, and hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, and glauconite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic taeniolite, and particularly preferred are smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, and hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic taeniolite.

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. Also, shape control such as pulverization or granulation, or drying treatment may be performed.

In the method for producing an olefin polymer of the present invention, the polymerization reaction can be carried out in the presence or absence of known additives in addition to the cocatalyst. The additive is preferably an additive that has an effect of stabilizing the resulting polymer. For example, quinone derivatives and hindered phenol derivatives are given as examples of preferred additives.
Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl-4-methylphenol (BHT), a reaction product of trimethylaluminum with BHT, a reaction product of alkoxide of tetravalent titanium with BHT, and the like can be used.
Furthermore, inorganic and/or organic fillers may be used as additives, and the polymerization may be carried out in the presence of these fillers or by adding an ionic liquid.

A preferred additive in the present invention is a Lewis base. By selecting an appropriate Lewis base, the activity, molecular weight, and copolymerizability of the acrylic ester can be improved. The amount of the Lewis base is 0.0001 to 1000 equivalents, preferably 0.1 to 100 equivalents, and more preferably 0.3 to 30 equivalents, relative to the transition metal M in the catalyst component present in the polymerization system. There is no particular restriction on the method of adding the Lewis base to the polymerization system, and any method can be used. For example, the Lewis base may be added to the olefin polymerization catalyst of the present invention, may be added by mixing with the monomer, or may be added to the polymerization system independently of the catalyst component or monomer. In addition, multiple Lewis bases may be used in combination.

Examples of the Lewis base include aromatic amines, aliphatic amines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkyl nitriles, aryl nitriles, alcohols, amides, aliphatic esters, aromatic esters, phosphates, phosphites, thiophenes, thianthrenes, thiazoles, oxazoles, morpholines, and cyclic unsaturated hydrocarbons.
Among these, particularly preferred Lewis bases are aromatic amines, aliphatic amines, cyclic ethers, aliphatic esters, and aromatic esters, and particularly preferred Lewis bases are pyridine derivatives, pyrimidine derivatives, piperidine derivatives, imidazole derivatives, aniline derivatives, piperidine derivatives, triazine derivatives, pyrrole derivatives, and furan derivatives.

Specific Lewis base compounds include pyridine, pentafluoropyridine, 2,6-lutidine, 2,4-lutidine, 3,5-lutidine, pyrimidine, N,N-dimethylaminopyridine, N-methylimidazole, 2,2'-bipyridine, aniline, piperidine, 1,3,5-triazine, 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, 2,4,6-tris(2-pyridyl)-s-triazine, quinoline, 8-methylquinoline, phenazine, 1,10-phenanthroline, N-methylpyrrole, and 1,8-diazabicyclo-[5.4.0]-undeca. 7-ene, 1,4-diazabicyclo-[2,2,2]-octane, triethylamine, benzonitrile, picoline, triphenylamine, N-methyl-2-pyrrolidone, 4-methylmorpholine, benzoxazole, benzothiazole, furan, 2,5-dimethylfuran, dibenzofuran, xanthene, 1,4-dioxane, 1,3,5-trioxane, dibenzothiophene, thianthrene, triphenylphosphonium cyclopentadienide, triphenylphosphite, triphenylphosphate, tripyrrolidinophosphine, etc.

In the present invention, there is no particular restriction on the polymerization type. As the polymerization type, solution polymerization in which all the generated polymer is dissolved in the medium, slurry polymerization in which at least a part of the generated polymer becomes a slurry in the medium, bulk polymerization in which the liquefied monomer itself is the medium, gas phase polymerization in vaporized monomer, or high pressure ion polymerization in which at least a part of the generated polymer is dissolved in the monomer liquefied at high temperature and high pressure, etc. are preferably used. In addition, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used. As the environment in which the polymerization reaction is performed, it is preferable to use it under an inert gas atmosphere such as a nitrogen atmosphere. There is no particular restriction on the use conditions of the metal complex catalyst as long as it is under general polymerization conditions. There is no particular restriction on the amount of the metal complex catalyst used as long as it is within a range appropriate for use as a catalyst, and a person skilled in the art can set it appropriately.

In the present invention, when a monomer that is preferably polymerized in a liquid phase is used, the polymerization reaction is carried out in the presence or absence of a liquid such as a hydrocarbon solvent such as n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, or methylcyclohexane, a liquefied olefin, a halogenated hydrocarbon solvent such as chlorobenzene or 1,2-dichlorobenzene, or a polar solvent such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropyl alcohol, or ethylene glycol. A mixture of the liquid compounds described here may also be used as a solvent. Liquefied olefins can also be used as a monomer to be subjected to bulk polymerization. Furthermore, ionic liquids can also be used as solvents. In order to obtain high polymerization activity and high molecular weight, the above-mentioned hydrocarbon solvents and ionic liquids are more preferable.

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 may be separated from the unreacted monomers and media by a conventional method. For example, filtration, centrifugation, solvent extraction, reprecipitation using a poor solvent, etc. may be used.

There are no particular limitations on the polymerization temperature, polymerization pressure, and polymerization time, but they can usually be set optimally from the following ranges, taking into account productivity and process capacity. That is, the polymerization temperature is usually -20°C to 290°C, preferably 0°C to 250°C, more preferably 0°C to 200°C, even more preferably 10°C to 150°C, and particularly preferably 20°C to 100°C. The copolymerization pressure is 0.1 MPa to 300 MPa, preferably 0.3 MPa to 200 MPa, more preferably 0.5 MPa to 150 MPa, even more preferably 1.0 MPa to 100 MPa, and particularly preferably 1.3 MPa to 50 MPa. The polymerization time can be selected from the range of 0.1 minutes to 100 hours, preferably 0.5 minutes to 70 hours, and more preferably 1 minute to 60 hours.

In the present invention, the polymerization is generally carried out under an inert gas atmosphere. For example, a nitrogen or argon atmosphere can be used, and a nitrogen atmosphere is preferably used. A small amount of oxygen or air may be mixed in. However, when a monomer that is gaseous at room temperature, such as ethylene, is used, the reaction system can be filled with ethylene before polymerization.
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 the catalyst is supplied thereto. In this case, additional monomer and additional catalyst may be supplied to the polymerization reactor.

Regarding the control of the composition of the copolymer, a method of controlling by supplying multiple monomers to a reactor and changing the supply ratio can generally be used. Other examples include a method of controlling the copolymerization composition by utilizing the difference in monomer reactivity ratio due to the difference in catalyst structure, and a method of controlling the copolymerization composition by utilizing the polymerization temperature dependency of the monomer reactivity ratio. In the present invention, when at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins is copolymerized with a non-cyclic olefin, the total content ratio of the non-cyclic olefin monomer in all monomers in the copolymerization may be appropriately selected according to the desired physical properties, and the lower limit is usually 60.00 mol% or more, and may be 70.00 mol% or more, 80.00 mol% or more, 85.00 mol% or more, or 90.00 mol% or more with respect to 100 mol% of all monomers. On the other hand, the upper limit is usually 99.90 mol% or less, and may be 99.80 mol% or less, 99.70 mol% or less, 99.60 mol% or less, or 99.50 mol% or less. By setting it in this range, it is possible to impart affinity and adhesiveness with paint without significantly impairing the inherent properties of polyolefins, such as heat resistance, and it is also possible to control the physical properties.

For controlling the molecular weight of the polymer, a conventionally known method can be used, and examples thereof include the following methods.
1) Control of polymerization temperature; 2) Control of monomer concentration; 3) Control of ligand structure in transition metal complex; 4) Use of known chain transfer agents such as hydrogen and metal alkyls.

The weight average molecular weight (Mw) of the olefin polymer obtained by the method for producing an olefin polymer of the present invention is not particularly limited. The lower limit of the weight average molecular weight (Mw) of the olefin polymer may be 5,000 or more, or may be 10,000 or more. The upper limit of the weight average molecular weight (Mw) of the olefin polymer may be 1,000,000 or less, or may be 500,000 or less.
The weight average molecular weight (Mw) of the olefin polymer is determined by gel permeation chromatography (GPC). The GPC measurement in the present invention can be performed by the method described in the Examples below.

In addition, when the olefin polymer obtained by the method for producing an olefin polymer of the present invention is an ethylene polymer, the methyl branching degree of the ethylene polymer calculated by ^13C -NMR is not particularly limited, but may be 10 or less, or 5 or less, per 1,000 carbons.
In the present invention, the number of methyl branches can be measured by the method described in the Examples below.

The method for producing an olefin polymer of the present invention can provide an olefin polymer or copolymer with high activity, and in particular can provide a copolymer of at least one monomer selected from the group consisting of a polar group-containing monomer and a cyclic olefin with a non-cyclic olefin, and can therefore be used as a method for providing polymers with a variety of properties. Furthermore, the catalyst used in the method of the present invention has a well-balanced catalytic performance, is highly active, and not only can it produce a high molecular weight (co)polymer, but it does not need to be isolated as a catalyst, and can therefore be used for the efficient synthesis of olefin polymers.

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The synthesis examples, synthesis of ligands and metal complexes, and polymerization reactions in the following examples were all carried out under a nitrogen or argon atmosphere unless otherwise specified.
The following abbreviations used in the examples are explained below.
tBA: t-butyl acrylate MA: methyl acrylate VC: vinylene carbonate NB: norbornene TNOA: tri-n-octyl aluminum MU: methyl 10-undecenoate

[Method of analyzing structures in synthesis examples]
The structures of the compounds disclosed in the synthesis examples were analyzed by ¹ H-NMR, ¹³ C-NMR, ¹⁹ F-NMR and ³¹ P{ ¹ H}-NMR using a JEOL JEOL JNM-ECS400 NMR apparatus, a Bruker Avance 400 NMR apparatus, or a Bruker Avance 500 NMR apparatus. The specific measurement methods are as follows.
[Sample preparation]
5 to 20 mg of a sample was dissolved in 0.6 mL of deuterated chloroform (CDCl ₃ ) containing no tetramethylsilane, 0.6 mL of deuterated chloroform containing 0.03% (v/v) tetramethylsilane, 0.6 mL of deuterated toluene (C ₆ D ₅ CD ₃ ) containing 0.03% (v/v) tetramethylsilane, or 0.6 mL of dimethylsulfoxide (DMSO)-d ₆ containing no tetramethylsilane, and placed in an NMR sample tube with an inner diameter of 5 mm.

[ ^1H -NMR measurement conditions]
Probe: 5 mmφ probe Sample temperature: room temperature Pulse angle: 45°
Pulse interval: 2.8 seconds Number of integrations: 8 Chemical shift: When deuterated chloroform was used as the solvent, the chemical shift was set to 0 ppm for the proton signal of tetramethylsilane or 7.26 ppm for the proton signal of chloroform, and the chemical shifts of the signals due to other protons were based on this. When deuterated toluene was used as the solvent, the chemical shift was set to 0 ppm for the proton signal of tetramethylsilane, and the chemical shifts of the signals due to other protons were based on this. When dimethylsulfoxide- _d6 was used as the solvent, the proton signal of dimethylsulfoxide- _d5 was set to 2.50 ppm, and the chemical shifts of the signals due to other protons were based on this.

[ ^19F -NMR]
Probe: 5 mmφ probe Sample temperature: room temperature Pulse angle: 45°
Pulse interval: 1.8 seconds Number of accumulations: 8 Chemical shift: The chemical shift was set to 0 ppm using CFCl ₃ as an external standard, and the chemical shifts of signals due to other fluorines were based on this.

[ ³¹ P{ ¹ H}-NMR]
Probe: 5 mmφ probe Sample temperature: room temperature Pulse angle: 30°
Pulse interval: 0.5 seconds Number of accumulations: 64-256 Chemical shift: The chemical shift was set at 0 ppm using an 85% aqueous phosphoric acid solution as an external standard, and the chemical shifts of signals due to other phosphoruses were based on this.

[Method of analyzing polymer structure]
The structures of the polymers obtained in the examples were determined by ¹ H-NMR and ¹³ C-NMR analysis using a Bruker Biospin AV400 NMR apparatus. The specific measurement methods are as follows.
[Sample preparation]
100 to 500 mg of the sample was placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 ml of a mixed solution of dichlorobenzene (ODCB) and deuterated bromide benzene (C ₆ D ₅ Br) (volume ratio: ODCB/C ₆ D ₅ Br = 3/1) and hexamethyldisiloxane as a chemical shift standard substance, and dissolved uniformly in a block heater at 150°C.

[ ^1H -NMR measurement conditions]
Probe: 10 mmφ cryoprobe Sample temperature: 120° C.
Pulse angle: 4.5°
Pulse interval: 2 seconds Number of integrations: 256-1024 Chemical shift: The proton signal of hexamethyldisiloxane was set at 0.09 ppm, and the chemical shifts of signals due to other protons were set to this as the reference.

[ ^13C -NMR measurement conditions]
<Ethylene/tBA>
<Ethylene/MA>
<Propylene/MU>
Probe: 10 mmφ cryoprobe Sample temperature: 120° C.
Pulse angle: 90°
Pulse interval: 51.5 seconds Number of integrations: 256-768 times Decoupling conditions: inverse gate decoupling method Chemical shift: The chemical shift of the ¹³ C signal of hexamethyldisiloxane was set to 1.98 ppm, and the chemical shifts of other ¹³ C signals were based on this.

<Ethylene (E) homopolymer>
Probe: 10 mmφ cryoprobe Sample temperature: 120° C.
Pulse angle: 45°
Pulse interval: 27.5 seconds Number of integrations: 768-1024 Decoupling conditions: broadband decoupling method Chemical shift: The ¹³ C signal of hexamethyldisiloxane was set at 1.98 ppm, and the chemical shifts of other ¹³ C signals were set to this as the reference.

<Ethylene (E)/NB Copolymer>
<Propylene (P) homopolymer>
Probe: 10 mmφ cryoprobe Sample temperature: 120° C.
Pulse angle: 45°
Pulse interval: 38.5 seconds Number of integrations: 256-512 Decoupling conditions: broadband decoupling method Chemical shift: The 13C signal of hexamethyldisiloxane was set at 1.98 ppm, and the chemical shifts of other 13C signals were set to this as the reference.

<Ethylene (E)/VC Copolymer>
Probe: 10 mmφ cryoprobe Sample temperature: 120° C.
Pulse angle: 90°
Pulse interval: 51.5 seconds Number of integrations: 512 Decoupling conditions: inverse gate decoupling method Chemical shift: The ¹³ C signal of hexamethyldisiloxane was set at 1.98 ppm, and the chemical shifts of other ¹³ C signals were set to this as the reference.

[Comonomer calculation method]
In the following, I represents the integrated intensity, and the subscript number of I represents the range of chemical shifts. For example, I _80.0-2.0 represents the integrated intensity of the signal detected between 80.0 ppm and 2.0 ppm.
<Ethylene (E)/tBA Copolymer>
The tBA content was calculated from the signals in the ¹³ C-NMR spectrum according to the following formula.
tBA content (mol%)=I _(tBA) ×100/(I _(E) +I _(tBA) )
Here, I _(tBA) and I _(E) are quantities represented by the following formulas.
I _(tBA) = I _79.5-79.0
I _(E) = (I _180.0-136.0 + I _120.0-100.0 + I _80.0-2.0 - I _(tBA) x 7) / 2

<Ethylene (E)/MA Copolymer>
MA content (mol%)
= I _(MA) × 100/(I _(E) + I _(MA) )
Here, I _(MA) and I _(E) are quantities expressed by the following formulas, respectively.
I _(MA) = _I51.5-50.5
I _(E) = (I _180.0-136.0 + I _120.0-100.0 + I _55.0-2.0 - I _(MA) x 4) / 2
<Ethylene (E)/NB Copolymer>
The NB content was calculated from the following formula using the signals of the ¹³ C-NMR spectrum.
NB content (mol%) = I _(NB) × 100 / (I _(E) + I _(NB) )
Here, I _(NB) and I _(E) are quantities expressed by the following formulas, respectively.
I _(NB) = _I48.3-41.3 /4
I _(E) = (I _180.0-136.0 + I _120.0-100.0 + I _50.0-2.0 - I _(NB) x 7) / 2

<Ethylene (E)/VC Copolymer>
The polar group-containing monomer content was calculated from the signals at 77.7 to 80.2 ppm in the ¹³ C-NMR spectrum according to the following formula.
VC (ring closure) amount (mol%) = I _(VC) × 100 / [I _(VC) + I _(E) ]
Here, I _(VC) and I _(E) are quantities expressed by the following formulas, respectively.
I _(VC) = ( _I78.8-80.2 + _I77.7-78.2 )/2
I _(E) = (I _2.0-120.0 + I _135.0-200.0 - I(VC) x 3) / 2

<Propylene/MU Copolymer>
The MU content was calculated from the signals in the ¹³ C-NMR spectrum according to the following formula.
MU content (mol%)=I _(MU) ×100/(I _(P) +I _(MU) )
Here, I _(MU) and I _(P) are quantities expressed by the following formulas, respectively.
I _(MU) = I _50.8-50.6
I _(P) = ( _I180.0-136.0 + _I120.0-100.0 + _I55.0-2.0 - I _(MU) x 12)/3

The branched structure can be determined from the spectrum of tertiary carbon atoms in ¹³ C-NMR. For example, the number of methyl branches per 1,000 carbon atoms was calculated using the value IB1 obtained by dividing the sum of the integrated intensities of the signals from 20.0 to 19.8 ppm of the ¹³ _C -NMR spectrum (corresponding to v in the structural formula below) and 37.6 to 37.3 methylene carbons (corresponding to x in the structural formula below) by 3, using the following formula:
Number of methyl branches (/1000 carbon atoms) = I _B1 × 1000/I _total
Here, I _B1 and I _total are amounts expressed by the following formulas, respectively.
I _B1 = (I _{20.0 to 19.8} + I _{37.6 to 37.3} ) / 3
I _total = I _180.0-136.0 + I _120.0-100.0 + I _80.0-2.0

[Stereoregularity in propylene polymerization]
Similarly, the stereoregularity of polypropylene can be analyzed by quantitative ^13C -NMR. For example, in the ^13C -NMR spectrum, three peaks from 21.1 ppm to 22.4 ppm correspond to mm, three peaks from 20.3 ppm to 21.1 ppm correspond to mr, and three peaks from 19.4 ppm to 20.3 ppm correspond to rr. The ratios of mm, mr, and rr can be calculated by calculating the integral ratios of these peaks.

[Number average molecular weight and weight average molecular weight]
The number average molecular weight and the weight average molecular weight were calculated by size exclusion chromatography using polystyrene as a molecular weight standard. The specific measurement method of GPC is as follows.
Apparatus: Agilent Technologies GPC (PL-GPC220)
Detector: IR detector Column: Showa Denko AT806MS (3 in series)
Mobile phase solvent: ODCB
Measurement temperature: 140°C
Flow rate: 1.0 mL / min
Injection volume: 0.3 mL
[Sample preparation]
The sample is dissolved in ODCB containing 0.24 mg/mL TMP (2,3,6-trimethylphenol) at 140° C. for about 1 hour to prepare a 1 mg/mL sample solution.
The conversion from the retention volume obtained by GPC measurement to molecular weight is performed using a calibration curve of standard polystyrene (PS) prepared in advance. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000. A calibration curve is prepared using a standard polystyrene solution dissolved in ODCB containing 0.24 mg/mL TMP so that each is 0.5 mg/mL. The calibration curve uses a cubic equation obtained by approximation using the least squares method. The viscosity equation [η] = K × M ^α used for conversion to molecular weight uses the following values.
PS: K = 1.38 × 10 ^-4 , α = 0.700
PP: K=1.03×10 ⁻⁴ , α=0.780
PE: K=3.92×10 ⁻⁴ , α=0.733

The catalytic activity was calculated by the following formula:
Catalytic activity (kg/mol/h)=yield of polymer obtained (kg)/{amount of ligand used (mol)×reaction time (h)}

(Synthesis Example 1: Synthesis of AL-39)
(1) Synthesis of 2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxole) The compound of the following chemical formula was synthesized according to the description in Bioorg. Med. Chem. Lett. 2014, 24, 2379-2382.

(2) Synthesis of bis(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxole)-4-yl)chlorophosphine 2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxole) (5 g, 22.5 mmol, 1 eq) was dissolved in 50 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, n-BuLi (24.8 mmol, 1.1 eq) was slowly added, and the mixture was stirred at 20°C for 2.5 hours to obtain a yellow solution. This solution was cooled to -78°C, and PCl ₃ (1.39 g, 10.1 mmol, 0.45 eq) was added all at once. The mixture was warmed to 20°C and stirred for 1.5 hours to obtain a yellow suspension. This suspension was dried to obtain 5.72 g of a yellow viscous mixture containing the target product. The resulting mixture was used in the next synthesis without purification.
^31P { ^1H }NMR (162MHz, _CDCl3 ) δ: 46.3 (integral ratio 100%)

(3) Synthesis of bis(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxol)-4-yl)phosphine Bis(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxol)-4-yl)chlorophosphine (5.72 g, 11.2 mmol, 1 eq) was dissolved in 50 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, lithium aluminum hydride (0.64 g, 16.9 mmol, 1.5 eq) was added, and the mixture was stirred at 20°C for 12 hours to obtain a colorless suspension. The resulting suspension was cooled to 0°C, and 0.6 mL of water, 0.6 mL of 10% aqueous sodium hydroxide solution, and 1.8 mL of water were added in this order, and the resulting mixture was stirred at room temperature for 30 minutes to quench the reaction. The mixture was filtered, and the filtrate was evaporated to dryness to obtain a colorless solid. Subsequently, 30 mL of water was added to the obtained solid, and the product was extracted three times with 30 mL of dichloromethane. The collected organic layer was dried over sodium sulfate, the solid was filtered off, and the filtrate was concentrated to obtain a yellow crude product. The crude product was purified by silica gel chromatography (developing solvent: petroleum ether/ethyl acetate = 20/1) under air and washed with 10 mL of hexane to obtain 3.1 g (6.5 mmol, 58%) of the target compound as a colorless solid.
^1H NMR (400MHz, _CDCl3 ) δ: 6.26 (s, 2H), 5.15 (d, J=235Hz, 1H), 1.57 (s, 24H)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ:-126.8(s)

(4) Synthesis of AL-39 300 mg (0.63 mmol) of bis(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxol)-4-yl)phosphine was weighed out in a Schlenk flask, and 8 mL of tetrahydrofuran was added. The resulting solution was cooled to 0°C, and 0.44 mL (0.69 mmol) of n-BuLi was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour and 10 minutes. Then, the mixture was cooled to 0°C, and 119 mg (0.63 mmol) of α-(trifluoromethyl)styrene oxide dissolved in 2.1 mL of tetrahydrofuran was slowly added. The mixture was stirred at room temperature for 3 hours, cooled to 0°C, and 0.76 mL (0.76 mmol) of a diethyl ether solution of hydrogen chloride (hereinafter also referred to as "hydrochloric acid ether solution") was slowly added dropwise. The mixture was stirred at 0° C. for 1 hour, and the solvent was then distilled off. The resulting solid was purified by silica gel column chromatography (developing solvent: hexane/tetrahydrofuran/triethylamine=100/10/1 instead of 100/5/1) under air. After purification, the solid was recrystallized with 1 mL of tetrahydrofuran and 10 mL of hexane to obtain 157 mg of a solid. The purity of AL-39 determined by ³¹ P NMR was 99% or more.
^1H NMR (400MHz, _CDCl3 ) δ: 7.56 (d, J = 7.4 Hz, 2H), 7.34-7.31 (m, 3H), 6.27 (s, 1H), 6.24 (s, 1H), 4.66 (s, 1H), 4.02 (dd, J = 15.4, 4.7 Hz, 1H), 2.85 (d, J = 15.6 Hz, 1H), 1.59 (s, 6H), 1.58 (s, 6H), 1.51 (s, 6H), 1.44 (s, 6H).
^19F NMR (376MHz, _CDCl3 ) δ: -80.7 (br)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ: -61.2 (q, J=5.2Hz)

(Synthesis Example 2: Synthesis of AL-40)
In a Schlenk flask, 400 mg (0.84 mmol) of bis(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxol)-4-yl)phosphine was weighed out, and 11 mL of tetrahydrofuran was added. The resulting solution was cooled to -78°C, and then 0.58 mL (0.92 mmol) of n-BuLi was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred at -78°C for 1 hour. The mixture was then warmed to 0°C, and then 92 μL (0.84 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 2.8 mL of tetrahydrofuran was slowly added. The mixture was stirred at room temperature for 1 hour, and then the solvent was distilled off. 14 mL of tetrahydrofuran was added to the residue, and then cooled to 0°C, and then 1.0 mL (1.0 mmol) of a hydrochloric acid ether solution was slowly added dropwise. The mixture was stirred at 0°C for 1 hour, and then 8 mL of water was added under air to wash and separate the organic layer. The operation of adding 4 mL of diethyl ether to the aqueous layer and extracting the organic layer was repeated three times. The collected organic layer was dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane/acetone = 10/1) under air to obtain 242 mg of solid.
The purity of AL-40 determined by ³¹ P NMR was 99% or more.
^1H NMR (400MHz, _CDCl3 ) δ: 6.30 (s, 2H), 4.76 (d, J=3.4Hz, 1H), 3.25 (brs, 2H), 1.58 (s, 12H), 1.55 (s, 12H).
^19F NMR (376MHz, _CDCl3 ) δ: -77.0 (d, J = 22.0Hz) ^31P { ^1H }NMR (162MHz, _CDCl3 ) δ: -62.1 (septet, J = 22.9Hz)

(Synthesis Example 3: Synthesis of AL-58)
(1) Synthesis of tert-butyl(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxole)-4-yl)phosphineborane A tetrahydrofuran solution (20 mL) of 2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxole) (2 g, 9 mmol, 1 eq) was cooled to 0° C., and n-BuLi (2.5 M, 4.0 mL, 1.1 eq) was added, and the mixture was stirred at 20° C. for 2 hours. The resulting mixture was added to a tetrahydrofuran solution (10 mL) of tert-butyldichlorophosphine (1.72 g, 10.8 mmol, 1.2 eq) cooled to −78° C. The mixture was stirred at 20° C. for 12 hours to obtain a yellow suspension. The suspension was cooled to 0°C, and dimethylsulfide borane (10M, 2.7mL, 3eq) was added. The resulting mixture was stirred at 20°C for 12 hours to obtain a pale yellow solution. The solution was cooled to 0°C, and lithium aluminum hydride (2.5M, 10.8mL, 27.0mmol) was added. The resulting mixture was stirred at 20°C for 12 hours to obtain a yellow solution. The reaction mixture was poured into 100mL of water and stirred well, and the organic layer was extracted with dichloromethane (50mL x 2). The collected organic layer was washed with 50mL of saturated saline, the organic layer was dried over sodium sulfate, and the sodium sulfate was filtered off. The filtrate was concentrated under reduced pressure to obtain a crude product. The synthesis of this crude product was repeated several times to obtain 3.73g of crude product. The crude product was crushed and washed with 15mL of petroleum ether at 20°C for 30 minutes to obtain 3.26g (10.1mmol) of the target product as a white solid.
^1H NMR (400MHz, _CDCl3 ) δ: 6.42 (s, 1H), 5.32 (dq, J = 375, 7.2Hz, 1H), 1.65 (s, 6H), 1.64 (s, 6H), 1.25 (d, J = 15.5Hz, 9H).
^31P NMR (162MHz, _CDCl3 ) δ: 3.6 (br).

(2) Synthesis of AL-58 69 mg (0.20 mmol) of tetrabutylammonium hydrogen sulfate and 10.0 g of 5% aqueous sodium hypochlorite solution (13.0 mmol) were mixed and cooled to 0°C. 1.09 g (6.49 mmol) of methyl 2-trifluoromethylacrylate was added to the mixture and stirred at 0°C for 3 hours. The product was extracted from the mixture three times with 5 mL of diethyl ether, and the collected organic layer was washed with water. The product was extracted twice with 3 mL of diethyl ether from the washing water. 5 mL of diethyl ether and 5 mL of water were added to the emulsified aqueous layer and cooled at -15°C overnight. The organic layers were all collected and dried over sodium sulfate, filtered, and the filtrate was concentrated at room temperature under a reduced pressure of 74-17 mmHg. 8 mL of diethyl ether was added thereto, and sodium sulfate was further added thereto for drying, followed by filtration, and the filtrate was concentrated under a slightly reduced pressure to obtain 391 mg of a colorless liquid epoxide.
300 mg (0.925 mmol) of tert-butyl(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxol)-4-yl)phosphineborane synthesized in (1) above was weighed out in a Schlenk flask, and 8 mL of tetrahydrofuran was added. The resulting solution was cooled to -78°C, and 1.88 mL (1.13 mmol) of a toluene solution of 0.6 M potassium hexamethyldisilazide was slowly added dropwise. After the dropwise addition was completed, the mixture was heated to 0°C, and a mixture of 155 mg of the colorless liquid epoxide synthesized earlier and 1.6 mL of THF was slowly added. The mixture was stirred at room temperature for 3 hours, cooled to 0°C, and then 0.87 M hydrochloric acid (3.5 mmol) was slowly added dropwise. The product was extracted from this mixture three times with 5 mL of diethyl ether, and the collected organic layer was washed with 5 mL of water. The organic layer was dried over sodium sulfate, and then filtered through absorbent cotton to remove sodium sulfate. The filtrate was evaporated to dryness, and the resulting solid was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=1/3 instead of 1/2) under air to obtain 216 mg of a white solid.

201 mg (0.407 mmol) of the solid obtained above and 55 mg (0.49 mmol) of 1,4-diazabicyclo[2.2.2]octane were dissolved in 3.5 mL of toluene. The resulting solution was heated to 60° C. and stirred for one and a half hours. After stirring, the solution was purified by silica gel column chromatography (developing solvent: hexane/acetone=3/1) under nitrogen to obtain 180 mg of a solid. The diastereomer ratio determined from ¹ H NMR was 1:0.3.
^1H NMR (400MHz, _CDCl3 ) δ: 6.33 (s, 1H), 3.92 (s, 3H), 3.76 (dd, J = 14.8, 4.4 Hz, 1H), 3.44 (s, 1H), 2.05 (d, J = 14.6 Hz, 1H), 1.66 (s, 6H), 1.59 (s, 6H), 1.09 (d, J = 13.2 Hz, 9H).
^19F NMR (376MHz, _CDCl3 ) δ: -79.1 (br)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ: -18.2(q, J=5.5Hz)
Diastereomers
^1H NMR (400MHz, _CDCl3 ) δ: 6.35 (s, 1H), 4.07 (br, 1H), 3.73 (s, 3H), 3.43 (dd, J = 14.8, 4.0Hz, 1H), 2.00 (dd, J = 14.8, 1.4Hz, 1H), 1.65 (s, 6H), 1.62 (s, 6H), 1.11 (d, J = 13.7Hz, 9H).
^19F NMR (376MHz, _CDCl3 ) δ: -78.8 (s)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ: -21.7(s)

(Synthesis Example 4: Synthesis of AL-59)
296 mg (0.913 mmol) of tert-butyl(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxol)-4-yl)phosphineborane synthesized in the same manner as in Synthesis Example 3 (1) was weighed out in a Schlenk flask, and 10 mL of tetrahydrofuran was added. The resulting solution was cooled to -78°C, and then 2.0 mL (1.2 mmol) of a 0.6 M toluene solution of potassium hexamethyldisilazide was slowly added dropwise. After completion of the dropwise addition, the mixture was warmed to 0°C and stirred for 1 hour. 0.133 mL (1.22 mmol) of 2,2-bis(trifluoromethyl)oxirane was slowly added to the mixture. The mixture was warmed to room temperature and stirred for 2 hours, then cooled to 0°C, and 4 mL (3.48 mmol) of 0.87 M hydrochloric acid was slowly added dropwise. The product was extracted from this mixture three times with 5 mL of diethyl ether, and the collected organic layer was washed with 5 mL of water. The collected organic layer was dried over sodium sulfate, and then filtered using absorbent cotton to remove sodium sulfate. The filtrate was evaporated to dryness, and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 2/1) under air to obtain 283 mg of a white solid.
To 200 mg (0.397 mmol) of the solid obtained above, 54 mg (0.48 mmol) of 1,4-diazabicyclo[2.2.2]octane dissolved in 3.5 mL of toluene was added, and the mixture was heated to 60° C. and stirred for one and a half hours. After stirring, the resulting solution was purified under nitrogen by silica gel column chromatography (developing solvent: hexane/acetone=5/1) to obtain 234 mg of a solid. The purity of AL-59 determined from ³¹ P{ ¹ H} NMR was 100%.
^1H NMR (400MHz, _CDCl3 ) δ: 6.38 (s, 1H), 4.26 (d, J = 8.7Hz, 1H), 3.63 (dd, J = 16.0, 3.2Hz, 1H), 2.03 (d, J = 16.0Hz, 1H), 1.65 (s, 6H), 1.61 (s, 6H), 1.13 (d, J = 14.2Hz, 9H).
^19F NMR (376MHz, _CDCl3 ) δ: -76.7 (dq, J=10.9, 10.9Hz), -77.7 (dq, J=10.9, 10.9Hz)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ: -30.2(m)

(Synthesis Example 5: Synthesis of AL-63)
(1) Synthesis of 1,2,4,5-tetrahydroxybenzene Sodium dithionite (37.28 g, 214.14 mmol, 46.60 mL, 2 eq) and hydrochloric acid (12 M, 49.07 mL, 5.5 eq) were added to a solution of 2,5-dihydroxy-1,4-benzoquinone (15 g, 107.7 mmol, 1 eq) in 200 mL of water. The resulting solution was stirred at 20° C. for 30 minutes to obtain a white suspension. This suspension was filtered, and 200 mL of ethyl acetate was added to the filtrate twice to obtain a brown solution. The obtained organic layer was washed twice with 200 mL of water and dried by adding sodium sulfate. Thereafter, the solid was filtered off, and the filtrate was concentrated to obtain 14 g of a brown solid residue. The obtained compound was used in the next synthesis without purification.
^1H NMR (500MHz, dimethylsulfoxide- _d6 ) δ: 7.93 (brs, 4H), 6.20 (s, 2H)

(2) Synthesis of dispiro[cyclopentane-1,2'-benzo[1,2-d:4,5-d']bis([1,3]dioxole)-6',1"-cyclopentane] 1,2,4,5-Tetrahydroxybenzene (8 g, 56 mmol, 1 eq) was dissolved in 80 mL of dichloromethane. Cyclopentanone (18.94 g, 225.2 mmol, 19.9 mL, 4 eq) and dichlorodimethylsilane (14.53 g, 112.6 mmol, 13.6 mL, 2 eq) were added to the resulting solution, and the mixture was stirred at 20°C for 12 hours to obtain a brown solution. The resulting solution was concentrated, and 10 mL of heptane was added to the resulting crude product and stirred for 3 minutes. After stirring, the resulting solution was filtered, 1.5 mL of acetone was added to the filtrate, and the mixture was refluxed and then cooled to -10°C for recrystallization to obtain a black solid crude product. This solid was purified by silica gel column chromatography (developing solvent: petroleum ether/dichloromethane = 10/1) to obtain a white solid (5 g, 18 mmol).
^1H NMR (400MHz, _CDCl3 ) δ: 6.34 (s, 2H), 2.09-2.05 (m, 8H), 1.83-1.79 (m, 8H).

(3) Synthesis of bis(dispiro[cyclopentane-1,2'-benzo[1,2-d:4,5-d']bis([1,3]dioxole)-6',1"-cyclopentane]-4'-yl)phosphine Dispiro[cyclopentane-1,2'-benzo[1,2-d:4,5-d']bis([1,3]dioxole)-6',1"-cyclopentane] (1 g, 3.7 mmol, 1 eq) was dissolved in 15 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, and n-BuLi (2.5 M, 1.60 mL, 4.0 mmol, 1.1 eq) was slowly added and the mixture was stirred at 20°C for 2.5 hours to obtain a yellow solution. The resulting solution was cooled to -78°C, and PCl ₃ (225 mg, 1.64 mmol, 143 μL, 0.45 eq) was added. The mixture was warmed to 20° C. and stirred for 1.5 hours to give a yellow suspension, which was evaporated to dryness to give 1.12 g of a yellow viscous compound.
The resulting yellow viscous compound was dissolved in 15 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, lithium aluminum hydride (2.5M, 1.1 mL, 2.8 mmol) was slowly added, and the mixture was stirred at 20°C for 12 hours to obtain a brown suspension. The suspension was cooled to 0°C, and 0.6 mL of water, 0.6 mL of 10% aqueous sodium hydroxide solution, and 1.8 mL of water were added in that order, and the resulting mixture was stirred at room temperature for 30 minutes. The mixture was filtered, and the filtrate was evaporated to dryness to obtain a white solid. Subsequently, 30 mL of water was added to the white solid, and the resulting organic matter was extracted with dichloromethane (30 mL x 3). The collected organic layer was dried over sodium sulfate, the solid was filtered off, and the filtrate was concentrated to obtain a crude product as a yellow solid. The crude product was purified by silica gel chromatography (developing solvent: petroleum ether/ethyl acetate = 20/1) and washed with 10 mL of hexane to obtain 0.16 g (0.28 mmol) of the target compound as a white solid.
^1H NMR (400MHz, _CDCl3 ) δ: 6.28 (s, 2H), 5.19 (d, J=234Hz, 1H), 1.99 (br, 16H), 1.76 (br, 16H)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ: -125.2(s)

(4) Synthesis of AL-63 In a Schlenk flask, 300 mg (0.52 mmol) of bis(dispiro[cyclopentane-1,2'-benzo[1,2-d:4,5-d']bis([1,3]dioxole)-6',1"-cyclopentane]-4'-yl)phosphine synthesized in (3) above was weighed out, and 6.8 mL of tetrahydrofuran was added. The resulting solution was cooled to -78°C, and 0.38 mL (0.57 mmol) of n-BuLi was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred at -78°C for 1 hour and 20 minutes. Thereafter, the mixture was heated to 0°C, and 57 μL (0.52 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 1.3 mL of tetrahydrofuran was slowly added. The container containing 2,2-bis(trifluoromethyl)oxirane was poured with 0.2 mL of The mixture was washed twice with tetrahydrofuran, and the washings were also added to the Schlenk flask. The mixture was stirred at room temperature for 2 hours and 40 minutes, and the solvent was then distilled off. 8 mL of tetrahydrofuran was added to the residue, which was then cooled to 0°C, and 0.62 mL (0.62 mmol) of a hydrochloric acid ether solution was slowly added dropwise. The mixture was stirred at 0°C for 15 minutes, and then 5 mL of water was added under air to wash the mixture, and the organic layer was separated. All subsequent operations were performed under air. The operation of adding 3 mL of diethyl ether to the aqueous layer and extracting the organic layer was repeated three times. The collected organic layer was dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane/acetone = 10/1) to obtain 120 mg of a solid. The purity of AL-63 determined from ³¹ P NMR was 97%.
^1H NMR (400MHz, _CDCl3 ) δ: 6.32 (s, 2H), 4.67 (s, 1H), 3.25 (s, 2H), 2.01-1.92 (m, 16H), 1.77-1.73 (m, 16H).
^19F NMR (376MHz, _CDCl3 ) δ: -76.9 (d, J=22.2Hz)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ:-62.2 (septet, J=22.0Hz)

(Synthesis Example 6: Synthesis of AL-64)
(1) Synthesis of 2,3,7,8-tetrahydrobenzo[1,2-b:4,5-b']bis([1,4]dioxin) 1,2,4,5-tetrahydroxybenzene (8 g, 56 mmol, 1 eq) and 1,2-dibromoethane (42.30 g, 225.2 mmol, 17.0 mL, 4 eq) were dissolved in 500 mL of dimethylformamide. Potassium carbonate (31.12 g, 225.2 mmol, 4 eq) was added to the resulting solution, and the mixture was stirred at 90° C. for 12 hours to obtain a brown suspension. After confirming the completion of the reaction by ¹ H-NMR, 500 mL of water was added to the reaction solution and filtered to obtain a crude product. The obtained crude product was dissolved in 200 mL of methanol, 450 mL of toluene was added, and the mixture was dried to obtain 19 g of a gray compound.
^1H NMR (400MHz, _CDCl3 ) δ: 6.42 (s, 2H), 4.20 (s, 8H)

(2) Synthesis of bis(2,3,7,8-tetrahydrobenzo[1,2-b:4,5-b']bis([1,4]dioxin)-5-yl)phosphine 2,3,7,8-Tetrahydrobenzo[1,2-b:4,5-b']bis([1,4]dioxine (4.4 g, 23 mmol) was dissolved in 100 mL of tetrahydrofuran. The resulting solution was cooled to 0° C., n-BuLi (2.5 M, 9.5 mL, 23.8 mmol) was added, and the mixture was stirred at 0° C. for 1 hour to give a yellow suspension. The resulting suspension was added to a toluene solution (10 mL) of (diethylamino)dichlorophosphine (1.58 g, 9.08 mmol) cooled to 0° C. The mixture was stirred at 0° C. for 1 hour to give a yellow suspension. A dioxane solution of hydrogen chloride (4 M, 20 mL) was added to this suspension at 0° C., and the mixture was stirred at 20° C. for 1 hour to give a yellow suspension. The resulting yellow suspension was evaporated to dryness to give 4.11 g of a yellow solid.
The above yellow solid was dissolved in 80 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, lithium aluminum hydride (2.5M, 7.3 mL, 18.3 mmol) was slowly added, and the mixture was stirred at 20°C for 12 hours to obtain a brown suspension. The suspension was cooled again to 0°C, and 0.7 mL of water, 0.7 mL of 10% aqueous sodium hydroxide solution, and 2.1 mL of water were added in that order, and the resulting mixture was stirred at room temperature for 30 minutes. The mixture was filtered, and the filtrate was evaporated to dryness to obtain a white solid. Subsequently, 80 mL of water was added to the white solid, and the organic matter was extracted with dichloromethane (40 mL x 3). The collected organic layer was dried over sodium sulfate, the solid was filtered off, and the filtrate was concentrated to obtain the crude product as a yellow solid. The crude product was purified by silica gel chromatography (developing solvent: petroleum ether/ethyl acetate = changed from 10/1 to 5/1), and pulverized and washed with 10 mL of hexane to obtain 1.03 g (2.46 mmol) of the target compound as a white solid.
^1H NMR (500MHz, _CDCl3 ) δ: 6.36 (s, 2H), 5.40 (d, J=243Hz, 1H), 4.14 (s, 16H).
^31P { ^1H }NMR(202MHz, _CDCl3 ) δ:-132.3(s)

(3) Synthesis of AL-64 250 mg (0.60 mmol) of bis(2,3,7,8-tetrahydrobenzo[1,2-b:4,5-b']bis([1,4]dioxin)-5-yl)phosphine synthesized in (2) above was weighed out in a Schlenk flask, and 8 mL of tetrahydrofuran was added. The resulting solution was cooled to -78°C, and 0.43 mL (0.66 mmol) of n-BuLi was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred at -78°C for 45 minutes. The mixture was then heated to 0°C, and 65 μL (0.60 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 2.0 mL of tetrahydrofuran was slowly added. The inside of the container containing 2,2-bis(trifluoromethyl)oxirane was washed twice with 0.2 mL of tetrahydrofuran, and the washings were also added to the Schlenk flask. The resulting mixture was stirred at room temperature for 1 hour and 40 minutes, then cooled to 0°C, and 0.72 mL (0.72 mmol) of hydrochloric acid ether solution was slowly dropped. After stirring this mixture at 0°C for 40 minutes, 5.7 mL of water was added under air to wash, and the organic layer was separated. All subsequent operations were performed under air. The operation of adding 3 mL of diethyl ether to the aqueous layer and extracting the organic layer was repeated three times. The collected organic layer was dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the obtained solid was purified by silica gel column chromatography (the developing solvent: hexane/acetone = 10/1 was changed from 5/1, then 4/1, and further to 2/1), and 131 mg of solid was obtained. The purity of AL-64 determined from ³¹ P-NMR was 98%.
^1H NMR (400MHz, _CDCl3 ) δ: 6.41 (s, 2H), 5.09 (d, J=5.2Hz, 1H) 4.15-4.08 (m, 16H), 3.21 (s, 2H).
^19F NMR (376MHz, _CDCl3 ) δ: -77.3 (d, J=22.2Hz)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ:-59.5 (septet, J=21.1Hz)

(Synthesis Example 7: Synthesis of AL-66)
(1) Synthesis of benzo[1,2-d:4,5-d']bis([1,3]dioxole) Potassium carbonate (62.2 g, 450 mmol) and dibromomethane (31.6 mL, 78.3 g, 450 mmol) were added to a dimethylformamide solution (50 mL) of 1,2,4,5-tetrahydroxybenzene (8 g, 56 mmol) at 25°C or lower, and the resulting mixture was stirred at 100°C for 16 hours to obtain a red suspension. The suspension was added to water (150 mL), and the organic layer was extracted with ethyl acetate (150 mL x 3). The collected organic layer was washed with 150 mL of saturated saline and dried over sodium sulfate. The sodium sulfate was filtered off, and the filtrate was concentrated to obtain a crude product. The crude product was purified by silica gel chromatography (developing solvent: petroleum ether/ethyl acetate = 10/1) to obtain 0.8 g (4.8 mmol) of the target compound as a yellow solid.
^1H NMR (400MHz, _CDCl3 ) δ: 6.50 (s, 2H), 5.88 (s, 4H)

(2) Synthesis of bis(benzo[1,2-d:4,5-d']bis([1,3]dioxole)-4-yl)-N,N-diethylaminophosphine Benzo[1,2-d:4,5-d']bis([1,3]dioxole) (2 g, 12 mmol, 1 eq) was dissolved in 20 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, n-BuLi (2.5 M, 5.3 mL, 13.3 mmol, 1.1 eq) was slowly added, and the mixture was slowly warmed to 20°C and stirred for 2 hours to obtain a yellow solution. The resulting solution was cooled to 0°C, and (diethylamino)dichlorophosphine (942 mg, 5.41 mmol, 0.45 eq) dissolved in 10 mL of tetrahydrofuran was added. The mixture was stirred at 0°C for 1 hour to obtain a yellow solution. The solution was dried to obtain 2.61 g of crude product as a yellow solid. The resulting solid was used in the next synthesis without purification.
^31P { ^1H }NMR (162MHz, _CDCl3 ) δ: 21.6 (s, integral ratio 100%)

(3) Synthesis of bis(benzo[1,2-d:4,5-d']bis([1,3]dioxol)-4-yl)chlorophosphine The crude product (2.61 g) obtained in (2) above was dissolved in 40 mL of toluene. The resulting solution was cooled to 0°C, and a solution of hydrogen chloride in dioxane (4 M, 20 mL) was added, and the mixture was stirred at 20°C for 1 hour to obtain a yellow solution. The resulting solution was used in the next synthesis without purification.
^31P { ^1H }NMR (162MHz, _CDCl3 ) δ: 41.9 (s, integral ratio 44%)

(4) Synthesis of bis(benzo[1,2-d:4,5-d']bis([1,3]dioxol)-4-yl)phosphine The solvent of the yellow solution obtained in (3) above was changed to 30 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, lithium aluminum hydride (2.5 M, 3.6 mL, 9.0 mmol) was added, and the mixture was slowly stirred at 20°C for 12 hours to obtain a yellow solution. The yellow solution was cooled to 0°C, and 0.4 mL of water, 0.4 mL of 10% aqueous sodium hydroxide solution, and 1.2 mL of water were added in this order, and the resulting mixture was stirred at 20°C for 30 minutes. The mixture was filtered, and the filtrate was evaporated to dryness to obtain a yellow solid. The resulting solid was purified by silica gel chromatography (developing solvent: petroleum ether/dichloromethane = changed from 5/1 to 1/1, and then to 0/1), and 0.22 g of the target compound was obtained as a white solid.
^1H NMR (400MHz, _CDCl3 ) δ: 6.47 (s, 2H), 5.89 (s, 8H), 5.26 (d, J=235Hz, 1H).
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ: -126.0(s)

(5) Synthesis of AL-66 200 mg (0.55 mmol) of bis(benzo[1,2-d:4,5-d']bis([1,3]dioxol)-4-yl)phosphine synthesized in (4) above was weighed out in a Schlenk flask, and 7.3 mL of tetrahydrofuran was added. The resulting solution was cooled to -78°C, and 1.0 mL (0.61 mmol) of a toluene solution of potassium hexamethyldisilazane was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred at -78°C for 45 minutes. The mixture was then heated to 0°C, and 60 μL (0.55 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 1.8 mL of tetrahydrofuran was slowly added. The inside of the container containing 2,2-bis(trifluoromethyl)oxirane was washed twice with 0.3 mL of tetrahydrofuran, and the washings were also added to the Schlenk flask. The mixture was stirred at room temperature for 1 hour and 30 minutes, and the solvent was distilled off. 9.7 mL of tetrahydrofuran was added to the residue, which was then cooled to 0°C, and 0.66 mL (0.66 mmol) of hydrochloric acid ether solution was slowly added dropwise. The resulting mixture was stirred at 0°C for 1 hour, and then 5.2 mL of water was added under air to wash and separate the organic layer. All subsequent operations were performed under air. The operation of adding 2.6 mL of diethyl ether to the aqueous layer and extracting the organic layer was repeated three times. The collected organic layer was dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the obtained solid was purified by silica gel column chromatography (the developing solvent: hexane/acetone = 10/1 was changed to 5/1), and 136 mg of solid was obtained. The purity of AL-66 determined from ³¹ P-NMR was 99% or more.
^1H NMR (400MHz, _CDCl3 ) δ: 6.50 (s, 2H), 5.86 (d, J = 1.2Hz, 4H), 5.84 (d, J = 1.6Hz, 4H), 4.10 (d, J = 2.8Hz, 1H), 3.24 (d, J = 1.6Hz, 2H).
^19F NMR (376MHz, _CDCl3 ) δ: -77.1 (d, J=22.2Hz)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ:-64.7(septet, J=20.6Hz)

(Synthesis Example 8: Synthesis of AL-40/NiArPy)
393 mg (1.4 mmol) of Ni(cod) ₂ was weighed out in a Schlenk flask, and 6 mL of toluene was added. 0.21 mL (1.4 mmol) of tetramethylethylenediamine and 0.16 mL (1.4 mmol) of 4-bromofluorobenzene were added to the solution, and the mixture was stirred at room temperature for 3 hours. After stirring, the supernatant was separated, and the residue was washed with 2 mL of hexane, which was repeated three times. After washing, the solvent was distilled off to obtain solid 1.
Next, 92 mg (0.14 mmol) of AL-40 was weighed out in a Schlenk flask, and 5.3 mL of tetrahydrofuran was added thereto. The solution was cooled to 0°C, and 79 μL (0.15 mmol) of a tetrahydrofuran solution of sodium hexamethyldisilazane was slowly added thereto. The mixture was stirred at room temperature for 1 hour, and the solvent was then completely distilled off. 1.9 mL of tetrahydrofuran was added to the resulting residue to obtain a sodium solution of AL-40.
70 mg (0.20 mmol) of the solid 1 was weighed out in a Schlenk flask, and 1.0 mL of tetrahydrofuran was added to obtain a transition metal compound solution. The sodium AL-40 solution was added to this transition metal compound solution at room temperature. The Schlenk flask containing the sodium AL-40 solution was washed twice with 0.2 mL of tetrahydrofuran, and the washings were added to the transition metal compound solution. The mixture was stirred at room temperature for 2 hours and 30 minutes, and then filtered through Celite. After filtration, the solvent was distilled off from the filtrate, and the residue was washed eight times with 2 mL of hexane. The residue was completely dried to obtain 98 mg of solid 2.
Next, 71 mg of the above solid 2 was weighed out in a Schlenk flask, and 3.2 mL of tetrahydrofuran was added thereto. 13 μL (0.16 mmol) of pyridine was added to the resulting solution, which was then stirred at room temperature for 1 hour and filtered through Celite. After filtration, the solvent was distilled off from the filtrate to obtain 42 mg of a solid. The purity of AL-40/NiArPy determined from ³¹ P-NMR was 99% or more.
^1H NMR (400MHz, _C6D5CD3 ) δ: 8.57 (br, _2H ), 7.57 (dd, J=8.0 _, 6.8Hz, 2H), 6.73 (t, J=7.6Hz, 1H), 6.64 (dd, J=9.2Hz, 2H), 6.40 (br, 2H), 6.30 (s, 2H), 3.95 (d, J=12.4Hz, 2H), 1.43 (s, 12H), 1.32 (s, 12H).
^19F NMR ( _376MHz , _C6D5CD3 ) δ: -77.8 (s), -124.0 (t, J= _13.7Hz )
^31P { ^1H }NMR( _{162MHz , C6D5CD3} ) δ: 4.4(s)

(Synthesis Example 9: Synthesis of AL-70)
(1) Synthesis of 5-methoxy-1,3-benzodioxole Potassium carbonate (5.00 g, 36.2 mmol) was added to an acetone solution (5 mL) of sesamol (1 g, 7.2 mmol), and the resulting mixture was stirred at 80° C. for 1 hour. Methyl iodide (0.9 mL, 2.06 g, 14.5 mmol) was added dropwise to the mixture, and the mixture was stirred at 80° C. for 12 hours to obtain a white suspension. The suspension was cooled to room temperature, filtered, and the filtrate was concentrated to obtain a yellow oily substance. The oily substance was purified by silica gel chromatography (developing solvent: petroleum ether/ethyl acetate=10/1) to obtain 1 g (6.6 mmol) of the target product as a colorless liquid.
^1H NMR (400MHz, _CDCl3 ) δ: 6.72 (d, J = 8.4 Hz, 1H), 6.50 (d, J = 2.4 Hz, 1H), 6.33 (dd, J = 8.4, 2.4 Hz, 1H), 5.92 (s, 2H), 3.76 (s, 3H).

(2) Synthesis of tert-butyl(5-methoxy-1,3-benzodioxol-4-yl)chlorophosphine 5-Methoxy-1,3-benzodioxole (5.3 g, 35 mmol, 1 eq) was dissolved in 40 mL of tetrahydrofuran. The resulting solution was cooled to −78° C., n-BuLi (2.5 M, 15.3 mL, 38.3 mmol, 1.1 eq) was added, and the mixture was stirred at −78° C. for 2 hours. To the resulting mixture, tert-butyldichlorophosphine (6.09 g, 38.3 mmol, 1.1 eq) dissolved in 5 mL of tetrahydrofuran was quickly added. The mixture was stirred at 25° C. for 1 hour to obtain a white suspension. The suspension was dried to obtain a crude product. The obtained crude product was used in the next synthesis without purification.
^31P { ^1H }NMR (162MHz, _CDCl3 ) δ: 100.6 (s, integral ratio 69%)

(3) Synthesis of tert-butyl(5-methoxy-1,3-benzodioxol-4-yl)phosphine 30 mL of tetrahydrofuran was added to the tert-butyl(5-methoxy-1,3-benzodioxol-4-yl)chlorophosphine (9.57 g) obtained in (2) above. The resulting suspension was cooled to 0° C., lithium aluminum hydride (2.5 M, 13 mL, 32.5 mmol) was added, and the mixture was stirred at 25° C. for 16 hours to obtain a white suspension. The resulting suspension was used in the next synthesis without purification.
³¹ P{ ¹ H} NMR (162 MHz, CDCl ₃ ) δ: −56.9 (s, integral ratio 76%)

(4) Synthesis of tert-butyl(5-methoxy-1,3-benzodioxol-4-yl)phosphineborane The white suspension obtained in (3) above was cooled to 0°C, and borane dimethylsulfide complex (10M, 4.74mL, 2eq) was added. The mixture was stirred at 25°C for 16 hours to obtain a colorless solution. 1.5mL of water, 1.5mL of 10% aqueous sodium hydroxide solution, and 4.5mL of water were slowly added to this solution in this order, and the resulting mixture was stirred at room temperature for 30 minutes. The mixture was filtered, and the filtrate was evaporated to dryness to obtain a colorless liquid. The resulting liquid was purified by silica gel chromatography (developing solvent: petroleum ether/ethyl acetate=20/1) to obtain 2.8g (11.0mmol) of the target compound as a white solid.
^1H NMR (400MHz, _CDCl3 ) δ: 6.84 (d, J = 8.4 Hz, 1H), 6.33 (dd, J = 8.4, 3.2 Hz, 1H), 5.98 (dd, J = 10.4 Hz, 1.2 Hz, 2H), 5.48 (d, J = 386 Hz, 1H), 3.79 (s, 3H), 1.23 (d, J = 15.6 Hz, 9H), 1.10-0.17 (br, 3H).
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ:6.0-(-5.0)(br)

(5) Synthesis of AL-70 250 mg (0.98 mmol) of tert-butyl(5-methoxy-1,3-benzodioxol-4-yl)phosphineborane obtained in (4) above was weighed out in a Schlenk flask, and 13 mL of tetrahydrofuran was added. The resulting solution was cooled to −78° C., and then 1.8 mL (1.1 mmol) of a toluene solution of potassium hexamethyldisilazane was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred at −78° C. for 1 hour. The mixture was then heated to 0° C., and 0.11 mL (0.98 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 3.2 mL of tetrahydrofuran was slowly added. Furthermore, the inside of the container containing 2,2-bis(trifluoromethyl)oxirane was washed twice with 0.5 mL of tetrahydrofuran, and the washings were also added to the Schlenk flask. The mixture was stirred at room temperature for 2 hours, and the solvent was then completely removed by distillation. The obtained solid was purified by silica gel column chromatography in the atmosphere (developing solvent: hexane/dichloromethane=15/1 changed to 10/1, and further changed to 2/1) to obtain 245 mg of a solid.
3.6 mL of methanol was added to 245 mg of the above solid, and the mixture was heated to 60° C. and stirred for 5 hours and 30 minutes. After stirring, the solvent was completely removed and the mixture was purified by silica gel column chromatography to obtain a pale pink liquid. This liquid was vacuum-dried for 9 hours while heating to 65° C. to obtain 131 mg of a solid. The purity determined by ³¹ P-NMR was 99% or more.
^1H NMR (400MHz, _CDCl3 ) δ: 6.80 (d, J = 8.0 Hz, 1H), 6.33 (dd, J = 8.8, 3.6 Hz, 1H), 5.95 (d, J = 1.6 Hz, 1H), 5.87 (d, J = 1.2 Hz, 1H), 4.47 (d, J = 9.2 Hz, 1H), 3.78 (s, 3H), 3.69 (dd, J = 16.0, 1.2 Hz, 1H), 2.06 (ddd, J = 16.0, 1.2, 1.2 Hz, 1H), 1.10 (d, J = 14.0 Hz, 9H).
^19F NMR (376MHz, _CDCl3 ) δ: -77.0 (q, J=12.8Hz), -77.9 (q, J=12.9Hz)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ:-29.7-(-30.5)(m)

(Synthesis Example 10: Synthesis of AL-72)
(1) Synthesis of 8-trimethylsilyl-2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxole) 2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxole) (1 g, 4.5 mmol, 1 eq) was dissolved in 20 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, n-BuLi (2.5 M, 2.1 mL, 5.3 mmol, 1.2 eq) was slowly added dropwise, and the mixture was stirred at 0°C for 30 minutes. While keeping the resulting solution at 0°C, chlorotrimethylsilane (0.98 g, 9.0 mmol, 1.1 mL, 2 eq) was slowly added dropwise. The mixture was stirred at 0°C for 30 minutes to obtain a yellow solution. 50 mL of aqueous sodium bicarbonate solution was added to this solution to stop the reaction, and the product was extracted with ethyl acetate (50 mL x 3). The combined organic layer was dried over sodium sulfate, the solid was filtered off, and the filtrate was concentrated to obtain a crude product as a yellow solid. The crude product was purified by silica gel chromatography (developing solvent: petroleum ether/ethyl acetate=50/1) to obtain 1 g (3.40 mmol) of the target compound as a pale yellow solid.
^1H NMR (400MHz, _CDCl3 ) δ: 6.30 (s, 1H), 1.61 (s, 12H), 0.31 (s, 9H)

(2) Synthesis of bis(8-trimethylsilyl-2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxole)-4-yl)chlorophosphine 8-Trimethylsilyl-2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxole) (5.5 g, 18.7 mmol, 1 eq) was dissolved in 55 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, and n-BuLi (2.5 M, 8.2 mL, 20.5 mmol, 1.1 eq) was slowly added dropwise, and the mixture was stirred at 0°C for 2.5 hours to obtain a yellow solution. The resulting solution was added to a tetrahydrofuran solution (8 mL) of PCl ₃ (1.15 g, 8.4 mmol, 735 μL, 0.45 eq) cooled to -78°C. The mixture was stirred at 0° C. for 1.5 hours to give a yellow suspension. The resulting suspension was evaporated to dryness to give 12.2 g of a yellow solid. The resulting compound was used in the next synthesis without purification.

(3) Synthesis of bis(8-trimethylsilyl-2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxol)-4-yl)phosphine Bis(8-trimethylsilyl-2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxol)-4-yl)chlorophosphine (6.1 g) obtained in (2) above was dissolved in 60 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, lithium aluminum hydride (2.5 M, 5.6 mL, 14.0 mmol) was added, and the mixture was slowly heated to 20°C and stirred for 12 hours to obtain a yellow solution. This solution was cooled to 0°C, and 1 mL of water, 1 mL of 10% aqueous sodium hydroxide solution, and 3 mL of water were added in this order, and the resulting mixture was stirred at 20°C for 30 minutes to stop the reaction. The mixture was filtered, and the filtrate was evaporated to dryness to obtain a yellow solid. The resulting solid was purified by silica gel chromatography to obtain 5.7 g (9.21 mmol, 49%) of the target compound as a white solid.
^1H NMR (400MHz, _CDCl3 ) δ: 5.13 (d, J=241Hz, 1H), 1.54 (s, 24H), 0.26 (s, 18H).
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ: -126.5(s)

(4) Synthesis of AL-72 300 mg (0.485 mmol) of bis(8-trimethylsilyl-2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxol)-4-yl)phosphine obtained in (3) above was weighed out in a Schlenk flask, and 10 mL of tetrahydrofuran was added. The resulting solution was cooled to -78°C, and 1.05 mL (0.630 mmol) of a 0.6 M toluene solution of potassium hexamethyldisilazide was slowly added dropwise. After completion of the dropwise addition, the mixture was warmed to 0°C, 2 mL of tetrahydrofuran was added, and the mixture was stirred for 1 hour. 60.0 μL (0.549 mmol) of 2,2-bis(trifluoromethyl)oxirane was added to the mixture, and the mixture was warmed to room temperature and stirred for 2.5 hours. The mixture was stirred at 0°C for 20 minutes, and then 5 mL (1.45 mmol) of 0.3 M hydrochloric acid was slowly added dropwise. 5 mL of dichloromethane and 5 mL of water were added to the mixture to separate the organic layer, and then 5 mL of dichloromethane was added to the aqueous layer to extract the organic layer. This operation was repeated three times. The collected organic layer was dried over sodium sulfate, and then sodium sulfate was removed by filtration, and the residue was washed three times with 3 mL of dichloromethane. The filtrate was evaporated to dryness, and the solid obtained under air was purified by silica gel column chromatography (developing solvent: hexane/acetone = 5/1) to obtain 249 mg of solid.
^1H NMR (400MHz, _CDCl3 ) δ: 5.07 (s, 1H), 3.24 (s, 2H), 1.53 (s, 12H), 1.51 (s, 12H), 0.26 (s, 18H).
^19F NMR (376MHz, _CDCl3 ) δ: -76.8 (d, J=22.0Hz)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ:-60.8 (septet, J=24.8Hz)

(Synthesis Example 11: Synthesis of AL-73)
(1) Synthesis of 5-methoxy-2,2-dimethyl-1,3-benzodioxole The compound of the following chemical formula was synthesized with reference to Organic & Biomolecular Chemistry, 2021, 19, 1555-1564.

(2) Synthesis of tert-butyl(5-methoxy-2,2-dimethyl-1,3-benzodioxol-4-yl)chlorophosphine To a THF solution (40 mL) of 5-methoxy-2,2-dimethyl-1,3-benzodioxole (5 g, 28 mmol) cooled to 0° C., n-BuLi (2.5 M, 12.2 mL, 30.5 mmol) was added, and the resulting mixture was stirred at 25° C. for 2 hours. The mixture was cooled to −78° C., and a THF solution (5 mL) of tert-butyldichlorophosphine (4.85 g, 30.5 mmol) was quickly added to the mixture, and the mixture was stirred at 25° C. for 1 hour to obtain a white suspension. The solvent was evaporated to obtain a crude product as a yellow solid.
^31P { ^1H }NMR (202MHz, _CDCl3 ) δ: 100.8 (s, integrated intensity ratio 100%)

(3) Synthesis of tert-butyl(5-methoxy-2,2-dimethyl-1,3-benzodioxol-4-yl)phosphineborane Lithium aluminum hydride (2.5 M, 13.7 mL, 34.3 mmol) was added to a THF solution (45 mL) of tert-butyl(5-methoxy-2,2-dimethyl-1,3-benzodioxol-4-yl)chlorophosphine (8.4 g, 28 mmol) cooled to 0° C., and the resulting mixture was stirred at 25° C. for 16 hours to obtain a yellow solution. Dimethylsulfide borane (10 M, 5.6 mL, 56 mmol) was added to this solution at 0° C., and the resulting mixture was stirred at 25° C. for 16 hours to obtain a colorless solution. Water (1.5 mL) was slowly added to the solution, followed by the slow addition of 15% aqueous sodium hydroxide solution (1.5 mL), and then water (4.5 mL) was slowly added. The resulting mixture was stirred at room temperature for 30 minutes, filtered, and the filtrate was concentrated to obtain a colorless oil. The oily substance was purified by silica gel chromatography (developing solvent: petroleum ether/ethyl acetate=20/1) to obtain 1.8 g (6.4 mmol) of the target product as a white solid.
^1H NMR (400MHz, _CDCl3 ) δ: 6.74 (d, J = 7.6Hz, 1H), 6.29 (br, 1H), 5.41 (d, J = 376Hz, 1H), 3.77 (s, 3H), 1.67 (br, 6H), 1.23 (d, J = 15.2Hz, 9H), 1.00-0.20 (br, 3H).
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ: 4.0-(-3.0)(br)

(4) Synthesis of AL-73 250 mg (0.89 mmol) of tert-butyl(5-methoxy-2,2-dimethyl-1,3-benzodioxol-4-yl)phosphineborane from (3) above was weighed out in a Schlenk flask, and 12 mL of tetrahydrofuran was added. The resulting solution was cooled to −78° C., and then 1.6 mL (0.98 mmol) of a toluene solution of potassium hexamethyldisilazane was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred at −78° C. for 1 hour. The mixture was then heated to 0° C., and 97 μL (0.89 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 3.3 mL of tetrahydrofuran was slowly added. The mixture was stirred at room temperature for 1 hour and 30 minutes, and the solvent was completely distilled off. The obtained solid was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=changed from 4/1 to 2/1) under air, and 134 mg of solid was obtained.
1.9 mL of methanol was added to 134 mg of the above solid, and the mixture was heated to 60° C. and stirred for 5 hours and 30 minutes. After stirring, the solvent was completely distilled off to obtain 116 mg of a solid. The purity determined by ³¹ P-NMR was 98%.
^1H NMR (400MHz, _CDCl3 ) δ: 6.70 (d, J = 8.4 Hz, 1H), 6.28 (dd, J = 8.8, 3.6 Hz, 1H), 4.55 (d, J = 9.2 Hz, 1H), 3.76 (s, 3H), 3.71 (dd, J = 16.0, 1.6 Hz, 1H), 2.04 (d, J = 16.0 Hz, 1H), 1.66 (s, 3H), 1.63 (s, 3H), 1.09 (d, J = 14.0 Hz, 9H).
^19F NMR (376MHz, _CDCl3 ) δ: -76.9 (q, J = 12.8Hz), -77.8 (q, J = 11.0Hz)
^31P { ^1H }NMR(162MHz, _CDCl3 ) δ: -30.5(m)

Comparative Synthesis Example 1 (Synthesis of AL-2al)
AL-2al represented by the following chemical formula was synthesized with reference to pages 51-52 of International Publication No. 2001/092342. A complex having ^{a 31P} { ^1H }-NMR purity of 90% was used in Comparative Example 1, and a complex having a ^31P { ^1H }-NMR purity of 76% was used in Comparative Example 2.

The autoclave used in the following polymerization experiments was thoroughly dried and purged with nitrogen before use.
[Example 1]
68.3 mg (0.25 mmol) of Ni(cod) ₂ was weighed out into a flask and dissolved in 25 mL of toluene. In addition, 13.3 mg (0.020 mmol) of AL-39 obtained in Synthesis Example 1 was weighed out into a separate flask. 20 mL of the toluene solution of Ni(cod) ₂ was weighed out and added to the flask containing AL-39. The resulting solution of the catalyst composition was warmed in a water bath at 40° C. and stirred for 15 minutes to obtain a catalyst composition solution (hereinafter referred to as the catalyst solution; AL-39 concentration: approximately 1 mM).
94 mL of toluene was added to a 0.2 L autoclave, and the temperature was raised to 90°C. Nitrogen was added so that the internal pressure of the autoclave was 0.5 MPa. Then, ethylene was added so that the internal pressure of the autoclave was 3.0 MPa. 0.1 mL of the above catalyst solution was injected into the catalyst cylinder, and 3 mL of toluene was added very slowly. Then, the obtained catalyst solution was pushed into the autoclave with high-pressure nitrogen, and this point was set as the reaction start time. 0.4 mL of the catalyst solution was injected into the catalyst cylinder, and 2 mL of toluene was added very slowly, and the obtained catalyst solution was added to the autoclave with high-pressure nitrogen 5 minutes after the start of the reaction. Furthermore, 0.5 mL of the catalyst solution was injected into the catalyst cylinder, and then 3 mL of toluene was added very slowly, and the obtained catalyst solution was added to the autoclave with high-pressure nitrogen 11 minutes after the start of the reaction. 12 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene, and the washing liquid was added to the autoclave with high-pressure nitrogen. 45 minutes after the start of the reaction, 3 mL of a toluene solution (0.2 M) of 1,2-butanediol was added to stop the reaction. The ethylene pressure was released, the autoclave was returned to room temperature, and 100 mL of acetone was added. The precipitated solid was collected by filtration, washed twice with 100 mL of acetone, and dried under reduced pressure. The obtained polymer weighed 3.17 g.

[Example 2]
A 10 mL catalyst solution (AL-39 concentration: about 2 mM) was prepared in the same manner as in Example 1, except that 68.9 mg (0.25 mmol) of Ni(cod) ₂ , 12 mL of toluene, 13.7 mg (0.020 mmol) of AL-39 and the toluene solution of Ni(cod) ₂ added to AL-39 were changed to 10 mL.
90 mL of toluene (hereinafter, toluene) was added to a 0.2 L autoclave. 0.3 mL (2.1 mmol) of tBA (hereinafter, comonomer and its added amount) and 0.3 mL of a toluene solution of TNOA (0.1 M) were injected from the reagent inlet (hereinafter, TNOA added amount). The temperature inside the autoclave was raised to 90° C., and nitrogen was added so that the internal pressure of the autoclave was 0.5 MPa (hereinafter, nitrogen pressure). Then, ethylene was added so that the internal pressure of the autoclave was 3.0 MPa (hereinafter, ethylene pressure). 2 mL of the above catalyst solution (hereinafter, initial catalyst) was injected into the catalyst cylinder and added to the autoclave with high-pressure nitrogen, and this point was the reaction start time. 3 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene, and the washing liquid was added to the autoclave with high-pressure nitrogen (hereinafter, initial washing and its time). 60 minutes after the start of the reaction (hereinafter, reaction time), 3 mL of a toluene solution (0.2 M) of 1,2-butanediol was added to stop the reaction (hereinafter, reaction stopper), and the ethylene pressure was released. The autoclave was returned to room temperature, and 100 mL of acetone was added. The precipitated solid was collected by filtration, washed twice with 100 mL of acetone (hereinafter, purification method), and dried under reduced pressure. The polymer obtained was 0.83 g.

[Example 3]
The same procedure as in Example 1 was carried out except that 87.6 mg (0.32 mmol) of Ni(cod) ₂ , 8 mL of toluene, 15.9 mg (0.024 mmol) of AL-39 and the toluene solution of Ni(cod) ₂ added to AL-39 were changed to 6 mL, and 6 mL of catalyst solution (AL-39 concentration: about 4 mM) was prepared.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the catalyst was added as described below and the polymerization conditions were changed as described below, to obtain 2.85 g of a polymer.
Toluene: 87 mL
Comonomer and its amount added: tBA (1.2 mL, 8.3 mmol)
Amount of TNOA added: 1.0 mL (0.10 mmol)
Initial catalyst: 3 mL of catalyst solution
Addition of catalyst: 15 minutes after the start of the reaction, 2 mL of catalyst solution was injected into the catalyst cylinder and added to the autoclave with high-pressure nitrogen. Furthermore, 17 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene and the washing liquid was added to the autoclave with high-pressure nitrogen.

[Example 4]
The same procedure as in Example 1 was carried out except that 87.9 mg (0.32 mmol) of Ni(cod) ₂ , 8 mL of toluene, 16.0 mg (0.024 mmol) of AL-39 and the toluene solution of Ni(cod) ₂ added to AL-39 were changed to 6 mL, and 6 mL of catalyst solution (AL-39 concentration: about 4 mM) was prepared.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the catalyst was added as described below and the polymerization conditions were changed as described below, to obtain 3.06 g of a polymer.
Toluene: 88 mL
Comonomer and its amount added: tBA (2.2 mL, 15 mmol)
Amount of TNOA added: 1.0 mL (0.10 mmol)
Initial catalyst: 2.5 mL of catalyst solution
Initial washing and its time: No washing. Addition of catalyst: 3 minutes after the start of the reaction, 2.5 mL of catalyst solution was poured into the catalyst cylinder and added to the autoclave with high-pressure nitrogen. 5 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene and the washing solution was added to the autoclave with high-pressure nitrogen.

[Example 5]
The same procedure as in Example 1 was carried out except that 65.8 mg (0.24 mmol) of Ni(cod) ₂ , 6 mL of toluene, 10.5 mg (0.016 mmol) of AL-39, and the toluene solution of Ni(cod) ₂ added to AL-39 were changed to 4 mL, to prepare 4 mL of catalyst solution (AL-39 concentration: about 4 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 1.04 g of a polymer.
Toluene: 90 mL
Comonomer and its amount added: tBA (3.6 mL, 25 mmol)
Amount of TNOA added: 0.5 mL (0.050 mmol)
Initial catalyst: 2.5 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Purification method: After the polymer was precipitated with 100 mL of acetone, 100 mL of acetone and 1 mL of an aqueous hydrochloric acid solution (10 wt%) were added and stored in a refrigerator overnight. After that, the polymer was washed twice with 100 mL of acetone.

[Example 6]
The same procedure as in Example 1 was carried out except that 77.0 mg (0.28 mmol) of Ni(cod) ₂ , 7 mL of toluene, 13.4 mg (0.020 mmol) of AL-39, and the toluene solution of Ni(cod) ₂ added to AL-39 were changed to 5 mL, to prepare 5 mL of a catalyst solution (AL-39 concentration: about 4 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the catalyst was added as described below and the polymerization conditions were changed as described below, to obtain 2.46 g of a polymer.
Toluene: 93 mL
Comonomer and its amount added: MA (0.9 mL, 10 mmol)
Amount of TNOA added: 0.5 mL (0.050 mmol)
Initial catalyst: 2.5 mL of catalyst solution
Addition of catalyst: 15 minutes after the start of the reaction, 1.5 mL of catalyst solution was injected into the catalyst cylinder and added to the autoclave with high-pressure nitrogen. 19 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene and the washings were added to the autoclave with high-pressure nitrogen.
Purification method: After the polymer was precipitated with 100 mL of acetone, 100 mL of acetone and 1 mL of an aqueous hydrochloric acid solution (10 wt%) were added and stored in a refrigerator overnight. After that, the polymer was washed twice with 100 mL of acetone.

[Example 7]
The same procedure as in Example 1 was carried out except that 10.7 mg (0.04 mmol) of Ni(acac) ₂ was used instead of Ni(cod) ₂ , 8 mL of toluene, 19.7 mg (0.03 mmol) of AL-39, and the amount of the toluene solution of the metal complex added to AL-39 was changed to 6 mL, to prepare 6 mL of a catalyst solution (AL-39 concentration: about 5 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 1.30 g of a polymer.
Toluene: 93 mL
Comonomer and its amount added: MA (0.9 mL, 10 mmol)
Amount of TNOA added: 0.5 mL (0.050 mmol)
Initial catalyst: 2 mL of catalyst solution
Initial washing and its time: 5 minutes after the start of the reaction, washing with 3 mL of toluene was performed.
Reaction quencher: Instead of the 1,2-butanediol in toluene, 1.0 mL of a 2M solution of diacetic acid in toluene was added.

[Example 8]
The same procedure as in Example 7 was carried out except that 10.3 mg (0.04 mmol) of Ni(acac) ₂ , 8 mL of toluene, 9.9 mg (0.015 mmol) of AL-39 and the toluene solution of Ni(acac) ₂ added to AL-39 were changed to 3 mL, and 3 mL of the catalyst solution (AL-39 concentration: about 5 mM) was prepared.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 1.33 g of a polymer.
Toluene: 94 mL
Comonomer and its amount added: MA (0.9 mL, 10 mmol)
Amount of TNOA added: 0.3 mL (0.030 mmol)
Reaction temperature: 100°C
Initial catalyst: 1.2 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing with 3 mL of toluene was performed.
Reaction quencher: Instead of the toluene solution of 1,2-butanediol, 0.3 mL of a toluene solution of diacetic acid (2 M) was added.

[Example 9]
Except for changing the amount of Ni(cod) ₂ to 68.4 mg (0.25 mmol) and the amount of AL-39 to 13.2 mg (0.02 mmol), the same procedure as in Example 1 was carried out to prepare 20 mL of a catalyst solution (AL-39 concentration: about 1 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the catalyst was added as described below and the polymerization conditions were changed as described below, to obtain 0.55 g of a polymer.
Toluene: 64 mL
Comonomer and its amount added: VC (approximately 9.9 mL, 13.5 g, 157 mmol)
Amount of TNOA added: 0.5 mL (0.050 mmol)
Nitrogen pressure: 0 MPa
Ethylene pressure: 2.5 MPa
Initial catalyst: 1 mL of catalyst solution
Initial washing and its time: 2.5 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Addition of catalyst: 7 minutes after the start of the reaction, 2 mL of catalyst solution, and 10 minutes, 14 minutes, and 16 minutes after the start of the reaction, 3 mL of catalyst solution were injected into the catalyst cylinder and added to the autoclave with high-pressure nitrogen. 19 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene, and the washings were added to the autoclave with high-pressure nitrogen.
Reaction time: 35 min

[Example 10]
The same procedure as in Example 1 was carried out except that 66.0 mg (0.24 mmol) of Ni(cod) ₂ , 24 mL of toluene, 12.9 mg (0.02 mmol) of AL-40 obtained in Synthesis Example 2 instead of AL-39, and 20 mL of the toluene solution of Ni(cod) ₂ added to AL-40 were used, to prepare 20 mL of a catalyst solution (AL-40 concentration: about 1 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the catalyst was added as described below and the polymerization conditions were changed as described below, to obtain 3.17 g of a polymer.
Toluene: 96 mL
Comonomer and its amount added: tBA (0.3 mL, 2.1 mmol)
Amount of TNOA added: 0.1 mL (0.010 mmol)
Initial catalyst: 1 mL of catalyst solution
Addition of catalyst: 17 minutes after the start of the reaction, 1 mL of catalyst solution was injected into the catalyst cylinder and added to the autoclave with high-pressure nitrogen. 19 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene and the washings were added to the autoclave with high-pressure nitrogen.
Reaction time: 42 min

[Example 11]
The same procedure as in Example 10 was carried out to prepare 10 mL of a catalyst solution (AL-40 concentration: approximately 2 mM), except that 65.7 mg (0.24 mmol) of Ni(cod) ₂ , 12 mL of toluene, 13.6 mg (0.02 mmol) of AL-40, and the toluene solution of Ni(cod) ₂ added to AL-40 were changed to 10 mL.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 2.83 g of a polymer.
Toluene: 92 mL
Comonomer and its amount added: tBA (1.2 mL, 8.3 mmol)
Amount of TNOA added: 0.3 mL (0.030 mmol)
Initial catalyst: 3 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Reaction time: 21 min

[Example 12]
The same procedure as in Example 10 was carried out except that the amount of Ni(cod) ₂ was changed to 55.3 mg (0.20 mmol), toluene to 10 mL, AL-40 to 10.0 mg (0.016 mmol), and the amount of the toluene solution of Ni(cod) ₂ added to AL-40 was changed to 8 mL, to prepare 8 mL of catalyst solution (AL-40 concentration: about 2 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 2.42 g of a polymer.
Toluene: 91 mL
Comonomer and its amount added: tBA (3.5 mL, 24 mmol)
Amount of TNOA added: 0.25 mL (0.025 mmol)
Initial catalyst: 2.5 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.

[Example 13]
The same procedure as in Example 10 was carried out to prepare 8 mL of a catalyst solution (AL-40 concentration: approximately 2 mM), except that 54.7 mg (0.20 mmol) of Ni(cod) ₂ , 10 mL of toluene, 10.6 mg (0.016 mmol) of AL-40, and the toluene solution of Ni(cod) ₂ added to AL-40 were changed to 8 mL.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 1.85 g of a polymer.
Toluene: 87 mL
Comonomer and its amount added: tBA (7.0 mL, 49 mmol)
Amount of TNOA added: 0.25 mL (0.025 mmol)
Initial catalyst: 2.5 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Purification method: After the polymer was precipitated with 100 mL of acetone, 100 mL of acetone and 1 mL of an aqueous hydrochloric acid solution (10 wt%) were added and stirred at room temperature for 30 minutes. Then, the polymer was washed twice with 100 mL of acetone.

[Example 14]
The same procedure as in Example 10 was carried out to prepare 8 mL of a catalyst solution (AL-40 concentration: approximately 2 mM), except that 54.8 mg (0.20 mmol) of Ni(cod) ₂ , 10 mL of toluene, 10.6 mg (0.016 mmol) of AL-40, and the toluene solution of Ni(cod) ₂ added to AL-40 were changed to 8 mL.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 2.44 g of a polymer.
Toluene: 92 mL
Comonomer and its amount added: MA (1.6 mL, 18 mmol)
Amount of TNOA added: 0.3 mL (0.030 mmol)
Initial catalyst: 3 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Purification method: After the polymer was precipitated with 100 mL of acetone, 100 mL of acetone and 1 mL of an aqueous hydrochloric acid solution (10 wt%) were added and stored in a refrigerator overnight. After that, the polymer was washed twice with 100 mL of acetone.

[Example 15]
The _{same procedure as in Example 10 was carried out to prepare 3 mL of a catalyst solution (AL-40 concentration: approximately 5 mM), except that 10.3 mg (0.04 mmol) of Ni(acac)2 was} used instead of Ni(cod)2, 8 mL of toluene, 9.7 mg (0.015 mmol) of AL-40, and 3 mL of the toluene solution of the metal complex added to AL-40 were used.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 1.99 g of a polymer.
Toluene: 94 mL
Comonomer and its amount added: MA (1.6 mL, 18 mmol)
Amount of TNOA added: 0.3 mL (0.030 mmol)
Initial catalyst: 1.2 mL of catalyst solution
Reaction quencher: Instead of the toluene solution of 1,2-butanediol, 0.3 mL of a toluene solution of diacetic acid (2 M) was added.
Reaction time: 43 min

[Example 16]
The same procedure as in Example 10 was carried out except that 55.7 mg (0.20 mmol) of Ni(cod) ₂ , 20 mL of toluene, 10.4 mg (0.016 mmol) of AL-40 and the toluene solution of Ni(cod) ₂ added to AL-40 were changed to 16 mL, and 16 mL of catalyst solution (AL-40 concentration: about 1 mM) was prepared.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the catalyst was added as described below and the polymerization conditions were changed as described below, to obtain 1.01 g of a polymer.
Toluene: 90 mL
Comonomer and its amount added: Toluene solution of NB (approximately 3.9 mL, 3.64 g, 0.753 g/g, 29 mmol)
TNOA: None Nitrogen pressure: 0.2 MPa
Ethylene pressure: 0.8 MPa (internal pressure 1.0 MPa)
Initial catalyst: 1 mL of catalyst solution was injected, followed by very slow addition of 2 mL of toluene, after which the resulting catalyst solution was added to the autoclave with high pressure nitrogen.
Initial washing and its time: 4 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Addition of catalyst: 15 minutes and 18 minutes after the start of the reaction, 2 mL of catalyst solution was injected into the catalyst cylinder and added to the autoclave with high-pressure nitrogen. 20 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene, and the washing liquid was added to the autoclave with high-pressure nitrogen. Furthermore, 26 minutes and 29 minutes after the start of the reaction, 3 mL of catalyst solution was injected into the catalyst cylinder and added to the autoclave with high-pressure nitrogen. 33 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene, and the washing liquid was added to the autoclave with high-pressure nitrogen.
Reaction time: 48 min

[Example 17]
The same procedure as in Example 10 was carried out except that 88.1 mg (0.32 mmol) of Ni(cod) ₂ , 8 mL of toluene, 15.7 mg (0.024 mmol) of AL-40, and the toluene solution of Ni(cod) ₂ added to AL-40 were changed to 6 mL, to prepare 6 mL of catalyst solution (AL-40 concentration: about 4 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 2.82 g of a polymer.
Toluene: 64 mL
Comonomer and its amount added: VC (approximately 9.7 mL, 13.2 g, 153 mmol)
TNOA: 0.5 mL (0.05 mmol)
Nitrogen pressure: 0 MPa
Ethylene pressure: 2.5 MPa
Initial catalyst: 2.5 mL of catalyst solution
Initial washing and its time: None Reaction time: 1 minute

[Example 18]
13.1 mg (0.015 mmol) of AL-40/NiArPy obtained in Synthesis Example 8 was weighed out, and 3 mL of toluene was added thereto to prepare a metal complex solution (hereinafter referred to as catalyst solution) (AL-40 concentration: about 5 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 2.48 g of a polymer.
Toluene: 94 mL
Comonomer and its amount added: MA (1.6 mL, 18 mmol)
Initial catalyst: 1.2 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Reaction time: 48 min

[Example 19]
The same procedure as in Example 1 was carried out except that 15.1 mg (0.06 mmol) of Ni(acac) ₂ was used instead of Ni(cod) ₂ , 6 mL of toluene was used, 19.0 mg (0.04 mmol) of AL-58 obtained in Synthesis Example 3 was used instead of AL-39, and the amount of the toluene solution of Ni(acac) ₂ added to AL-58 was changed to 4 mL, and 4 mL of the catalyst solution (AL-58 concentration: about 10 mM) was prepared.
Using the catalyst solution prepared above, the polymerization was carried out in the same manner as in Example 2, except that the catalyst was added as described below and the polymerization conditions were changed as described below, to obtain 0.17 g of a polymer.
Toluene: 93 mL
Comonomer and its amount added: MA (1.6 mL, 18 mmol)
Amount of TNOA added: 1.0 mL (0.10 mmol)
Initial catalyst: 1.0 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Addition of catalyst: 23 minutes after the start of the reaction, 2 mL of catalyst solution was injected into the catalyst cylinder and added to the autoclave with high-pressure nitrogen. 26 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene and the washings were added to the autoclave with high-pressure nitrogen.

[Example 20]
The same procedure as in Example 1 was carried out except that 15.6 mg (0.06 mmol) of Ni(acac) ₂ was used instead of Ni(cod) ₂ , 6 mL of toluene was used, 19.6 mg (0.04 mmol) of AL-59 obtained in Synthesis Example 4 was used instead of AL-39, and the amount of the toluene solution of Ni(acac) ₂ added to AL-59 was changed to 4 mL, and 4 mL of the catalyst solution (AL-59 concentration: about 10 mM) was prepared.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 1.64 g of a polymer.
Toluene: 93 mL
Comonomer and its amount added: MA (1.6 mL, 18 mmol)
Amount of TNOA added: 1.0 mL (0.10 mmol)
Initial catalyst: 1.0 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.

[Example 21]
The same procedure as in Example 1 was carried out except that 10.2 mg (0.04 mmol) of Ni(acac) ₂ was used instead of Ni(cod) ₂ , 8 mL of toluene, 11.2 mg (0.015 mmol) of AL-63 obtained in Synthesis Example 5 was used instead of AL-39, and the amount of the toluene solution of Ni(acac) ₂ added to AL-63 was changed to 3 mL, and 3 mL of the catalyst solution (AL-63 concentration: about 5 mM) was prepared.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 3.79 g of a polymer.
Toluene: 94 mL
Comonomer and its amount added: MA (1.6 mL, 18 mmol)
Initial catalyst: 1.2 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.

[Example 22]
The same procedure as in Example 1 was carried out except that 15.4 mg (0.06 mmol) of Ni(acac) ₂ was used instead of Ni(cod) ₂ , 6 mL of toluene was used, 23.8 mg (0.04 mmol) of AL-64 obtained in Synthesis Example 6 was used instead of AL-39, and the amount of the toluene solution of Ni(acac) ₂ added to AL-64 was changed to 4 mL, and 4 mL of the catalyst solution (AL-64 concentration: about 10 mM) was prepared.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 4.80 g of a polymer.
Toluene: 94 mL
Amount of TNOA added: 1.0 mL (0.10 mmol)
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Reaction time: 45 min

[Example 23]
The same procedure as in Example 1 was carried out except that 15.6 mg (0.060 mmol) of Ni(acac) ₂ was used instead of Ni(cod) ₂ , 6 mL of toluene was used, 21.9 mg (0.040 mmol) of AL-66 obtained in Synthesis Example 7 was used instead of AL-39, and the amount of the toluene solution of Ni(acac) ₂ added to AL-66 was changed to 4 mL, and 4 mL of the catalyst solution (AL-66 concentration: about 10 mM) was prepared.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 3.11 g of a polymer.
Toluene: 94 mL
Amount of TNOA added: 0.5 mL (0.05 mmol)
Comonomer and its amount added: MA (0.9 mL, 10 mmol)
Initial catalyst: 1.0 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Reaction quencher: 0.5 mL of diacetic acid was added in place of 1,2-butanediol.
Reaction time: 43 min

[Example 24]
The same procedure as in Example 1 was carried out except that 15.4 mg (0.060 mmol) of Ni(acac) ₂ was used instead of Ni(cod) ₂ , 6 mL of toluene was used, 16.9 mg (0.040 mmol) of AL-70 obtained in Synthesis Example 9 was used instead of AL-39, and the amount of the toluene solution of Ni(acac) ₂ added to AL-70 was changed to 4 mL, and 4 mL of the catalyst solution (AL-70 concentration: about 10 mM) was prepared.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 0.25 g of a polymer.
Toluene: 94 mL
Amount of TNOA added: 1.0 mL (0.10 mmol)
Comonomer and its amount added: MA (0.3 mL, 3.3 mmol)
Initial catalyst: 1.0 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Reaction quencher: 0.5 mL of diacetic acid was added in place of 1,2-butanediol.

[Example 25]
The same procedure as in Example 1 was carried out except that 10.3 mg (0.040 mmol) of Ni(acac) ₂ was used instead of Ni(cod) ₂ , 8 mL of toluene, 12.4 mg (0.015 mmol) of AL-72 obtained in Synthesis Example 10 was used instead of AL-39, and the amount of the toluene solution of Ni(acac) ₂ added to AL-72 was changed to 3 mL, and 3 mL of the catalyst solution (AL-72 concentration: about 5 mM) was prepared.
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 2, except that the polymerization conditions were changed as follows, to obtain 2.29 g of a polymer.
Toluene: 94 mL
Comonomer and its amount added: MA (1.6 mL, 18 mmol)
Initial catalyst: 1.2 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Reaction quencher: 0.3 mL of diacetic acid was added in place of 1,2-butanediol.

[Example 26]
The same procedure as in Example 1 was carried out except that 15.1 mg (0.060 mmol) of Ni(acac) ₂ was used instead of Ni(cod) ₂ , 6 mL of toluene was used, 17.6 mg (0.040 mmol) of AL-73 obtained in Synthesis Example 11 was used instead of AL-39, and the amount of the toluene solution of Ni(acac) ₂ added to AL-73 was changed to 4 mL, and 4 mL of the catalyst solution (AL-73 concentration: about 10 mM) was prepared.
Using the catalyst solution prepared above, the polymerization was carried out in the same manner as in Example 2, except that the catalyst was added as described below and the polymerization conditions were changed as described below, to obtain 2.72 g of a polymer.
Toluene: 95 mL
Comonomer and its amount added: MA (0.3 mL, 3.3 mmol)
Amount of TNOA added: 1.0 mL (0.10 mmol)
Initial catalyst: 1.0 mL of catalyst solution
Initial washing and its time: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Addition of catalyst: 9 minutes after the start of the reaction, 1 mL of catalyst solution was injected into the catalyst cylinder and added to the autoclave with high-pressure nitrogen. 14 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene and the washings were added to the autoclave with high-pressure nitrogen.
Reaction time: 39 min

[Example 27]
The same procedure as in Example 1 was carried out except that 16.8 mg (0.060 mmol) of Ni(cod) ₂ , 6 mL of toluene, 19.8 mg (0.040 mmol) of AL-58 obtained in Synthesis Example 3 was used instead of AL-39, and the amount of the toluene solution of Ni(cod) ₂ added to AL-58 was changed to 4 mL, to prepare 4 mL of a catalyst solution (AL-58 concentration: about 10 mM).
50 mL of toluene was added to a 0.2 L autoclave. 25 g of propylene was added, and the temperature inside the autoclave was raised to 50°C. 2 mL of the above catalyst solution (hereinafter, initial catalyst-2) was poured into the catalyst cylinder and added to the autoclave with high-pressure nitrogen, and this point was the reaction start time. 3 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene, and the washing solution was added to the autoclave with high-pressure nitrogen (hereinafter, initial washing and its time-2). 60 minutes after the start of the reaction (hereinafter, reaction time-2), 3 mL of a toluene solution of 1,2-butanediol (0.2 M) was added to stop the reaction, and propylene was depressurized.
Purification method: The collected toluene solution was concentrated to obtain a yellow oily polymer. The obtained polymer was dissolved in 10 mL of heptane, and 100 mg of ISOLUTE (registered trademark) SCX-2 (Biotage) was added. The mixture was stirred at 80°C for one hour, the SCX-2 was removed by filtration, and the mixture was concentrated in an evaporator to obtain a colorless and transparent polymer. The polymer was vacuum-dried at 80°C for more than 3 hours to obtain 0.03 g of polymer.

[Example 28]
The same procedure as in Example 1 was carried out except that 16.4 mg (0.060 mmol) of Ni(cod) ₂ , 6 mL of toluene, 19.9 mg (0.040 mmol) of AL-59 obtained in Synthesis Example 4 instead of AL-39, and 4 mL of the toluene solution of Ni(cod) ₂ added to AL-59 were used, to prepare 4 mL of a catalyst solution (AL-59 concentration: about 10 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 27, except that the polymerization conditions were changed as follows, to obtain 6.11 g of a polymer.
Initial washing and its time-2: Five minutes after the start of the reaction, washing was performed with 3 mL of toluene.

[Example 29]
The same procedure as in Example 1 was carried out except that 16.3 mg (0.060 mmol) of Ni(cod) ₂ , 6 mL of toluene, 14.9 mg (0.030 mmol) of AL-59 obtained in Synthesis Example 4 instead of AL-39, and 3 mL of the toluene solution of Ni(cod) ₂ added to AL-59 were used, to prepare 3 mL of a catalyst solution (AL-59 concentration: about 10 mM).
43 mL of toluene was added to a 0.2 L autoclave. 2.2 mL (10 mmol) of MU and 0.2 mL of a toluene solution (0.1 M) of Al(OiPr) ₃ were added from the reagent inlet. 25 g of propylene was added, and the temperature inside the autoclave was raised to 50°C. 2 mL of the above catalyst solution was injected into the catalyst cylinder and added to the autoclave with high-pressure nitrogen, and this point was designated as the reaction start time. Two minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene, and the washings were added to the autoclave with high-pressure nitrogen. 60 minutes after the start of the reaction, 3 mL of a toluene solution (0.2 M) of 1,2-butanediol was added to stop the reaction, and the propylene was depressurized.
Purification method: The recovered toluene solution was concentrated to obtain a yellow oily liquid. The obtained liquid was heated to 120°C and dried in vacuum for 20 minutes. The polymer was then heated to 150°C and dried in vacuum for 40 minutes. 10 mL of heptane was added, and 100 mg of ISOLUTE® SCX-2 (Biotage) was added. The mixture was stirred at 80°C for 1 hour, the SCX-2 was removed by filtration, and the mixture was concentrated in an evaporator to obtain a colorless and transparent polymer. The obtained liquid was dried at 80°C for more than 3 hours to obtain 0.57 g of polymer.

[Example 30]
The same procedure as in Example 1 was carried out except that 13.8 mg (0.050 mmol) of Ni(cod) ₂ , 5 mL of toluene, 23.0 mg (0.030 mmol) of AL-63 obtained in Synthesis Example 5 instead of AL-39, and 3 mL of the toluene solution of Ni(cod) ₂ added to AL-63 were used, to prepare 3 mL of a catalyst solution (AL-63 concentration: about 10 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 27, except that the polymerization conditions were changed as follows, to obtain 4.80 g of a polymer.
Initial catalyst-2: 1.0 mL
Initial washing and its time-2: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.
Reaction time-2: 6 minutes

[Example 31]
The same procedure as in Example 1 was carried out except that 13.8 mg (0.050 mmol) of Ni(cod) ₂ , 5 mL of toluene, 17.9 mg (0.030 mmol) of AL-64 obtained in Synthesis Example 6 was used instead of AL-39, and the amount of the toluene solution of Ni(cod) ₂ added to AL-64 was changed to 3 mL, to prepare 3 mL of a catalyst solution (AL-64 concentration: about 10 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 27, except that the polymerization conditions were changed as follows, to obtain 6.87 g of a polymer.
Initial catalyst-2: 1.0 mL
Initial washing and its time-2: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.

[Example 32]
The same procedure as in Example 1 was carried out except that 13.8 mg (0.050 mmol) of Ni(cod) ₂ , 5 mL of toluene, 16.3 mg (0.030 mmol) of AL-66 obtained in Synthesis Example 7 was used instead of AL-39, and the amount of the toluene solution of Ni(cod) ₂ added to AL-66 was changed to 3 mL, to prepare 3 mL of a catalyst solution (AL-66 concentration: about 10 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 27, except that the polymerization conditions were changed as follows, to obtain 6.30 g of a polymer.
Initial catalyst-2: 1.0 mL
Initial washing and its time-2: 2 minutes after the start of the reaction, washing was performed with 3 mL of toluene.

[Example 33]
The same procedure as in Example 1 was carried out except that 16.9 mg (0.060 mmol) of Ni(cod) ₂ , 6 mL of toluene, 17.2 mg (0.040 mmol) of AL-70 obtained in Synthesis Example 9 was used instead of AL-39, and the amount of the toluene solution of Ni(cod) ₂ added to AL-70 was changed to 4 mL, to prepare 4 mL of a catalyst solution (AL-70 concentration: about 10 mM).
Using the catalyst solution prepared above, polymerization was carried out in the same manner as in Example 27, except that the polymerization conditions were changed as follows, to obtain 1.11 g of a polymer.
Initial catalyst-2: 1.0 mL

[Comparative Example 1]
92.6 mg (0.18 mmol) of tris(pentafluorophenyl)borane was weighed out in a flask, and 6 mL of toluene was added to dissolve it. 13.0 mg (0.03 mmol) of AL-2al was weighed out in a separate flask, and 5 mL of a toluene solution of tris(pentafluorophenyl)borane was added thereto. This solution was stirred at room temperature for 30 minutes to prepare a catalyst solution (6 mM).
92 mL of toluene was added to a 0.2 L autoclave, and the temperature was raised to 90°C. Nitrogen was added so that the internal pressure of the autoclave was 0.5 MPa. Then, ethylene was added so that the internal pressure of the autoclave was 3.0 MPa. 0.5 mL of the above catalyst solution and 2.5 mL of toluene were added to the catalyst cylinder, and the resulting catalyst solution was added to the autoclave with 3.3 MPa of nitrogen, and this point was the reaction start time. 5 minutes and 12 minutes after the start of the reaction, 1.0 mL and 2.5 mL of the catalyst solution were added, respectively. 16 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene, and the washing solution was added to the autoclave. 60 minutes after the start of the reaction, a toluene solution (0.2 M) of 1,2-butanediol was added to stop the reaction, and ethylene was depressurized. The autoclave was returned to room temperature, and acetone (100 mL) was added. The precipitated solid was collected by filtration, washed with acetone (100 mL x 2), and dried under reduced pressure. The obtained polymer was 0.57 g.

[Comparative Example 2]
A catalyst solution (10 mM) was prepared in the same manner as in Comparative Example 1, except that the amount of tris(pentafluorophenyl)borane was changed to 383.5 mg (0.75 mmol), the amount of toluene was changed to 15 mL, the amount of AL-2al was changed to 25.9 mg (0.06 mmol), and the amount of the toluene solution of tris(pentafluorophenyl)borane was changed to 6 mL.
To a 0.2 L autoclave, 91 mL of toluene, 0.3 mL (2.1 mmol) of tBA, and 100 μL of a toluene solution of TNOA (0.1 M) were added, and the temperature was raised to 90°C.
Nitrogen was added to the autoclave so that the internal pressure was 0.5 MPa. Ethylene was then added to the autoclave so that the internal pressure was 3.0 MPa. 2.5 mL of the above catalyst solution was added to the catalyst cylinder, and the reaction was started when 3.3 MPa of nitrogen was added to the autoclave. 3 minutes after the reaction started, 2.5 mL of the catalyst solution was added. 6 minutes after the reaction started, the catalyst cylinder was washed with 3 mL of toluene, and the washings were added to the autoclave. 60 minutes after the reaction started, a toluene solution (0.2 M) of 1,2-butanediol was added to stop the reaction, and the ethylene was depressurized. The autoclave was returned to room temperature, and 100 mL of acetone was added. The precipitated solid was collected by filtration, washed twice with 100 mL of acetone, and dried under reduced pressure. The polymer obtained was 0.016 g.

[Comparative Example 3]
384.0 mg (0.75 mmol) of tris(pentafluorophenyl)borane was weighed out into a flask, and 15 mL of toluene was added to dissolve it. 26.0 mg (0.06 mmol) of AL-2al was weighed out into another flask, and 6 mL of a toluene solution of tris(pentafluorophenyl)borane was added thereto. This solution was stirred at room temperature for 30 minutes to prepare a catalyst solution (10 mM).
50 mL of toluene and 25 g of propylene were added to a 0.2 L autoclave, and the temperature inside the autoclave was raised to 50°C. 2.5 mL of the above catalyst solution was poured into the catalyst cylinder and added to the autoclave with high-pressure nitrogen, and this point was the reaction start time. 4 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene, and the washing liquid was added to the autoclave with high-pressure nitrogen. 8 minutes after the start of the reaction, 2.5 mL of the above catalyst solution was poured into the catalyst cylinder and added to the autoclave with high-pressure nitrogen. 10 minutes after the start of the reaction, the catalyst cylinder was washed with 3 mL of toluene, and the washing liquid was added to the autoclave with high-pressure nitrogen. 60 minutes after the start of the reaction, 3 mL of a toluene solution of 1,2-butanediol (0.2 M) was added to stop the reaction, and propylene was depressurized. The autoclave was returned to room temperature, and toluene was distilled off to obtain oily polypropylene. The obtained polypropylene was purified by silica gel column chromatography (developing solvent: 100% hexane) under air. The resulting oily substance was dried under reduced pressure to give 0.021 g of polypropylene.

The polymerization conditions for Examples 1 to 26 are summarized in Table 1, the results obtained are summarized in Table 2, the polymerization conditions for Examples 27 to 33 are summarized in Table 3, the results obtained are summarized in Table 4, the polymerization conditions for Comparative Examples 1 to 3 are summarized in Table 5, and the results obtained are summarized in Table 6 or 7. In the tables, "n.m." means not measured (sufficient sample amount for measurement was not obtained), and "n.d." means not detected (below detection limit).

By comparing the above-mentioned examples of the present invention with the comparative examples, it has been revealed that the novel compound that can be used as a ligand of the present invention, the metal complex using the novel compound, the catalyst composition for olefin polymerization, and the catalyst for olefin polymerization, as well as the process for producing an olefin-based polymer using the catalyst, have improved catalytic performance such as activity and molecular weight, and can be used for the polymerization or copolymerization of olefins, and in particular can copolymerize a non-cyclic olefin with at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins.

Claims (16)

A compound represented by the following general formula (A):
[In the formula (A),
^X1 represents an oxygen atom or a sulfur atom;
^E1 represents a nitrogen atom, a phosphorus atom, an arsenic atom, or an antimony atom;
Z represents a hydrogen atom, a leaving group, or a cation having a valence of 1 to 4,
m is an integer from 1 to the valence of Z,
n is 0, 1, 2, 3 or 4, and when n is 0, E ¹ is directly bonded to the carbon atom to which X ¹ , R ⁵ and R ⁶ are bonded;
R ¹ represents a hydrocarbon group represented by the following general formula (B) or (C):
^R2 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom and which is different from the hydrocarbon group represented by the following general formula (B) or (C),
l is 1 or 2, and when l is 2, ^R2 is absent.
R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent 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 contain at least one heteroatom; (iv) OR ^b , C(O)OR ^b , C(O)OM', C(O)N(R ^a ) ₂ , C(O)R ^b , OC(O)R ^b , SR ^b , S(O) ₂ R ^b , S(O)R ^b , OS(O) ₂ R ^b , SF ₅ , P(O)(OR ^b ) _2-y (R ^a ) _y , CN, N(H)R ^a , N(R ^b ) ₂ , Si(OR ^a ) _3-x (R ^a ) _x , OSi(OR ^a ) _3-x (R ^a ) _x , NO ₂ , S(O) ₂ OM', P(O)(OM') ₂ , P(O)(OR ^b ) ₂ M', or an epoxy-containing group (wherein R ^a each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ^b each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents 0, 1, 2 or 3, and y represents 0, 1 or 2). Adjacent substituents of R ³ , R ⁴ , R ⁵ and R ⁶ may be linked together to form a 5-8 membered alicyclic ring or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom. ]
[In formula (B) and formula (C),
* represents a bond to ^E1 ;
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent an atom or group selected from the group consisting of (i) to (iv) defined in formula (A), and adjacent substituents of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be bonded to each other to form a 5- to 8-membered alicyclic ring, aromatic ring, or heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom;
A ¹ , A ² , A ³ and A ⁴ each independently represent an oxygen atom, a sulfur atom, -C(R) ₂ -, -S(O)-, -S(O) ₂ -, -N(R)-, -P(R)- or -P(O)(R)- (wherein each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom).
however,
In formula (B), at least three of A ¹ , A ² , A ³ and A ⁴ are other than —C(R) ₂ —;
In formula (C), ^A3 and ^A4 are both other than -C(R) _2- , and at least one of ^R12 and ^R13 is an atom or group selected from the group consisting of (ii) and (iv) (excluding epoxy-containing groups).
W ¹ and W ² each independently represent a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O) ₂ -; when W 1 and W 2 represent a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R ⁸ and R ¹⁰ do not exist, and when W 1 and W 2 represent an oxygen atom or -S(O) ₂ -, R ⁷ and R ⁸ , as well as R ⁹ and R ¹⁰ do not exist.
h and i each independently represent an integer of 1 to 6, and when a plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are present, the plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different.] A metal complex represented by the following general formula (D):
[In the formula (D),
^X1 represents an oxygen atom or a sulfur atom;
^E1 represents a nitrogen atom, a phosphorus atom, an arsenic atom, or an antimony atom;
n is 0, 1, 2, 3 or 4, and when n is 0, E ¹ is directly bonded to the carbon atom to which X ¹ , R ⁵ and R ⁶ are bonded;
R ¹ represents a hydrocarbon group represented by the following general formula (B) or (C):
^R2 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom and which is different from the hydrocarbon group represented by the following general formula (B) or (C),
l is 1 or 2, and when l is 2, ^R2 is absent.
R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent 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 contain at least one heteroatom; (iv) OR ^b , C(O)OR ^b , C(O)OM', C(O)N(R ^a ) ₂ , C(O)R ^b , OC(O)R ^b , SR ^b , S(O) ₂ R ^b , S(O)R ^b , OS(O) ₂ R ^b , SF ₅ , P(O)(OR ^b ) _2-y (R ^a ) _y , CN, N(H)R ^a , N(R ^b ) ₂ , Si(OR ^a ) _3-x (R ^a ) _x , OSi(OR ^a ) _3-x (R ^a ) _x , NO ₂ , S(O) ₂ OM', P(O)(OM') ₂ , P(O)(OR ^b ) ₂ M' or an epoxy-containing group (wherein R ^a each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ^b each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents 0, 1, 2 or 3, y represents 0, 1 or 2). Adjacent substituents of R ³ , R ⁴ , R ⁵ and R ⁶ may be linked together to form a 5-8 membered alicyclic ring or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom.
^M1 represents a nickel atom or a palladium atom;
^L1 and ^L2 each independently represent a ligand coordinated to ^M1 ;
^L1 and ^L2 may be bonded to each other to form a ring containing ^M1 .
[In formula (B) and formula (C),
* represents a bond to ^E1 ;
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent an atom or group selected from the group consisting of (i) to (iv) defined in formula (A), and adjacent substituents of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be bonded to each other to form a 5- to 8-membered alicyclic ring, aromatic ring, or heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom;
A ¹ , A ² , A ³ and A ⁴ each independently represent an oxygen atom, a sulfur atom, -C(R) ₂ -, -S(O)-, -S(O) ₂ -, -N(R)-, -P(R)- or -P(O)(R)- (wherein each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom).
however,
In formula (B), at least three of A ¹ , A ² , A ³ and A ⁴ are other than —C(R) ₂ —;
In formula (C), ^A3 and ^A4 are both other than -C(R) _2- , and at least one of ^R12 and ^R13 is an atom or group selected from the group consisting of (ii) and (iv) (excluding epoxy-containing groups).
W ¹ and W ² each independently represent a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O) ₂ -; when W 1 and W 2 represent a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R ⁸ and R ¹⁰ do not exist, and when W 1 and W 2 represent an oxygen atom or -S(O) ₂ -, R ⁷ and R ⁸ , as well as R ⁹ and R ¹⁰ do not exist.
h and i each independently represent an integer of 1 to 6, and when a plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are present, the plurality of W ¹ , W ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different.] A catalyst composition for olefin polymerization comprising the compound represented by the general formula (A) according to claim 1 and a transition metal compound represented by the following general formula (E) or (F):
[In the formula (E) and the formula (F),
^M1 represents a nickel atom or a palladium atom;
^L1 and ^L2 each independently represent a ligand coordinated to ^M1 ;
^L1 and ^L2 may be bonded to each other to form a ring containing ^M1 .
^M2 and ^M3 each independently represent a nickel atom or a palladium atom;
^L3 , ^L4 , ^L5 , ^L6 , ^L9 and ^L10 each independently represent a ligand coordinated to ^M1 , ^M2 or ^M3 ; ^L7 and ^L8 each independently represent a ligand coordinated to ^M2 and ^M3 ;
q is 0, 1 or 2;
^L3 and ^L4 may be bonded to each other to form a ring containing ^M1 ;
^L5 and ^L6 may be bonded to each other to form a ring containing ^M2 ;
^L9 and ^L10 may be bonded to each other to form a ring including ^M3 . The compound according to claim 1, wherein at least one of ^R5 and ^R6 is an atom or group selected from the group consisting of (i), (iii) and (iv). 3. The metal complex according to claim 2, wherein at least one of ^R5 and ^R6 is an atom or group selected from the group consisting of (i), (iii) and (iv). The catalyst composition for olefin polymerization according to claim 3, wherein at least one of ^R5 and ^R6 is an atom or group selected from the group consisting of (i), (iii) and (iv). The compound according to claim 1, characterized in that R ⁵ is an atom or group selected from the group consisting of (i) and (iii), and R ⁶ is an atom or group selected from the group consisting of (i), (iii), C(O)OR ^b , C(O)N(R ^a ) ₂ , C(O)R ^b , S(O) ₂ R ^b and P(O)(OR ^b ) _2-y (R ^a ) _y (wherein R ^a , R ^b and y are as defined in claim 1). The metal complex according to claim 2, wherein R ⁵ is an atom or group selected from the group consisting of (i) and (iii), and R ⁶ is an atom or group selected from the group consisting of (i), (iii), C(O)OR ^b , C(O)N(R ^a ) ₂ , C(O)R ^b , S(O) ₂ R ^b and P(O)(OR ^b ) _2-y (R ^a ) _y (wherein R ^a , R ^b and y are as defined in claim 2). The catalyst composition for olefin polymerization according to claim 3, characterized in that R ⁵ is an atom or group selected from the group consisting of (i) and (iii), and R ⁶ is an atom or group selected from the group consisting of (i), (iii), C(O)OR ^b , C(O)N(R ^a ) ₂ , C(O)R ^b , S(O) ₂ R ^b and P(O)(OR ^b ) _2-y (R ^a ) _y (wherein R ^a , R ^b and y are as defined in claim 1). The compound according to any one of claims 1, 4 and 7, characterized in that at least one of ^R3 and ^R4 is an atom or group selected from the group consisting of (i), (iii) and (iv). The metal complex according to any one of claims 2, 5 and 8, wherein at least one of ^R3 and ^R4 is an atom or group selected from the group consisting of (i), (iii) and (iv). The catalyst composition for olefin polymerization according to any one of claims 3, 6 and 9, characterized in that at least one of ^R3 and ^R4 is an atom or group selected from the group consisting of (i), (iii) and (iv). An olefin polymerization catalyst comprising the olefin polymerization catalyst composition according to claim 3. An olefin polymerization catalyst comprising the metal complex according to claim 2. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 13 or 14. The method for producing an olefin-based polymer according to claim 15, characterized in that a non-cyclic olefin is copolymerized with at least one monomer selected from the group consisting of a polar group-containing monomer and a cyclic olefin.